| WO/1996/033177 | 3-PHENYL-1,4-DIALKYL-1,2,4-TRIAZOLIUM SALTS AND THEIR USE AS ANTIDEPRESSANTS |
| WO/1995/028374 | PROCESS FOR PRODUCING TRIAZOLE DERIVATIVE |
| JPS5671078 | MANUFACTURE OF 1*2*44TRIAZOLE |
BOUDET NADEGE (DE)
MUELLER BERND (DE)
QUINTERO PALOMAR MARIA ANGELICA (DE)
ESCRIBANO CUESTA ANA (DE)
LAUTERWASSER ERICA MAY WILSON (DE)
LOHMANN JAN KLAAS (DE)
GROTE THOMAS (DE)
KRETSCHMER MANUEL (DE)
CRAIG IAN ROBERT (DE)
| WO2015014733A1 | 2015-02-05 |
| GB2145717A | 1985-04-03 | |||
| FR2535321A1 | 1984-05-04 |
| Claims 1. Compounds of the formula I wherein A is CH or N; R1 is Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl or C3-C6-cycloalkyl; wherein the aliphatic moieties of R1 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R1a which independently of one another are selected from: R1a halogen, OH, CN, Ci-C4-alkoxy, C3-C6-cycloalkyl, C3-C5-halogencycloalkyl and Ci-C4-halogenalkoxy; wherein the cycloalkyi moieties of R1 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R1b which independently of one another are selected from: R1b halogen, OH, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C6- cycloalkyl, C3-C6-halogencycloalkyl and Ci-C4-halogenalkoxy; R2 is hydrogen, Ci-C4-alkyl, C2-C4-alkenyl or C2-C4-alkynyl; wherein the aliphatic moieties of R2 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R2a which independently of one another are selected from: R2a halogen, OH, CN, Ci-C4-alkoxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl and Ci-C4-halogenalkoxy; R3 is selected from halogen, CN, Ci-C4-alkyl, Ci-C4-alkoxy, C2-C4-alkenyl, C2-C4- alkynyl, C3-C6-cycloalkyl and S(0)p(Ci-C4-alkyl), wherein each of R3 is unsubstituted or further substituted by one, two, three or four R3a; wherein R3a is independently selected from halogen, CN, OH, Ci-C4-alkyl, C1-C4- halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, Ci-C4-alkoxy and Ci- C4-halogenalkoxy; p is 0, 1 or 2; Z is halogen, CN, Ci-C6-alkyl, Si(Ci-C4-alkyl)3, Ci-C6-alkoxy or C(=0)-0-(Ci-C6-alkyl); wherein the aliphatic moieties of Z are not further substituted or carry one, two, three or four identical or different groups Rz, which independently of one another are selected from Rz halogen, CN, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6- halogencycloalkyl, O-C6H5, Ci-C4-alkoxy and Ci-C4-halogenalkoxy; and the N-oxides and the agriculturally acceptable salts thereof. 2. The compounds of claim 1 , wherein A is N. 3. The compounds of claim 1 , wherein A is CH. 4. The compounds of any one of claims 1 to 3, wherein Z is halogen. 5. The compounds of any one of claims 1 to 3, wherein Z is Ci-C6-alkyl that is unsubstituted or substituted as defined in claim 1. 6. The compounds of any one of claims 1 to 3, wherein Z is Ci-C6-alkoxy that is unsubstituted or substituted as defined in claim 1. 7. The compounds of any one of claims 1 to 3, wherein Z is Si(Ci-C4-alkyl)3 8. The compounds of any one of claims 1 to 7, wherein R2 is hydrogen. 9. The compounds of any one of claims 1 to 8, wherein R3 is F, CI, Br, CN, Ci-C4-alkyl, Ci- C4-halogenalkyl, Ci-C4-alkoxy or S(Ci-C4-alkyl). 10. A composition, comprising one compound of formula I, as defined in any of the claims 1 to 9, an N-oxide or an agriculturally acceptable salt thereof. 1 1. The composition according to claim 10, comprising additionally a further active substance. 12. A use of a compound of the formula I, as defined in any of the claims 1 to 9, and/or of an agriculturally acceptable salt thereof or of the compositions, as defined in any of the claims 10 or 1 1 , for combating phytopathogenic fungi. 13. A method for combating phytopathogenic fungi, comprising treating the fungi or the materials, plants, the soil or seeds to be protected against fungal attack with an effective amount of at least one compound of formula I , as defined in any of the claims 1 to 9 or with a composition, as defined in any of the claims 10 or 1 1. 14. Seed, coated with at least one compound of the formula I, as defined in any of the claims 1 to 9, and/or an agriculturally acceptable salt thereof or with a composition, as defined in any of the claims 10 or 11 , in an amount of from 0.1 to 10 kg per 100 kg of seed. |
Description
The present invention relates to substituted [1 ,2,4]triazole and imidazole compounds and the N- oxides and the salts thereof for combating phytopathogenic fungi, and to the use and methods for combating phytopathogenic fungi and to seeds coated with at least one such compound. The invention also relates to processes for preparing these compounds, intermediates, processes for preparing such intermediates, and to compositions comprising at least one compound I.
DE 3430833 relates to alpha-(ethynylphenyl)-alpha-hydrocarbyl-1 H-azol-1 -ethanoles and their use as fungicides.
In many cases, in particular at low application rates, the fungicidal activity of the known fungicidal compounds is unsatisfactory. Based on this, it was an object of the present invention to provide compounds having improved activity and/or a broader activity spectrum against phyto- pathogenic harmful fungi.
Surprisingly, this object is achieved by the use of the inventive substituted [1 ,2,4]triazole and imidazole compounds of formula I having favorable fungicidal activity against phytopathogenic fungi.
Accordingly, the present invention relates to the com ounds of the formula I
wherein
A is CH or N;
R 1 is Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl or C3-C6-cycloalkyl;
wherein the aliphatic moieties of R 1 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R 1a which independently of one another are selected from:
R 1a halogen, OH , CN, Ci-C4-alkoxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl and C1-C4- halogenalkoxy;
wherein the cycloalkyl moieties of R 1 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R 1 which independently of one another are selected from:
R 1b halogen, OH , CN , Ci-C 4 -alkyl, Ci-C 4 -alkoxy, Ci-C 4 -halogenalkyl, C 3 -C 6 -cycloalkyl, C 3 -C 5 - halogencycloalkyl and Ci-C 4 -halogenalkoxy;
R 2 is hydrogen, Ci-C 4 -alkyl, C2-C 4 -alkenyl or C2-C 4 -alkynyl;
wherein the aliphatic moieties of R 2 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R 2a which independently of one another are selected from:
R 2a halogen, OH, CN, Ci-C4-alkoxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl and C1-C4- halogenalkoxy;
R 3 is selected from halogen, CN, Ci-C4-alkyl, Ci-C4-alkoxy, C2-C4-alkenyl, C2-C4-alkynyl, C3- C6-cycloalkyl and S(0) p (Ci-C4-alkyl), wherein each of R 3 is unsubstituted or further substituted by one, two, three or four R 3a ; wherein
R 3a is independently selected from halogen, CN, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, C3-C6- cycloalkyl, C3-C6-halogencycloalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy;
p is 0, 1 or 2;
Z is halogen, CN, Ci-C 3 -alkyl, Si(Ci-C 4 -alkyl) 3 , Ci-C 3 -alkoxy or C(=0)-0-(Ci-C 6 -alkyl);
wherein the aliphatic moieties of Z are not further substituted or carry one, two, three or four identical or different groups R z , which independently of one another are selected from
R z halogen, CN, OH, Ci-C 4 -alkyl, Ci-C 4 -halogenalkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 - halogencycloalkyl, O-C6H5, Ci-C4-alkoxy and Ci-C4-halogenalkoxy;
and the N-oxides and the agriculturally acceptable salts thereof.
Compounds I can be accessed from compounds II by using a suitable cross coupling method known to a skilled person. In particular, compounds II can be reacted with alkynes in the presence of a transition metal catalyst such as copper(l) salts, palladium, platinum, rhodium, iridium or aluminium complexes. Preferably Cul, Pd(PPh3)C or Pd(PPh3)4 or Pd(dppf)2Cl2, or mixtures thereof are used in a solvent (such as THF, DMF, MeCN, NEt.3, Et(iPr2)N, pyrrolidine, piperidine, pyridine, diethylamine) and using a base (such as NEt 3 , Et(iPr 2 )N, pyrrolidine, piperidine, pyridine, diethylamine). (See e.g. Tetrahedron: Asymmetry, 18(17), 2086-2090; 2007; Angewandte Chemie, International Edition, 43(29), 3814-3818; 2004; Organometallics, 25(24), 5768-5773; 2006
I (R 2
"Hal" in compound II is Br, CI or F; preferably, Hal is Br or CI. It may be appropriate to exchange these halogens by an iodide (resulting in compounds lla) using a method described in Journal of the American Chemical Society, 2002, 124, 14844-14845 before following the procedure described above.
It may be appropriate to prepare compounds I in an alternative manner as follows: Compounds la can be exposed to a strong base, preferably n-BuLi, in a solvent, preferably THF at low temperatures and subsequent addition of an electrophile Z-E, wherein E is either a nucleophilically replaceable leaving group such as halogen, alkylsulfonyl, alkylsulfonyloxy and arylsulfonyloxy or a suitable electrophile, preferably an aldehyde.
Compounds of type la can be synthesized from compounds I, wherein Z is trimethylsilyl, by exposure to conditions which either involve a base (preferably K2CO3) in a protic solvent (preferably MeOH) or a source of fluoride (preferably but not limited to tetra-butyl ammonium fluoride) in a suitable solvent such as THF, MeCN.
Compounds I, wherein 2 is different from hydrogen can be obtained from alcohol compounds I (R 2 =H) by reacting the alcohol compound with R 2 -LG, wherein LG represents a nucleophilically replaceable leaving group, such as halogen, alkylsulfonyl, alkylsulfonyloxy and arylsulfonyloxy, preferably chloro, bromo or iodo, particularly preferably bromo, preferably in the presence of a base, such as for example, NaH in a suitable solvent such as THF.
Halo compounds II can be obtained as follows. For example, a phenyliodide of type V bearing additional substituents with Hal preferably being Br can be transformed into an acetophenone of type IVa by several methods known to a skilled person. Preferably, V is transformed into a Gri- gnard reagent by the reaction with a suitable transmetallation agent such as iso-propyl magne- sium chloride under inert conditions in an ethereal solvent such as THF and reacted with acetyl chloride. If necessary, an additive such as LaCU, CuC , AICI3 or mixtures hereof can be added. Acetyl compounds of type IVa can be halogenated using a method known to the skilled person. Preferably, IVa is chlorinated using a chlorination agent such as C , NCS or SC^C o afford a- chloro ketones of type IVb which subsequently can be treated with an appropriate organometal- lie species preferably a Grignard compound, to furnish a tertiary alcohol of type Ilia:
IVb Ilia
Exposure of Ilia to a suitable azole compound in the presence of base leads to the formation of compounds of type II through nucleophilic replacement of the chloride:
Alternatively, intermediate compounds of type II can be prepared as follows: Compounds V can be transformed into their respective Grignard analoga using the methodology described above before bein treated with an appropriate acid chloride to furnish compounds of type VI:
Thereafter, intermediates IV are e.g. reacted with trimethylsulf(ox)onium halides, preferably dide preferably in the presence of a base such as sodium hydride, to result in epoxides III.
IV III
The epoxides III are then reacted with 1 H-1 ,2,4-triazole preferably in the presence of a base such as potassium carbonate and preferably in the presence of an organic solvent such as DMF to obtain intermediate II.
The N-oxides may be prepared from the inventive compounds according to conventional oxidation methods, e. g. by treating compounds I with an organic peracid such as metachloroper- benzoic acid (cf. WO 03/64572 or J. Med. Chem. 38(1 1 ), 1892-903, 1995); or with inorganic oxidizing agents such as hydrogen peroxide (cf. J. Heterocyc. Chem. 18(7), 1305-8, 1981) or oxone (cf. J. Am. Chem. Soc. 123(25), 5962-5973, 2001 ). The oxidation may lead to pure mono-N-oxides or to a mixture of different N-oxides, which can be separated by conventional methods such as chromatography.
If the synthesis yields mixtures of isomers, a separation is generally not necessarily required since in some cases the individual isomers can be intercon verted during work-up for use or during application (e. g. under the action of light, acids or bases). Such conversions may also take place after use, e. g. in the treatment of plants in the treated plant, or in the harmful fungus to be controlled.
In the following, the intermediate compounds are further described. A skilled person will readily understand that the preferences for the substituents, also in particular the ones given in the tables below for the respective substituents, given herein in connection with compounds I apply for the intermediates accordingly. Thereby, the substituents in each case have independently of each other or more preferably in combination the meanings as defined herein.
Compounds of formula V are at least partially new. Consequently, a further embodiment of the present invention are compounds of formula V (see above), wherein the variables are as defined and preferably defined for formula I herein.
Compounds of formula IV are at least partially new. Consequently, a further embodiment of the present invention are compounds of formula IV (see above), wherein the variables are as de- fined and preferably defined for formula I herein.
Compounds of formula IVa are at least partially new. Consequently, a further embodiment of the present invention are compounds of formula IVa (see above), wherein the variables are as defined and preferably defined for formula I herein.
Compounds of formula IVb are at least partially new. Consequently, a further embodiment of the present invention are compounds of formula IVb (see above), wherein the variables are as defined and preferably defined for formula I herein.
Compounds of formula III are at least partially new. Consequently, a further embodiment of the present invention are compounds of formula I II (see above), wherein the variables are as defined and preferably defined for formula I herein.
Compounds of formula I lia are at least partially new. Consequently, a further embodiment of the present invention are compounds of formula I l ia (see above), wherein the variables are as defined and preferably defined for formula I herein.
Compounds of formula I I are at least partially new. Consequently, a further embodiment of the present invention are compounds of formula I I (see above), wherein the variables are as de- fined and preferably defined for formula I herein. In particular, a further particular embodiment of the present invention are compounds of formula I I, wherein Hal stands for iodide (compounds Ma :
Ha
In particular, A stands for N. Preferred R 1 can be found in the description for formula I. In particular with a view to their use, according to one embodiment, preference is given to the compounds Ma are compounds, wherein A is N and the combination of R 1 and R 3 for each individual compound I la corresponds to one line of table R13 (compounds l la-1 to compounds lla-540):
Table R13
impound Ma R 1 R 3 impound Ma R 1 R3 lla-1 CH 3 CH 3 l la-7 CH 2 CH(CH 3 ) 2 CH 3 lla-2 CH2CH3 CH 3 l la-8 CH 2 CH 2 CH 2 CH3 CH 3 lla-3 CH 2 CH 2 CH3 CH 3 l la-9 CF 3 CH 3 lla-4 CH(CH 3 ) 2 CH 3 lla-10 CHF2 CH 3 lla-5 C(CH 3 ) 3 CH 3 lla-1 1 CH 2 F CH 3 lla-6 CH(CH 3 )CH 2 CH 3 CH 3 lla-12 CHCI2 CH 3 impound Ma R 1 R 3 impound Ma R 1 R 3
1 a-13 CH 2 CI CH 3 Ma-54 CH 2 C≡CCH 3 CH 3
1 a-14 CF2CH3 CH 3 lla-55 CH 2 C≡CH CH 3
1 a-15 CHFCH3 CH 3 Ma-56 CH 2 C ≡ CCH 2 CH3 CH 3
1 a-16 CH 2 OH CH 3 Na-57 C≡CCH(CH 3 ) 2 CH 3
1 a-17 CH 2 CH 2 OH CH 3 Ma-58 C ≡ CC(CH 3 ) 3 CH 3
1 a-18 CH 2 CH 2 CH 2 OH CH 3 Na-59 C≡C(C 3 H 5 ) CH 3
1 a-19 CH(CH 3 )CH 2 OH CH 3 lla-60 C≡C(C H 7 ) CH 3
1 a-20 CH 2 CH(CH 3 )OH CH 3 Na-61 C≡C(1 -CI-C 3 H 4 ) CH 3
1 a-21 n-C 4 H 8 OH CH 3 Ma-62 C≡C(1 -CI-C 4 H 6 ) CH 3
1 a-22 CH2OCH3 CH 3 Na-63 C≡C-CI CH 3
1 a-23 CH2OCH2CH3 CH 3 Ma-64 C≡C-Br CH 3
1 a-24 CH(CH 3 )OCH 3 CH 3 lla-65 C≡C-\ CH 3
1 a-25 CH2OCF3 CH 3 Ma-66 CH 2 C≡C-CI CH 3
1 a-26 CH2CH2OCF3 CH 3 Na-67 CH 2 C≡C-Br CH 3
1 a-27 CH2OCCI3 CH 3 Ma-68 CH 2 C≡C-I CH 3
1 a-28 CH2CH2OCCI3 CH 3 Na-69 C≡CCH 2 OCH 3 CH 3
1 a-29 CH=CH 2 CH 3 lla-70 C≡CCH(OH)CH 3 CH 3
1 a-30 CH 2 CH=CH 2 CH 3 Na-71 C≡COCH 3 CH 3
1 a-31 CH 2 CH=CHCH 3 CH 3 Ma-72 CH 2 C≡COCH 3 CH 3
1 a-32 CH 2 C(CH 3 )=CH 2 CH 3 Na-73 OCCH2OCCI3 CH 3
1 a-33 CH=CHCH 3 CH 3 Ma-74 C≡CCH 2 OCF 3 CH 3
1 a-34 C(CH 3 )=CH 2 CH 3 lla-75 C≡CCH 2 (C 3 H 5 ) CH 3
1 a-35 CH=C(CH 3 ) 2 CH 3 Ma-76 C≡C(1 -CI-C 3 H 4 ) CH 3
1 a-36 C(CH 3 )=C(CH 3 ) 2 CH 3 Na-77 C≡C(1 -F-C 3 H 4 ) CH 3
1 a-37 C(CH 3 )=CH(CH 3 ) CH 3 Ma-78 C3H5 (cyclopropyl) CH 3
1 a-38 C(CI)=CH 2 CH 3 Na-79 CH(CH 3 )-C 3 H 5 CH 3
1 a-39 C(H)=CHCI CH 3 lla-80 CH2-C3H5 CH 3
1 a-40 C(CI)=CHCI CH 3 Na-81 1 -(CI)-C 3 H 4 CH 3
1 a-41 CH=CCI 2 CH 3 Ma-82 1 -(F)-C 3 H 4 CH 3
1 a-42 C(CI)=CCI 2 CH 3 Na-83 1 -(CH 3 )-C 3 H 4 CH 3
1 a-43 C(H)=CH(F) CH 3 Ma-84 1 -(CN)-C 3 H 4 CH 3
1 a-44 C(H)=CF 2 CH 3 lla-85 2-(CI)-C 3 H 4 CH 3
1 a-45 C(F)=CF 2 CH 3 Ma-86 2-(F)-C 3 H 4 CH 3
1 a-46 C(F)=CHF CH 3 Na-87 1 -C 3 H5-C 3 H 4 CH 3
1 a-47 CH=CHCH 2 OH CH 3 Ma-88 2-C 3 H5-C 3 H 4 CH 3
1 a-48 CH=CHOCH 3 CH 3 Na-89 CH 2 -(1 -CI-C 3 H 4 ) CH3
1 a-49 CH=CHCH 2 OCH 3 CH 3 lla-90 CH 2 -(1 -F-C 3 H ) CH 3
1 a-50 CH=CHCH 2 OCF 3 CH 3 Na-91 CH3 CF 3
1 a-51 CH=CH(C 3 H 5 ) CH 3 Ma-92 CH2CH3 CF 3
1 a-52 C≡CH CH 3 Na-93 CH 2 CH 2 CH3 CF 3
