| WO/1989/003812 | CROSS COUPLING OF TITANIUM ORGANYLS |
| WO/2016/004136 | HETEROARYL COMPOUNDS USEFUL AS INHIBITORS OF SUMO ACTIVATING ENZYME |
| JPH0770033 | BENZ(E)INDENE DERIVATIVE |
ZURFLUEH RENE (CH)
| WO1994026700A1 | 1994-11-24 |
| EP0528681A1 | 1993-02-24 |
| 1. | A thiamide Soxide of the formula in which the substituents have the following meanings: Ri is hydrogen or CιC4alkyl, and R2 is hydrogen, C1C4alkyI, C2C alkenyl, C2C4alkynyl or C3C6cycloalkyl, and in which R3 and R4 independently of one another are hydrogen, cyano, C|C4alkyl, halodC alkyl, C2C4alkenyl, C2C4alkynyl, C3C6cycloalkyl, cyclo¬ propylmethyl, CιC4alkoxy, C2C5alkoxyalkyl, CιC4alkoxycarbonyl, CιC alkylthio, C2C5alkylthioalkyl; an unsubstituted or up to trisubstituted ring which has not more than 15 ring carbon atoms, which can be polycyclic and which contains 03 hetero atoms N, O or S, it being possible for this ring to be bonded via an aliphatic bridge having not more than 4 carbon atoms and/or via either CO, oxygen or sulfur; or in which R3 and R together with the joint carbon atom form an unsubstituted or up to trisubstituted ring which has not more than 15 ring carbon atoms, which can be polycyclic and which contains 03 hetero atoms N, O or S, the substituents which are possible for all of these rings mentioned individually or in combination for R3 and R being selected from the series consisting of CrC4alkyl, C2C4alkenyl, C2C alkynyl, CrC4alkoxy, CrC^lkylthio, CιC4haloalkyl, C2C4haloalkenyl, C2C haloalkynyl, CrC haloalkoxy, dihalocyclopropylmethoxy, halogen, cyano, cyano CιC2alkyl, cyanoCιC2alkoxy; OH, NO2, SCN, OCN, thiocyanomethyl, SF5, Si(CH3)3, NH2, NH(C1C4alkyl), N(CιC4alkyl)2, CrC4alkoxymethyl, CrC4alkylcarbonyl, CrC4alkoxy carbonyl, ddalkoximinomethyl, CSNH2l SH, ddalkylthio, CιC alkylthiomethyl, C2C alkenyloxy, C2C4alkynyloxy, C2C4haloalkenyloxy, CιC alkylsulfinylmethyl, dC alkyl sulfonylmethyl, phenylsulfinylmethyl, phenylsulfonylmethyl, trifluoromethylsulfonyl, C3C6cycloalkyl; phenyl, benzyl, phenoxy, phenylthio, benzyloxy and benzylthio; it being possible for the lastmentioned aromatic substituents to have not more than three further substituents in the phenyl ring which are selected from the series consisting of halogen, CιC4alkyl, CιC alkoxy, dC haloalkyl, CrC haloalkoxy, CN and N02, and where two of the not more than 3 substituents can form a vicinal aliphatic bridge composed of not more than 5 members which contains 02 oxygen atoms and 01 carbonyl group and which can be not more than tetrasubstituted by halogen, CrC alkyl, CιC4alkoxy and/or by a single phenyl group. |
| 2. | A compound according to claim 1 , in which RT is hydrogen and R2 is methyl. |
| 3. | A compound according to claim 2, in which RT is hydrogen, R2 is methyl and R3 is methyl, ethyl, methoxy, methylthio, cyano or cyclopropyl. |
| 4. | A compound according to claim 1 in which Ri = H, C C2alkyl R2 = H, dCalkyl R3 = H, CιC4alkyl, cyclopropyl, CrC2alkoxy, CrC2alkylthio, methoxymethyl, cyano, trifluoromethyl R = halophenyl having 1 to 2 halogen atoms, monoCιC2alkylphenyl, monoCιC alkoxy phenyl, monohalomono(CιC2alkoxy)phenyl, 3halodC alkylphenyl having 1 to 3 halogen atoms, trifluoromethylphenyl which is substituted by fluorine or chlorine, 3haloC1C4alkoxy phenyl having 1 to 6 halogen atoms (in particular fluorine), 3C2C4alkenyloxyphenyl, 3C2C4alkynyloxyphenyl, 3C3C6cycloalkylmethoxyphenyl, 3cyanoCrC3alkoxyphenyl, bis(trifluoromethyl)phenyl, tolyl which is substituted by fluorine or chlorine, monocyano¬ phenyl, trifluoromethylphenyl which is substituted by methylthio; 3trimethylsilylphenyl, methoxynitrophenyl, 3 or 4phenoxyphenyl, or 3methylsulfinyl or 3methylsulfonyl methylphenyl which is optionally substituted by methoxy; 3trifluoromethyl4chlorobenzyl, 3trifluoromethylphenoxymethyl, 3trifluoromethylbenzoyl, 2naphthyl, phenyl which is substituted in the 3 and 4position by straightchain dC3alkylenedioxy (in particular methylenedioxy, ethylenedioxy, 2,2difluoromethylenedioxy, 2methoxymethylenedioxy), dihydrobenzofur5yl, 