1 a-53 C≡CCH 3 CH 3 Na-94 CH(CH 3 )2 CF 3 impound Ma R 1 R 3 impound Ma R 1 R 3 lla-95 C(CH 3 ) 3 CF 3 Ma-136 C(F)=CHF CF 3 lla-96 CH(CH 3 )CH 2 CH 3 CF 3 Na-137 CH=CHCH 2 OH CF 3 lla-97 CH 2 CH(CH 3 ) 2 CF 3 Ma-138 CH=CHOCH 3 CF 3 lla-98 CH 2 CH 2 CH 2 CH 3 CF 3 Na-139 CH=CHCH 2 OCH 3 CF 3 lla-99 CF 3 CF 3 Ma-140 CH=CHCH 2 OCF 3 CF 3 la-100 CHF 2 CF 3 Na-141 CH=CH(C 3 H 5 ) CF 3 la-101 CH 2 F CF 3 Ma-142 C≡CH CF 3 la-102 CHCI 2 CF 3 Na-143 C≡CCH 3 CF 3 la-103 CH2CI CF 3 Ma-144 CH 2 C≡CCH 3 CF 3 la-104 CF 2 CH 3 CF 3 Na-145 CH 2 C≡CH CF 3 la-105 CHFCH 3 CF 3 Ma-146 CH 2 C ≡ CCH 2 CH 3 CF 3 la-106 CH 2 OH CF 3 Na-147 C≡CCH(CH 3 ) 2 CF 3 la-107 CH 2 CH 2 OH CF 3 Ma-148 C ≡ CC(CH 3 ) 3 CF 3 la-108 CH 2 CH 2 CH 2 OH CF 3 Na-149 C≡C(C 3 H 5 ) CF 3 la-109 CH(CH 3 )CH 2 OH CF 3 Ma-150 C≡C(C H 7 ) CF 3 la-110 CH 2 CH(CH 3 )OH CF 3 Na-151 C≡C(1-CI-C 3 H 4 ) CF 3 la-11 1 n-C 4 H 8 OH CF 3 Ma-152 C≡C(1-CI-C 4 H 6 ) CF 3 la-112 CH 2 OCH 3 CF 3 Na-153 C≡C-CI CF 3 la-113 CH 2 OCH 2 CH 3 CF 3 Ma-154 C≡C-Br CF 3 la-114 CH(CH 3 )OCH 3 CF 3 Na-155 C≡C-I CF 3 la-115 CH2OCF3 CF 3 Ma-156 CH 2 C≡C-CI CF 3 la-116 CH 2 CH 2 OCF 3 CF 3 Na-157 CH 2 C≡C-Br CF 3 la-117 CH2OCCI3 CF 3 Ma-158 CH 2 C≡C-I CF 3 la-118 CH 2 CH 2 OCCI 3 CF 3 Na-159 C≡CCH 2 OCH 3 CF 3 la-119 CH=CH 2 CF 3 Ma-160 C≡CCrl(Orl)CH 3 CF 3 la-120 CH 2 CH=CH 2 CF 3 Na-161 C≡COCH 3 CF 3 la-121 CH 2 CH=CHCH 3 CF 3 Ma-162 CH 2 C≡COCH 3 CF 3 la-122 CH 2 C(CH 3 )=CH 2 CF 3 Na-163 C≡CCH 2 OCCI 3 CF 3 la-123 CH=CHCH 3 CF 3 Ma-164 C≡CCH 2 OCF 3 CF 3 la-124 C(CH 3 )=CH 2 CF 3 Na-165 C≡CCH 2 (C 3 H 5 ) CF 3 la-125 CH=C(CH 3 ) 2 CF 3 Ma-166 C≡C(1-CI-C 3 H 4 ) CF 3 la-126 C(CH 3 )=C(CH 3 ) 2 CF 3 Na-167 C≡C(1-F-C 3 H 4 ) CF 3 la-127 C(CH 3 )=CH(CH 3 ) CF 3 Ma-168 C 3 H 5 (cyclopropyl) CF 3 la-128 C(CI)=CH 2 CF 3 Na-169 CH(CH 3 )-C 3 H 5 CF 3 la-129 C(H)=CHCI CF 3 Ma-170 CH2-C 3 H5 CF 3 la-130 C(CI)=CHCI CF 3 Na-171 1 -(CI)-C 3 H 4 CF 3 la-131 CH=CCI 2 CF 3 Ma-172 1 -(F)-C 3 H 4 CF 3 la-132 C(CI)=CCI 2 CF 3 Na-173 1 -(CH 3 )-C 3 H 4 CF 3 la-133 C(H)=CH(F) CF 3 Ma-174 1 -(CN)-C 3 H 4 CF 3 la-134 C(H)=CF 2 CF 3 Na-175 2-(CI)-C 3 H 4 CF 3 la-135 C(F)=CF 2 CF 3 Na-176 2-(F)-C 3 H 4 CF 3 impound Ma R 1 R 3 impound Ma R 1 R 3 la-177 I-C3H 5 -C3H 4 CF 3 lla-218 C(CI)=CH 2 OCH3 la-178 2-C3H 5 -C3H 4 CF 3 lla-219 C(H)=CHCI OCH3 la-179 CH2-CI-CI-C3H4) CF 3 lla-220 C(CI)=CHCI OCH3 la-180 CH 2 -(1-F-C 3 H 4 ) CF 3 lla-221 CH=CCI 2 OCH3 la-181 CH 3 OCH3 lla-222 C(CI)=CCI 2 OCH3 la-182 CH2CH3 OCH3 lla-223 C(H)=CH(F) OCH3 la-183 CH 2 CH 2 CH3 OCH3 lla-224 C(H)=CF 2 OCH3 la-184 CH(CH 3 )2 OCH3 lla-225 C(F)=CF 2 OCH3 la-185 C(CH 3 ) 3 OCH3 lla-226 C(F)=CHF OCH3 la-186 CH(CH 3 )CH 2 CH 3 OCH3 lla-227 CH=CHCH 2 OH OCH3 la-187 CH 2 CH(CH 3 ) 2 OCH3 Ma-228 CH=CHOCH 3 OCH3 la-188 CH 2 CH 2 CH 2 CH3 OCH3 Na-229 CH=CHCH 2 OCH 3 OCH3 la-189 CF 3 OCH3 lla-230 CH=CHCH 2 OCF 3 OCH3 la-190 CHF 2 OCH3 Na-231 CH=CH(C 3 H 5 ) OCH3 la-191 CH 2 F OCH3 Ma-232 C≡CH OCH3 la-192 CHC OCH3 Na-233 C≡CCH 3 OCH3 la-193 CH2CI OCH3 Ma-234 CH 2 C≡CCH 3 OCH3 la-194 CF2CH3 OCH3 lla-235 CH 2 C≡CH OCH3 la-195 CHFCH3 OCH3 Ma-236 CH 2 C≡CCH 2 CH 3 OCH3 la-196 CH 2 OH OCH3 Na-237 C≡CCH(CH 3 ) 2 OCH3 la-197 CH2CH2OH OCH3 Ma-238 C ≡ CC(CH 3 ) 3 OCH3 la-198 CH 2 CH 2 CH 2 OH OCH3 Na-239 C≡C(C 3 H 5 ) OCH3 la-199 CH(CH 3 )CH 2 OH OCH3 lla-240 C≡C(C H 7 ) OCH3 la-200 CH 2 CH(CH 3 )OH OCH3 Na-241 C≡C(1-CI-C 3 H 4 ) OCH3 la-201 n-C 4 H 8 OH OCH3 Ma-242 C≡C(1-CI-C 4 H 6 ) OCH3 la-202 CH2OCH3 OCH3 Na-243 C≡C-CI OCH3 la-203 CH 2 OCH 2 CH 3 OCH3 Ma-244 C≡C-Br OCH3 la-204 CH(CH 3 )OCH 3 OCH3 lla-245 C≡C-I OCH3 la-205 CH2OCF3 OCH3 Ma-246 CH 2 C≡C-CI OCH3 la-206 CH2CH2OCF3 OCH3 Na-247 CH 2 C≡C-Br OCH3 la-207 CH2OCCI3 OCH3 Ma-248 CH 2 C≡C-I OCH3 la-208 CH2CH2OCCI3 OCH3 Na-249 C≡CCH 2 OCH 3 OCH3 la-209 CH=CH 2 OCH3 lla-250 C≡CCH(OH)CH 3 OCH3 la-210 CH 2 CH=CH 2 OCH3 Na-251 C≡COCH 3 OCH3 la-21 1 CH 2 CH=CHCH 3 OCH3 Ma-252 CH 2 C≡COCH 3 OCH3 la-212 CH 2 C(CH 3 )=CH 2 OCH3 Na-253 OCCH2OCCI3 OCH3 la-213 CH=CHCH 3 OCH3 Ma-254 C≡CCH 2 OCF 3 OCH3 la-214 C(CH 3 )=CH 2 OCH3 lla-255 C≡CCH 2 (C 3 H 5 ) OCH3 la-215 CH=C(CH 3 ) 2 OCH3 Ma-256 C≡C(1-CI-C 3 H 4 ) OCH3 la-216 C(CH 3 )=C(CH 3 ) 2 OCH3 Na-257 C≡C(1-F-C 3 H 4 ) OCH3 la-217 C(CH 3 )=CH(CH 3 ) OCH3 Na-258 C3H5 (cyclopropyl) OCH3 impound Ma R 1 R 3 impound Ma R 1 R 3 la-259 CH(CH 3 )-C 3 H 5 OCH 3 lla-300 CH 2 CH=CH 2 F la-260 CH2-C3H5 OCH3 lla-301 CH 2 CH=CHCH 3 F la-261 1-(CI)-C 3 H 4 OCH 3 lla-302 CH 2 C(CH 3 )=CH 2 F la-262 1-(F)-C 3 H 4 OCH3 lla-303 CH=CHCH 3 F la-263 1-(CH 3 )-C 3 H 4 OCH 3 lla-304 C(CH 3 )=CH 2 F la-264 1-(CN)-C 3 H 4 OCH3 lla-305 CH=C(CH 3 ) 2 F la-265 2-(CI)-C 3 H 4 OCH 3 lla-306 C(CH 3 )=C(CH 3 ) 2 F la-266 2-(F)-C 3 H 4 OCH3 lla-307 C(CH 3 )=CH(CH 3 ) F la-267 1-C 3 H5-C 3 I-I 4 OCH 3 lla-308 C(CI)=CH 2 F la-268 2-C 3 H5-C 3 H 4 OCH3 Na-309 C(H)=CHCI F la-269 CH 2 -(1-CI-C 3 H 4 ) OCH 3 Ma-310 C(CI)=CHCI F la-270 CH 2 -(1-F-C 3 H 4 ) OCH3 Na-31 1 CH=CCI 2 F la-271 CH 3 F Ma-312 C(CI)=CCI 2 F la-272 CH 2 CH 3 F lla-313 C(H)=CH(F) F la-273 CH2CH2CH 3 F Ma-314 C(H)=CF 2 F la-274 CH(CH 3 ) 2 F Na-315 C(F)=CF 2 F la-275 C(CH 3 ) 3 F Ma-316 C(F)=CHF F la-276 CH(CH 3 )CH 2 CH 3 F Na-317 CH=CHCH 2 OH F la-277 CH 2 CH(CH 3 ) 2 F lla-318 CH=CHOCH 3 F la-278 CH2CH2CH2CH 3 F Na-319 CH=CHCH 2 OCH 3 F la-279 CF 3 F Ma-320 CH=CHCH 2 OCF 3 F la-280 CHF 2 F Na-321 CH=CH(C 3 H 5 ) F la-281 CH 2 F F Ma-322 C≡CH F la-282 CHCI2 F lla-323 C≡CCH 3 F la-283 CH2CI F Ma-324 CH2OCCH3 F la-284 CF2CH3 F Na-325 CH 2 C≡CH F la-285 CHFCH3 F Ma-326 CH 2 C≡CCH 2 CH 3 F la-286 CH2OH F Na-327 C≡CCH(CH 3 ) 2 F la-287 CH2CH2OH F lla-328 C≡CC(CH 3 ) 3 F la-288 CH2CH2CH2OH F Na-329 C≡C(C 3 H 5 ) F la-289 CH(CH 3 )CH 2 OH F Ma-330 C≡C(C H 7 ) F la-290 CH 2 CH(CH 3 )OH F Na-331 C≡C(1-CI-C 3 H 4 ) F la-291 n-C 4 H 8 OH F Ma-332 C≡C(1-CI-C 4 H 6 ) F la-292 CH 2 OCH 3 F lla-333 C≡C-CI F la-293 CH2OCH2CH3 F Ma-334 C≡C-Br F la-294 CH(CH 3 )OCH 3 F Na-335 C≡C-I F la-295 CH2OCF3 F Ma-336 CH 2 C≡C-CI F la-296 CH2CH2OCF3 F Na-337 CH 2 C≡C-Br F la-297 CH2OCCI3 F lla-338 CH 2 C≡C-I F la-298 CH2CH2OCCI3 F Na-339 C≡CCH 2 OCH 3 F la-299 CH=CH 2 F Na-340 C≡CCH(OH)CH 3 F impound Ma R 1 R 3 impound Ma R 1 R 3 la-341 C≡COCH 3 F lla-382 CH 2 OCH 3 CI la-342 CH 2 C≡COCH 3 F lla-383 CH 2 OCH 2 CH 3 CI la-343 C≡CCH 2 OCCI 3 F lla-384 CH(CH 3 )OCH 3 CI la-344 C≡CCH 2 OCF 3 F lla-385 CH 2 OCF 3 CI la-345 C ≡ CCH 2 (C 3 H 5 ) F lla-386 CH 2 CH 2 OCF 3 CI la-346 C≡C(1 -CI-C 3 H 4 ) F lla-387 CH 2 OCCI 3 CI la-347 C≡C(1 -F-C 3 H 4 ) F lla-388 CH 2 CH 2 OCCI 3 CI la-348 C 3 H 5 (cyclopropyl) F lla-389 CH=CH 2 CI la-349 CH(CH 3 )-C 3 H 5 F lla-390 CH 2 CH=CH 2 CI la-350 CH 2 -C 3 H5 F lla-391 CH 2 CH=CHCH 3 CI la-351 1-(CI)-C 3 H 4 F lla-392 CH 2 C(CH 3 )=CH 2 CI la-352 1-(F)-C 3 H 4 F lla-393 CH=CHCH 3 CI la-353 1-(CH 3 )-C 3 H 4 F lla-394 C(CH 3 )=CH 2 CI la-354 1-(CN)-C 3 H 4 F lla-395 CH=C(CH 3 ) 2 CI la-355 2-(CI)-C 3 H 4 F lla-396 C(CH 3 )=C(CH 3 ) 2 CI la-356 2-(F)-C 3 H 4 F lla-397 C(CH 3 )=CH(CH 3 ) CI la-357 1-C 3 H5-C 3 H 4 F lla-398 C(CI)=CH 2 CI la-358 2-C 3 H5-C 3 H 4 F lla-399 C(H)=CHCI CI la-359 CH 2 -(1-CI-C 3 H 4 ) F lla-400 C(CI)=CHCI CI la-360 CH 2 -(1-F-C 3 H 4 ) F lla-401 CH=CCI 2 CI la-361 CH 3 CI lla-402 C(CI)=CCI 2 CI la-362 CH 2 CH 3 CI lla-403 C(H)=CH(F) CI la-363 CH 2 CH2CH 3 CI lla-404 C(H)=CF 2 CI la-364 CH(CH 3 ) 2 CI lla-405 C(F)=CF 2 CI la-365 C(CH 3 ) 3 CI lla-406 C(F)=CHF CI la-366 CH(CH 3 )CH 2 CH 3 CI lla-407 CH=CHCH 2 OH CI la-367 CH 2 CH(CH 3 ) 2 CI lla-408 CH=CHOCH 3 CI la-368 CH 2 CH 2 CH 2 CH 3 CI lla-409 CH=CHCH 2 OCH 3 CI la-369 CF 3 CI lla-410 CH=CHCH 2 OCF 3 CI la-370 CHF 2 CI lla-41 1 CH=CH(C 3 H 5 ) CI la-371 CH 2 F CI lla-412 C≡CH CI la-372 CHCI 2 CI lla-413 C≡CCH 3 CI la-373 CH 2 CI CI lla-414 CH 2 C≡CCH 3 CI la-374 CF 2 CH 3 CI lla-415 CH 2 C≡CH CI la-375 CHFCHs CI lla-416 CH 2 C≡CCH 2 CH 3 CI la-376 CH 2 OH CI lla-417 C≡CCH(CH 3 ) 2 CI la-377 CH 2 CH 2 OH CI lla-418 C≡CC(CH 3 ) 3 CI la-378 CH 2 CH 2 CH 2 OH CI lla-419 C≡C(C 3 H 5 ) CI la-379 CH(CH 3 )CH 2 OH CI lla-420 C≡C(C H 7 ) CI la-380 CH 2 CH(CH 3 )OH CI lla-421 C≡C(1-CI-C 3 H 4 ) CI la-381 n-C H 8 OH CI lla-422 C≡C(1-CI-C 4 H 6 ) CI impound Ma R 1 R 3 impound Ma R 1 R 3 la-423 C≡C-CI CI lla-464 CF 2 CH 3 Br la-424 C≡C-Br CI lla-465 CHFCHs Br la-425 C≡C-I CI lla-466 CH 2 OH Br la-426 CH 2 C≡C-CI CI lla-467 CH 2 CH 2 OH Br la-427 CH 2 C≡C-Br CI lla-468 CH 2 CH 2 CH 2 OH Br la-428 CH 2 C≡C-I CI lla-469 CH(CH 3 )CH 2 OH Br la-429 C≡CCH 2 OCH 3 CI lla-470 CH 2 CH(CH 3 )OH Br la-430 C≡CCH(OH)CH 3 CI lla-471 n-C H 8 OH Br la-431 C≡COCH 3 CI lla-472 CH 2 OCH 3 Br la-432 CH 2 C≡COCH 3 CI lla-473 CH 2 OCH 2 CH 3 Br la-433 C≡CCH 2 OCCI 3 CI lla-474 CH(CH 3 )OCH 3 Br la-434 C≡CCH 2 OCF 3 CI lla-475 CH 2 OCF 3 Br la-435 C ≡ CCH 2 (C 3 H 5 ) CI lla-476 CH 2 CH 2 OCF 3 Br la-436 C≡C(1 -CI-C 3 H 4 ) CI lla-477 CH 2 OCCI 3 Br la-437 C≡C(1 -F-C 3 H 4 ) CI lla-478 CH 2 CH 2 OCCI 3 Br la-438 C 3 H 5 (cyclopropyl) CI lla-479 CH=CH 2 Br la-439 CH(CH 3 )-C 3 H 5 CI lla-480 CH 2 CH=CH 2 Br la-440 CH 2 -C 3 H5 CI lla-481 CH 2 CH=CHCH 3 Br la-441 1-(CI)-C 3 H 4 CI lla-482 CH 2 C(CH 3 )=CH 2 Br la-442 1-(F)-C 3 H 4 CI lla-483 CH=CHCH 3 Br la-443 1-(CH 3 )-C 3 H 4 CI lla-484 C(CH 3 )=CH 2 Br la-444 1-(CN)-C 3 H 4 CI lla-485 CH=C(CH 3 ) 2 Br la-445 2-(CI)-C 3 H 4 CI lla-486 C(CH 3 )=C(CH 3 ) 2 Br la-446 2-(F)-C 3 H 4 CI lla-487 C(CH 3 )=CH(CH 3 ) Br la-447 1-C 3 H5-C 3 H 4 CI lla-488 C(CI)=CH 2 Br la-448 2-C 3 H5-C 3 H 4 CI lla-489 C(H)=CHCI Br la-449 CH 2 -(1-CI-C 3 H ) CI lla-490 C(CI)=CHCI Br la-450 CH 2 -(1-F-C 3 H 4 ) CI lla-491 CH=CCI 2 Br la-451 CH 3 Br lla-492 C(CI)=CCI 2 Br la-452 CH 2 CH 3 Br lla-493 C(H)=CH(F) Br la-453 CH 2 CH 2 CH 3 Br lla-494 C(H)=CF 2 Br la-454 CH(CH 3 ) 2 Br lla-495 C(F)=CF 2 Br la-455 C(CH 3 ) 3 Br lla-496 C(F)=CHF Br la-456 CH(CH 3 )CH 2 CH 3 Br lla-497 CH=CHCH 2 OH Br la-457 CH 2 CH(CH 3 ) 2 Br lla-498 CH=CHOCH 3 Br la-458 CH 2 CH 2 CH 2 CH 3 Br lla-499 CH=CHCH 2 OCH 3 Br la-459 CF 3 Br lla-500 CH=CHCH 2 OCF 3 Br la-460 CHF 2 Br lla-501 CH=CH(C 3 H 5 ) Br la-461 CH 2 F Br lla-502 C≡CH Br la-462 CHCI 2 Br lla-503 C≡CCH 3 Br la-463 CH 2 CI Br lla-504 CH 2 C≡CCH 3 Br impound Ma R 1 R 3 impound Ma R 1 R 3 la-505 CH 2 C≡CH Br Ma-523 C≡CCH 2 OCCI 3 Br la-506 CH 2 C≡CCH 2 CH3 Br Na-524 C≡CCH 2 OCF 3 Br la-507 C≡CCH(CH 3 ) 2 Br Ma-525 C ≡ CCH 2 (C 3 H 5 ) Br la-508 C≡CC(CH 3 ) 3 Br Na-526 C≡C(1-CI-C 3 H 4 ) Br la-509 C≡C(C 3 H 5 ) Br Ma-527 C≡C(1-F-C 3 H 4 ) Br la-510 C≡C(C 4 H 7 ) Br Na-528 C 3 H 5 (cyclopropyl) Br la-51 1 C≡C(1 -CI-C 3 H 4 ) Br Ma-529 CH(CH 3 )-C 3 H 5 Br la-512 C≡C(1 -CI-C 4 H 6 ) Br Na-530 CH 2 -C 3 H5 Br la-513 C≡C-CI Br Ma-531 1 -(CI)-C 3 H 4 Br la-514 C≡C-Br Br Na-532 1 -(F)-C 3 H 4 Br la-515 C≡C-I Br Ma-533 1 -(CH 3 )-C 3 H 4 Br la-516 CH 2 C≡C-CI Br Na-534 1 -(CN)-C 3 H 4 Br la-517 CH 2 C≡C-Br Br Ma-535 2-(CI)-C 3 H 4 Br la-518 CH 2 C≡C-I Br Na-536 2-(F)-C 3 H 4 Br la-519 C≡CCH 2 OCH 3 Br Ma-537 1 -C 3 H5-C 3 H 4 Br la-520 C≡CCH(OH)CH 3 Br Na-538 2-C 3 H5-C 3 H 4 Br la-521 C≡COCH 3 Br Ma-539 CH 2 -(1 -CI-C 3 H 4 ) Br la-522 CH 2 C≡COCH 3 Br Na-540 CH 2 -(1 -F-C 3 H 4 ) Br
Compounds M and Ma, respectively, can also be suitable as fungicides as decribed later.
Compounds of formula la are at least partially new. Consequently, a further embodiment of the present invention are compounds of formula la (see above), wherein the variables are as defined and preferably defined for formula I herein.
In the definitions of the variables given above, collective terms are used which are generally representative for the substituents in question. The term "C n -C m " indicates the number of carbon atoms possible in each case in the substituent or substituent moiety in question.
The term "halogen" refers to fluorine, chlorine, bromine and iodine.
The term "Ci-C6-alkyl" refers to a straight-chained or branched saturated hydrocarbon group having 1 to 6 carbon atoms, e.g. methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2- methylpropyl, 1 ,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,
2.2- dimethylpropyl, 1 -ethyl propyl, 1 ,1-dimethylpropyl, 1 ,2-dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -dimethylbutyl, 1 ,2-dimethylbutyl,
1.3- dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl,
2-ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1-ethyl-1 -methylpropyl and 1 -ethyl-2- methylpropyl. Likewise, the term "C 2 -C 4 -alkyl" refers to a straight-chained or branched alkyl group having 2 to 4 carbon atoms, such as ethyl, propyl (n-propyl), 1-methylethyl (iso-propoyl), butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (iso-butyl), 1 ,1-dimethylethyl (tert. -butyl).
The term "Ci-C6-haloalkyl" refers to an alkyl group having 1 or 6 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above. Examples are "Ci-C 2 -haloalkyl" groups such as chloromethyl, bro- momethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloro- fluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1 -bromoethyl, 1 - fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-
2.2- difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl or pentafluoroethyl.
The term "Ci-C6-hydroxyalkyl" refers to an alkyl group having 1 or 6 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by OH groups.
The term "C2-C6-alkenyl" refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and a double bond in any position. Examples are "C2-C4-alkenyl" groups, such as ethenyl, 1 -propenyl, 2-propenyl (allyl), 1 -methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1 -methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl.
The term "C2-C6-alkynyl" refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and containing at least one triple bond. Examples are "C2-C4- alkynyl" groups, such as ethynyl, prop-1-ynyl, prop-2-ynyl (propargyl), but-1-ynyl, but-2-ynyl, but-3-ynyl , 1 -methyl-prop-2-ynyl .
The term "C3-C6-cycloalkyl" refers to monocyclic saturated hydrocarbon radicals having 3 to 6 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.
The term "C3-C6-cycloalkenyl" refers to a monocyclic partially unsaturated 3-, 4- 5- or 6- membered carbocycle having 3 to 6 carbon ring members and at least one double bond, such as cyclopentenyl, cyclopentadienyl, cyclohexadienyl.
The term "C3-C8-cycloalkyl-Ci-C4-alkyl" refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a cycloalkyl radical having 3 to 8 carbon atoms (as defined above).
The term "Ci-C6-alkoxy" refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms which is bonded via an oxygen, at any position in the alkyl group. Examples are "C1-C4- alkoxy" groups, such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1- methyhpropoxy, 2-methylpropoxy or 1 ,1 -dimethylethoxy.
The term "Ci-C6-haloalkoxy" refers to a Ci-C6-alkoxy radical as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above. Examples are "Ci-C4-haloalkoxy" groups, such as OCH 2 F, OCHF 2 , OCF 3 , OCH 2 CI, OCHCI2, OCCI3, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoro- ethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-tri- chloro-"ethoxy, OC2F5, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy,
2.3- difluoro-"propoxy, 2 chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bro- mo-'propoxy, 3 bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2-C2F5,
OCF2-C2F5, 1-fluoromethyl-2-fluoroethoxy, 1 -chloromethyl-2-chloroethoxy, 1 -bromomethyl-2- bromo-'ethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy.
The term "Ci-C4-alkoxy-Ci-C4-alkyl" refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a Ci-C4-alkoxy group (as defined above). Likewise, the term "Ci-C6-alkoxy-Ci-C4-alkyl" refers to alkyl having 1 to 4 car- bon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a Ci-C6-alkoxy group (as defined above).
The term "Ci-C6-alkylthio" as used herein refers to straight-chain or branched alkyl groups having 1 to 6 carbon atoms (as defined above) bonded via a sulfur atom. Accordingly, the term "Ci- C6-haloalkylthio" as used herein refers to straight-chain or branched haloalkyi group having 1 to 6 carbon atoms (as defined above) bonded through a sulfur atom, at any position in the haloalkyi group.
The term "Ci-C6-alkylsulfinyl" refers to straight-chain or branched alkyl groups having 1 to 6 carbon atoms (as defined above) bonded through a -S(=0)- moiety, at any position in the alkyl group, for example methylsulfinyl and ethylsulfinyl, and the like. Accordingly, the term "C1-C6- haloalkylsulfinyl" refers to straight-chain or branched haloalkyi group having 1 to 6 carbon atoms (as defined above), bonded through a -S(=0)- moiety, at any position in the haloalkyi group.
The term "Ci-C6-alkylsulfonyl" refers to straight-chain or branched alkyl groups having 1 to 6 carbon atoms (as defined above), bonded through a -S(=0)2- moiety, at any position in the alkyl group, for example methylsulfonyl. Accordingly, the term "Ci-C6-haloalkylsulfonyl" refers to straight-chain or branched haloalkyi group having 1 to 6 carbon atoms (as defined above), bonded through a -S(=0)2- moiety, at any position in the haloalkyi group.
The term "C 3 -C8-cycloalkyl-C 3 -C8-cycloalky refers to a cycloalkyl radical having 3 to 8 carbon atoms (as defined above), which is substituted by a further cycloalkyl radical having 3 to 8 car- bon atoms.
The term "C 3 -Ce-cycloalkoxy" refers to a cycloalkyl radical having 3 to 8 carbon atoms (as defined above) , which is bonded via an oxygen.
The term "C(=0)-Ci-C6-alkyl" refers to a radical which is attached through the carbon atom of the group C(=0) as indicated by the number valence of the carbon atom. The number of va- lence of carbon is 4, that of nitrogen is 3. Likewise the following terms are to be construed:
N H(Ci-C 6 -alkl), N(Ci-C 6 -alkyl) 2 , N H(C 3 -C 6 -cycloalkyl), N(C 3 -C 6 -cycloalkyl) 2 , C(=0)OH, C(=0)-0- Ci-C 6 -alkyl, C(=0)-N H(Ci-C 6 -alkyl), C(=0)-NH(C 3 -C 6 -cycloalkyl), C(=0)- N(C 3 -C 6 -cycloalkyl) 2 .
Agriculturally acceptable salts of the inventive compounds encompass especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of said compounds. Suitable cations are thus in particular the ions of the alkali metals, preferably sodium and potassium , of the alkaline earth metals, preferably calcium, magnesium and barium , of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may carry one to four Ci-C4-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammoni- um, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phos- phonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium. Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting such inventive compound with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
The inventive compounds can be present in atropisomers arising from restricted rotation about a single bond of asymmetric groups. They also form part of the subject matter of the present invention.
Depending on the substitution pattern, the compounds of formula I and their N-oxides may have one or more centers of chirality, in which case they are present as pure enantiomers or pure diastereomers or as enantiomer or diastereomer mixtures. Both, the pure enantiomers or dia- stereomers and their mixtures are subject matter of the present invention.
In the following, particular embodiments of the inventive compounds are described. Therein, specific meanings of the respective substituents are further detailled, wherein the meanings are in each case on their own but also in any combination with one another, particular embodiments of the present invention.
Furthermore, in respect of the variables, generally, the embodiments of the compounds I also apply to the intermediates.
A according to the invention is N or CH. According to one embodiment A is N. According to a further embodiment A is CH.
R 1 according to the invention is Ci-C6-alkyl, C 2 -C6-alkenyl, C 2 -C6-alkynyl or C3-C6-cycloalkyl; wherein the aliphatic moieties of R 1 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R 1a which independently of one another are selected from R 1a halogen, OH, CN, Ci-C4-alkoxy, Ca-Cs-cycloalkyl, C3-C8- halocycloalkyl and Ci-C4-halogenalkoxy; and wherein the cycloalkyl moieties of R 1 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R 1b which independently of one another are selected from halogen, OH, CN, Ci-C 4 -alkyl, Ci-C 4 -alkoxy, Ci-C 4 -halogenalkyl, Ca-Cs-cycloalkyl, Ca-Ce-halocycloalkyl and C 1 -C 4 - halogenalkoxy.
According to a further embodiment of the invention, R 1 is selected from Ci-C6-alkyl, C 2 -C6- alkenyl, C 2 -C6-alkynyl, C3-C6-cycloalkyl and C3-C6-cycloalkyl-Ci-C 4 -alkyl, wherein the R 1 are in each case unsubstituted or are substituted by R 1a and/or R 1b as defined and preferably defined herein. Specific embodiments thereof can be found in the below Table P1.
According to one particular embodiment, R 1 is Ci-C6-alkyl, in particular Ci-C 4 -alkyl, such as CH 3 , C2H5, CH(CH 3 )2 or C(CH 3 )3. A further embodiment relates to compounds, wherein R 1 is Ci- C6-alkyl, in particular Ci-C 4 -alkyl that is substituted by one, two or three or up to the maximum possible number of identical or different groups R 1a , as defined and preferably defined herein. According to a specific embodiment thereof, R 1 is Ci-C6-haloalkyl, in particular Ci-C 4 -haloalkyl, more particularly Ci-C 2 -haloalkyl such as CF3 or CHF 2 . According to a further specific embodiment thereof, R 1 is Ci-C 4 -alkoxy-Ci-C6-alkyl, in particular Ci-C 4 -alkoxy-Ci-C4-alkyl, such as CH2-OCH3. Further specific embodiments thereof can be found in the below Table P1.
According to still another embodiment, R 1 is C3-C8-cycloalkyl-Ci-C6-alkyl, in particular C3-C6- cycloalkyl-Ci-C4-alkyl. A further embodiment relates to compounds, wherein R 1 is C3-C8- cycloalkyl-Ci-C6-alkyl, in particular C3-C6-cycloalkyl-Ci-C4-alkyl, that is substituted by one, two or three or up to the maximum possible number of identical or different groups R 1a in the alkyl moiety and/or substituted by one, two, three four or five or up to the maximum possible number of identical or different groups R 1b in the cycloalkyl moiety. R 1a are in each case as defined and preferably defined herein. Specific embodiments thereof can be found in the below Table P1.
According to another embodiment, R 1 is C 2 -C6-alkenyl, in particular C 2 -C4-alkenyl, such as CH=CH 2 , CH 2 CH=CH 2 , CH=CHCH 3 or C(CH 3 )=CH 2 . A further embodiment relates to compounds, wherein R 1 is C 2 -C6-alkenyl, in particular C 2 -C4-alkenyl that is substituted by one, two or three or up to the maximum possible number of identical or different groups R 1a as defined and preferably defined herein. According to a specific embodiment thereof, R 1 is C2-C6-haloalkenyl, in particular C2-C4-haloalkenyl. Further specific embodiments thereof can be found in the below Table P1.
According to still another embodiment, R 1 is C2-C6-alkynyl, in particular C2-C4-alkynyl, such as C≡CH, C≡CCH 3 , CH 2 -C≡C-H or CH 2 -C≡C-CH 3 .
A further embodiment relates to compounds, wherein R 1 is C 2 -C6-alkynyl, in particular C 2 -C4- alkynyl that is substituted by one, two or three or up to the maximum possible number of identical or different groups R 1a , as defined and preferably defined herein. According to a specific embodiment thereof, R 1 is C 2 -C6-haloalkynyl, in particular C 2 -C4-haloalkynyl. According to a further specific embodiment thereof, R 1 is C 3 -C6-cycloalkyl-C2-C6-alkynyl or C 3 -C6-halocycloalkyl-C2-C6- alkynyl, in particular C 3 -C6-cycloalkyl-C 2 -C4-alkynyl or C 3 -C6-halocycloalkyl-C 2 -C4-alkynyl. Further specific embodiments thereof can be found in the below Table P1.
According to still another embodiment, R 1 is C3-C6-cycloalkyl, such as C3H5 (cyclopropyl), C4H7 (cyclobutyl), cyclopentyl or cyclohexyl. A further embodiment relates to compounds, wherein R 1 is C3-C6-cycloalkyl, such as C3H5 (cyclopropyl) or C4H 7 (cyclobutyl), that is substituted by one, two, three four or five or up to the maximum possible number of identical or different groups R 1 as defined and preferably defined herein. According to a specific embodiment thereof, R 1 is C 3 - C6-halocycloalkyl, such as halocyclopropyl, in particular 1 -F-cyclopropyl or 1 -CI-cyclopropyl. According to a further specific embodiment thereof, R 1 C 3 -C6-cycloalkyl-C 3 -C6-cycloalkyl, wherein each of said cycloalkyl-cycloalkyl moieties is unsubstituted or carries one, two or three R 1b as defined and preferably defined herein, such as 1 -cyclopropyl-cyclopropyl or 2-cyclopropyl- cyclopropyl. Specific embodiments thereof can be found in the below Table P1.
Specifically, it may be preferred, if R 1 is selected from Ci-C4-alkyl, such as methyl, ethyl, n- propyl, iso-propyl, tert-butyl, CH 2 C(CH 3 )3 and CH 2 CH(CH 3 )2, Ci-C 4 -haloalkyl, such as CF 3 , C 2 - C6-alkenyl, C2-C6-alkynyl, such as C≡CCH 3 , and C3-C6-cycloalkyl, such as cyclopropyl.
Particularly preferred embodiments of R 1 according to the invention are in Table P1 below, wherein each line of lines P1-1 to P1-137 corresponds to one particular embodiment of the invention, wherein P1-1 to P1-137 are also in any combination a preferred embodiment of the present invention.
Table P1 : line R 1 line R 1 line R 1
P1-83 CH 2 C≡CBr P1-110 1-(CI)-cyclobutyl
P1-84 CH 2 C≡C-I P1-111 1-(F)-cyclobutyl
P1-85 OCCH2OCH3 P1-112 2-(CI)-cyclobutyl
P1-86 C≡CCH(OH)CH 3 P1-113 3-(CI)-cyclobutyl
P1-87 C≡CCH(OCH 3 )CH 3 P1-114 2-(F)-cyclobutyl
P1-88 C≡COCH 3 P1-115 3-(F)-cyclobutyl
P1-89 CH 2 C≡COCH 3 P1-116 3,3-CI 2 -cyclobutyl
P1-90 C≡CCH 2 OCCI 3 P1-117 3,3-F 2 -cyclobutyl
P1-91 C≡CCH 2 OCF 3 P1-118 2-(CH 3 )-cyclopropyl
P1-92 C≡CCH 2 (C 3 H 5 ) P1-119 1-(CH 3 )-cyclobutyl
P1-93 C≡CCH 2 (C 4 H 7 ) P1-120 2-(CH 3 )-cyclobutyl
P1-94 C≡C(1-CI-C 3 H 4 ) P1-121 3-(CH 3 )-cyclobutyl
P1-95 C≡C(1-F-C 3 H 4 ) P1-122 3,3-(CH 3 ) 2 -cyclobutyl
P1-96 C≡C(1-CI-C 4 H 6 ) P1-123 2-(CN)-cyclopropyl
P1-97 C≡C(1-F-C 4 H 6 ) P1-124 1 -cyclopropyl-cyclopropyl
P1-98 C 3 H 5 (cyclopropyl) P1-125 2-cyclopropyl-cyclopropyl
P1-99 C 4 H 7 (cyclobutyl) P1-126 CH(CH 3 )(cyclobutyl)
P1-100 C5H9 (cyclopentyl) P1-127 CH 2 -(cyclobutyl)
P1-101 cyclohexyl P1-128 CH 2 CH 2 -(cyclopropyl)
P1-102 CH(CH 3 )-C 3 H 5 P1-129 CH 2 CH 2 -(cyclobutyl)
(CH(CH 3 )-cyclopropyl) P1-130 CH2-(1 -Cl-cyclopropyl)
P1-103 CH 2 -C 3 H 5 (CH 2 -cyclopropyl) P1-131 CH 2 -(1 -F-cyclopropyl)
P1-104 1-(CI)-cyclopropyl P1-132 CH 2 -(1-CI-cyclobutyl)
P1-105 1-(F)-cyclopropyl P1-133 CH 2 -(1-F-cyclobutyl)
P1-106 1-(CH 3 )-cyclopropyl P1-134 CHCH 3 -(1 -Cl-cyclopropyl)
P1-107 1-(CN)-cyclopropyl P1-135 C(CH 3 ) 2 -(1 -F-cyclopropyl)
P1-108 2-(CI)-cyclopropyl P1-136 CF 2 CH 3
P1-109 2-(F)-cyclopropyl P1-137 CHFCH 3
R 1a are the possible substituents for the aliphatic moieties of R 1 .
R 1a according to the invention is independently selected from halogen, OH, CN, Ci-C 4 -alkoxy, C 3 -C6-cycloalkyl, C 3 -C6-halocycloalkyl and Ci-C 4 -halogenalkoxy.
According to one embodiment R 1a is independently selected from halogen, OH, CN, Ci-C 2 - alkoxy, C 3 -C6-cycloalkyl, C 3 -C6-halocycloalkyl and Ci-C 2 -halogenalkoxy. Specifically, R 1a is independently selected from F, CI, OH, CN, Ci-C 2 -alkoxy, cyclopropyl, 1-F-cyclopropyl, 1 -Cl- cyclopropyl and Ci-C 2 -halogenalkoxy.
R 1b are the possible substituents for the cycloalkyl moieties of R 1 .
R 1b according to the invention is independently selected from halogen, OH, CN, CrC 4 -alkyl, Ci- C 4 -alkoxy, Ci-C 4 -halogenalkyl, C 3 -C6-cycloalkyl, C 3 -C6-halocycloalkyl and Ci-C 4 -halogenalkoxy. According to one embodiment thereof R 1b is independently selected from halogen, CN, C1-C2- alkyl, Ci-C 2 -alkoxy, Ci-C 2 -halogenalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl and C 1 -C 2 - halogenalkoxy. Specifically, R 1b is independently selected from F, CI, OH, CN, CH 3 , OCH 3 , cyclopropyl, 1 -F-cyclopropyl, 1 -Cl-cyclopropyl and halogenmethoxy.
According to the invention, R 2 is hydrogen, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, wherein the aliphatic moieties of R 2 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R 2a which independently of one another are selected from halogen, OH, CN, Ci-C 4 -alkoxy, C3-C6-cycloalkyl, C3-C6-halocycloalkyl and Ci-C4-halogenalkoxy.
According to one embodiment, R 2 is H.
According to a further embodiment of the invention, R 2 is selected from Ci-C 4 -alkyl, C 2 -C 4 - alkenyl and C 2 -C 4 -alkynyl.
According to a further embodiment of the invention, R 2 is selected from H, Ci-C4-alkyl, in particular methyl or ethyl, C 2 -C 4 -alkenyl, in particular CH 2 CH=CH 2 , and C 2 -C 4 -alkynyl, in particular CH2C≡CH. Specific embodiments thereof can be found in the below Table P2.
According to one particular embodiment, R 2 is Ci-C4-alkyl, such as CH 3 , C2H5, CH(CH 3 )2, CH2CH2CH3, CH2CH2CH2CH3, CH 2 CH(CH 3 ) 2 .
A further embodiment relates to compounds, wherein R 2 is Ci-C 4 -alkyl, that is substituted by one, two or three or up to the maximum possible number of identical or different groups R 2a , as defined and preferably defined herein. According to a specific embodiment thereof, R 2 is C1-C4- haloalkyl, more particularly Ci-C 2 -haloalkyl. According to a further specific embodiment thereof, R 2 is Ci-C 4 -alkoxy-Ci-C4-alkyl, such as CH2OCH3 or CH 2 CH 2 OCH 3 . According to still a further specific embodiment thereof, R 2 is hydroxyl-Ci-C 4 -alkyl, such as CH 2 CH 2 OH. Further specific embodiments thereof can be found in the below Table P2.
According to still another embodiment, R 2 is C3-C6-cycloalkyl-Ci-C 4 -alkyl. A further embodiment relates to compounds, wherein R 2 is C 3 -C6-cycloalkyl-Ci-C4-alkyl, more particularly C3-C6- cycloalkyl-Ci-C2-alkyl that is substituted by one, two or three or up to the maximum possible number of identical or different groups R 2a . A further embodiment relates to compounds, wherein R 2 is C3-C6-halocycloalkyl-Ci-C 4 -alkyl, more particularly C3-C6-halocycloalkyl-Ci-C 2 -alkyl. Specific embodiments thereof can be found in the below Table P2.
According to another embodiment, R 2 is C2-C4-alkenyl, such as CH2CH=CH2, CH2C(CH3)=CH2 or CH2CH=CHCH3. A further embodiment relates to compounds, wherein R 2 is C2-C4-alkenyl that is substituted by one, two or three or up to the maximum possible number of identical or different groups R 2a as defined and preferably defined herein. According to a specific embodi- ment thereof, R 2 is C 2 -C 4 -haloalkenyl, such as CH 2 C(CI)=CH 2 and CH 2 C(H)=CHCI . According to a further specific embodiment thereof, R 2 is C3-C6-cycloalkyl-C2-C4-alkenyl or C3-C6- halocycloalkyl-C 2 -C 4 -alkenyl. Further specific embodiments thereof can be found in the below Table P2.
According to still another embodiment, R 2 is C 2 -C 4 -alkynyl, such as CH 2 C≡CH or CH 2 C≡CCH3. A further embodiment relates to compounds, wherein R 2 is C 2 -C 4 -alkynyl that is substituted by one, two or three or up to the maximum possible number of identical or different groups R 2a , as defined and preferably defined herein. According to a specific embodiment thereof, R 2 is C2-C4- haloalkynyl. According to a further specific embodiment thereof, R 2 is C 3 -C6-cycloalkyl-C2-C4- alkynyl or C3-C6-halocycloalkyl-C 2 -C4-alkynyl. Specific embodiments thereof can be found in the below Table P2.
Particularly preferred embodiments of R 2 according to the invention are in Table P2 below, wherein each line of lines P2-1 to P2-79 corresponds to one particular embodiment of the invention, wherein P2-1 to P2-79 are also in any combination a preferred embodiment of the present invention.
Table P2:
R 3 according to the present invention is independently selected from halogen, CN, Ci-C4-alkyl, Ci-C4-alkoxy, C 2 -C 4 -alkenyl, C 2 -C4-alkynyl, C 3 -C6-cycloalkyl and S(0) p (Ci-C 4 -alkyl), wherein each of R 3 is unsubstituted or further substituted by one, two, three or four R 3a ; wherein R 3a is independently selected from halogen, CN, OH, Ci-C4-alkyl, Ci-C 4 -halogenalkyl, C 3 -C6- cycloalkyi, C 3 -C6-halogencycloalkyl, Ci-C 4 -alkoxy and d-Crhalogenalkoxy, and wherein p is 0, 1 or 2.
R 3 according to one embodiment is independently selected from halogen, CN, Ci-C 4 -alkyl, Ci- C 4 -alkoxy, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, C3-C6-cycloalkyl and S(0) p (Ci-C 4 -alkyl), wherein each of R 3 is unsubstituted or further substituted by one, two, three or four R 3a ; wherein R 3a is inde- pendently selected from halogen, CN, OH, Ci-C 4 -alkyl, Ci-C 4 -halogenalkyl, C 3 -C8-cycloalkyl, C 3 - Ce-halogencycloalkyl, Ci-C 4 -alkoxy and Ci-C 4 -halogenalkoxy, and wherein p is 0, 1 or 2.
According to a further embodiment, R 3 is selected from F, CI, Br, CN, Ci-C 4 -alkyl, C 1 -C 4 - halogenalkyl, Ci-C 4 -alkoxy, Ci-C 4 -halogenalkoxy, S(Ci-C 4 -alkyl), S(0)(Ci-C 4 -alkyl) and
S(0) 2 (Ci-C 4 -alkyl).
According to still a further embodiment, R 3 is selected from CI, F, Br, CN, Ci-C 2 -alkyl, in particular CH 3 , Ci-C 2 -haloalkyl, in particular CF 3 , Ci-C 2 -alkoxy, in particular OCH 3 , and Ci-C 2 - halogenalkoxy, in particular OCF 3 .
According to still a further embodiment, R 3 is selected from CI, F, Br, Ci-C 2 -alkyl, in particular CH 3 , Ci-C 2 -haloalkyl, in particular CF 3 , Ci-C 2 -alkoxy, in particular OCH 3 , and Ci-C 2 - halogenalkoxy, in particular OCF 3 .
According to a further embodiment, R 3 is selected from C 2 -C 4 -alkenyl, C 2 -C 4 -halogenalkenyl, C 2 - C4-alkynyl and C 2 -C 4 -halogenalkynyl. According to one particular embodiment, R 3 is C 2 -C 4 -alk- enyl or C 2 -C 4 -halogenalkenyl, such as CH=CH 2 . According to a further particular embodiment, R 3 is C 2 -C 4 -alkynyl or C 2 -C 4 -halogenalkynyl, such as C CH.
According to a further embodiment, R 3 is selected from C 3 -C6-cycloalkyl and C 3 -C6- halogencycloalkyl.
According to a further embodiment, R 3 is selected from S(Ci-C 2 -alkyl), S(0)(Ci-C 2 -alkyl) and S(0) 2 (Ci-C 2 -alkyl). According to a particular embodiment thereof, R 3 is selected from SCH 3 , S(0)(CH 3 ) and S(0) 2 (CH 3 ). According to one specific embodiment, R 3 is halogen, in particular Br, F or CI, more specifically F or CI.
According to a further specific embodiment, R 3 is CN.
According to a further specific embodiment, R 3 is Ci-C 4 -alkyl, such as CH3, or Ci-C 4 -haloalkyl, such as CF 3 , CHF 2 , CH 2 F, CCI 3 , CHCI 2 or CH 2 CI.
According to a further specific embodiment, R 3 is Ci-C4-alkoxy, more specifically Ci-C2-alkoxy such as OCH3 or OCH2CH3, or Ci-C4-haloalkoxy, more specifically Ci-C2-haloalkoxy such as OCF3, OCHF2, OCH2F, OCCI3, OCHCI 2 or OCH2CI, in particular OCF 3 , OCHF 2 , OCCI 3 or OCHC .
R 3a is selected from halogen, CN, OH, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 - halocycloalkyl, Ci-C 4 -alkoxy and Ci-C 4 -halogenalkoxy, in particular selected from halogen, CN, Ci-C 2 -alkyl, Ci-C 2 -haloalkyl, C3-C6-cycloalkyl, C 3 -C6-halocycloalkyl, Ci-C 2 -alkoxy and C 1 -C 2 - halogenalkoxy. Specifically, R 3a is independently selected from F, CI, CN, OH, CH 3 , halomethyl, cyclopropyl, halocyclopropyl, OCH 3 and halogenmethoxy.
Particularly preferred embodiments of R 3 according to the invention are in Table P3 below, wherein each line of lines P3-1 to P3-15 corresponds to one particular embodiment of the invention, wherein P3-1 to P3-15 are also in any combination with one another a preferred embodiment of the present invention. Thereby, for every R 3 that is present in the inventive compounds, these specific embodiments and preferences apply independently of the meaning of any other R 3 that may be present in the phenyl ring:
Table P3:
Z is is halogen, CN, Ci-C 6 -alkyl, Si(Ci-C 4 -alkyl) 3 , d-Ce-alkoxy or C(=0)-0-(Ci-C 6 -alkyl); wherein the aliphatic moieties of Z are not further substituted or carry one, two, three or four identical or different groups R z , which independently of one another are selected from R z halogen, CN, OH, Ci-C 4 -alkyl, Ci-C 4 -halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, O-C6H 5 (phenoxy), Ci-C4-alkoxy, and Ci-C4-halogenalkoxy.
According to one embodiment, Z is halogen, in particular F, CI, Br or I.
According to one particular embodiment, Z is CN.
According to a further particular embodiment, Z is Ci-C6-alkyl, wherein said alkyl is unsubstitut- ed or substituted by one, two, three or four identical or different groups R z , wherein R z are defined and preferably defined as given herein. According to one specific embodiment, Z is C1-C6- alkyl, that is not further substituted. According to a further specific embodiment, Z is Ci-C6-alkyl, substituted by one, two, three or four identical or different groups R z , wherein R z is preferably selected from halogen, CN, OH, O-C6H5 and Ci-C4-alkoxy, more preferably selected from F, CI, Br, CN, OH, O-C5H5 and Ci-C 2 -alkoxy.
According to still a further particular embodiment, Z is Si(Ci-C4-alkyl)3, more specifically
Si(CH 3 ) 3 .
According to still a further particular embodiment, Z is Ci-C6-alkoxy, wherein the alkyl moieties are unsubstituted or substituted by one, two, three or four identical or different groups R z , wherein R z are defined and preferably defined as given herein.
According to still a further particular embodiment, Z is C(=0)-0-(Ci-C6-alkyl), wherein the alkyl moieties are unsubstituted or substituted by one, two, three or four identical or different groups R z , wherein R z are defined and preferably defined as given herein.
According to the invention, each R z is selected from halogen, CN, OH, Ci-C4-alkyl, C 1 -C4- halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, O-C6H5, Ci-C4-alkoxy and C1-C4- halogenalkoxy, more specifically selected from F, CI, Br, CN, OH, Ci-C2-alkyl, C1-C2- halogenalkyl, O-C6H5, Ci-C2-alkoxy and Ci-C2-halogenalkoxy.
One embodiment of the invention relates to compounds I, wherein A is N (I.A).
One particular embodiment thereof relates to compounds I.A, wherein R 3 is CI, corresponding to compounds I.A1 . One further particular embodiment relates to compounds I.A, wherein R 3 is F, corresponding to compounds I.A2. Still one further particular embodiment relates to compounds I.A, wherein R 3 is Br, corresponding to compounds I.A3. Still one further particular embodiment relates to compounds I.A, wherein R 3 is CF3, corresponding to compounds I.A4. Still one further particular embodiment relates to compounds I.A, wherein R 3 is CH3, corresponding to compounds I.A5. Still one further particular embodiment relates to compounds I.A, wherein R 3 is OCH3, corres onding to compounds I.A6:
I.A1 I.A2 I.A3
A further embodiment relates to com ounds I, wherein A is CH (I.B).
One particular embodiment thereof relates to compounds I.B, wherein R 3 is CI, corresponding to compounds I.B1 . One further particular embodiment relates to compounds I.B, wherein R 3 is F, corresponding to compounds I.B2. Still one further particular embodiment relates to compounds I.B, wherein R 3 is Br, corresponding to compounds I.B3. Still one further particular embodiment relates to compounds I.B, wherein R 3 is CF3, corresponding to compounds I.B4. Still one further particular embodiment relates to compounds I.B, wherein R 3 is CH3, corresponding to com- pounds I.B5. Still one further particular embodiment relates to compounds I.B, wherein R 3 is OCH3, corres onding to compounds I.B6:
In particular with a view to their use, according to one embodiment, preference is given to the compounds of the formula I.A1 , I.A2, I.A3, I.A4, I.A5 and I.A6 that are compiled in the Tables 1 a to 21 a, Tables 1 b to 21 b, Tables 1 c to 21 c, Tables 1 d to 21 d, Tables 1 e to 21 e and Tables 1f to 21f below. Each of the groups mentioned for a substituent in the tables is furthermore per se, independently of the combination in which it is mentioned, a particularly preferred aspect of the substituent in question.
Table 1 a Compounds of the formula I.A1 in which Z corresponds to line D1 -1 of Table Dl and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A1.D1-1.B1 to I.A1.D1-1 .B450).
Table 2a Compounds of the formula I.A1 in which Z corresponds to line D1 -2 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A1.D1-2.B1 to I.A1.D1-2.B450).
Table 3a Compounds of the formula I.A1 in which Z corresponds to line D1 -3 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A1.D1-3.B1 to I.A1.D1-3.B450).
Table 4a Compounds of the formula I.A1 in which Z corresponds to line D1 -4 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A1.D1-4.B1 to I.A1.D1-4.B450).
Table 5a Compounds of the formula I.A1 in which Z corresponds to line D1 -5 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A1.D1-5.B1 to I.A1.D1-5.B450).
Table 6a Compounds of the formula I.A1 in which Z corresponds to line D1 -6 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A1.D1-6.B1 to I.A1.D1-6.B450).
Table 7a Compounds of the formula I.A1 in which Z corresponds to line D1 -7 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A1.D1-7.B1 to I.A1.D1-7.B450).
Table 8a Compounds of the formula I.A1 in which Z corresponds to line D1 -8 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A1.D1-8.B1 to I.A1.D1-8.B450).
Table 9a Compounds of the formula I.A1 in which Z corresponds to line D1 -9 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A1.D1-9.B1 to I.A1.D1-9.B450).
Table 10a Compounds of the formula I.A1 in which Z corresponds to line D1 -10 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A1.D1-10.B1 to I.A1.D1 -10.B450).
Table 1 1 a Compounds of the formula I.A1 in which Z corresponds to line D1 -1 1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A1.D1-1 1.B1 to I.A1.D1 -1 1.B450).
Table 12a Compounds of the formula I.A1 in which Z corresponds to line D1 -12 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A1.D1-12.B1 to I.A1.D1 -12.B450).
Table 13a Compounds of the formula I.A1 in which Z corresponds to line D1 -13 of Table D1 and the meaning for the combination of R and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A1.D1-13.B1 to I.A1.D1 -13.B450).
Table 14a Compounds of the formula I.A1 in which Z corresponds to line D1 -14 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A1.D1-14.B1 to I.A1.D1 -14.B450).
Table 15a Compounds of the formula I.A1 in which Z corresponds to line D1 -15 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A1.D1-15.B1 to I.A1.D1 -15.B450). Table 16a Compounds of the formula I.A1 in which Z corresponds to line D1 -16 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A1.D1 -16.B1 to I.A1.D1-16.B450).
Table 17a Compounds of the formula I.A1 in which Z corresponds to line D1 -17 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A1.D1-17.B1 to I.A1.D1 -17.B450).
Table 18a Compounds of the formula I.A1 in which Z corresponds to line D1 -18 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A1.D1-18.B1 to I.A1.D1 -18.B450).
Table 19a Compounds of the formula I.A1 in which Z corresponds to line D1 -19 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A1.D1-19.B1 to I.A1.D1 -19.B450).
Table 20a Compounds of the formula I.A1 in which Z corresponds to line D1 -20 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A1.D1-20.B1 to I.A1.D1 -20.B450).
Table 21 a Compounds of the formula I.A1 in which Z corresponds to line D1 -21 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A1.D1-21.B1 to I.A1.D1 -21.B450).
Table 1 b Compounds of the formula I.A2 in which Z corresponds to line D1 -1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A2.D1-1.B1 to I.A2.D1-1 .B450).
Table 2b Compounds of the formula I.A2 in which Z corresponds to line D1 -2 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A2.D1-2.B1 to I.A2.D1-2.B450).
Table 3b Compounds of the formula I.A2 in which Z corresponds to line D1 -3 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A2.D1-3.B1 to I.A2.D1-3.B450).
Table 4b Compounds of the formula I.A2 in which Z corresponds to line D1 -4 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A2.D1-4.B1 to I.A2.D1-4.B450).
Table 5b Compounds of the formula I.A2 in which Z corresponds to line D1 -5 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A2.D1-5.B1 to I.A2.D1-5.B450).
Table 6b Compounds of the formula I.A2 in which Z corresponds to line D1 -6 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A2.D1-6.B1 to I.A2.D1-6.B450).
Table 7b Compounds of the formula I.A2 in which Z corresponds to line D1 -7 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A2.D1-7.B1 to I.A2.D1-7.B450).
Table 8b Compounds of the formula I.A2 in which Z corresponds to line D1 -8 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A2.D1-8.B1 to I.A2.D1-8.B450).
Table 9b Compounds of the formula I.A2 in which Z corresponds to line D1 -9 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A2.D1-9.B1 to I.A2.D1-9.B450).
Table 10b Compounds of the formula I.A2 in which Z corresponds to line D1 -10 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A2.D1-10.B1 to I.A2.D1 -10.B450).
Table 1 1 b Compounds of the formula I.A2 in which Z corresponds to line D1 -1 1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A2.D1-1 1.B1 to I.A2.D1 -1 1.B450).
Table 12b Compounds of the formula I.A2 in which Z corresponds to line D1 -12 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A2.D1-12.B1 to I.A2.D1 -12.B450).