2thienyl, benzofur2yl, 2furyl, 5chloro or 5bromothien2yl, 3methylbenzo[b]thien2yl, 1 methyl pyrrol2yl, 2thiazolyl, benzothien2yl, pyrazin2yl, 2pyridyl which is substituted or unsubstituted by halogen or trifluoromethyl; 6 or 7 quinolinyl, 6quinoxalinyl; substituted or unsubstituted 2quinolinyl, substituted or unsubstituted 2quinoxalinyl, 2pyrimidinyl which is monoto disubstituted by halogen, methyl, trifluoromethyl, cyclopropyl, CιC3alkoxy or methylthio; 1(2,6dimethylmorpholinyl), substituted or unsubstituted benzisoxazol3yl, substituted or unsubstituted benzisothiazol 3yl, substituted or unsubstituted indazol3yl, or R3 and R together are a 5,6dihydro2H1 ,4thiazin ring which s substituted in the 3position by substituted phenyl, or R3 and R4 together are a cyclopentane or tetrahydro¬ pyran ring to which an unsubstituted or halogensubstituted benzene ring is fused. |
| 5. | A compound according to claim 1 in which Ri is hydrogen, R2 is methyl and R3 is methyl, ethyl, methoxy, methylthio, cyano or cyclopropyl and in which R is phenyl which is mono or disubstituted by substituents selected from the series consisting of halogen, methoxy, trifluoromethyl and trifluoromethoxy. |
| 6. | A compound according claim 5 in which R4 is 3chlorophenyl 3bromophenyl, 4chlorophenyl, 4bromophenyl, 3trifluoromethylphenyl, 3trifluoromethoxyphenyl, 3,5dichlorophenyl, 3fluoro4methoxyphenyl or 3chloro4methoxyphenyl bedeutet. |
| 7. | A compound according to claim 1 in which R is hydrogen, R2 is methyl, R3 is methyl or cyclopropyl and R4 is 3chlorophenyl, 3trifluoromethylphenyl, 3trifluoromethoxyphenyl, 3difluorochloromethoxyphenyl or 4chlorophenyl. |
| 8. | A process for the preparation of a thioamide Soxide of the formula I according to claim 1 by oxidizing a thioamide of the formula II in which R to R have the meanings given for formula I. |
| 9. | A process according to claim 8 which comprises carrying out the oxidation with hydrogen peroxide. |
| 10. | A pesticide which comprises, as active ingredient, a compound of the formula I according to claim 1 together with a suitable carrier material. |
| 11. | A method of controlling and preventing infestation of plants by microorganisms, which comprises applying, as active ingredient, a compound of the formula I to the plant, to parts of the plants or into the plant substrate. |
| 12. | A method according to claim 11, which comprises treating the propagation material. |
| 13. | A method according to claim 12, which comprises treating seed. |
| 14. | The use of a compound of the formula I for controlling or preventing infestation with microorganisms. |
The present invention relates to thioamide S-oxides of the formula
in which the substituents have the following meanings:
R-i is hydrogen or C-|-C 4 alkyl, and
R 2 is hydrogen, Cι-C -alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl or C 3 -C 6 cycloalkyl,
and in which R3 and R4 independently of one another are hydrogen, cyano, C-|-C4alkyl, halo-C C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 - cycloalkyl, cyclopropylmethyl, C C alkoxy, C 2 -C 5 alkoxyalkyl, (VC 4 aIkoxycarbonyl, C 1 -C 4 alkylthio, C 2 -C 5 alkylthioalkyl; an unsubstituted or up to trisubstituted ring which has not more than 15 ring carbon atoms, which can be polycyclic and which contains 0-3 hetero atoms N, O or S, it being possible for this ring to be bonded via an aliphatic bridge having not more than 4 carbon atoms and/or via either CO, oxygen or sulfur; or
in which R 3 and R A together with the joint carbon atom form an unsubstituted or up to trisubstituted ring which has not more than 15 ring carbon atoms, which can be polycyclic and which contains 0-3 hetero atoms N, O or S,
the substituents which are possible for all of these rings mentioned individually or in- combination for R 3 and R 4 being selected from the series consisting of Cι-C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C C 4 alkoxy, Cι-C 4 alkylthio, C C 4 haloalkyl, C 2 -C 4 halo- alkenyl, C 2 -C haloalkynyl, C C haloalkoxy, dihalocyclopropylmethoxy, halogen, cyano, cyano-C 1 -C 2 alkyl, cyano-C Caalkoxy, OH, N0 2 , -SCN, -OCN, thiocyano- methyl, -SF 5l Si(CH 3 ) 3 , NH 2) NH(CτC 4 alkyl), N(C C 4 alkyl) 2 , CVO-alkoxymethyl,