Table 13b Compounds of the formula I.A2 in which Z corresponds to line D1 -13 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A2.D1-13.B1 to I.A2.D1 -13.B450).
Table 14b Compounds of the formula I.A2 in which Z corresponds to line D1 -14 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A2.D1-14.B1 to I.A2.D1 -14.B450).
Table 15b Compounds of the formula I.A2 in which Z corresponds to line D1 -15 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A2.D1-15.B1 to I.A2.D1 -15.B450).
Table 16b Compounds of the formula I.A2 in which Z corresponds to line D1 -16 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A2.D1 -16.B1 to I.A2.D1-16.B450).
Table 17b Compounds of the formula I.A2 in which Z corresponds to line D1 -17 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A2.D1-17.B1 to I.A2.D1 -17.B450).
Table 18b Compounds of the formula I.A2 in which Z corresponds to line D1 -18 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A2.D1-18.B1 to I.A2.D1 -18.B450).
Table 19b Compounds of the formula I.A2 in which Z corresponds to line D1 -19 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A2.D1-19.B1 to I.A2.D1 -19.B450).
Table 20b Compounds of the formula I.A2 in which Z corresponds to line D1 -20 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A2.D1-20.B1 to I.A2.D1 -20.B450).
Table 21 b Compounds of the formula I.A2 in which Z corresponds to line D1 -21 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A2.D1-21.B1 to I.A2.D1 -21.B450).
Table 1 c Compounds of the formula I.A3 in which Z corresponds to line D1 -1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A3.D1-1.B1 to I.A3.D1-1 .B450).
Table 2c Compounds of the formula I.A3 in which Z corresponds to line D1 -2 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A3.D1-2.B1 to I.A3.D1-2.B450).
Table 3c Compounds of the formula I.A3 in which Z corresponds to line D1 -3 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A3.D1-3.B1 to I.A3.D1-3.B450).
Table 4c Compounds of the formula I.A3 in which Z corresponds to line D1 -4 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A3.D1-4.B1 to I.A3.D1-4.B450).
Table 5c Compounds of the formula I.A3 in which Z corresponds to line D1 -5 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A3.D1-5.B1 to I.A3.D1-5.B450).
Table 6c Compounds of the formula I.A3 in which Z corresponds to line D1 -6 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A3.D1-6.B1 to I.A3.D1-6.B450).
Table 7c Compounds of the formula I.A3 in which Z corresponds to line D1 -7 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A3.D1-7.B1 to I.A3.D1-7.B450).
Table 8c Compounds of the formula I.A3 in which Z corresponds to line D1 -8 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A3.D1-8.B1 to I.A3.D1-8.B450).
Table 9c Compounds of the formula I.A3 in which Z corresponds to line D1 -9 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A3.D1-9.B1 to I.A3.D1-9.B450).
Table 10c Compounds of the formula I.A3 in which Z corresponds to line D1 -10 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A3.D1-10.B1 to I.A3.D1 -10.B450).
Table 1 1 c Compounds of the formula I.A3 in which Z corresponds to line D1 -1 1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A3.D1-1 1.B1 to I.A3.D1 -1 1.B450).
Table 12c Compounds of the formula I.A3 in which Z corresponds to line D1 -12 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A3.D1-12.B1 to I.A3.D1 -12.B450).
Table 13c Compounds of the formula I.A3 in which Z corresponds to line D1 -13 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A3.D1-13.B1 to I.A3.D1 -13.B450).
Table 14c Compounds of the formula I.A3 in which Z corresponds to line D1 -14 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A3.D1-14.B1 to I.A3.D1 -14.B450).
Table 15c Compounds of the formula I.A3 in which Z corresponds to line D1 -15 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A3.D1-15.B1 to I.A3.D1 -15.B450).
Table 16c Compounds of the formula I. A3 in which Z corresponds to line D1 -16 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A3.D1 -16.B1 to I.A3.D1-16.B450). Table 17c Compounds of the formula I.A3 in which Z corresponds to line D1 -17 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A3.D1-17.B1 to I.A3.D1 -17.B450).
Table 18c Compounds of the formula I.A3 in which Z corresponds to line D1 -18 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A3.D1-18.B1 to I.A3.D1 -18.B450).
Table 19c Compounds of the formula I.A3 in which Z corresponds to line D1 -19 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A3.D1-19.B1 to I.A3.D1 -19.B450).
Table 20c Compounds of the formula I.A3 in which Z corresponds to line D1 -20 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A3.D1-20.B1 to I.A3.D1 -20.B450).
Table 21 c Compounds of the formula I.A3 in which Z corresponds to line D1 -21 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A3.D1-21.B1 to I.A3.D1 -21.B450).
Table 1 d Compounds of the formula I.A4 in which Z corresponds to line D1 -1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A4.D1-1.B1 to I.A4.D1-1 .B450).
Table 2d Compounds of the formula I.A4 in which Z corresponds to line D1 -2 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A4.D1-2.B1 to I.A4.D1-2.B450).
Table 3d Compounds of the formula I.A4 in which Z corresponds to line D1 -3 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A4.D1-3.B1 to I.A4.D1-3.B450).
Table 4d Compounds of the formula I.A4 in which Z corresponds to line D1 -4 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A4.D1-4.B1 to I.A4.D1-4.B450).
Table 5d Compounds of the formula I.A4 in which Z corresponds to line D1 -5 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A4.D1-5.B1 to I.A4.D1-5.B450).
Table 6d Compounds of the formula I.A4 in which Z corresponds to line D1 -6 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A4.D1-6.B1 to I.A4.D1-6.B450).
Table 7d Compounds of the formula I.A4 in which Z corresponds to line D1 -7 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A4.D1-7.B1 to I.A4.D1-7.B450).
Table 8d Compounds of the formula I.A4 in which Z corresponds to line D1 -8 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A4.D1-8.B1 to I.A4.D1-8.B450).
Table 9d Compounds of the formula I.A4 in which Z corresponds to line D1 -9 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A4.D1-9.B1 to I.A4.D1-9.B450).
Table 10d Compounds of the formula I.A4 in which Z corresponds to line D1 -10 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A4.D1-10.B1 to I.A4.D1 -10.B450).
Table 1 1 d Compounds of the formula I.A4 in which Z corresponds to line D1 -1 1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A4.D1-1 1.B1 to I.A4.D1 -1 1.B450).
Table 12d Compounds of the formula I.A4 in which Z corresponds to line D1 -12 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A4.D1-12.B1 to I.A4.D1 -12.B450).
Table 13d Compounds of the formula I.A4 in which Z corresponds to line D1 -13 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A4.D1-13.B1 to I.A4.D1 -13.B450).
Table 14d Compounds of the formula I.A4 in which Z corresponds to line D1 -14 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A4.D1-14.B1 to I.A4.D1 -14.B450).
Table 15d Compounds of the formula I.A4 in which Z corresponds to line D1 -15 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A4.D1-15.B1 to I.A4.D1 -15.B450).
Table 16d Compounds of the formula I.A4 in which Z corresponds to line D1 -16 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corre- sponds in each case to one line of Table B (compounds I.A4.D1 -16.B1 to I.A4.D1-16.B450).
Table 17d Compounds of the formula I.A4 in which Z corresponds to line D1 -17 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A4.D1-17.B1 to I.A4.D1 -17.B450).
Table 18d Compounds of the formula I.A4 in which Z corresponds to line D1 -18 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A4.D1-18.B1 to I.A4.D1 -18.B450).
Table 19d Compounds of the formula I.A4 in which Z corresponds to line D1 -19 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A4.D1-19.B1 to I.A4.D1 -19.B450).
Table 20d Compounds of the formula I.A4 in which Z corresponds to line D1 -20 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A4.D1-20.B1 to I.A4.D1 -20.B450).
Table 21 d Compounds of the formula I.A4 in which Z corresponds to line D1 -21 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A4.D1-21.B1 to I.A4.D1 -21.B450).
Table 1 e Compounds of the formula I.A5 in which Z corresponds to line D1 -1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A5.D1-1.B1 to I.A5.D1-1 .B450).
Table 2e Compounds of the formula I.A5 in which Z corresponds to line D1 -2 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A5.D1-2.B1 to I.A5.D1-2.B450).
Table 3e Compounds of the formula I.A5 in which Z corresponds to line D1 -3 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A5.D1 -3.B1 to I.A5.D1 -3.B450).
Table 4e Compounds of the formula I.A5 in which Z corresponds to line D1 -4 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A5.D1 -4.B1 to I.A5.D1 -4.B450).
Table 5e Compounds of the formula I.A5 in which Z corresponds to line D1 -5 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A5.D1 -5.B1 to I.A5.D1 -5.B450).
Table 6e Compounds of the formula I.A5 in which Z corresponds to line D1 -6 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A5.D1 -6.B1 to I.A5.D1 -6.B450).
Table 7e Compounds of the formula I.A5 in which Z corresponds to line D1 -7 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A5.D1 -7.B1 to I.A5.D1 -7.B450).
Table 8e Compounds of the formula I.A5 in which Z corresponds to line D1 -8 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A5.D1 -8.B1 to I.A5.D1 -8.B450).
Table 9e Compounds of the formula I.A5 in which Z corresponds to line D1 -9 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A5.D1 -9.B1 to I.A5.D1 -9.B450).
Table 10e Compounds of the formula I.A5 in which Z corresponds to line D1 -10 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A5.D1 -10.B1 to I.A5.D1 -10.B450).
Table 1 1 e Compounds of the formula I.A5 in which Z corresponds to line D1 -1 1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A5.D1 -1 1.B1 to I.A5.D1 -1 1 .B450).
Table 12e Compounds of the formula I.A5 in which Z corresponds to line D1 -12 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A5.D1 -12.B1 to I.A5.D1 -12.B450).
Table 13e Compounds of the formula I.A5 in which Z corresponds to line D1 -13 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A5.D1 -13.B1 to I.A5.D1 -13.B450).
Table 14e Compounds of the formula I.A5 in which Z corresponds to line D1 -14 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A5.D1 -14.B1 to I.A5.D1 -14.B450).
Table 15e Compounds of the formula I.A5 in which Z corresponds to line D1 -15 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A5.D1 -15.B1 to I.A5.D1 -15.B450).
Table 16e Compounds of the formula I .A5 in which Z corresponds to line D1 -16 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corre- sponds in each case to one line of Table B (compounds I.A5.D1 -16.B1 to I.A5.D1 -16.B450).
Table 17e Compounds of the formula I.A5 in which Z corresponds to line D1 -17 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A5.D1 -17.B1 to I.A5.D1 -17.B450). Table 18e Compounds of the formula I.A5 in which Z corresponds to line D1 -18 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A5.D1-18.B1 to I.A5.D1 -18.B450).
Table 19e Compounds of the formula I.A5 in which Z corresponds to line D1 -19 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A5.D1-19.B1 to I.A5.D1 -19.B450).
Table 20e Compounds of the formula I.A5 in which Z corresponds to line D1 -20 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A5.D1-20.B1 to I.A5.D1 -20.B450).
Table 21 e Compounds of the formula I.A5 in which Z corresponds to line D1 -21 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A5.D1-21.B1 to I.A5.D1 -21.B450).
Table 1f Compounds of the formula I.A6 in which Z corresponds to line D1 -1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A6.D1-1.B1 to I.A6.D1-1 .B450).
Table 2f Compounds of the formula I.A6 in which Z corresponds to line D1 -2 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A6.D1-2.B1 to I.A6.D1-2.B450).
Table 3f Compounds of the formula I.A6 in which Z corresponds to line D1 -3 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A6.D1-3.B1 to I.A6.D1-3.B450).
Table 4f Compounds of the formula I.A6 in which Z corresponds to line D1 -4 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A6.D1-4.B1 to I.A6.D1-4.B450).
Table 5f Compounds of the formula I.A6 in which Z corresponds to line D1 -5 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A6.D1-5.B1 to I.A6.D1-5.B450).
Table 6f Compounds of the formula I.A6 in which Z corresponds to line D1 -6 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A6.D1-6.B1 to I.A6.D1-6.B450).
Table 7f Compounds of the formula I.A6 in which Z corresponds to line D1 -7 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A6.D1-7.B1 to I.A6.D1-7.B450).
Table 8f Compounds of the formula I.A6 in which Z corresponds to line D1 -8 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A6.D1-8.B1 to I.A6.D1-8.B450).
Table 9f Compounds of the formula I.A6 in which Z corresponds to line D1 -9 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A6.D1-9.B1 to I.A6.D1-9.B450).
Table 10f Compounds of the formula I.A6 in which Z corresponds to line D1 -10 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A6.D1-10.B1 to I.A6.D1 -10.B450).
Table 1 1f Compounds of the formula I.A6 in which Z corresponds to line D1 -1 1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A6.D1 -1 1.B1 to I.A6.D1 -1 1 .B450).
Table 12f Compounds of the formula I.A6 in which Z corresponds to line D1 -12 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A6.D1 -12.B1 to I.A6.D1 -12.B450).
Table 13f Compounds of the formula I.A6 in which Z corresponds to line D1 -13 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A6.D1 -13.B1 to I.A6.D1 -13.B450).
Table 14f Compounds of the formula I.A6 in which Z corresponds to line D1 -14 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A6.D1 -14.B1 to I.A6.D1 -14.B450).
Table 15f Compounds of the formula I.A6 in which Z corresponds to line D1 -15 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A6.D1 -15.B1 to I.A6.D1 -15.B450).
Table 16f Compounds of the formula I .A6 in which Z corresponds to line D1 -16 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A6.D1 -16.B1 to I.A6.D1 -16.B450).
Table 17f Compounds of the formula I.A6 in which Z corresponds to line D1 -17 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A6.D1 -17.B1 to I.A6.D1 -17.B450).
Table 18f Compounds of the formula I.A6 in which Z corresponds to line D1 -18 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A6.D1 -18.B1 to I.A6.D1 -18.B450).
Table 19f Compounds of the formula I.A6 in which Z corresponds to line D1 -19 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A6.D1 -19.B1 to I.A6.D1 -19.B450).
Table 20f Compounds of the formula I.A6 in which Z corresponds to line D1 -20 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A6.D1 -20.B1 to I.A6.D1 -20.B450).
Table 21f Compounds of the formula I.A6 in which Z corresponds to line D1 -21 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.A6.D1 -21.B1 to I.A6.D1 -21 .B450).
In particular with a view to their use, according to a further embodiment, preference is given to the compounds of the formula I .B1 , I .B2, I.B3, I .B4, I .B5 and I.B6 that are compiled in the Ta- bles 1 g to 21 g, Tables 1 h to 21 h, Tables 1 i to 21 i, Tables 1j to 21j, Tables 1 k to 21 k and Tables 11 to 211 below. Each of the groups mentioned for a substituent in the tables is furthermore per se, independently of the combination in which it is mentioned, a particularly preferred aspect of the substituent in question.
Table 1 g Compounds of the formula I. B1 in which Z corresponds to line D1 -1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B1 .D1 -1.B1 to I.B1.D1 -1 .B450).
Table 2g Compounds of the formula I.B1 in which Z corresponds to line D1 -2 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B1.D1-2.B1 to I.B1.D1-2.B450).
Table 3g Compounds of the formula I.B1 in which Z corresponds to line D1 -3 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B1.D1-3.B1 to I.B1.D1-3.B450).
Table 4g Compounds of the formula I. B1 in which Z corresponds to line D1 -4 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B1.D1-4.B1 to I.B1.D1-4.B450).
Table 5g Compounds of the formula I.B1 in which Z corresponds to line D1 -5 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B1.D1-5.B1 to I.B1.D1-5.B450).
Table 6g Compounds of the formula I.B1 in which Z corresponds to line D1 -6 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B1.D1-6.B1 to I.B1.D1-6.B450).
Table 7g Compounds of the formula I.B1 in which Z corresponds to line D1 -7 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B1.D1-7.B1 to I.B1.D1-7.B450).
Table 8g Compounds of the formula I. B1 in which Z corresponds to line D1 -8 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B1.D1-8.B1 to I.B1.D1-8.B450).
Table 9g Compounds of the formula I. B1 in which Z corresponds to line D1 -9 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B1.D1-9.B1 to I.B1.D1-9.B450).
Table 10g Compounds of the formula I.B1 in which Z corresponds to line D1 -10 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B1.D1-10.B1 to I.B1.D1 -10.B450).
Table 1 1 g Compounds of the formula I. B1 in which Z corresponds to line D1 -1 1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B1.D1-1 1.B1 to I.B1.D1 -1 1.B450).
Table 12g Compounds of the formula I.B1 in which Z corresponds to line D1 -12 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B1.D1-12.B1 to I.B1.D1 -12.B450).
Table 13g Compounds of the formula I.B1 in which Z corresponds to line D1 -13 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B1.D1-13.B1 to I.B1.D1 -13.B450).
Table 14g Compounds of the formula I. B1 in which Z corresponds to line D1 -14 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B1.D1-14.B1 to I.B1.D1 -14.B450).
Table 15g Compounds of the formula I.B1 in which Z corresponds to line D1 -15 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B1.D1-15.B1 to I.B1.D1 -15.B450).
Table 16g Compounds of the formula I.B1 in which Z corresponds to line D1 -16 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B1.D1 -16.B1 to I.B1.D1-16.B450). Table 17g Compounds of the formula I.B1 in which Z corresponds to line D1 -17 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B1.D1-17.B1 to I.B1.D1 -17.B450).
Table 18g Compounds of the formula I.B1 in which Z corresponds to line D1 -18 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B1.D1-18.B1 to I.B1.D1 -18.B450).
Table 19g Compounds of the formula I.B1 in which Z corresponds to line D1 -19 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B1.D1-19.B1 to I.B1.D1 -19.B450).
Table 20g Compounds of the formula I. B1 in which Z corresponds to line D1 -20 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B1.D1-20.B1 to I.B1.D1 -20.B450).
Table 21 g Compounds of the formula I. B1 in which Z corresponds to line D1 -21 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B1.D1-21.B1 to I.B1.D1 -21.B450).
Table 1 h Compounds of the formula I. B2 in which Z corresponds to line D1 -1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B2.D1-1.B1 to I.B2.D1-1 .B450).
Table 2h Compounds of the formula I.B2 in which Z corresponds to line D1 -2 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B2.D1-2.B1 to I.B2.D1-2.B450).
Table 3h Compounds of the formula I.B2 in which Z corresponds to line D1 -3 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B2.D1-3.B1 to I.B2.D1-3.B450).
Table 4h Compounds of the formula I.B2 in which Z corresponds to line D1 -4 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B2.D1-4.B1 to I.B2.D1-4.B450).
Table 5h Compounds of the formula I.B2 in which Z corresponds to line D1 -5 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B2.D1-5.B1 to I.B2.D1-5.B450).
Table 6h Compounds of the formula I.B2 in which Z corresponds to line D1 -6 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B2.D1-6.B1 to I.B2.D1-6.B450).
Table 7h Compounds of the formula I.B2 in which Z corresponds to line D1 -7 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B2.D1-7.B1 to I.B2.D1-7.B450).
Table 8h Compounds of the formula I.B2 in which Z corresponds to line D1 -8 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B2.D1-8.B1 to I.B2.D1-8.B450).
Table 9h Compounds of the formula I.B2 in which Z corresponds to line D1 -9 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B2.D1-9.B1 to I.B2.D1-9.B450).
Table 10h Compounds of the formula I.B2 in which Z corresponds to line D1 -10 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B2.D1-10.B1 to I.B2.D1 -10.B450).
Table 1 1 h Compounds of the formula I.B2 in which Z corresponds to line D1 -1 1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B2.D1-1 1.B1 to I.B2.D1 -1 1.B450).
Table 12h Compounds of the formula I.B2 in which Z corresponds to line D1 -12 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B2.D1-12.B1 to I.B2.D1 -12.B450).
Table 13h Compounds of the formula I.B2 in which Z corresponds to line D1 -13 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B2.D1-13.B1 to I.B2.D1 -13.B450).
Table 14h Compounds of the formula I.B2 in which Z corresponds to line D1 -14 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B2.D1-14.B1 to I.B2.D1 -14.B450).
Table 15h Compounds of the formula I.B2 in which Z corresponds to line D1 -15 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B2.D1-15.B1 to I.B2.D1 -15.B450).
Table 16h Compounds of the formula I.B2 in which Z corresponds to line D1 -16 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corre- sponds in each case to one line of Table B (compounds I.B2.D1 -16.B1 to I.B2.D1-16.B450).
Table 17h Compounds of the formula I.B2 in which Z corresponds to line D1 -17 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B2.D1-17.B1 to I.B2.D1 -17.B450).
Table 18h Compounds of the formula I.B2 in which Z corresponds to line D1 -18 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B2.D1-18.B1 to I.B2.D1 -18.B450).
Table 19h Compounds of the formula I.B2 in which Z corresponds to line D1 -19 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B2.D1-19.B1 to I.B2.D1 -19.B450).
Table 20h Compounds of the formula I.B2 in which Z corresponds to line D1 -20 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B2.D1-20.B1 to I.B2.D1 -20.B450).
Table 21 h Compounds of the formula I.B2 in which Z corresponds to line D1 -21 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B2.D1-21.B1 to I.B2.D1 -21.B450).
Table 1 i Compounds of the formula I. B3 in which Z corresponds to line D1 -1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B3.D1-1.B1 to I.B3.D1-1 .B450).
Table 2i Compounds of the formula I.B3 in which Z corresponds to line D1 -2 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B3.D1-2.B1 to I.B3.D1-2.B450).
Table 3i Compounds of the formula I.B3 in which Z corresponds to line D1 -3 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B3.D1-3.B1 to I.B3.D1-3.B450).
Table 4i Compounds of the formula I.B3 in which Z corresponds to line D1 -4 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B3.D1-4.B1 to I.B3.D1-4.B450).
Table 5i Compounds of the formula I.B3 in which Z corresponds to line D1 -5 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B3.D1-5.B1 to I.B3.D1-5.B450).
Table 6i Compounds of the formula I.B3 in which Z corresponds to line D1-6 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B3.D1-6.B1 to I.B3.D1-6.B450).
Table 7i Compounds of the formula I.B3 in which Z corresponds to line D1 -7 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B3.D1-7.B1 to I.B3.D1-7.B450).
Table 8i Compounds of the formula I.B3 in which Z corresponds to line D1 -8 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B3.D1-8.B1 to I.B3.D1-8.B450).
Table 9i Compounds of the formula I.B3 in which Z corresponds to line D1 -9 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B3.D1-9.B1 to I.B3.D1-9.B450).
Table 10i Compounds of the formula I.B3 in which Z corresponds to line D1 -10 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B3.D1-10.B1 to I.B3.D1 -10.B450).
Table 1 1 i Compounds of the formula I.B3 in which Z corresponds to line D1 -1 1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B3.D1-1 1.B1 to I.B3.D1 -1 1.B450).
Table 12i Compounds of the formula I.B3 in which Z corresponds to line D1 -12 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B3.D1-12.B1 to I.B3.D1 -12.B450).
Table 13i Compounds of the formula I.B3 in which Z corresponds to line D1 -13 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B3.D1-13.B1 to I.B3.D1 -13.B450).
Table 14i Compounds of the formula I.B3 in which Z corresponds to line D1 -14 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B3.D1-14.B1 to I.B3.D1 -14.B450).
Table 15i Compounds of the formula I.B3 in which Z corresponds to line D1 -15 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B3.D1-15.B1 to I.B3.D1 -15.B450).
Table 16iCompounds of the formula I.B3 in which Z corresponds to line D1 -16 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B3.D1-16.B1 to I.B3.D1 -16.B450).
Table 17i Compounds of the formula I.B3 in which Z corresponds to line D1 -17 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B3.D1-17.B1 to I.B3.D1 -17.B450). Table 18i Compounds of the formula I.B3 in which Z corresponds to line D1 -18 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B3.D1-18.B1 to I.B3.D1 -18.B450).
Table 19i Compounds of the formula I.B3 in which Z corresponds to line D1 -19 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B3.D1-19.B1 to I.B3.D1 -19.B450).
Table 20i Compounds of the formula I.B3 in which Z corresponds to line D1 -20 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B3.D1-20.B1 to I.B3.D1 -20.B450).
Table 21 i Compounds of the formula I. B3 in which Z corresponds to line D1 -21 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B3.D1-21.B1 to I.B3.D1 -21.B450).
Table 1j Compounds of the formula I. B4 in which Z corresponds to line D1 -1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B4.D1-1.B1 to I.B4.D1-1 .B450).
Table 2j Compounds of the formula I.B4 in which Z corresponds to line D1 -2 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B4.D1-2.B1 to I.B4.D1-2.B450).
Table 3j Compounds of the formula I.B4 in which Z corresponds to line D1 -3 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B4.D1-3.B1 to I.B4.D1-3.B450).
Table 4j Compounds of the formula I.B4 in which Z corresponds to line D1 -4 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B4.D1-4.B1 to I.B4.D1-4.B450).
Table 5j Compounds of the formula I.B4 in which Z corresponds to line D1 -5 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B4.D1-5.B1 to I.B4.D1-5.B450).
Table 6j Compounds of the formula I.B4 in which Z corresponds to line D1 -6 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B4.D1-6.B1 to I.B4.D1-6.B450).
Table 7j Compounds of the formula I.B4 in which Z corresponds to line D1 -7 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B4.D1-7.B1 to I.B4.D1-7.B450).
Table 8j Compounds of the formula I.B4 in which Z corresponds to line D1 -8 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B4.D1-8.B1 to I.B4.D1-8.B450).
Table 9j Compounds of the formula I.B4 in which Z corresponds to line D1 -9 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B4.D1-9.B1 to I.B4.D1-9.B450).
Table 10j Compounds of the formula I.B4 in which Z corresponds to line D1 -10 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B4.D1-10.B1 to I.B4.D1 -10.B450).
Table 1 1j Compounds of the formula I.B4 in which Z corresponds to line D1 -1 1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B4.D1-1 1.B1 to I.B4.D1 -1 1.B450).
Table 12j Compounds of the formula I.B4 in which Z corresponds to line D1 -12 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B4.D1-12.B1 to I.B4.D1 -12.B450).
Table 13j Compounds of the formula I.B4 in which Z corresponds to line D1 -13 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B4.D1-13.B1 to I.B4.D1 -13.B450).
Table 14j Compounds of the formula I.B4 in which Z corresponds to line D1 -14 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B4.D1-14.B1 to I.B4.D1 -14.B450).
Table 15j Compounds of the formula I.B4 in which Z corresponds to line D1 -15 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B4.D1-15.B1 to I.B4.D1 -15.B450).
Table 16jCompounds of the formula I.B4 in which Z corresponds to line D1 -16 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B4.D1-16.B1 to I.B4.D1 -16.B450).
Table 17j Compounds of the formula I.B4 in which Z corresponds to line D1 -17 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B4.D1-17.B1 to I.B4.D1 -17.B450).
Table 18j Compounds of the formula I.B4 in which Z corresponds to line D1 -18 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B4.D1-18.B1 to I.B4.D1 -18.B450).
Table 19j Compounds of the formula I.B4 in which Z corresponds to line D1 -19 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B4.D1-19.B1 to I.B4.D1 -19.B450).
Table 20j Compounds of the formula I.B4 in which Z corresponds to line D1 -20 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B4.D1-20.B1 to I.B4.D1 -20.B450).
Table 21j Compounds of the formula I. B4 in which Z corresponds to line D1 -21 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B4.D1-21.B1 to I.B4.D1 -21.B450).
Table 1 k Compounds of the formula I. B5 in which Z corresponds to line D1 -1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B5.D1-1.B1 to I.B5.D1-1 .B450).
Table 2k Compounds of the formula I.B5 in which Z corresponds to line D1 -2 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B5.D1-2.B1 to I.B5.D1-2.B450).
Table 3k Compounds of the formula I.B5 in which Z corresponds to line D1 -3 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B5.D1-3.B1 to I.B5.D1-3.B450).
Table 4k Compounds of the formula I.B5 in which Z corresponds to line D1 -4 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B5.D1-4.B1 to I.B5.D1-4.B450).
Table 5k Compounds of the formula I.B5 in which Z corresponds to line D1-5 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B5.D1-5.B1 to I.B5.D1-5.B450).
Table 6k Compounds of the formula I.B5 in which Z corresponds to line D1-6 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B5.D1-6.B1 to I.B5.D1-6.B450).
Table 7k Compounds of the formula I.B5 in which Z corresponds to line D1-7 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B5.D1-7.B1 to I.B5.D1-7.B450).
Table 8k Compounds of the formula I.B5 in which Z corresponds to line D1-8 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B5.D1-8.B1 to I.B5.D1-8.B450).
Table 9k Compounds of the formula I.B5 in which Z corresponds to line D1-9 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B5.D1-9.B1 to I.B5.D1-9.B450).
Table 10k Compounds of the formula I.B5 in which Z corresponds to line D1-10 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B5.D1-10.B1 to I.B5.D1-10.B450).
Table 11k Compounds of the formula I. B5 in which Z corresponds to line D1-11 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B5.D1-11.B1 to I.B5.D1-11.B450).
Table 12k Compounds of the formula I.B5 in which Z corresponds to line D1-12 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B5.D1-12.B1 to I.B5.D1-12.B450).
Table 13k Compounds of the formula I.B5 in which Z corresponds to line D1-13 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B5.D1-13.B1 to I.B5.D1-13.B450).
Table 14k Compounds of the formula I.B5 in which Z corresponds to line D1-14 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B5.D1-14.B1 to I.B5.D1-14.B450).
Table 15k Compounds of the formula I.B5 in which Z corresponds to line D1-15 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B5.D1-15.B1 to I.B5.D1-15.B450).
Table 16k Compounds of the formula I.B5 in which Z corresponds to line D1-16 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B5.D1-16.B1 to I.B5.D1-16.B450).
Table 17k Compounds of the formula I.B5 in which Z corresponds to line D1-17 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B5.D1-17.B1 to I.B5.D1-17.B450).
Table 18k Compounds of the formula I.B5 in which Z corresponds to line D1-18 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B5.D1-18.B1 to I.B5.D1-18.B450). Table 19k Compounds of the formula I.B5 in which Z corresponds to line D1 -19 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B5.D1-19.B1 to I.B5.D1 -19.B450).
Table 20k Compounds of the formula I.B5 in which Z corresponds to line D1 -20 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B5.D1-20.B1 to I.B5.D1 -20.B450).
Table 21 k Compounds of the formula I.B5 in which Z corresponds to line D1 -21 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B5.D1-21.B1 to I.B5.D1 -21.B450).
Table 11 Compounds of the formula I. B6 in which Z corresponds to line D1 -1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B6.D1-1.B1 to I.B6.D1-1 .B450).
Table 2I Compounds of the formula I.B6 in which Z corresponds to line D1 -2 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B6.D1-2.B1 to I.B6.D1-2.B450).
Table 3I Compounds of the formula I.B6 in which Z corresponds to line D1 -3 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B6.D1-3.B1 to I.B6.D1-3.B450).
Table 4I Compounds of the formula I.B6 in which Z corresponds to line D1 -4 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B6.D1-4.B1 to I.B6.D1-4.B450).
Table 5I Compounds of the formula I.B6 in which Z corresponds to line D1 -5 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B6.D1-5.B1 to I.B6.D1-5.B450).
Table 6I Compounds of the formula I.B6 in which Z corresponds to line D1 -6 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B6.D1-6.B1 to I.B6.D1-6.B450).
Table 7I Compounds of the formula I.B6 in which Z corresponds to line D1 -7 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B6.D1-7.B1 to I.B6.D1-7.B450).
Table 8I Compounds of the formula I.B6 in which Z corresponds to line D1 -8 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B6.D1-8.B1 to I.B6.D1-8.B450).
Table 9I Compounds of the formula I.B6 in which Z corresponds to line D1 -9 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B6.D1-9.B1 to I.B6.D1-9.B450).
Table 101 Compounds of the formula I.B6 in which Z corresponds to line D1 -10 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B6.D1-10.B1 to I.B6.D1 -10.B450).
Table 1 11 Compounds of the formula I. B6 in which Z corresponds to line D1 -1 1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B6.D1-1 1.B1 to I.B6.D1 -1 1.B450).
Table 121 Compounds of the formula I.B6 in which Z corresponds to line D1 -12 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B6.D1 -12.B1 to I.B6.D1 -12.B450).
Table 131 Compounds of the formula I.B6 in which Z corresponds to line D1 -13 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B6.D1 -13.B1 to I.B6.D1 -13.B450).
Table 141 Compounds of the formula I.B6 in which Z corresponds to line D1 -14 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B6.D1 -14.B1 to I.B6.D1 -14.B450).
Table 151 Compounds of the formula I.B6 in which Z corresponds to line D1 -15 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B6.D1 -15.B1 to I.B6.D1 -15.B450).
Table 16ICompounds of the formula I.B6 in which Z corresponds to line D1 -16 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B6.D1 -16.B1 to I.B6.D1 -16.B450).
Table 171 Compounds of the formula I.B6 in which Z corresponds to line D1 -17 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B6.D1 -17.B1 to I.B6.D1 -17.B450).
Table 181 Compounds of the formula I.B6 in which Z corresponds to line D1 -18 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B6.D1 -18.B1 to I.B6.D1 -18.B450).
Table 191 Compounds of the formula I.B6 in which Z corresponds to line D1 -19 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B6.D1 -19.B1 to I.B6.D1 -19.B450).
Table 20I Compounds of the formula I.B6 in which Z corresponds to line D1 -20 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B6.D1 -20.B1 to I.B6.D1 -20.B450).
Table 211 Compounds of the formula I.B6 in which Z corresponds to line D1 -21 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.B6.D1 -21.B1 to I.B6.D1 -21 .B450).
Table D1 :
Table B:
line R 1 R 2 line R 1 R 2
B-1 CH 3 H B-2 CH 2 CH 3 H
A further as ect of the invention relates to compounds I.C, wherein R 3 is hydrogen and A ist N:
The compounds I.C can be synthesized corresponding to the synthesis as described for compounds I above. The intermediates occurring are likewise an object of the present invention. In particular, one embodiment of this aspect of the present invention are compounds of formula I I.C
II.C
wherein the variables are as defined and preferably defined for formula I herein. In particular, a further particular embodiment of the present invention are compounds of formula II.C, wherein Hal stands for iodide compounds II. Ca):
ll.Ca
Preferred R 1 can be found in the description for formula I, in particular selected from P1-1 to P1- 137 above. Compounds II.C and II. Ca, respectively, can also be suitable as fungicides as de- cribed later.
The compounds I.C and the compositions according to the invention, respectively, are suitable as fungicides corresponding to the details as given for compounds I herein. In particular with a view to their use, according to one embodiment of this aspect of the invention, preference is given to the compounds of the formula I.C that are compiled in the Tables 1y to 21y below. Each of the groups mentioned for a substituent in the tables is furthermore per se, independently of the combination in which it is mentioned, a particularly preferred aspect of the substituent in question.
Table 1 y Compounds of the formula I.C in which Z corresponds to line D1 -1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.C.D1 -1.B1 to I.C.D1-1.B450).
Table 2y Compounds of the formula I.C in which Z corresponds to line D1 -2 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.C.D1 -2.B1 to I.C.D1-2.B450).
Table 3y Compounds of the formula I.C in which Z corresponds to line D1 -3 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.C.D1 -3.B1 to I.C.D1-3.B450).
Table 4y Compounds of the formula I.C in which Z corresponds to line D1 -4 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.C.D1 -4.B1 to I.C.D1-4.B450).
Table 5y Compounds of the formula I.C in which Z corresponds to line D1 -5 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.C.D1 -5.B1 to I.C.D1-5.B450).
Table 6y Compounds of the formula I.C in which Z corresponds to line D1 -6 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.C.D1 -6.B1 to I.C.D1-6.B450).
Table 7y Compounds of the formula I.C in which Z corresponds to line D1 -7 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.C.D1 -7.B1 to I.C.D1-7.B450).
Table 8y Compounds of the formula I.C in which Z corresponds to line D1 -8 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.C.D1 -8.B1 to I.C.D1-8.B450).
Table 9y Compounds of the formula I.C in which Z corresponds to line D1 -9 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.C.D1 -9.B1 to I.C.D1-9.B450).
Table 10y Compounds of the formula I.C in which Z corresponds to line D1 -10 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.C.D1 -10.B1 to I.C.D1-10.B450).
Table Hy Compounds of the formula I.C in which Z corresponds to line D1 -1 1 of Table DI and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.C.D1 -1 1.B1 to I.C.D1-1 1 .B450).
Table 12y Compounds of the formula I.C in which Z corresponds to line D1 -12 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.C.D1 -12.B1 to I.C.D1-12.B450).
Table 13y Compounds of the formula I.C in which Z corresponds to line D1 -13 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.C.D1 -13.B1 to I.C.D1-13.B450).
Table 14y Compounds of the formula I.C in which Z corresponds to line D1 -14 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.C.D1 -14.B1 to I.C.D1-14.B450).
Table 15y Compounds of the formula I.C in which Z corresponds to line D1 -15 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.C.D1 -15.B1 to I.C.D1-15.B450).
Table 16y Compounds of the formula I.C in which Z corresponds to line D1 -16 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.C.D1-16.B1 to I.C.D1 -16.B450).
Table 17y Compounds of the formula I.C in which Z corresponds to line D1 -17 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.C.D1 -17.B1 to I.C.D1-17.B450).
Table 18y Compounds of the formula I.C in which Z corresponds to line D1 -18 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.C.D1 -18.B1 to I.C.D1-18.B450).
Table 19y Compounds of the formula I.C in which Z corresponds to line D1 -19 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.C.D1 -19.B1 to I.C.D1-19.B450).
Table 20y Compounds of the formula I.C in which Z corresponds to line D1 -20 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.C.D1 -20.B1 to I.C.D1-20.B450).
Table 21y Compounds of the formula I.C in which Z corresponds to line D1 -21 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.C.D1 -21.B1 to I.C.D1-21 .B450).
A further aspect of the invention relates to compounds I.D, wherein R 3 is hydrogen and A ist CH:
The compounds I.D can be synthesized corresponding to the synthesis as described for com- pounds I above. The intermediates occurring are likewise an object of the present invention. In particular, one embodiment of this aspect of the present invention are compounds of formula II. D
II. D
wherein the variables are as defined and preferably defined for formula I herein. In particular, further particular embodiment of the present invention are compounds of formula I I.D, whereii Hal stands for iodide compounds II. Da):
II.Da
Preferred R 1 can be found in the description for formula I, in particular selected from P1-1 to P1- 137 above. Compounds II. D and II.Da, respectively, can also be suitable as fungicides as de- cribed later.
The compounds I.D and the compositions according to the invention, respectively, are suitable as fungicides corresponding to the details as given for compounds I herein. In particular with a view to their use, according to one embodiment of this aspect of the invention, preference is given to the compounds of the formula I.D that are compiled in the Tables 1z to 21z below. Each of the groups mentioned for a substituent in the tables is furthermore per se, independently of the combination in which it is mentioned, a particularly preferred aspect of the substituent in question. Table 1 z Compounds of the formula I. D in which Z corresponds to line D1 -1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.D.D1 -1.B1 to I.D.D1-1.B450).
Table 2z Compounds of the formula I.D in which Z corresponds to line D1 -2 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.D.D1 -2.B1 to I.D.D1-2.B450).
Table 3z Compounds of the formula I.D in which Z corresponds to line D1 -3 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.D.D1 -3.B1 to I.D.D1-3.B450).
Table 4z Compounds of the formula I.D in which Z corresponds to line D1 -4 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.D.D1 -4.B1 to I.D.D1-4.B450).
Table 5z Compounds of the formula I.D in which Z corresponds to line D1 -5 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.D.D1 -5.B1 to I.D.D1-5.B450).
Table 6z Compounds of the formula I.D in which Z corresponds to line D1 -6 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.D.D1 -6.B1 to I.D.D1-6.B450).
Table 7z Compounds of the formula I.D in which Z corresponds to line D1 -7 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.D.D1 -7.B1 to I.D.D1-7.B450).
Table 8z Compounds of the formula I.D in which Z corresponds to line D1 -8 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.D.D1 -8.B1 to I.D.D1-8.B450).
Table 9z Compounds of the formula I.D in which Z corresponds to line D1 -9 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.D.D1 -9.B1 to I.D.D1-9.B450).
Table 10z Compounds of the formula I.D in which Z corresponds to line D1 -10 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.D.D1 -10.B1 to I.D.D1-10.B450).
Table 1 1z Compounds of the formula I.D in which Z corresponds to line D1 -1 1 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.D.D1 -1 1.B1 to I.D.D1-1 1 .B450).
Table 12z Compounds of the formula I.D in which Z corresponds to line D1 -12 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.D.D1 -12.B1 to I.D.D1-12.B450).
Table 13z Compounds of the formula I.D in which Z corresponds to line D1 -13 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.D.D1 -13.B1 to I.D.D1-13.B450).
Table 14z Compounds of the formula I.D in which Z corresponds to line D1 -14 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.D.D1 -14.B1 to I.D.D1-14.B450). Table 15z Compounds of the formula I.D in which Z corresponds to line D1 -15 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.D.D1 -15.B1 to I.D.D1-15.B450).
Table 16z Compounds of the formula I.D in which Z corresponds to line D1 -16 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.D.D1-16.B1 to I.D.D1 -16.B450).
Table 17z Compounds of the formula I.D in which Z corresponds to line D1 -17 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.D.D1 -17.B1 to I.D.D1-17.B450).
Table 18z Compounds of the formula I.D in which Z corresponds to line D1 -18 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.D.D1 -18.B1 to I.D.D1-18.B450).
Table 19z Compounds of the formula I.D in which Z corresponds to line D1 -19 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.D.D1 -19.B1 to I.D.D1-19.B450).
Table 20z Compounds of the formula I.D in which Z corresponds to line D1 -20 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.D.D1 -20.B1 to I.D.D1-20.B450).
Table 21z Compounds of the formula I.D in which Z corresponds to line D1 -21 of Table D1 and the meaning for the combination of R 1 and R 2 for each individual compound corresponds in each case to one line of Table B (compounds I.D.D1 -21.B1 to I.D.D1-21 .B450).
The compounds I and the compositions according to the invention, respectively, are suitable as fungicides.
Furthermore, also the compounds II, in particular Ma, and II.C and II. D, in particular ll.Ca and II. Da, according to the invention, are suitable as fungicides. The following description referring to compounds I also applies to the compounds of formula II, lla, II.C, II. D, ll.Ca and II. Da, respectively.
Consequently, according to a further aspect, the present invention relates to the use of compounds of formula I , the N-oxides and the agriculturally acceptable salts thereof or of the com- positions of the invention for combating phytopathogenic fungi.
Accordingly, the present invention also encompasses a method for combating harmful fungi, comprising treating the fungi or the materials, plants, the soil or seeds to be protected against fungal attack with an effective amount of at least one compound of formula I or with a composition comprising according to the invention.
The compounds I and the compositions according to the invention, respectively, are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
The compounds I and the compositions according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e. g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants.
Preferably, compounds I and compositions thereof, respectively are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; or- namentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil.
These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
Preferably, treatment of plant propagation materials with compounds I and compositions thereof, respectively, is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
The term "cultivated plants" is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://cera-gmc.org/, see GM crop database therein). Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties. Plants that have been modified by breeding, mutagenesis or genetic engineering, e. g. have been rendered tolerant to applications of specific classes of herbicides, such as auxin herbicides such as dicamba or 2,4-D; bleacher herbicides such as hydroxylphenylpyruvate dioxy- genase (HPPD) inhibitors or phytoene desaturase (PDS) inhibitors; acetolactate synthase (ALS) inhibitors such as sulfonyl ureas or imidazolinones; enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate; glutamine synthetase (GS) inhibitors such as glufosinate; protoporphyrinogen-IX oxidase inhibitors; lipid biosynthesis inhibitors such as acetyl CoA carboxylase (ACCase) inhibitors; or oxynil (i. e. bromoxynil or ioxynil) herbicides as a result of conventional methods of breeding or genetic engineering. Furthermore, plants have been made resistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to both glyphosate and glufosinate or to both glyphosate and a herbicide from another class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors. These herbicide resistance technologies are e. g. described in Pest Managem. Sci. 61 , 2005, 246; 61 , 2005, 258; 61 , 2005, 277; 61 , 2005, 269; 61 , 2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Sci. 57, 2009, 108; Austral. J. Agricult. Res. 58, 2007, 708; Science 316, 2007, 1 185; and references quoted therein. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), e. g. Clearfield ® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g. imazamox, or ExpressSun ® sunflowers (DuPont, USA) being tolerant to sulfonyl ureas, e. g. tribenuron. Genetic engineering methods have been used to render cultivated plants such as soybean, cotton, corn, beets and rape, tolerant to herbicides such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady ® (glyphosate-tolerant, Monsanto, U.S.A.), Cul- tivance ® (imidazolinone tolerant, BASF SE, Germany) and LibertyLink ® (glufosinate-tolerant, Bayer CropScience, Germany).
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as δ-endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nema- todes, e. g. Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdyster- oid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilbene synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, e. g. WO 02/015701 ). Further examples of such toxins or genetically modified plants ca- pable of synthesizing such toxins are disclosed, e. g., in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of arthropods, especially to beetles (Coelop- tera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda). Genetically modified plants capable to synthesize one or more insecticidal proteins are, e. g., described in the publications mentioned above, and some of which are commercially available such as YieldGard ® (corn cultivars producing the CrylAb toxin), YieldGard ® Plus (corn cultivars producing CrylAb and Cry3Bb1 toxins), Starlink ® (corn cultivars producing the Cry9c toxin), Herculex ® RW (corn cultivars producing Cry34Ab1 , Cry35Ab1 and the enzyme phosphinothri- cin-N-acetyltransferase [PAT]); NuCOTN ® 33B (cotton cultivars producing the Cry1 Ac toxin), Bollgard ® I (cotton cultivars producing the CrylAc toxin), Bollgard ® II (cotton cultivars producing CrylAc and Cry2Ab2 toxins); VIPCOT ® (cotton cultivars producing a VIP-toxin); NewLeaf ® (potato cultivars producing the Cry3A toxin); Bt-Xtra ® , NatureGard ® , KnockOut ® , BiteGard ® , Pro- tecta ® , Bt1 1 (e. g. Agrisure ® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivars producing the CrylAb toxin and PAT enyzme), MIR604 from Syngenta Seeds SAS, France (corn cultivars producing a modified version of the Cry3A toxin, c.f. WO 03/018810), MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the CrylAc toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1 F toxin and PAT enzyme).
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capa- ble to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called "pathogenesis- related proteins" (PR proteins, see, e. g. EP-A 392 225), plant disease resistance genes (e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the Mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Er- winia amylvora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above.
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capa- ble to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e. g. oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera ® rape, DOW Agro Sciences, Canada).
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora ® potato, BASF SE, Germany).
The compounds I and compositions thereof, respectively, are particularly suitable for controlling the following plant diseases:
Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. Candida) and sunflowers (e. g. A. tragopogonis); Alternaria spp. (Alternaria leaf spot) on vegetables, rape (A. brassicola or brassi- cae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A. alternata), tomatoes (e. g. A. solani or A. alternata) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A. tritici (anthracnose) on wheat and A. hordei on barley; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e. g. Southern leaf blight (D. maydis) or Northern leaf blight (B. zeicola) on corn, e. g. spot blotch (B. sorokiniana) on cereals and e. g. B. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad- leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cer- cospora leaf spots) on corn (e. g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice; Cladosporium spp. on tomatoes (e. g. C. fulvum: leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helmin- thosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C. sativus, anamorph: B. sorokiniana) and rice (e. g. C. miyabeanus, anamorph: H. oryzae); Colletotrichum (teleomorph: Clomerella) spp. (anthracnose) on cotton (e. g. C. gossypii), corn (e. g. C. gramini- co/a." Anthracnose stalk rot), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C. lindemuthianum) and soybeans (e. g. C. truncatum or C. gloeosporioides); Corticium spp., e. g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; Cycloconium spp., e. g. C. oleaginum on olive trees; Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e. g. C. liriodendri, teleomorph: Neonectria liriodendri: Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (E. pyri), soft fruits (E. veneta: anthracnose) and vines (E ampelina: anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (E. betae), vegetables (e. g. E. pisi), such as cucurbits (e. g. E. cichoracearum), cabbages, rape (e. g. E. cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (e. g. E. turci- cum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F graminearum or F. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. solani (f. sp. glycines now syn. F. virguliforme ) and F. tucumani- ae and F. brasiliense each causing sudden death syndrome on soybeans, and F. verticillioides on corn; Gaeumannomyces graminis (take-all) on cereals (e. g. wheat or barley) and corn; Gibberella spp. on cereals (e. g. G. zeae) and rice (e. g. G. fujikuror. Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grainstaining complex on rice; Guignardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e. g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochlioboius) on corn, cereals and rice; Hemileia spp., e. g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas; Peronospora spp. (downy mildew) on cabbage (e. g. P. brassicae), rape (e. g. P. parasitica), onions (e. g. P. destructor), tobacco (P. tabacina) and soybeans (e. g. P. manshurica);
Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Phy- soderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e. g. P.
megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P. infestans: late blight) and broad- leaved trees (e. g. P. ramorum: sudden oak death); Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants; Plasmopara spp., e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits, e. g. P. leucotricha on apples; Polymyxa spp., e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (eyespot, teleomorph: Tapesia yal- lundae) on cereals, e. g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensis on cucurbits or P. humili on hop; Pseudopezicula tracheiphila (red fire disease or ,rotbrenner', anamorph: Phialophora) on vines; Puccinia spp. (rusts) on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P. asparagi on asparagus; Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia spp., e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum); Ramularia spp., e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis (scald) on barley, rye and triticale; Sa- rocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum) and soy- beans (e. g. S. rolfsii or S. sclerotiorum); Septoria spp. on various plants, e. g. S. glycines
(brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) no- dorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines; Setospaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana: head smut), sorghum und sugar cane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Lepto- sphaeria [syn. Phaeosphaeria] nodorum) on wheat; Synchytrium endobioticum on potatoes (potato wart disease); Taphrina spp., e. g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e. g. U. appendiculatus, syn. U. phaseoli) and sugar beets (e. g. U. betae); Ustilago spp. (loose smut) on cereals (e. g. U. nuda and U. avaenae), corn (e. g. U. maydis: corn smut) and sugar cane; Venturia spp. (scab) on apples (e. g. V. inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dahliae on strawberries, rape, potatoes and tomatoes.
The compounds I and compositions thereof, respectively, are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials.
The term "protection of materials" is to be understood to denote the protection of technical and non-living materials, such as adhesives, glues, wood, paper and paperboard, textiles, leather, paint dispersions, plastics, cooling lubricants, fiber or fabrics, against the infestation and de- struction by harmful microorganisms, such as fungi and bacteria. As to the protection of wood and other materials, the particular attention is paid to the following harmful fungi: Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes such as Con/- ophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Pora spp., Ser- ptv/a spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., and in addition in the protection of stored products and harvest the following yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae.
The method of treatment according to the invention can also be used in the field of protecting stored products or harvest against attack of fungi and microorganisms. According to the present invention, the term "stored products" is understood to denote natural substances of plant or an- imal origin and their processed forms, which have been taken from the natural life cycle and for which long-term protection is desired. Stored products of crop plant origin, such as plants or parts thereof, for example stalks, leafs, tubers, seeds, fruits or grains, can be protected in the freshly harvested state or in processed form, such as pre-dried, moistened, comminuted, ground, pressed or roasted, which process is also known as post-harvest treatment. Also falling under the definition of stored products is timber, whether in the form of crude timber, such as construction timber, electricity pylons and barriers, or in the form of finished articles, such as furniture or objects made from wood. Stored products of animal origin are hides, leather, furs, hairs and the like. The combinations according the present invention can prevent disadvantageous effects such as decay, discoloration or mold. Preferably "stored products" is understood to denote natural substances of plant origin and their processed forms, more preferably fruits and their processed forms, such as pomes, stone fruits, soft fruits and citrus fruits and their processed forms.
The compounds I and compositions thereof, respectively, may be used for improving the health of a plant. The invention also relates to a method for improving plant health by treating a plant, its propagation material and/or the locus where the plant is growing or is to grow with an effective amount of compounds I and compositions thereof, respectively.
The term "plant health" is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e. g. improved plant growth and/or greener leaves ("greening effect")), quality (e. g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress. The above identified indicators for the health condition of a plant may be interdependent or may result from each other.
The compounds of formula I can be present in different crystal modifications whose biological activity may differ. They are likewise subject matter of the present invention.