C 1 -C 4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkoximinomethyl, -CSNH 2 , -SH, C C 4 alkylthio, C 1 -C 4 alkylthiomethyl, C 2 -C alkenyloxy, C 2 -C 4 alkynyloxy, C 2 -C 4 haloalkenyloxy, C r C alkylsulfinylmethyl, Cι-C 4 alkylsulfonylmethyl, phenylsulfinylmethyl, phenylsulfonylmethyl, trifluoromethylsulfonyl, C 3 -C 6 cycloalkyl; phenyl, benzyl, phenoxy, phenylthio, benzyloxy and benzylthio; it being possible for the last-mentioned aromatic substituents to have not more than three further substituents in the phenyl ring which are selected from the series consisting of halogen, C 1 -C 4 alkyl, CVC 4 alkoxy, CrC^aloalkyl, C|-C 4 haloalkoxy, CN and N0 2 , and where two of the not more than 3 substituents can form a vicinal aliphatic bridge composed of not more than 5 members which contains 0-2 oxygen atoms and 0-1 carbonyl group and which can be not more than tetrasubstituted by halogen, Cι-C alkyl, C-|-C alkoxy and/or by a single phenyl group.
In the event that asymmetric carbon atoms are present in the compounds of the formula I, the compounds exist in optically active form. In any case, the compounds exist in the [E] or [Z] form, merely on the basis of an imino double bond which is ' present. Atropisomerism can furthermore exist. The formula I is intended to embrace all these isomeric forms which are possible and their mixtures, for example racemic mixtures and any [E/Z] mixtures.
The compounds according to the invention have fungicidal, insecticidal and acaricidal properties and are suitable for use as active ingredients in crop protection.
If the compounds I have at least one basic centre, they may form acid addition salts. These are formed, for example, with strong inorganic acids such as mineral acids (for example sulfuric acid, phosphorus - containing acid or a hydrohalic acid), with strong organic carboxylic acids, such as substituted or unsubstituted (for example halogen-substituted) C C 4 alkanecarboxylic acids, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid; or they are formed with organic sulfonic acids, such as substituted or unsubstituted (for example halogen-substituted) C C 4 alkane- or arylsulfonic acids, for example methane- or p-toluenesulfonic acid. Since the compounds I in free form and in the form of their salts are closely related, the formula I is to be understood as meaning the relevant salts and also the free compounds I.
Unless otherwise defined, the general terms used hereinabove and hereinbelow have the meanings which follow.
Alkyl groups alone or as structural element of other groups can be straight-chain or branched, depending on the number of the carbon atoms. C,-C 4 alkyl is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.
Alkenyl as a group or as structural element of other groups and compounds such as alkenyloxy, arylalkenyl and heteroarylalkenyl, is either straight-chain, for example ethenyl, propen-1-yl or but-1-en-1-yl, or branched, for example propen-2-yl or but-1- en-2-yl.
Alkynyl as a group or as a structural element of other groups and compounds such as alkynyloxy is either straight-chain, for example ethynyl, propyn-1-yl or but-1-yn-1- yl, or branched, for example propyn-2-yl or but-1-yn-2-yl.
Cycloalkyl as a group or as a structural element of other groups and compounds, such as cycloalkylmethoxy, is, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Carbocyclic rings alone or as structural elements of other groups such as aryl- C C alkyl, aryloxy-C 1 -C alkyl, arylthio-C C^alkyl, arylcarbonyl and aryl-C 2 - C 4 alkenyl groups have, in particular, 6 to 14 C atoms and are, for example, naphthyl, tetrahydronaphthyl, indanyl, fluorenyl, phenanthryl or, in particular, phenyl. They can be aromatic, partially hydrogenated or fully saturated. One or two benzene rings may be fused onto carbocyclic rings.
Rings containing hetero atoms, as a group by themselves and as structural elements of other groups and compounds, such as heteroaryl-C C alkyl, heteroaryloxy- C 1 -C 4 alkyl, heteroarylthio-C-|-C 4 alkyl, heteroarylcarbonyl and heteroaryl-C 2 -C 4 alkenyl groups, have, in particular, 5 to 14 ring members, of which 1 to 3 members are hetero atoms selected from the group consisting of oxygen, sulfur and nitrogen. Examples which may be mentioned are benzimidazolyl, benzocoumarinyl, benzofuryl, benzothiadiazolyl, benzothiazolyl, benzisothiazolyl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzoxdiazolyl, quinazolinyl, quinolyl, quinoxalinyl, carbazolyl, dihydrobenzofuryl, ethylenedioxyphenyl, furyl, imidazolyl, indazolyl, indolyl, isoquinolyl, isothiazolyl, isoxazolyl, methylenedioxyphenyl, naphthyridinyl, oxazolyl, phenanthridinyl, phthalazinyl, pteridinyl, purinyl, pyrazinyl, pyrazolyl,
pyridazinyl, pyrazolo[3,4-b]pyridyl, pyridyl, pyrimidinyl, pyrrolyl, tetrazolyl, thiadiazolyl, thiazolyl, thienyl, triazinyl and triazolyl.
Preferred heteroaryl radicals R 3 and/or R 4 are benzofuryl, benzothienyl, quinolyl, quinoxalinyl, dihydrobenzofuryl, ethylenedioxy, furyl, methylenedioxy, pyridyl, pirimidinyl, pyrrolyl, thiazolyl, benzisoxazolyl, benzisothiazolyl, indazolyl and thienyl.
One or two benzene rings may be fused onto heterocyclic rings.
Halogen is fluorine, chlorine, bromine or iodine. Examples of haloalkyl and haloalkoxy groups are -CH 2 F, -CHF 2 , -CF 3 , -CH 2 CI, -CHCI 2 , -CCI 3 , -CCI 2 CCI 3> -CH 2 Br, -CH 2 CH 2 Br, -CHBrCI, -OCHF 2 , OCF 3 , OCH 2 CF 3 , OCF 2 CHF 2 , OCF 2 CHFCF 3 , OCF 2 Br, OCF 2 CI, OCF 2 CF 2 Br.
A preferred group of compounds of the formula I are those compounds in which Ri is hydrogen and R 2 is methyl (sub-group la).
Another preferred group of compounds of the formula I are those compounds in which R T is hydrogen, R 2 is methyl and R 3 is methyl, ethyl, methoxy, methylthio, cyano or cyclopropyl (sub-group Ib).
Another preferred group of compounds of the formula I are those compounds in which Ri is hydrogen, R 2 is methyl and R 3 is methyl, ethyl, methoxy, methylthio, cyano or cyclopropyl and in which R 4 is phenyl which is mono- or disubstituted by subsituents selected from the group consisting of halogen, methoxy, trifluoromethyl and trifluoromethoxy (sub-group Ic).
Compounds which are preferred amongst the last-mentioned ones are those in which R 4 is 3-chlorophenyl, 3-bromophenyl, 4-chlorophenyl, 4-bromophenyl, 3-trifluoromethylphenyl, 3-trifluoromethoxyphenyl, 3,5-dichlorophenyl, 3-fluoro-4- methoxyphenyl or 3-chloro-4-methoxyphenyl (sub-group Ice).