The compounds I are employed as such or in form of compositions by treating the fungi or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from fungal attack with a fungicidally effective amount of the active substances. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi. Plant propagation materials may be treated with compounds I as such or a composition comprising at least one compound I prophylactically either at or before planting or transplanting.
The invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I according to the invention.
An agrochemical composition comprises a fungicidally effective amount of a compound I. The term "effective amount" denotes an amount of the composition or of the compounds I, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound I used.
The compounds I, their N-oxides and salts can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e. g. SC, OD, FS), emulsifiable concentrates (e. g. EC), emulsions (e. g. EW, EO, ES, ME), capsules (e. g. CS, ZC), pastes, pastilles, wettable powders or dusts (e. g. WP, SP, WS, DP, DS), pressings (e. g. BR, TB, DT), granules (e. g. WG, SG, GR, FG, GG, MG), insecticidal articles (e. g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e. g. GF). These and further compositions types are defined in the "Catalogue of pesti- cide formulation types and international coding system", Technical Monograph No. 2, 6 th Ed. May 2008, CropLife International.
The compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil frac- tions of medium to high boiling point, e. g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e. g. ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, e. g. cyclohexanone; esters, e. g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e. g. N-methyl pyrroli- done, fatty acid dimethyl amides; and mixtures thereof.
Suitable solid carriers or fillers are mineral earths, e. g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e. g. cellulose, starch; fertilizers, e. g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e. g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof. Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & De- tergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl sulfonates, diphenyl sulfonates, alpha-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkyl naphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or al- kylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinyl pyrroli- done, vinyl alcohols, or vinyl acetate.
Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinyl amines or polyethylene amines.
Suitable adjuvants are compounds, which have a negligible or even no pesticidal activity them- selves, and which improve the biological performance of the compound I on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
Suitable thickeners are polysaccharides (e. g. xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
Suitable colorants (e. g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e. g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e. g. alizarin-, azo- and phthalocyanine colorants).
Suitable tackifiers or binders are polyvinyl pyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
Examples for composition types and their preparation are:
i) Water-soluble concentrates (SL, LS)
10-60 wt% of a compound I and 5-15 wt% wetting agent (e. g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e. g. alcohols) ad 100 wt%. The active substance dissolves upon dilution with water.
ii) Dispersible concentrates (DC)
5-25 wt% of a compound I and 1 -10 wt% dispersant (e. g. polyvinyl pyrrolidone) are dissolved in organic solvent (e. g. cyclohexanone) ad 100 wt%. Dilution with water gives a dispersion.
iii) Emulsifiable concentrates (EC)
15-70 wt% of a compound I and 5-10 wt% emulsifiers (e. g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in water-insoluble organic solvent (e. g. aromatic hydro- carbon) ad 100 wt%. Dilution with water gives an emulsion.
iv) Emulsions (EW, EO, ES)
5-40 wt% of a compound I and 1 -10 wt% emulsifiers (e. g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% water-insoluble organic solvent (e. g. aromatic hydrocarbon). This mixture is introduced into water ad 100 wt% by means of an emulsify- ing machine and made into a homogeneous emulsion. Dilution with water gives an emulsion. v) Suspensions (SC, OD, FS)
In an agitated ball mill, 20-60 wt% of a compound I are comminuted with addition of 2-10 wt% dispersants and wetting agents (e. g. sodium lignosulfonate and alcohol ethoxylate), 0.1 -2 wt% thickener (e. g. xanthan gum) and water ad 100 wt% to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt% binder (e. g. polyvinyl alcohol) is added.
vi) Water-dispersible granules and water-soluble granules (WG, SG)
50-80 wt% of a compound I are ground finely with addition of dispersants and wetting agents (e. g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt% and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluid- ized bed). Dilution with water gives a stable dispersion or solution of the active substance. vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)
50-80 wt% of a compound I are ground in a rotor-stator mill with addition of 1 -5 wt% dispersants (e. g. sodium lignosulfonate), 1-3 wt% wetting agents (e. g. alcohol ethoxylate) and solid carrier (e. g. silica gel) ad 100 wt%. Dilution with water gives a stable dispersion or solution of the ac- tive substance.
viii) Gel (GW, GF)
In an agitated ball mill, 5-25 wt% of a compound I are comminuted with addition of 3-10 wt% dispersants (e. g. sodium lignosulfonate), 1 -5 wt% thickener (e. g. carboxymethyl cellulose) and water ad 100 wt% to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
ix) Microemulsion (ME)
5-20 wt% of a compound I are added to 5-30 wt% organic solvent blend (e. g. fatty acid dimethyl amide and cyclohexanone), 10-25 wt% surfactant blend (e. g. alcohol ethoxylate and ar- ylphenol ethoxylate), and water ad 100 %. This mixture is stirred for 1 h to produce spontane- ously a thermodynamically stable microemulsion.
x) Microcapsules (CS)
An oil phase comprising 5-50 wt% of a compound I, 0-40 wt% water insoluble organic solvent (e. g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e. g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e. g. polyvinyl alcohol). Radical polymerization results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e. g. aromatic hydrocarbon), and an isocya- nate monomer (e. g. diphenylmethene-4,4'-diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e. g. polyvinyl alcohol). The addition of a polyamine (e. g. hexameth- ylenediamine) results in the formation of polyurea microcapsules. The monomers amount to 1 - 10 wt%. The wt% relate to the total CS composition.
xi) Dustable powders (DP, DS)
1-10 wt% of a compound I are ground finely and mixed intimately with solid carrier (e. g. finely divided kaolin) ad 100 wt%.
xii) Granules (GR, FG)
0.5-30 wt% of a compound I is ground finely and associated with solid carrier (e. g. silicate) ad 100 wt%. Granulation is achieved by extrusion, spray-drying or fluidized bed.
xiii) Ultra-low volume liquids (UL)
1-50 wt% of a compound I are dissolved in organic solvent (e. g. aromatic hydrocarbon) ad 100 wt%.
The compositions types i) to xiii) may optionally comprise further auxiliaries, such as 0.1 -1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1-1 wt% anti-foaming agents, and 0.1 -1 wt% col- orants.
The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of active substance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (ac- cording to NMR spectrum).
For the purposes of treatment of plant propagation materials, particularly seeds, solutions for seed treatment (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC), and gels (GF) are usually employed. The com- positions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying compound I and compositions thereof, respectively, onto plant propagation material, especially seeds, include dressing, coating, pelleting, dusting, and soaking as well as in-furrow application methods. Preferably, com- pound I or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.
In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seeds) are generally required.
When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides (e. g. herbicides, insecticides, fungicides, growth regulators, safeners, biopesticides) may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
A pesticide is generally a chemical or biological agent (such as pestidal active ingredient, com- pound, composition, virus, bacterium, antimicrobial or disinfectant) that through its effect deters, incapacitates, kills or otherwise discourages pests. Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microbes that destroy property, cause nuisance, spread disease or are vectors for disease. The term pesticides includes also plant growth regulators that alter the expected growth, flowering, or repro- duction rate of plants; defoliants that cause leaves or other foliage to drop from a plant, usually to facilitate harvest; desiccants that promote drying of living tissues, such as unwanted plant tops; plant activators that activate plant physiology for defense of against certain pests; safen- ers that reduce unwanted herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant.
Biopesticides have been defined as a form of pesticides based on micro-organisms (bacteria, fungi, viruses, nematodes, etc.) or natural products (compounds, such as metabolites, proteins, or extracts from biological or other natural sources) (U.S. Environmental Protection Agency: http://www.epa.gov/pesticides/biopesticides/).
Biopesticides are typically created by growing and concentrating naturally occurring organisms and/or their metabolites including bacteria and other microbes, fungi, viruses, nematodes, proteins, etc. They are often considered to be important components of integrated pest management (IPM) programs.
Biopesticides fall into two major classes, microbial and biochemical pesticides:
(1 ) Microbial pesticides consist of bacteria, fungi or viruses (and often include the metabolites that bacteria and fungi produce). Entomopathogenic nematodes are also classed as microbial pesticides, even though they are multi-cellular.
(2) Biochemical pesticides are naturally occurring substances that control pests or provide other crop protection uses as defined below, but are relatively non-toxic to mam- mals.
The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemi- cal composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pelleting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.
When living microorganisms, such as pesticides from groups L1 ), L3) and L5), form part of such kit, it must be taken care that choice and amounts of the components (e. g. chemical pesticidal agents) and of the further auxiliaries should not influence the viability of the microbial pesticides in the composition mixed by the user. Especially for bactericides and solvents, compatibility with the respective microbial pesticide has to be taken into account.
Consequently, one embodiment of the invention is a kit for preparing a usable pesticidal composition, the kit comprising a) a composition comprising component 1 ) as defined herein and at least one auxiliary; and b) a composition comprising component 2) as defined herein and at least one auxiliary; and optionally c) a composition comprising at least one auxiliary and optionally a further active component 3) as defined herein.
Mixing the compounds I or the compositions comprising them in the use form as fungicides with other fungicides results in many cases in an expansion of the fungicidal spectrum of activity being obtained or in a prevention of fungicide resistance development. Furthermore, in many cases, synergistic effects are obtained.
The following list of pesticides II (e. g. pesticidally-active substances and biopesticides), in conjunction with which the compounds I can be used, is intended to illustrate the possible combinations but does not limit them:
A) Respiration inhibitors
- Inhibitors of complex III at Q 0 site (e. g. strobilurins): azoxystrobin (A.1.1 ), coumethoxy- strobin (A.1.2), coumoxystrobin (A.1.3), dimoxystrobin (A.1.4), enestroburin (A.1.5), fenaminstrobin (A.1.6), fenoxystrobin/flufenoxystrobin (A.1.7), fluoxastrobin (A.1.8), kresox- im-methyl (A.1.9), mandestrobin (A.1.10), metominostrobin (A.1.1 1 ), orysastrobin (A.1.12), picoxystrobin (A.1.13), pyraclostrobin (A.1.14), pyrametostrobin (A.1.15), pyraoxystrobin (A.1.16), trifloxystrobin (A.1.17) and 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylidene- aminooxymethyl)-phenyl)-2-methoxyimino-N-methyl-acetamide (A.1.18), pyribencarb (A.1.19), triclopyricarb/chlorodincarb (A.1.20), famoxadone (A.1.21 ), fenamidone (A.1.21 ); methyl-/V-[2-[(1 ,4-dimethyl-5-phenyl-pyrazol-3-yl)oxylmethyl]phenyl]-N-metho xy-carbamate (A.1.22), 1 -[3-chloro-2-[[1 -(4-chlorophenyl)-1 H-pyrazol-3-yl]oxymethyl]phenyl]- -methyl- tetrazol-5-one (A.1.23), 1 -[3-bromo-2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]pheny l]-4- methyl-tetrazol-5-οηβ (A.1.24), 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl- phenyl]-4-methyl-tetrazol-5-one (A.1.25), 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3- fluoro-phenyl]-4-methyl-tetrazol-5-one (A.1.26), 1 -[2-[[1 -(2,4-dichlorophenyl)pyrazol-3- yl]oxymethyl]-3-fluoro-phenyl]-4-methyl-tetrazol-5-one (A.1.27),
1 - [2-[[4-(4-chlorophenyl)thiazol-2-yl]oxymethyl]-3-methyl-phen yl]-4-methyl-tetrazol-5-one (A.1.28), 1-i3-chloro-2-[[4-(p-tolyl)thiazol-2-yl]oxymethyl]phenyl]-4- rnethyl-tetrazol-5-on0 (A.1.29), 1-[3-cyclopropyl-2-[[2-methyl-4-(1 -methylpyrazol-3-yl)phenoxy]methyl]phenyl]-
4- methyl-tetrazol-5-one (A.1.30), 1-[3-(difluoromethoxy)-2-[[2-methyl-4-(1-methylpyrazol- 3-yl)phenoxy]methyl]phenyl]-4-methyl-tetrazol-5-one (A.1.31), 1 -methyl-4-[3-methyl-
2- [[2-methyl-4-(1-methylpyrazol-3-yl)phenoxy]methyl]phenyl]tet razol-5-one (A.1.32), 1 -me- thyl-4-[3-rnethyl"2 [1-[3-(trifluoromethyl)phenyl]-ethylideneamino]oxymethyl]phe nyl]tetrazol-
5- one (A.1.33), (Z,2F)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]-oxy-2-methoxyi mino- S/,3- dimethyl-pent-3-enamide (A.1.34), (Z,2E)-5-[1 -(4-chlorophenyl)pyrazol-3-yl]oxy-2- methoxyimino- v,3-dimethyl-pent-3-enamide (A.1 , 35), (Z,2£)-5-[1-(4-chloro-2-fluoro- phenyl)pyrazol-3-yl]oxy-2-methoxyimino-A/,3-dimethyl-pent-3- enamide (A.1.36);
- inhibitors of complex III at Q, site: cyazofamid (A.2.1 ), amisulbrom (A.2.2), [(3S,6S,7R,8R)- 8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]- 6-methyl-4,9-dioxo-1 ,5-di- oxonan-7-yl] 2-methylpropanoate (A.2.3), [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)- 4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl]
2-methylpropanoate (A.2.4), [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-meth- oxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate (A.2.5), [(3S,6S,7 ,8R)-8-benzyl-3-[[3-(1 ,3-benzodioxol-5-ylmethoxy)-4-methoxy-pyridine-2- carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate (A.2.6);
(3S,6S7R,8R)-3-[[(3-hydroxy-4-methoxy-2^yridinyl)carbonyl]am ino]-6-methyl-4,9-dioxo-8- (phenylmethyl)-1 ,5-dioxonan-7-yl 2-methylpropanoate (A.2.7); (3S,6S,7R,8R)-8-benzyl-
3-[3-[(isobutyryloxy)methoxy]-4-methoxypicolinamido]-6-me thyl-4,9-dioxo-1 ,5-dioxonan-7-yl isobutyrate (A.2.8);
- inhibitors of complex II (e. g. carboxamides): benodanil (A.3.1 ), benzovindiflupyr (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapyroxad (A.3.9), furametpyr (A.3.10), isofetamid (A.3.1 1 ), isopyrazam (A.3.12), mepronil (A.3.13), oxycarboxin (A.3.14), penflufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), tecloftalam (A.3.17), thifluzamide (A.3.18), N-(4'- trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1-methyl- 1 H-pyrazole-4-carboxamide (A.3.19), N-(2-(1 ,3,3-trimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole- 4-carboxamide (A.3.20), 3-(difluoromethyl)-1-methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4- carboxamide (A.3.21), 3-(trifluoromethyl)-1-methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4- carboxamide (A.3.22), 1 ,3-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.23), 3-(trifluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4- carboxamide (A.3.24), 1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.25), N-(7-fluoro-1 ,1 ,3-trimethyl-indan-4-yl)-1 ,3-dimethyl-pyrazole-4-carboxamide
(A.3.26), N-[2-(2,4-dichlorophenyl)-2-methoxy-1 -methyl-ethyl]-3-(difluoromethyl)-1-methyl- pyrazole-4-carboxamide (A.3.27);
- other respiration inhibitors (e. g. complex I, uncouplers): diflumetorim (A.4.1 ), (5,8-difluoro- quinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2- yloxy)-phenyl]-ethyl}-amine (A.4.2); nitrophenyl derivates: binapacryl (A.4.3), dinobuton (A.4.4), dinocap (A.4.5), fluazinam (A.4.6); ferimzone (A.4.7); organometal compounds: fentin salts, such as fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.11 ); and silthi- ofam (A.4.12);
B) Sterol biosynthesis inhibitors (SBI fungicides)
- C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole (B.1.1 ), bitertanol (B.1.2), bromuconazole (B.1.3), cyproconazole (B.1.4), difenoconazole (B.1.5), diniconazole (B.1.6), diniconazole-M (B.1.7), epoxiconazole (B.1 .8), fenbuconazole (B.1.9), fluquinconazole (B.1.10), flusilazole (B.1.1 1), flutriafol (B.1.12), hexaconazole (B.1 .13), imibenconazole (B.1.14), ipconazole (B.1 .15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1.19), paclobutrazole (B.1 .20), penconazole (B.1.21 ), propiconazole (B.1.22), prothioconazole
(B.1.23), simeconazole (B.1.24), tebuconazole (B.1.25), tetraconazole (B.1 .26), triadimefon (B.1.27), triadimenol (B.1.28), triticonazole (B.1.29), uniconazole (B.1.30), 1-[re/-(2S;3R)-3-(2- chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thioc yanato-1 H-[1 ,2,4]triazolo (B.1.31 ), 2- [re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxira nylmethyl]-2H-[1 ,2,4]triazole-3-thiol (B.1.32), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1 ,2,4-triazol-1 -yl)pentan-2-ol (B.1.33), 1 -[4- (4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-cyclopropyl-2 -(1 ,2,4-triazol-1-yl)ethanol (B.1.34), 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1.35), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1-yl)butan-2-ol (B.1.36), 2-[4-(4-chloro- phenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1.37), 2-[4-(4- chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol (B.1.38), 2-[2-chloro- 4-(4-chlorophenoxy)phenyl]-3-methyl-1-(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1.39), 2-[4-(4- chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1-yl)pentan-2-ol (B.1.40), 2-[4-(4- fluorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1 ,2,4-triazol-1 -yl)propan-2-ol (B.1 .41 ); imidazoles: imazalil (B.1.42), pefurazoate (B.1 .43), prochloraz (B.1.44), triflumizol (B.1.45); pyrimidines, pyridines and piperazines: fenarimol (B.1.46), nuarimol (B.1.47), pyrifenox (B.1 .48), triforine (B.1.49), [3-(4-chloro-2-fluoro-phenyl)-5-(2,4-difluorophenyl)isoxazol -4-yl]-(3-pyridyl)methanol (B.1.50), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pent-3-yn-2-ol (B.1.51 );
Delta14-reductase inhibitors: aldimorph (B.2.1 ), dodemorph (B.2.2), dodemorph-acetate (B.2.3), fenpropimorph (B.2.4), tridemorph (B.2.5), fenpropidin (B.2.6), piperalin (B.2.7), spirox- amine (B.2.8);
- Inhibitors of 3-keto reductase: fenhexamid (B.3.1 );
C) Nucleic acid synthesis inhibitors
phenylamides or acyl amino acid fungicides: benalaxyl (C.1.1 ), benalaxyl-M (C.1.2), kiral- axyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (mefenoxam, C.1.5), ofurace (C.1 .6), oxadixyl (C.1.7);
- others: hymexazole (C.2.1 ), octhilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4), 5-fluorocytosine (C.2.5), 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine (C.2.6), 5-fluoro-2-(4- fluorophenylmethoxy)pyrimidin-4-amine (C.2.7);
D)lnhibitors of cell division and cytoskeleton
- tubulin inhibitors, such as benzimidazoles, thiophanates: benomyl (D1.1 ), carbendazim (D1.2), fuberidazole (D1.3), thiabendazole (D1.4), thiophanate-methyl (D1.5); triazolopyrim- idines: 5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine (D1.6);
- other cell division inhibitors: diethofencarb (D2.1 ), ethaboxam (D2.2), pencycuron (D2.3), fluopicolide (D2.4), zoxamide (D2.5), metrafenone (D2.6), pyriofenone (D2.7);
E) Inhibitors of amino acid and protein synthesis
- methionine synthesis inhibitors (anilino-pyrimidines): cyprodinil (E.1.1 ), mepanipyrim (E.1.2), pyrimethanil (E.1 .3);
- protein synthesis inhibitors: blasticidin-S (E.2.1), kasugamycin (E.2.2), kasugamycin hy- drochloride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6), polyoxine (E.2.7), validamycin A (E.2.8);
F) Signal transduction inhibitors
- MAP / histidine kinase inhibitors: fluoroimid (F.1.1 ), iprodione (F.1.2), procymidone (F.1.3), vinclozolin (F.1 .4), fenpiclonil (F.1.5), fludioxonil (F.1.6); - G protein inhibitors: quinoxyfen (F.2.1 );
G) Lipid and membrane synthesis inhibitors
- Phospholipid biosynthesis inhibitors: edifenphos (G.1.1 ), iprobenfos (G.1.2), pyrazophos (G.1.3), isoprothiolane (G.1.4);
- lipid peroxidation: dicloran (G.2.1), quintozene (G.2.2), tecnazene (G.2.3), tolclofos-methyl (G.2.4), biphenyl (G.2.5), chloroneb (G.2.6), etridiazole (G.2.7);
- phospholipid biosynthesis and cell wall deposition: dimethomorph (G.3.1 ), flumorph (G.3.2), mandipropamid (G.3.3), pyrimorph (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6), valifenalate (G.3.7) and N-(1 -(1-(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester (G.3.8);
- compounds affecting cell membrane permeability and fatty acides: propamocarb (G.4.1 );
- fatty acid amide hydrolase inhibitors: oxathiapiprolin (G.5.1 ), 2-{3-[2-(1 -{[3,5-bis(di- fluoromethyl-1 H-pyrazol-1 -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5- yl}phenyl methanesulfonate (G.5.2), 2-{3-[2-(1 -{[3,5-bis(difluoromethyl)-1 H-pyrazol-1 - yl]acetyl}piperidin-4-yl) 1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate (G.5.3);
H) Inhibitors with Multi Site Action
- inorganic active substances: Bordeaux mixture (H.1.1 ), copper acetate (H.1.2), copper hydroxide (H.1.3), copper oxychloride (H.1.4), basic copper sulfate (H.1 .5), sulfur (H.1.6); - thio- and dithiocarbamates: ferbam (H.2.1 ), mancozeb (H.2.2), maneb (H.2.3), metam (H.2.4), metiram (H.2.5), propineb (H.2.6), thiram (H.2.7), zineb (H.2.8), ziram (H.2.9);
- organochlorine compounds (e. g. phthalimides, sulfamides, chloronitriles): anilazine (H.3.1 ), chlorothalonil (H.3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorphenole (H.3.9) and its salts, phthalide (H.3.10), tolylfluanid (H.3.1 1 ), N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl- benzenesulfonamide (H.3.12);
- guanidines and others: guanidine (H.4.1 ), dodine (H.4.2), dodine free base (H.4.3), guazatine (H.4.4), guazatine-acetate (H.4.5), iminoctadine (H.4.6), iminoctadine-triacetate (H.4.7), iminoctadine-tris(albesilate) (H.4.8), dithianon (H.4.9), 2,6-dimethyl-1 H,5H- [1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone (H.4.10);
I) Cell wall synthesis inhibitors
- inhibitors of glucan synthesis: validamycin (1.1.1 ), polyoxin B (1.1 .2);
- melanin synthesis inhibitors: pyroquilon (1.2.1 ), tricyclazole (1.2.2), carpropamid (I.2.3), di- cyclomet (I.2.4), fenoxanil (I.2.5);
J) Plant defence inducers
- acibenzolar-S-methyl (J.1.1 ), probenazole (J.1 .2), isotianil (J.1.3), tiadinil (J.1 .4), prohexa- dione-calcium (J.1.5); phosphonates: fosetyl (J.1.6), fosetyl-aluminum (J.1.7), phosphorous acid and its salts (J.1 .8), potassium or sodium bicarbonate (J.1.9);
K) Unknown mode of action
- bronopol (K.1.1), chinomethionat (K.1 .2), cyflufenamid (K.1.3), cymoxanil (K.1 .4), dazomet (K.1.5), debacarb (K.1.6), diclomezine (K.1 .7), difenzoquat (K.1.8), difenzoquat- methylsulfate (K.1 .9), diphenylamin (K.1.10), fenpyrazamine (K.1.11 ), flumetover (K.1.12), flusulfamide (K.1.13), flutianil (K.1 .14), methasulfocarb (K.1.15), nitrapyrin (K.1.16), nitrothal- isopropyl (K.1.18), oxathiapiprolin (K.1.19), tolprocarb (K.1.20), oxin-copper (K.1.21 ), pro- quinazid (K.1 .22), tebufloquin (K.1.23), tecloftalam (K.1.24), triazoxide (K.1.25), 2-butoxy-6- iodo-3-propylchromen-4-one (K.1.26), 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5- [2-(prop-2-yn-1 -yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yljetha- none (K.1.27), 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-fluoro-6-(prop-2-yn-1 - yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone (K.1.28),
2- [3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]- 4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone (K.1.29), N-(cyclo- propylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)- methyl)-2-phenyl acetamide (K.1.30), N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phen yl)-N-ethyl-N-methyl formamidine (K.1.31 ), N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phen yl)-N- ethyl-N-methyl formamidine (K.1.32), N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl- propoxy)-phenyl)-N-ethyl-N-methyl formamidine (K.1.33), N'-(5-difluoromethyl-2-methyl-4-(3- trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine (K.1.34), methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester (K.1.35), 3-[5-(4-methylphenyl)-2,3- dimethyl-isoxazolidin-3-yl]-pyridine (K.1.36), 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-
3- yl]-pyridine (pyrisoxazole) (K.1.37), N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide (K.1.38), 5-chloro-1 -(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole (K.1.39), 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-y l]-2-prop-2-ynyloxy- acetamide, ethyl (Z)-3-amino-2-cyano-3-phenyl-prop-2-enoate (K.1.40), picarbutrazox (K.1.41 ), pentyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]o xymethyl]-2- pyridyl]carbamate (K.1.42), 2-[2-[(7,8-difluoro-2-methyl-3-quinolyl)oxy]-6-fluoro- phenyl]propan-2-ol (K.1.43), 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phen-yl]pro pan- 2-ol (K.1.44), 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1 -yl)quinoline (K.1.45), 3- (4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quino line (K.1.46), 3-(4,4,5-trifluoro- 3,3-dimethyl-3,4-dihydroisoquinolin-1 -yl)quinoline (K.1.47), 9-fluoro-2,2-dimethyl-5-(3- quinolyl)-3H-1 ,4-benzoxazepine (K.1.48);
M) Growth regulators
abscisic acid (M.1.1 ), amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat, chlormequat chloride, choline chloride, cyclanilide, daminozide, dikegulac, dime- thipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gib- berellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat, mepiquat chloride, naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione, prohexadi- one-calcium, prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate,
2,3,5-tri-iodobenzoic acid , trinexapac-ethyl and uniconazole; N) Herbicides
- acetamides: acetochlor (N.1.1 ), alachlor, butachlor, dimethachlor, dimethenamid (N.1.2), flufenacet (N.1.3), mefenacet (N.1 .4), metolachlor (N.1 .5), metazachlor (N.1.6), napropa- mide, naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor;
- amino acid derivatives: bilanafos, glyphosate (N.2.1 ), glufosinate (N.2.2), sulfosate (N.2.3);
- aryloxyphenoxypropionates: clodinafop (N.3.1 ), cyhalofop-butyl, fenoxaprop (N.3.2), flua- zifop (N.3.3), haloxyfop (N.3.4), metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl;
- Bipyridyls: diquat, paraquat (N.4.1 );
- (thio)carbamates: asulam, butylate, carbetamide, desmedipham, dimepiperate, eptam
(EPTC), esprocarb, molinate, orbencarb, phenmedipham (N.5.1 ), prosulfocarb, pyributicarb, thiobencarb, triallate;
- cyclohexanediones: butroxydim, clethodim (N.6.1 ), cycloxydim (N.6.2), profoxydim (N.6.3), sethoxydim (N.6.4), tepraloxydim (N.6.5), tralkoxydim;
- dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin (N.7.1 ), prodiamine (N.7.2), trifluralin (N.7.3);
- diphenyl ethers: acifluorfen (N.8.1 ), aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lac- tofen, oxyfluorfen;
- hydroxybenzonitriles: bomoxynil (N.9.1), dichlobenil, ioxynil;
- imidazolinones: imazamethabenz, imazamox (N.10.1 ), imazapic (N.10.2), imazapyr (N.10.3), imazaquin (N.10.4), imazethapyr (N.10.5);
- phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D) (N.1 1.1 ), 2,4- DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, Mecoprop;
- pyrazines: chloridazon (N.1 1.1 ), flufenpyr-ethyl, fluthiacet, norflurazon, pyridate;
- pyridines: aminopyralid, clopyralid (N.12.1), diflufenican, dithiopyr, fluridone, fluroxypyr (N.12.2), picloram (N.12.3), picolinafen (N.12.4), thiazopyr;
- sulfonyl ureas: amidosulfuron, azimsulfuron, bensulfuron (N.13.1), chlorimuron-ethyl (N.13.2), chlorsulfuron, cinosulfuron, cyclosulfamuron (N.13.3), ethoxysulfuron, flazasulfu- ron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron (N.13.4), mesosulfuron (N.13.5), metazosulfuron, metsulfuron-methyl (N.13.6), nicosulfuron (N.13.7), oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron (N.13.8), sul- fometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron (N.13.9), tritosulfuron, 1-((2-chloro-6-propyl-imidazo[1 ,2-b]pyridazin-3-yl)sulfonyl)-3-(4,6- dimethoxy-pyrimidin-2-yl)urea;
- triazines: ametryn, atrazine (N.14.1), cyanazine, dimethametryn, ethiozin, hexazinone
(N.14.2), metamitron, metribuzin, prometryn, simazine, terbuthylazine, terbutryn, triaziflam;
- ureas: chlorotoluron, daimuron, diuron (N.15.1 ), fluometuron, isoproturon, linuron, metha- benzthiazuron, tebuthiuron;
- other acetolactate synthase inhibitors: bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam (N.16.1 ), flucarbazone, flumetsulam, metosulam, ortho-sulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrim- isulfan, pyrithiobac, pyroxasulfone (N.16.2), pyroxsulam;
- others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, bencarba- zone,benfluresate, benzofenap, bentazone (N.17.1 ), benzobicyclon, bicyclopyrone, broma- cil, bromobutide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon-ethyl (N.17.2), chlorthal, cinmethylin (N.17.3), clomazone (N.17.4), cumyluron, cyprosulfamide, dicamba (N.17.5), difenzoquat, diflufenzopyr (N.17.6), Drechslera monoceras, endothal,
ethofumesate, etobenzanid, fenoxasulfone, fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac (N.17.7), quinmerac (N.17.8), mesotrione (N.17.9), methyl arsonic acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate, quinoclamine, saflufenacil
(N.17.10), sulcotrione (N.17.1 ), sulfentrazone, terbacil, tefuryltrione, tembotrione, thien- carbazone, topramezone (N.17.12), (3-[2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4- trifluoromethyl-3,6-dihydro-2H-pyrimidin-1 -yl)-phenoxy]-pyridin-2-yloxy)-acetic acid ethyl ester, 6-amino-5-chloro-2-cyclopropyl-pyrimidine-4-carboxylic acid methyl ester, 6-chloro-3-(2- cyclopropyl-6-methyl-phenoxy)-pyridazin-4-ol, 4-amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro- pyridine-2-carboxylic acid, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)- pyridine-2-carboxylic acid methyl ester, and 4-amino-3-chloro-6-(4-chloro-3-dimethylamino- 2-fluoro-phenyl)-pyridine-2-carboxylic acid methyl ester;
O) Insecticides
- organo(thio)phosphates: acephate (0.1.1 ), azamethiphos (0.1.2), azinphos-methyl
(0.1.3), chlorpyrifos (0.1 .4), chlorpyrifos-methyl (0.1.5), chlorfenvinphos (0.1.6), diazinon (0.1.7), dichlorvos (0.1.8), dicrotophos (0.1.9), dimethoate (0.1.10), disulfoton (0.1.1 1 ), ethion (0.1 .12), fenitrothion (0.1.13), fenthion (0.1 .14), isoxathion (0.1.15), malathion (0.1.16), methamidophos (0.1.17), methidathion (0.1 .18), methyl-parathion (0.1.19), mevinphos (O.1.20), monocrotophos (0.1.21 ), oxydemeton-methyl (0.1.22), paraoxon
(0.1.23), parathion (0.1 .24), phenthoate (0.1.25), phosalone (0.1.26), phosmet (0.1.27), phosphamidon (0.1.28), phorate (0.1 .29), phoxim (0.1.30), pirimiphos-methyl (0.1.31 ), profenofos (0.1.32), prothiofos (0.1.33), sulprophos (0.1.34), tetrachlorvinphos (0.1.35), terbufos (0.1 .36), triazophos (0.1 .37), trichlorfon (0.1.38);
- carbamates: alanycarb (0.2.1 ), aldicarb (0.2.2), bendiocarb (0.2.3), benfuracarb (0.2.4), carbaryl (0.2.5), carbofuran (0.2.6), carbosulfan (0.2.7), fenoxycarb (0.2.8), furathiocarb (0.2.9), methiocarb (O.2.10), methomyl (0.2.1 1 ), oxamyl (0.2.12), pirimicarb (0.2.13), propoxur (0.2.14), thiodicarb (0.2.15), triazamate (0.2.16);
- pyrethroids: allethrin (0.3.1 ), bifenthrin (0.3.2), cyfluthrin (0.3.3), cyhalothrin (0.3.4), cy- phenothrin (0.3.5), cypermethrin (0.3.6), alpha-cypermethrin (0.3.7), beta-cypermethrin (0.3.8), zeta-cypermethrin (0.3.9), deltamethrin (O.3.10), esfenvalerate (0.3.1 1 ), etofenprox (0.3.1 1 ), fenpropathrin (0.3.12), fenvalerate (0.3.13), imiprothrin (0.3.14), lambda- cyhalothrin (0.3.15), permethrin (0.3.16), prallethrin (0.3.17), pyrethrin I and I I (0.3.18), resmethrin (0.3.19), silafluofen (O.3.20), tau-fluvalinate (0.3.21 ), tefluthrin (0.3.22), tetrame- thrin (0.3.23), tralomethrin (0.3.24), transfluthrin (0.3.25), profluthrin (0.3.26), dimefluthrin (0.3.27);
- insect growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron
(0.4.1 ), cyramazin (0.4.2), diflubenzuron (0.4.3), flucycloxuron (0.4.4), flufenoxuron
(0.4.5), hexaflumuron (0.4.6), lufenuron (0.4.7), novaluron (0.4.8), teflubenzuron (0.4.9), triflumuron (0.4.10); buprofezin (0.4.1 1 ), diofenolan (0.4.12), hexythiazox (0.4.13), etox- azole (0.4.14), clofentazine (0.4.15); b) ecdysone antagonists: halofenozide (0.4.16), methoxyfenozide (0.4.17), tebufenozide (0.4.18), azadirachtin (0.4.19); c) juvenoids:
pyriproxyfen (O.4.20), methoprene (0.4.21 ), fenoxycarb (0.4.22); d) lipid biosynthesis inhibitors: spirodiclofen (0.4.23), spiromesifen (0.4.24), spirotetramat (0.4.24);
- nicotinic receptor agonists/antagonists compounds: clothianidin (0.5.1 ), dinotefuran
(0.5.2), flupyradifurone (0.5.3), imidacloprid (0.5.4), thiamethoxam (0.5.5), nitenpyram
(0.5.6), acetamiprid (0.5.7), thiacloprid (0.5.8), 1 -2-chloro-thiazol-5-ylmethyl)-2-nitrimino- 3,5-dimethyl-[1 ,3,5]triazinane (0.5.9);
- GABA antagonist compounds: endosulfan (0.6.19, ethiprole (0.6.2), fipronil (0.6.3), vaniliprole (0.6.4), pyrafluprole (0.6.5), pyriprole (0.6.6), 5-amino-1 -(2,6-dichloro-4-methyl- phenyl)-4-sulfinamoyl-1 H-pyrazole-3-carbothioic acid amide (0.6.7);
- macrocyclic lactone insecticides: abamectin (0.7.1 ), emamectin (0.7.2), milbemectin (0.7.3), lepimectin (0.7.4), spinosad (0.7.5), spinetoram (0.7.6);
- mitochondrial electron transport inhibitor (METI) I acaricides: fenazaquin (0.8.1 ), pyrida- ben (0.8.2), tebufenpyrad (0.8.3), tolfenpyrad (0.8.4), flufenerim (0.8.5);
- METI I I and II I compounds: acequinocyl (0.9.1 ), fluacyprim (0.9.2), hydramethylnon
(0.9.3);
- Uncouplers: chlorfenapyr (O.10.1 );
- oxidative phosphorylation inhibitors: cyhexatin (0.1 1 .1 ), diafenthiuron (0.1 1 .2), fenbutatin oxide (0.1 1.3), propargite (0.1 1 .4);
- moulting disruptor compounds: cryomazine (0.12.1 );
- mixed function oxidase inhibitors: piperonyl butoxide (0.13.1 );
- sodium channel blockers: indoxacarb (0.14.1 ), metaflumizone (0.14.2);
- ryanodine receptor inhibitors: chlorantraniliprole (0.15.1 ), cyantraniliprole (0.15.2), flu- bendiamide (0.15.3), N-[4,6-dichloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl ]-phenyl]-
2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carb oxamide (0.15.4); N-[4-chloro-2-[(di- ethyl-lambda-4-sulfanylidene)carbamoyl]-6-methyl-phenyl]-2-( 3-chloro-2-pyridyl)-5-(triflu- oromethyl)pyrazole-3-carboxamide (0.15.5); N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanyli- dene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(t rifluoromethyl)pyrazole-^ boxamide (0.15.6); N-[4,6-dichloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carba moyl]- phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3 -carboxamide (0.15.7); N-[4,6-di- chloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl] -2-(3-chloro-2-pyridyl)-5-(^ fluoromethyl)pyrazole-3-carboxamide (0.15.8); N-[4,6-dibromo-2-[(di-2-propyl-lambda-4-sul- fanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trif luoromethyl)pyrazole-3-carbox- amide (0.15.9); N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl ]-6-cyano- phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3 -carboxamide (0.15.10); N-[4,6- dibromo-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl ]-2-(3-chloro-2-pyridyl)-5-(tri- fluoromethyl)pyrazole-3-carboxamide (0.15.1 1 );
- others: benclothiaz (0.16.1 ), bifenazate (0.16.2), artap (0.16.3), flonicamid (0.16.4), pyridalyl (0.16.5), pymetrozine (0.16.6), sulfur (0.16.7), thiocyclam (0.16.8), cyenopyrafen (0.16.9), flupyrazofos (0.16.10), cyflumetofen (0.16.1 1 ), amidoflumet (0.16.12), imicyafos (0.16.13), bistrifluron (0.16.14), pyrifluquinazon (0.16.15) and
1 ,1 '-[(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-4-[[(2-cyclopropylacetyl )oxy]methyl]-
1 ,3,4,4a,5,6,6a,12, 12a,12b-decahydro-12-hydroxy-4,6a,12b-trimethyl-1 1 -oxo-9-(3-pyridinyl)- 2H,1 1 H-naphtho[2, 1 -b]pyrano[3,4-e]pyran-3,6-diyl] cyclopropaneacetic acid ester (0.16.16); tioxazafen (0.16.17).
The active substances referred to as component 2, their preparation and their activity e. g. against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available. The compounds described by l UPAC nomenclature, their preparation and their pesticidal activity are also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968; EP-A 141 317; EP-A 152 031 ; EP-A 226 917; EP-A 243 970; EP-A 256 503; EP-A 428 941 ; EP- A 532 022; EP-A 1 028 125; EP-A 1 035 122; EP-A 1 201 648; EP-A 1 122 244,
JP 2002316902; DE 19650197; DE 10021412; DE 102005009458; US 3,296,272;
US 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501 ; WO 01/56358; WO 02/22583; WO 02/40431 ; WO 03/10149; WO 03/1 1853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491 ; WO 04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO 05/63721 ; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07/90624, WO 1 1/028657, WO2012/168188, WO
2007/006670, WO 201 1/77514; WO13/047749, WO 10/069882, WO 13/047441 , WO 03/16303, WO 09/90181 , WO 13/007767, WO 13/010862, WO 13/127704, WO 13/024009,
WO 13/024010 and WO 13/047441 , WO 13/162072, WO 13/092224, WO 1 1/135833).
The present invention furthermore relates to agrochemical compositions comprising a mixture of at least one compound I (component 1 ) and at least one further active substance useful for plant protection, e. g. selected from the groups A) to O) (component 2), in particular one further fungicide, e. g. one or more fungicide from the groups A) to K), as described above, and if desired one suitable solvent or solid carrier. Those mixtures are of particular interest, since many of them at the same application rate show higher efficiencies against harmful fungi. Furthermore, combating harmful fungi with a mixture of compounds I and at least one fungicide from groups A) to K), as described above, is more efficient than combating those fungi with individual compounds I or individual fungicides from groups A) to K).
By applying compounds I together with at least one active substance from groups A) to O) a synergistic effect can be obtained, i.e. more then simple addition of the individual effects is ob- tained (synergistic mixtures).
This can be obtained by applying the compounds I and at least one further active substance simultaneously, either jointly (e. g. as tank-mix) or seperately, or in succession, wherein the time interval between the individual applications is selected to ensure that the active substance applied first still occurs at the site of action in a sufficient amount at the time of application of the further active substance(s). The order of application is not essential for working of the present invention.
When applying compound I and a pesticide II sequentially the time between both applications may vary e. g. between 2 hours to 7 days. Also a broader range is possible ranging from 0.25 hour to 30 days, preferably from 0.5 hour to 14 days, particularly from 1 hour to 7 days or from 1.5 hours to 5 days, even more preferred from 2 hours to 1 day.
In the binary mixtures and compositions according to the invention the weight ratio of the component 1 ) and the component 2) generally depends from the properties of the active components used, usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 , even more preferably in the range of from 1 :4 to 4:1 and in particular in the range of from 1 :2 to 2:1.
According to a further embodiments of the binary mixtures and compositions, the weight ratio of the component 1 ) and the component 2) usually is in the range of from 1000:1 to 1 :1 , often in the range of from 100: 1 to 1 :1 , regularly in the range of from 50:1 to 1 :1 , preferably in the range of from 20:1 to 1 :1 , more preferably in the range of from 10:1 to 1 :1 , even more preferably in the range of from 4:1 to 1 :1 and in particular in the range of from 2:1 to 1 :1.
According to a further embodiments of the binary mixtures and compositions, the weight ratio of the component 1 ) and the component 2) usually is in the range of from 1 :1 to 1 :1000, often in the range of from 1 :1 to 1 :100, regularly in the range of from 1 :1 to 1 :50, preferably in the range of from 1 :1 to 1 :20, more preferably in the range of from 1 :1 to 1 :10, even more preferably in the range of from 1 :1 to 1 :4 and in particular in the range of from 1 :1 to 1 :2.
In the ternary mixtures, i.e. compositions according to the invention comprising the component 1 ) and component 2) and a compound III (component 3), the weight ratio of component 1 ) and component 2) depends from the properties of the active substances used, usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :4 to 4: 1 , and the weight ratio of component 1 ) and component 3) usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :4 to 4:1. Any further active components are, if desired, added in a ratio of from 20:1 to 1 :20 to the component 1 ).
These ratios are also suitable for inventive mixtures applied by seed treatment.
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group A), which is particularly selected from (A.1.1 ), (A.1 .4), (A.1 .8), (A.1.9),
(A.1.12), (A.1.13), (A.1.14), (A.1.17), (A.1.19), (A.1.21 ), (A.2.1 ), (A.2.2), (A.3.2), (A.3.3), (A.3.4), (A.3.7), (A.3.8), (A.3.9), (A.3.12), (A.3.14), (A.3.15), (A.3.16), (A.3.19), (A.3.20), (A.3.21), (A.3.22), (A.3.23), (A.3.24), (A.3.25), (A.3.26), (A.3.27); (A.4.5), (A.4.6), (A.4.8), (A.4.9) and (A.4.11 ).
Preference is given to mixtures as component 2) at least one active substance selected from group B), which is particularly selected from (B.1.4), (B.1.5), diniconazole (B.1 .6), (B.1.8), (B.1.10), (B.1.1 1 ), (B.1.12), (B.1.17), (B.1 .18), (B.1.21), (B.1 .22), (B.1.23), (B.1.25), (B.1.26), (B.1.27), (B.1 .28), (B.1.29), uni (B.1.31), (B.1.32), (B.1.33), (B.1.34), (B.1.35), (B.1.36), (B.1.37), (B.1.38), (B.1.39), (B.1.40), (B.1.41 ), (B.1 .42), (B.1.44), (B.1 .46), (B.1.49) and (B.1.50; (B.2.2), (B.2.4), (B.2.5), (B.2.6), piperalin (B.2.7), (B.2.8); and (B.3.1 ).
Preference is given to mixtures comprising as component 2) at least one active substance selected from group C), which is particularly selected from (C.1.4), C.1.5), (C.1.6), and (C.2.4).
Preference is given to mixtures comprising as component 2) at least one active substance selected from group D), which is particularly selected from (D1 .1 ), (D1.2), (D1.4), (D1.5); (D2.2), (D2.4), (D2.5), (D2.6) and (D2.7);
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group E), which is particularly selected from (E.1.1), (E.1.2), and (E.1.3);
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group F), which is particularly selected from (F.1.2), (F.1.4), (F.1.5), (F.1.6) and (F.2.1 ).
Preference is also given to mixtures as component 2) at least one active substance selected from group G), which is particularly selected from (G.3.1 ), (G.3.2), (G.3.3), (G.3.4), (G.3.5), (G.3.6), (G.4.1 ) and (G.5.1 ).
Preference is also given to mixtures comprising as component 2) at least one active sub- stance selected from group H), which is and particularly selected from (H.1.2), (H.1.3), copper oxychloride (H.1.4), (H.1.5), (H.1.6); (H.2.2), (H.2.5), (H.2.7), (H.3.2), (H.3.3), (H.3.4), (H.3.5), (H.3.6), (H.3.12); (H.4.2), (H.4.6), dithianon (H.4.9) and (H.4.10).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group I), which is particularly selected from (I.2.3) and (1.2.5).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group J), which is particularly selected from (J.1.1 ), (J.1.2), (J.1.3), (J.1.4), (J.1 .6), (J.1 .7), (J.1.8) and (J.1.9).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group K), which is particularly selected from (K.1.4), (K.1.5), (K.1.8), (K.1.12), (K.1.14), (K.1.15), (K.1.19) and(K.1.22).
Accordingly, the present invention furthermore relates to compositions comprising one compound I (component 1) and one pesticide II (component 2), which pesticide II is selected from the column "Co.2" of the lines C-1 to C-593 of Table C.
A further embodiment relates to the compositions C-1 to C-593 listed in Table C, where a row of Table C corresponds in each case to a fungicidal composition comprising as active components one of the in the present specification individualized compounds of formula I (component 1) and the respective pesticide II from groups A) to O) (component 2) stated in the row in question. Preferably, the compositions described comprise the active components in synergistically effective amounts.
Table C: Compositions comprising as active components one individualized compound I (I) (in Column Co.1) and as component 2) (in Column Co.2) one pesticide from groups A) to O) [which is coded e. g. as (A.1.1) for azoxystrobin as defined above].