An important group of compounds of the formula I consists of those in which the substituents having the following meanings:
R-i = H, C C 2 alkyl R 2 = H, C C 4 alkyl
R 3 = H, C C 4 alkyl, cyclopropyl, CrC 2 alkoxy, C C 2 -alkylthio, methoxymethyl, cyano, trifluoromethyl
R 4 = halophenyl having 1 to 2 halogen atoms, mono-C C 2 alkylphenyl, mono- Cr^alkoxyphenyl, monohalomono(Cι-C 2 alkoxy)phenyl, 3-halo-C C 4 alkylphenyl having 1 to 3 halogen atoms, trifluoromethylphenyl which is substituted by fluorine or chlorine, 3-halo-Cι-C 4 alkoxyphenyl having 1 to 6 halogen atoms (in particular fluorine), 3-C 2 -C 4 alkenyloxyphenyl, 3-C 2 -C 4 alkynyloxyphenyl, 3-C 3 -C 6 cycloalkyl- methoxyphenyl, 3-cyano-Ci-C-jalkoxyphenyl, bis(trifluoromethyl)phenyl, tolyl which is substituted by fluorine or chlorine, monocyanophenyl, trifluoro- methylphenyl which is substituted by methylthio; 3-trimethylsilylphenyl, methoxy- nitrophenyl, 3- or 4- phenoxyphenyl, or 3-methylsulfinyl- or 3-methylsulfonyl methylphenyl which is optionally substituted by methoxy; 3-trifluoromethyl-4-chloro- benzyl, 3-trifluoro- methylphenoxymethyl, 3-trifluoromethylbenzoyl, 2-naphthyl, phenyl which is substituted in the 3- and 4-position by straight-chain C C 3 -alkylenedioxy (in particular methylenedioxy, ethylenedioxy, 2,2-difluoromethylenedioxy, 2-methoxy- methylenedioxy), dihydrobenzofur-5-yl, 2-thienyl, benzofur-2-yl, 2-furyl, 5-chloro- or 5-bromo-thien-2-yl, 3-methylbenzo[b]thien-2-yl, 1-methylpyrrol-2-yl, 2-thiazolyl, benzothien-2-yi, pyrazin-2-yl, 2-pyridyl which is unsubstituted or substituted by halogen or trifluoromethyl; 6- or 7-quinolinyl, 6-quinoxalinyl; substituted or unsubstituted 2-quinolinyl, substituted or unsubstituted 2-quinoxalinyl, 2-pyrimidinyl which is mono-to disubstituted by halogen, methyl, trifluoromethyl, cyclopropyl, C-|-C 3 alkoxy or methylthio; 1-(2,6-dimethylmorpholinyl), substituted or unsubstituted benzisoxazol-3-yl, substituted or unsubstituted benzisothiazol-3-yl, substituted or unsubstituted indazol-3-yl, or R 3 and R 4 together are a 5,6-dihydro-2H-1 ,4-thiazin ring which is substituted in the 3-position by substituted phenyl, or R 3 and R 4 together are a cyclopentane or tetrahydropyran ring to which an unsubstituted or halogen-substituted benzene ring is fused.
Within the scope of this group, preferred compounds are those in which the substitutents have the following meanings:
Ri = H, C 1 -C 2 alkyl,
R 2 = H, C 1 -C 4 alkyl,
R 3 = H, CτC 2 alkyl, cyclopropyl, methoxy, methylthio, methoxymethyl, cyano, trifluoromethyl
R = monohalophenyl, dihalophenyl, mono-C C 2 alkylphenyl, mono-C 1 -C alkoxy- phenyl, halomethoxyphenyl, 2-naphthyl, 3,4-methylenedioxyphenyl, 3,4-ethylene-
dioxyphenyl, 2,2-difluoro-5-benzodioxolyl, 2-methoxy-5-benzodioxolyl, 3-fluoro- C-|-C 2 alkoxyphenyl having 1-3 fluorine atoms, 3-trifluoromethylphenyl, 3,5-bis- (trifluoromethyl)phenyl, 4-fluoro-3-trifluoromethyiphenyl, 3-fluoro-5-trifluoro- methylphenyl, 4-chloro-3-trifluoromethylphenyl, 4-chloro-3-tolyl, monocyanophenyl, 3-cyanomethoxyphenyl, 2-methylthio-5-trifluoromethylphenyl, 4-methoxy-3- nitrophenyl, 3- or 4-phenoxyphenyl, 3-methylsulfinylmethyl-4-methoxyphenyl, 3-methylsulfonyl-4-methoxy-phenyl, 3-prop-1 -en-3-yloxyphenyl, 3-prop-1 -yn-3- yloxyphenyl, 3-cyciopropylmethoxyphenyl, 2,3-dihydrobenzofur-5-yl, 3-trifluoro- methyl-4-chlorobenzyl, 3-trifluoromethyl-phenoxymethyl, 2-pyridyl, 6-bromo-2-pyridyl, 4-trifluoromethyl-2-pyridyl, 6- or 7-quinolinyl, 6-quinoxalinyl, 2-thienyl, 5-chloro- or bromothien-2-yl, 3-methylbenzo[b]thien-2-yl, 2-furyl, benzo[b]fur-2-yl, 1-methylpyrrol-2-yl, 2-thiazolyl, 1-(2,6-dimethylmorpholinyl), benzothien-2-yl, pyrazin- 2-yl, 2-quinolinyl, 2-quinoxalinyl, 6-chloro-2-quinoxalinyl, 3-benzisoxazolyl, 3-benziso- thiazolyl and 1-methyl-3-indazolyl, it being possible in each case for a fused benzene ring to be mono or disubstituted; or
R 3 and R 4 together are a 5,6-dihydro-2H-1 ,4-thiazin ring which is subsituted in the 3-position by mono- or dihalophenyl, methoxyphenyl, trifluoromethylphenyl, phenoxy or 3,4-methylenedioxyphenyl, or R 3 and R 4 together are a cyclopentane or tetrahydropyran ring to which an unsubstituted or fluorine-substituted benzene ring is fused.