Mixt Co.1 Co.2 Mixt Co.1 Co.2 Mixt Co.1 Co.2
C-1 (I) (A.1.1) C-25 (I) (A.1.25) C-49 (I) (A.3.5)
C-2 (I) (A.1.2) C-26 (I) (A.1.26) C-50 (I) (A.3.6)
C-3 (I) (A.1.3) C-27 (I) (A.1.27) C-51 (I) (A.3.7)
C-4 (I) (A.1.4) C-28 (I) (A.1.28) C-52 (I) (A.3.8)
C-5 (I) (A.1.5) C-29 (I) (A.1.29) C-53 (I) (A.3.9)
C-6 (I) (A.1.6) C-30 (I) (A.1.30) C-54 (I) (A.3.10)
C-1 (I) (A.1.7) C-31 (I) (A.1.31) C-55 (I) (A.3.11)
C-8 (I) (A.1.8) C-32 (I) (A.1.32) C-56 (I) (A.3.12)
C-9 (I) (A.1.9) C-33 (I) (A.1.33) C-57 (I) (A.3.13)
C-10 (I) (A.1.10) C-34 (I) (A.1.34) C-58 (I) (A.3.14)
C-11 (I) (A.1.11) C-35 (I) (A.1.35) C-59 (I) (A.3.15)
C-12 (I) (A.1.12) C-36 (I) (A.1.36) C-60 (I) (A.3.16)
C-13 (I) (A.1.13) C-37 (I) (A.2.1) C-61 (I) (A.3.17)
C-14 (I) (A.1.14) C-38 (I) (A.2.2) C-62 (I) (A.3.18)
C-15 (I) (A.1.15) C-39 (I) (A.2.3) C-63 (I) (A.3.19)
C-16 (I) (A.1.16) C-40 (I) (A.2.4) C-64 (I) (A.3.20)
C-17 (I) (A.1.17) C-41 (I) (A.2.5) C-65 (I) (A.3.21)
C-18 (I) (A.1.18) C-42 (I) (A.2.6) C-66 (I) (A.3.22)
C-19 (I) (A.1.19) C-43 (I) (A.2.7) C-67 (I) (A.3.23)
C-20 (I) (A.1.20) C-44 (I) (A.2.8) C-68 (I) (A.3.24)
C-21 (I) (A.1.21) C-45 (I) (A.3.1) C-69 (I) (A.3.25)
C-22 (I) (A.1.22) C-46 (I) (A.3.2) C-70 (I) (A.3.26)
C-23 (I) (A.1.23) C-47 (I) (A.3.3) C-71 (I) (A.3.27)
C-24 (I) (A.1.24) C-48 (I) (A.3.4) C-72 (I) (A.4.1) Mixt Co.1 Co.2 Mixt Co.1 Co.2 Mixt Co.1 Co.2
C-73 (I) (A.4.2) C-112 (I) (B.1.29) C-151 (I) (C.2.1)
C-74 (I) (A.4.3) C-113 (I) (B.1.30) C-152 (I) (C.2.2)
C-75 (I) (A.4.4) C-114 (I) (B.1.31) C-153 (I) (C.2.3)
C-76 (I) (A.4.5) C-115 (I) (B.1.32) C-154 (I) (C.2.4)
C-77 (I) (A.4.6) C-116 (I) (B.1.33) C-155 (I) (C.2.5)
C-78 (I) (A.4.7) C-117 (I) (B.1.34) C-156 (I) (C.2.6)
C-79 (I) (A.4.8) C-118 (I) (B.1.35) C-157 (I) (C.2.7)
C-80 (I) (A.4.9) C-119 (I) (B.1.36) C-158 (I) (D.1.1)
C-81 (I) (A.4.10) C-120 (I) (B.1.37) C-159 (I) (D.1.2)
C-82 (I) (A.4.11) C-121 (I) (B.1.38) C-160 (I) (D.1.3)
C-83 (I) (A.4.12) C-122 (I) (B.1.39) C-161 (I) (D.1.4)
C-84 (I) (B.1.1) C-123 (I) (B.1.40) C-162 (I) (D.1.5)
C-85 (I) (B.1.2) C-124 (I) (B.1.41) C-163 (I) (D.1.6)
C-86 (I) (B.1.3) C-125 (I) (B.1.42) C-164 (I) (D.2.1)
C-87 (I) (B.1.4) C-126 (I) (B.1.43) C-165 (I) (D.2.2)
C-88 (I) (B.1.5) C-127 (I) (B.1.44) C-166 (I) (D.2.3)
C-89 (I) (B.1.6) C-128 (I) (B.1.45) C-167 (I) (D.2.4)
C-90 (I) (B.1.7) C-129 (I) (B.1.46) C-168 (I) (D.2.5)
C-91 (I) (B.1.8) C-130 (I) (B.1.47) C-169 (I) (D.2.6)
C-92 (I) (B.1.9) C-131 (I) (B.1.48) C-170 (I) (D.2.7)
C-93 (I) (B.1.10) C-132 (I) (B.1.49) C-171 (I) (E.1.1)
C-94 (I) (B.1.11) C-133 (I) (B.1.50) C-172 (I) (E.1.2)
C-95 (I) (B.1.12) C-134 (I) (B.1.51) C-173 (I) (E.1.3)
C-96 (I) (B.1.13) C-135 (I) (B.2.1) C-174 (I) (E.2.1)
C-97 (I) (B.1.14) C-136 (I) (B.2.2) C-175 (I) (E.2.2)
C-98 (I) (B.1.15) C-137 (I) (B.2.3) C-176 (I) (E.2.3)
C-99 (I) (B.1.16) C-138 (I) (B.2.4) C-177 (I) (E.2.4)
C-100 (I) (B.1.17) C-139 (I) (B.2.5) C-178 (I) (E.2.5)
C-101 (I) (B.1.18) C-140 (I) (B.2.6) C-179 (I) (E.2.6)
C-102 (I) (B.1.19) C-141 (I) (B.2.7) C-180 (I) (E.2.7)
C-103 (I) (B.1.20) C-142 (I) (B.2.8) C-181 (I) (E.2.8)
C-104 (I) (B.1.21) C-143 (I) (B.3.1) C-182 (I) (F.1.1)
C-105 (I) (B.1.22) C-144 (I) (C.1.1) C-183 (I) (F.1.2)
C-106 (I) (B.1.23) C-145 (I) (C.1.2) C-184 (I) (F.1.3)
C-107 (I) (B.1.24) C-146 (I) (C.1.3) C-185 (I) (F.1.4)
C-108 (I) (B.1.25) C-147 (I) (C.1.4) C-186 (I) (F.1.5)
C-109 (I) (B.1.26) C-148 (I) (C.1.5) C-187 (I) (F.1.6)
C-110 (I) (B.1.27) C-149 (I) (C.1.6) C-188 (I) (F.2.1)
C-111 (I) (B.1.28) C-150 (I) (C.1.7) C-189 (I) (G.1.1) Mixt Co.1 Co.2 Mixt Co.1 Co.2 Mixt Co.1 Co.2
C-190 (I) (G.1.2) C-229 (I) (H.3.3) C-268 (I) (K.1.5)
C-191 (I) (G.1.3) C-230 (I) (H.3.4) C-269 (I) (K.1.6)
C-192 (I) (G.1.4) C-231 (I) (H.3.5) C-270 (I) (K.1.7)
C-193 (I) (G.2.1) C-232 (I) (H.3.6) C-271 (I) (K.1.8)
C-194 (I) (G.2.2) C-233 (I) (H.3.7) C-272 (I) (K.1.9)
C-195 (I) (G.2.3) C-234 (I) (H.3.8) C-273 (I) (K.1.10)
C-196 (I) (G.2.4) C-235 (I) (H.3.9) C-274 (I) (K.1.11)
C-197 (I) (G.2.5) C-236 (I) (H.3.10) C-275 (I) (K.1.12)
C-198 (I) (G.2.6) C-237 (I) (H.3.11) C-276 (I) (K.1.13)
C-199 (I) (G.2.7) C-238 (I) (H.4.1) C-277 (I) (K.1.14)
C-200 (I) (G.3.1) C-239 (I) (H.4.2) C-278 (I) (K.1.15)
C-201 (I) (G.3.2) C-240 (I) (H.4.3) C-279 (I) (K.1.16)
C-202 (I) (G.3.3) C-241 (I) (H.4.4) C-280 (I) (K.1.17)
C-203 (I) (G.3.4) C-242 (I) (H.4.5) C-281 (I) (K.1.18)
C-204 (I) (G.3.5) C-243 (I) (H.4.6) C-282 (I) (K.1.19)
C-205 (I) (G.3.6) C-244 (I) (H.4.7) C-283 (I) (K.1.20)
C-206 (I) (G.3.7) C-245 (I) (H.4.8) C-284 (I) (K.1.21)
C-207 (I) (G.3.8) C-246 (I) (H.4.9) C-285 (I) (K.1.22)
C-208 (I) (G.4.1) C-247 (I) (H.4.10) C-286 (I) (K.1.23)
C-209 (I) (G.5.1) C-248 (I) (1.1.1) C-287 (I) (K.1.24)
C-210 (I) (G.5.2) C-249 (I) (1.1.2) C-288 (I) (K.1.25)
C-211 (I) (G.5.3) C-250 (I) (1.2.1) C-289 (I) (K.1.26)
C-212 (I) (H.1.1) C-251 (I) (I.2.2) C-290 (I) (K.1.27)
C-213 (I) (H.1.2) C-252 (I) (I.2.3) C-291 (I) (K.1.28)
C-214 (I) (H.1.3) C-253 (I) (I.2.4) C-292 (I) (K.1.29)
C-215 (I) (H.1.4) C-254 (I) (I.2.5) C-293 (I) (K.1.30)
C-216 (I) (H.1.5) C-255 (I) (J.1.1) C-294 (I) (K.1.31)
C-217 (I) (H.1.6) C-256 (I) (J.1.2) C-295 (I) (K.1.32)
C-218 (I) (H.2.1) C-257 (I) (J.1.3) C-296 (I) (K.1.33)
C-219 (I) (H.2.2) C-258 (I) (J.1.4) C-297 (I) (K.1.34)
C-220 (I) (H.2.3) C-259 (I) (J.1.5) C-298 (I) (K.1.35)
C-221 (I) (H.2.4) C-260 (I) (J.1.6) C-299 (I) (K.1.36)
C-222 (I) (H.2.5) C-261 (I) (J.1.7) C-300 (I) (K.1.37)
C-223 (I) (H.2.6) C-262 (I) (J.1.8) C-301 (I) (K.1.38)
C-224 (I) (H.2.7) C-263 (I) (J.1.9) C-302 (I) (K.1.39)
C-225 (I) (H.2.8) C-264 (I) (K.1.1) C-303 (I) (K.1.40)
C-226 (I) (H.2.9) C-265 (I) (K.1.2) C-304 (I) (K.1.41)
C-227 (I) (H.3.1) C-266 (I) (K.1.3) C-305 (I) (K.1.42)
C-228 (I) (H.3.2) C-267 (I) (K.1.4) C-306 (I) (K.1.43) Mixt Co.1 Co. 2 Mixt Co.1 Co. 2 Mixt Co.1 Co. 2
C-307 (I) (K.1 .44) C-346 (I) (M.1.35) C-385 (I) (N.9.1 )
C-308 (I) (K.1 .45) C-347 (I) (M.1.36) C-386 (I) (N.10.1 )
C-309 (I) (K.1 .46) C-348 (I) (M.1.37) C-387 (I) (N.10.2)
C-310 (I) (K.1 .47) C-349 (I) (M.1.38) C-388 (I) (N.10.3)
C-31 1 (I) (K.1 .48) C-350 (I) (M.1.39) C-389 (I) (N.10.4)
C-312 (I) (M.1.1 ) C-351 (I) (M.1.40) C-390 (I) (N.10.5)
C-313 (I) (M.1.2) C-352 (I) (M.1.41 ) C-391 (I) (N.1 1.1 )
C-314 (I) (M.1.3) C-353 (I) (M.1.42) C-392 (I) (N.12.1 )
C-315 (I) (M.1.4) C-354 (I) (M.1.43) C-393 (I) (N.12.2)
C-316 (I) (M.1.5) C-355 (I) (M.1.44) C-394 (I) (N.12.3)
C-317 (I) (M.1.6) C-356 (I) (M.1.45) C-395 (I) (N.12.4)
C-318 (I) (M.1.7) C-357 (I) (M.1.46) C-396 (I) (N.13.1 )
C-319 (I) (M.1.8) C-358 (I) (M.1.47) C-397 (I) (N.13.2)
C-320 (I) (M.1.9) C-359 (I) (M.1.48) C-398 (I) (N.13.3)
C-321 (I) (M.1.10) C-360 (I) (M.1.49) C-399 (I) (N.13.4)
C-322 (I) (M.1.11 ) C-361 (I) (M.1.50) C-400 (I) (N.13.5)
C-323 (I) (M.1.12) C-362 (I) (N.1.1 ) C-401 (I) (N.13.6)
C-324 (I) (M.1.13) C-363 (I) (N.1.2) C-402 (I) (N.13.7)
C-325 (I) (M.1.14) C-364 (I) (N.1.3) C-403 (I) (N.13.8)
C-326 (I) (M.1.15) C-365 (I) (N.1.4) C-404 (I) (N.13.9)
C-327 (I) (M.1.16) C-366 (I) (N.1.5) C-405 (I) (N.14.1 )
C-328 (I) (M.1.17) C-367 (I) (N.2.1 ) C-406 (I) (N.14.2)
C-329 (I) (M.1.18) C-368 (I) (N.2.2) C-407 (I) (N.15.1 )
C-330 (I) (M.1.19) C-369 (I) (N.2.3) C-408 (I) (N.16.1 )
C-331 (I) (M.1.20) C-370 (I) (N.3.1 ) C-409 (I) (N.16.2)
C-332 (I) (M.1.21 ) C-371 (I) (N.3.2) C-410 (I) (N.17.1 )
C-333 (I) (M.1.22) C-372 (I) (N.3.3) C-41 1 (I) (N.17.2)
C-334 (I) (M.1.23) C-373 (I) (N.3.4) C-412 (I) (N.17.3)
C-335 (I) (M.1.24) C-374 (I) (N.4.1 ) C-413 (I) (N.17.4)
C-336 (I) (M.1.25) C-375 (I) (N.5.1 ) C-414 (I) (N.17.5)
C-337 (I) (M.1.26) C-376 (I) (N.6.1 ) C-415 (I) (N.17.6)
C-338 (I) (M.1.27) C-377 (I) (N.6.2) C-416 (I) (N.17.7)
C-339 (I) (M.1.28) C-378 (I) (N.6.3) C-417 (I) (N.17.8)
C-340 (I) (M.1.29) C-379 (I) (N.6.4) C-418 (I) (N.17.9)
C-341 (I) (M.1.30) C-380 (I) (N.6.5) C-419 (I) (N.17.10)
C-342 (I) (M.1.31 ) C-381 (I) (N.7.1 ) C-420 (I) (N.17.11 )
C-343 (I) (M.1.32) C-382 (I) (N.7.2) C-421 (I) (N.17.12)
C-344 (I) (M.1.33) C-383 (I) (N.7.3) C-422 (I) (0.1.1 )
C-345 (I) (M.1.34) C-384 (I) (N.8.1 ) C-423 (I) (0.1.2) Mixt Co.1 Co.2 Mixt Co.1 Co.2 Mixt Co.1 Co.2
C-424 (I) (0.1.3) C-463 (I) (0.2.4) C-502 (I) (0.3.27)
C-425 (I) (0.1.4) C-464 (I) (0.2.5) C-503 (I) (0.4.1)
C-426 (I) (0.1.5) C-465 (I) (0.2.6) C-504 (I) (0.4.2)
C-427 (I) (0.1.6) C-466 (I) (0.2.7) C-505 (I) (0.4.3)
C-428 (I) (0.1.7) C-467 (I) (0.2.8) C-506 (I) (0.4.4)
C-429 (I) (0.1.8) C-468 (I) (0.2.9) C-507 (I) (0.4.5)
C-430 (I) (0.1.9) C-469 (I) (O.2.10) C-508 (I) (0.4.6)
C-431 (I) (O.1.10) C-470 (I) (0.2.11) C-509 (I) (0.4.7)
C-432 (I) (0.1.11) C-471 (I) (0.2.12) C-510 (I) (0.4.8)
C-433 (I) (0.1.12) C-472 (I) (0.2.13) C-511 (I) (0.4.9)
C-434 (I) (0.1.13) C-473 (I) (0.2.14) C-512 (I) (O.4.10)
C-435 (I) (0.1.14) C-474 (I) (0.2.15) C-513 (I) (0.4.11)
C-436 (I) (0.1.15) C-475 (I) (0.2.16) C-514 (I) (0.4.12)
C-437 (I) (0.1.16) C-476 (I) (0.3.1) C-515 (I) (0.4.13)
C-438 (I) (0.1.17) C-477 (I) (0.3.2) C-516 (I) (0.4.14)
C-439 (I) (0.1.18) C-478 (I) (0.3.3) C-517 (I) (0.4.15)
C-440 (I) (0.1.19) C-479 (I) (0.3.4) C-518 (I) (0.4.16)
C-441 (I) (0.1.20) C-480 (I) (0.3.5) C-519 (I) (0.4.17)
C-442 (I) (0.1.21) C-481 (I) (0.3.6) C-520 (I) (0.4.18)
C-443 (I) (0.1.22) C-482 (I) (0.3.7) C-521 (I) (0.4.19)
C-444 (I) (0.1.23) C-483 (I) (0.3.8) C-522 (I) (O.4.20)
C-445 (I) (0.1.24) C-484 (I) (0.3.9) C-523 (I) (0.4.21)
C-446 (I) (0.1.25) C-485 (I) (0.3.10) C-524 (I) (0.4.22)
C-447 (I) (0.1.26) C-486 (I) (0.3.11) C-525 (I) (0.4.23)
C-448 (I) (0.1.27) C-487 (I) (0.3.12) C-526 (I) (0.4.24)
C-449 (I) (0.1.28) C-488 (I) (0.3.13) C-527 (I) (0.5.1)
C-450 (I) (0.1.29) C-489 (I) (0.3.14) C-528 (I) (0.5.2)
C-451 (I) (0.1.30) C-490 (I) (0.3.15) C-529 (I) (0.5.3)
C-452 (I) (0.1.31) C-491 (I) (0.3.16) C-530 (I) (0.5.4)
C-453 (I) (0.1.32) C-492 (I) (0.3.17) C-531 (I) (0.5.5)
C-454 (I) (0.1.33) C-493 (I) (0.3.18) C-532 (I) (0.5.6)
C-455 (I) (0.1.34) C-494 (I) (0.3.19) C-533 (I) (0.5.7)
C-456 (I) (0.1.35) C-495 (I) (O.3.20) C-534 (I) (0.5.8)
C-457 (I) (0.1.36) C-496 (I) (0.3.21) C-535 (I) (0.5.9)
C-458 (I) (0.1.37) C-497 (I) (0.3.22) C-536 (I) (0.6.1)
C-459 (I) (0.1.38) C-498 (I) (0.3.23) C-537 (I) (0.6.2)
C-460 (I) (0.2.1) C-499 (I) (0.3.24) C-538 (I) (0.6.3)
C-461 (I) (0.2.2) C-500 (I) (0.3.25) C-539 (I) (0.6.4)
C-462 (I) (0.2.3) C-501 (I) (0.3.26) C-540 (I) (0.6.5) Mixt Co.1 Co. 2 Mixt Co.1 Co. 2 Mixt Co.1 Co. 2
C-541 (I) (0.6.6) C-559 (I) (0.1 1 .2) C-577 (I) (0.16.1 )
C-542 (I) (0.6.7) C-560 (I) (0.1 1 .3) C-578 (I) (0.16.2)
C-543 (I) (0.7.1 ) C-561 (I) (0.1 1 .4) C-579 (I) (0.16.3)
C-544 (I) (0.7.2) C-562 (I) (0.12.1 ) C-580 (I) (0.16.4)
C-545 (I) (0.7.3) C-563 (I) (0.13.1 ) C-581 (I) (0.16.5)
C-546 (I) (0.7.4) C-564 (I) (0.14.1 ) C-582 (I) (0.16.6)
C-547 (I) (0.7.5) C-565 (I) (0.14.2) C-583 (I) (0.16.7)
C-548 (I) (0.7.6) C-566 (I) (0.15.1 ) C-584 (I) (0.16.8)
C-549 (I) (0.8.1 ) C-567 (I) (0.15.2) C-585 (I) (0.16.9)
C-550 (I) (0.8.2) C-568 (I) (0.15.3) C-586 (I) (O.16.10)
C-551 (I) (0.8.3) C-569 (I) (0.15.4) C-587 (I) (0.16.1 1 )
C-552 (I) (0.8.4) C-570 (I) (0.15.5) C-588 (I) (0.16.12)
C-553 (I) (0.8.5) C-571 (I) (0.15.6) C-589 (I) (0.16.13)
C-554 (I) (0.9.1 ) C-572 (I) (0.15.7) C-590 (I) (0.16.14)
C-555 (I) (0.9.2) C-573 (I) (0.15.8) C-591 (I) (0.16.15)
C-556 (I) (0.9.3) C-574 (I) (0.15.9) C-592 (I) (0.16.16)
C-557 (I) (O.10.1 ) C-575 (I) (O.15.10) C-593 (I) (0.16.17)
C-558 (I) (0.1 1 .1 ) C-576 (I) (0.15.1 1 )
The mixtures of active substances can be prepared as compositions comprising besides the active ingredients at least one inert ingredient (auxiliary) by usual means, e. g. by the means given for the compositions of compounds I .
Concerning usual ingredients of such compositions reference is made to the explanations given for the compositions containing compounds I .
The mixtures of active substances according to the present invention are suitable as fungicides, as are the compounds of formula I . They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, especially from the classes of the Ascomy- cetes, Basidiomycetes, Deuteromycetes and Peronosporomycetes (syn. Oomycetes). In addition, it is refered to the explanations regarding the fungicidal activity of the compounds and the compositions containing compounds I, respectively.
I . Synthesis examples
Example 1
Step 1 .1 :
To a solution of the bromide (20.0 g, 1.0 eq) in 1 ,4-dioxane (200 mL) were added copper(l) iodide (410 mg, 0.05 eq), sodium iodide (12.8 g, 2.0 eq), and Λ/,Λ -1 ,2-cyclohexanediamine (608 mg, 0.1 eq) and the mixture was warmed to reflux for 16 h. After cooling to room temperature, a saturated solution of NH4CI was added and the product was extracted into EtOAc. The combined organic extracts were dried over MgSC and concentrated. Purification of the residual crude product over a short plug of silica gel yielded the title compound (13.0 g, 76%) as oil. HPLC: t R = 1 .01 1 min; H NMR (298 K, CDC ): δ [ppm] = 1.60 (3H), 4.30 (1 H), 4.50 (1 H), 4.65 (1 H), 7.36 (2H), 7.80 (2H), 8.05 (1 H).
Step 1.2: Synthesis of compound 1-1
To a solution of the iodide (200 mg, 1.0 eq) in piperidine (2 mL) and pyridine (2 mL) was added Pd(PPh 3 ) 2 Cl2 (1 .7 mg, 0.05 eq), Cul (4.8 mg, 0.05 eq), and propargylic alcohol (70.6 mg, 2.5 eq) successively. The reaction mixture was stirred at room temperature until HPLC indicated complete conversion before it was concentrated under reduced pressure. The residue was dissolved in MTBE and filtered over silica gel. After removal of the solvent, the crude product was purified by preparative HPLC to afford the title compound (73.0 mg, 45%) as oil. HPLC: tR = 0.798 min.
Example 2:
Step 2.1 :
Corresponding to step 1.1 , the following compound was prepared with a yield of 70% (HPLC: tR = 1.149 min):
Example 3: Compound 1-22
To a cold (-78 °C) solution of di-/so-propylamine (1.68 g, 3.3 eq) in THF (50 mL) was added n- BuLi (8.31 mL, 2.0 M in hexanes, 3.3 eq) and the mixture was stirred at this temperature. After 30 minutes, 2-bromo-1 ,1 ,1 -trifluoroprop-2-ene (1.32 g, 1 .5 eq) and ZnCI 2 *TMEDA (2.1 g, 1.65 eq) were added successively. The reaction vessel was warmed to ambient temperature over 1 h before a solution of the aryl iodide (2.00 g, 1.0 eq) in THF (10 mL) and Pd(PPh 3 ) 4 (0.29 g, 0.05 eq) were added. Thr mixture was stirred at rt for 6 h, before the reaction was quenched by the addition of a saturated aqueous solution of NH 4 CI. The aqueous layer was separated and ex- tracted with EtOAc. The combined organic extracts were dried over Na2S04 and concentrated under reduced pressure to afford a crude product which was further purified by column chromatography. The title compound was isolated as colorless oil (0.79 g, 43%). HPLC:†R = 1.128 min; 1 H NMR (500 MHz, 298 K, CDCI 3 ): δ [ppm] = 1.65 (3H), 4.40-4.50 (2H), 4.70 (1 H), 7.66 (1 H), 7.75 (1 H), 7.80 (1 H), 7.90 (1 H), 8.05 (1 H).
The followin target compounds I. A were prepared in analogy to the steps above:
Example No. R 1 R2 R 3 Z HPLC ** min
1-1 CH 3 H CF 3 CH 2 OH 0.798
I-2 CH 3 H CF 3 (CH 2 ) 2 CH 2 CI 1.125
I-3 CH 3 H CF 3 CHCHsOH 0.852
I-4 CH 3 H CF 3 CH 2 OCH 3 0.958
I-5 CH 3 H CF 3 CH 2 CH 2 CH 3 1.153
I-6 CH 3 H CF 3 C(CH 3 ) 3 1.207
I-7 CH 3 H CF 3 CH 2 CH(CH 3 ) 2 1.234
I-8 CH 3 H CF 3 CH 2 CH 2 CH 2 CH 3 1.222
I-9 CH 3 H CF 3 CH 2 (CH 2 ) 3 CH 3 1.288
1-10 CH 3 H CF 3 CH 2 CH 2 CN 0.916
1-1 1 CH 3 H CF 3 CH 2 OCH(CH 3 ) 2 1.076
1-12 CH 3 H CF 3 C(CH 3 ) 2 OCH 3 1.068
1-13 C 3 H5 H CI CH 2 CH 2 CH 2 CI 1.208
C3H5 = cyclopropyl
** :HPLC method Data:
Mobile Phase: A: Wasser + 0.1 % T FA; B: acetonitrile; Gradient: 5% B to 100% B in 1.5min; Temperature: 60 °C; MS-Method: ESI positive; mass area (m/z): 100-700; Flow: 0.8ml/min to 1.0ml/min in 1.5min; Column: Kinetex XB C18 1.7μ 50 x 2.1 mm; Aparatus: Shimadzu Nexera LC-30 LCMS-2020.
The following target compounds I.C were prepared in analogy to the steps above:
Example R 1 R 2 Z HPLC ** t R /min
No.
I.C-1 C(CH 3 ) 3 H CH 2 CH 2 CH 2 OH 0.975
I.C-2 C(CH 3 ) 3 H CH 2 CH(CH 3 ) 2 1 .312
I.C-3 C(CH 3 ) 3 H C(C 2 H 3 ) 2 OH 1 .137
I.C-4 C(CH 3 ) 3 H CH 2 OH 0.903
I.C-5 C(CH 3 ) 3 H CH(CH 3 )OH 0.952
I.C-6 C(CH 3 ) 3 H CH 2 OCH 3 1 .062
I.C-7 C(CH 3 ) 3 H CH 2 CH 2 CH 3 1 .252
I.C-8 C(CH 3 ) 3 H C(CH 3 ) 3 1 .306
I.C-9 C(CH 3 ) 3 H CH 2 CH 2 CH 2 CH 2 CH 3 1 .381
I.C-10 C(CH 3 ) 3 H CH 2 CH 2 CH 2 CH 3 1 .346
I.C-1 1 C(CH 3 ) 3 H CH(CH 3 ) 2 1 .215
I.C-12 C(CH 3 ) 3 H CF 3 1 .228
:HPLC method Data:
Mobile Phase: A: Wasser + 0.1 % T FA; B: acetonitrile; Gradient: 5% B to 100% B in 1 .5min; Temperature: 60 °C; MS-Method: ESI positive; mass area (m/z): 100-700; Flow: 0.8ml/min to
I .0ml/min in 1.5min; Column: Kinetex XB C18 1.7μ 50 x 2.1 mm; Aparatus: Shimadzu Nexera LC-30 LCMS-2020.
I I. Examples of the action against harmful fungi
The fungicidal action of the compounds of the formula I was demonstrated by the following experiments:
Microtest
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
Ml Activity against the grey mold Botrytis cinerea in the microtiterplate test (Botrci)
The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Botrci cinerea in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. Compounds I- 19, I-25, 1-16, 1-17, 1-18, I-7, I-8, I-20, I-2, 1-1 1 , I-26, I-4, I-5, I-23, I-27, I-28, I-29, 1-31 , I- 32, I-33, 1-12, I-34, I-35, I-36, I-39 and I-22, respectively, showed a growth of 18 % or less at 31 ppm.
Compounds C. I-1 , C.I-2, C.I-3, C.I-6, C. I-7 and C. I-12, respectively, showed a growth of 13 % or less at 31 ppm.
M2. Activity against net blotch Pyrenophora teres on barley in the microtiter test (Pyrnte) The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Pyrenophora teres in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption pho- tometer, the MTPs were measured at 405 nm 7 days after the inoculation. Compounds 1-19, I- 25, 1-16, 1-17, 1-18, I-7, I-20, I-27, I-28, I-29, I-32, I-33, I-34 and I-35, respectively, showed a growth of 15 % or less at 31 ppm.
Compounds C.I-2, C.I-3 and C.I-8, respectively, showed a growth of 12 % or less at 31 ppm.M3. Activity against leaf blotch on wheat caused by Septoria tritici (Septtr)
The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Septoria tritici in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. Compounds 1-19, I-25, 1-14, 1-16, 1-17, I-7, I-8, I-20, I-2, 1-1 1 , I-26, I-4, I-5, I-23, I-27, I-29, 1-31 , I-32, 1-12, I-34, I-35, I-36, I-39 and I-22, respectively, showed a growth of 20 % or less at 31 ppm.
Compounds C. I-1 , C.I-3, I .C-5, C.I-6, C. I-7 and C. I-12, respectively, showed a growth of 15 % or less at 31 ppm.
M4. Activity against early blight caused by Alternaria solani (Alteso)
The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Alternaria solani in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. Compounds 1-19, I-25, 1-14, 1-16, 1-17, 1-18, I-7, I-8, I-20, I-2, 1-1 1 , I-4, I-5, I-23, I-27, I-28, I-29, I-30, 1-31 , I-32, I-33, 1-12, I-34 and I-35, respectively, showed a growth of 7 % or less at 31 ppm.
Compounds C. I-1 , C.I-2, C.I-5, C.I-6 and C.I-7, respectively, showed a growth of 13 % or less at 31 ppm.
M5. Activity against root rot caused by Fusarium culmorum (Fusacu)
The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Fusarium culmorum in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. Compounds 1-19, I-25, 1-16, 1-17, 1-18, I-7, I-8, I-5, I-23, I-28, I-29, I-32, I-33, I-34 and I-35, respectively, showed a growth of 17 % or less at 31 ppm.
Compound C.I-2 showed a growth of 0 % at 31 ppm.
M6. Activity against rice blast Pyricularia oryzae in the microtiterplate test (Pyrior) The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Pyricularia oryzae in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. Compounds 1-19, I-25, 1-16, 1-17, 1-18, I-7, I-8, I-20, I-2, 1-1 1 , I-5, I-23, I-27, I-28, I-29, 1-31 , I-32, I-33, 1-12, I-34, I- 35, I-36, I-39 and I-22, respectively, showed a growth of 9 % or less at 31 ppm.
Compounds C.I-2, C.I-3, I.C-6, C.I-7, I.C-8 and C.I-12, respectively, showed a growth of 20 % or less at 31 ppm.
The measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free and active compound-free blank value to determine the relative growth in % of the pathogens in the respective active compounds.