A special group within the scope of the formula I consists of compounds having the following meanings:
R 2 = methyl
R 3 = methyl, cyclopropyl
R 4 = 3-chlorophenyl, 3-trifluoromethylphenyl, 3-trifluoromethoxyphenyl, 3-difluoro- chloromethoxyphenyl or 4-chlorophenyl (sub-group Id).
The thioamide S-oxides according to the invention can be prepared from the corresponding thioamides by oxidation. Particularly suitable oxidants are peroxides or peracids, for example hydrogen peroxide, in, for example, glacial acetic acid.
Other methods can be found in Houben-Weyl, Vol. E5, p. 1272 (1985). Thioamides of the formula (II) have been disclosed by PCT Patent Application WO 94/26700 and can be prepared following the processes given therein.
The invention furthermore relates to a process for the preparation of the compounds of the formula I according to the invention, to pesticides which comprise such compounds as insecticidally, acaricidally, but in particular as fungicidally active ingredients, and to the use of such compounds and compositions for controlling noxious insects, pests from the order Acarina and, in particular, phytopathogenic fungi and for preventing fungus infestation.
It has now been found that compounds of the formula I which differ from benzyl oxime ethers known from the literature by, inter alia, the novel structural element of the formula j-, ave a microbicidal spectrum for controlling phytopathogenic microorganisms, in particular fungi, which is particularly advantageous for the practioner's requirements. They have very advantageous curative, preventive and, in particular, systemic properties and can be employed for protecting a large number of crop plants. Using the active ingredients of the formula I, the pests found on plants or parts of plants (fruits, flowers, foliage, stalks, tubers, roots) of a variety of crops of useful plants can be contianed or destroyed, and even parts of the plants which form at a later point in time remain free from phytopathogenic microorganisms.
The compounds of the formula I can furthermore be used as seed-dressing products for the treatment of seed (fruits, tubers, kernels) and propagation stock to protect these against fungal infection and against phytopathogenic soil-borne fungi.
Compounds of the formula I act for example against the phytopathogenic fungi which belong to the following classes: Fungi imperfecti (in particular Botrytis, furthermore Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora, Cercosporella and Alternaria); Basidiomycetes (for example Rhizoctonia, Hemileia, Puccinia). Moreover, they are active against the class of the Ascomycetes (for example Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula), but especially against the class of the Oomycetes (for example Phytophthora, Peronospora, Bremia, Pythium, Plasmopara).
A particular advantage of the compounds I in comparison with the analogous prior- art thioamide structures is a markedly Iower crop plant phytotoxicity and a favourable metastability which will have caused biodegradation of the compound at crop maturity at the lastest.
Target crops for the crop-protecting use disclosed herein are within the scope of the present invention for example the following plant species: cereals (wheat, barley, rye, oats, triticale, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomaceous fruit, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, gooseberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soya); oil crops (oil seed rape, mustard, poppies, olives, sunflowers, coconuts, castor, cocoa, groundnuts); cucurbits (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, tangerines); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, bell peppers); Lauraceae (avocado, Cinnamonium, camphor) or plants such as tobacco, nuts, coffee, sugar cane, tea, pepper and other spice plants, grape vines, hops, eggplants, Musaceae and latex plants, and ornamentals.
Active ingredients of the formula I are usually used in the form of compositions and can be applied to the plant or area to be treated simultaneously or in succession with other active ingredients. These other active ingredients can be fertilizers, trace element mediators or other preparations which affect plant growth. Selected herbicides, and insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of a plurality of these preparations, if desired together with other carriers,
surfactants or other application-enhancing additives conventionally used in the art of formulation may also be used.
Suitable carriers and additives can be solid or liquid and are the substances expediently used in the art of formulation, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.
The following are suitable as solvents: aromatic hydrocarbons, preferably the fractions C 8 to C 12 , for example xylene mixtures or substituted naphthalenes, phthalic esters such as dibutyl phthalate or dioctylphthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and free or • epoxidized vegetable oils, such as epoxidized coconut oil or soya oil; or water.
Solid carriers which are used for example for dusts and dispersible powders are, as a rule, ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite.
Particularly advantageous application-enhancing additives which may lead to a drastic reduction in application rate are furthermore natural (animal or vegetable) or synthetic phosphoiipids from the series of the cephalins and lecithins which can be obtained, for example, from soybeans.
Surface-active compounds are, depending on the nature of the active ingredient of the formula I to be formulated, non-ionic, cationic and/or anionic surfactants which have good emulsifying, dispersing and wetting properties. Surfactants are also to be understood as meaning surfactant mixtures.
Suitable anionic surfactants can be either so-called water-soluble soaps or water¬ soluble synthetic surface-active compounds.
Suitable soaps which may be mentioned are the alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts of higher fatty acids (C 10 - C 22 ), for example the sodium or potassium salts of oleic or stearic acid, or of natural
fatty acid mixtures which can be obtained, for example, from coconut oil or tallow oil. Fatty acid methyltaurides may furthermore be mentioned.
Suitable non-ionic surfactants are polyglycoi ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.
Examples of non-ionic surfactants which may be mentioned are nonylphenol polyethoxyethanols, castor oil polyglycoi ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethyleneglycol and octylphenoxypolyethoxyethanol.
Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate, are also suitable.
The cationic surfactants are mainly quaternary ammonium salts which have, as N-substituent, at least one alkyl radical having 8 to 22 C atoms and, as further substituents, Iower, free or halogenated alkyl, benzyl or Iower hydroxyalkyl radicals.
The anionic, non-ionic or cationic surfactants conventionally used in the art of formulation are known to those skilled in the art or can be found in the relevant specialist literature:
"Mc Cutcheon's Detergents and Emulsifiers Annual", Mc Publishing Corp., Glen Rock, New Jersey, 1988.
M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-1981.
Dr. Helmut Stache "Tensid-Taschenbuch", [Surfactants Guide], Carl Hanser Verlag, Munich/Vienna 1981.
As a rule, the agrochemical preparations comprise from 0.1 to 99 %, in particular 0.1 to 95 %, of active ingredient of the formula I, 99.9 to 1 %, in particular 99.9 to 5 %, of a solid or liquid additive and 0 to 25 %, in particular 0.1 to 25 %, of a surfactant.
While concentrated compositions are more preferred as commercially available goods, the end user uses, as a rule, dilute compositions.
The compositions can also comprise other additives such as stabilizers, antifoams, viscosity regulators, binders, adhesives and fertilizers, or other active ingredients for achieving specific effects.
The formulations, i.e. the compositions, preparations or combinations comprising the active ingredient of the formula I and, if desired, a solid or liquid additive, are prepared in a known manner, for example by intimately mixing and/or grinding the active ingredient with an extender, for example a solvent (mixture), a solid carrier material, and, if desired, surface-active compounds (surfactants).
A preferred method of applying an active ingredient of the formula I, or an agrochemical composition which comprises at least one of these active ingredients, is application to the foliage (foliar application). Frequency and rate of application depend on the danger of infestation with the pathogen in question. Alternatively, the active ingredients of the formula I can reach the plant via the soil through the root system (systemic action) by drenching the locus of the plant with a liquid preparation or by incorporating the substances into the soil in solid form, for example in the form of granules (soil application). In the case of paddy rice, such granules can be metered into the flooded paddy field. Alternatively, the compounds of the formula I can be applied to seed kernels (coating), either by soaking the kernels in a liquid preparation of the active ingredient or by coating them with a solid preparation. In principle, any type of plant propagation material can be protected using the compounds of the formula I, for example the seed, roots or stalk.
The compounds of the formula I are employed as pure active ingredients or, preferably, together with the auxiliaries conventionally used in the art of formulation. To this end, they are expediently processed in a manner known per se, for example to give emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or encapsulations for example in polymeric substances. The methods of application, such as spraying, atomizing, dusting, scattering, brushing on or pouring, and the type of composition are selected to suit the intended aims and the prevailing circumstances. Favourable rates of application are generally 5 g to 2 kg of active ingredient (a.i.) per ha, preferably 25g to 800g of a.i./ha, particularly preferably 50g to 400g of a.i./ha. When used as a seed-dressing product, it is advantageous to use dosage rates of from 0.001 g to 1.0g of active ingredient per kg of seed.
The examples which follow are intended to illustrate the invention in greater detail without imposing any limitation.
Preparation examples
H-1. Preparation of the compound
30 g of sodium acetate are added to a yellow solution of 43.95 g of N-methyl-2-[2- (methyl(3-trifluoromethoxyphenyl)oximinomethyl)phenyl]-2- methoximinothioacetamide in 300 ml of acetic acid. 10.2 ml of hydrogen peroxide (30 %) are added dropwise to this solution at 22°C in the course of 1 minute. After a brief induction period, a reaction commences, the reaction temperature rising to approximately 35°C after 10 minutes. After 30 minutes, a further 1 ml of hydrogen peroxide (30 %) is added, whereupon a fine precipitate is formed. After 50 minutes, the reaction mixture is carefully stirred into 4.3 litres of saturated sodium bicarbonate solution (5°C). The weakly basic yellow suspension is extracted three times using 600 ml of ethyl acetate. The combined organic extracts are washed twice using 100 ml of bicarbonate solution (10 %) and twice using 100 ml of water. After the solvent has been evaporated on a Rotavap evaporator, the dark oil obtained is dissolved by stirring in 80 ml of tert-butyl methyl ether, 80 ml of hexane are then added, and the product is brought to crystallization. After the mixture has been stirred for 1 hour, the crystals are filtered off with suction and washed using 20 ml of cold tert-butyl methyl ether/hexane (1 :1). This gives N-methyl-2-[2-(methyl(3-trifluoro- methoxyphenyl)oximinomethyl)phenyl]-2-methoximinothioacetami de S-oxide of m.p. 88-89°C.
The following compounds are also obtained in the same manner or analogously:
Table 1
Ex. No. i R 2 R3 R 4 Phys. data
1.1 H H Me 3-chlorophenyl
1.2 Me Me Me 3-chlorophenyl
1.3 H H Me 4-chlorophenyl m.p. 154°C
1.4 Me Me Me 4-chlorophenyl
1.5 Me Et Me 4-chlorophenyl
1.6 H H cyclopropyl 4-chlorophenyl
1.7 H H Me 3-trifluoromethylphenyl m.p. 125°C
1.8 Me Me Me 3-trifluoromethylphenyl Oil
1.9 Me Et Me 3-trifluoromethylphenyl Oil
1.10 Et Et Me 3-trifluoromethylphenyl Oil
1.11 H allyl Me 3-trifluoromethylphenyl
1.12 H propargyl Me 3-trifluoromethylphenyl
1.13 H cyclopropyl Me 3-trifluoromethylphenyl
1.14 H H Me 3-trifluoromethoxyphenyl
1.15 H H Et 3-trifluoromethoxyphenyl
1.16 Me Me Me 3-trifluoromethoxyphenyl
1.17 Me Et Me 3-trifluoromethoxyphenyl
Table 2
Ex. No. R 3 R 4 Phys. Data
2.1 Me phenyl
2.2 H 2-fluorophenyl
2.3 Me 2-fluorophenyl
2.4 Me 3-fluorophenyl
2.5 Me 4-fluorophenyl
2.6 cyclopropyl 4-fluorophenyl
2.7 Me 2-chlorophenyl
2.8 Me 3-chlorophenyl
2.9 H 4-chlorophenyl
2.10 Me 4-chlorophenyl m.p. 145°C
2.11 cyclopropyl 4-chlorophenyl
2.12 CH 3 S 4-chlorophenyl
2.13 CH 3 0 4-chlorophenyl
2.14 CH3OCH2 4-chlorophenyl
2.15 CH2SCH2 4-chlorophenyl
2.16 CF 3 4-chlorophenyl
2.17 CN 4-chlorophenyl
2.18 Et 4-chlorophenyl
2.19 propyl 4-chlorophenyl
2.20 i-propyl 4-chlorophenyl
2.21 Me 2-bromophenyl
2.22 Me 3-bromophenyl
2.23 Me 4-bromophenyl
2.24 cyclopropyl 4-bromophenyl
Ex. No. R 3 R 4 Phys. Data
2.25 Me 2,4-difluorophenyl
2.26 Me 3,4-difluorophenyl
2.27 Me 2,3-difluorophenyl
2.28 Me 3,4-difluorophenyl
2.29 Me 2,5-difluorophenyl
2.30 Me 3,5-difluorophenyl
2.31 Me 2,4-dichlorophenyl
2.32 Me 3,4-dichlorophenyl
2.33 Me 2,5-dichlorophenyl
2.34 Me 3,5-dichlorophenyI
2.35 Me 3-CI,4-F-phenyl
2.36 Me 4-CI,2-F-phenyl
2.37 Me 2,3,4-trifluorophenyl
2.38 Me 2,3,6-trifluorophenyl
2.39 Me 2,4,6-trifluorophenyl
2.40 Me 2,4,5-trifluorophenyI
2.41 Me 2,3,4-trichlorophenyl
2.42 Me 3,4,5-trichlorophenyl
2.43 Me 2,4,5-trichlorophenyl
2.44 Me 1 -naphthyl
2.45 Me 2-naphthyl
2.46 cyclopropyl 2-naphthyl
2.47 Me 2-methylphenyl
2.48 Me 3-methylphenyl
2.49 Me 4-methylphenyl
2.50 cyclopropyl 4-methylphenyl
2.51 Me 2,3-dimethylphenyl
2.52 Me 2,4-dimethylphenyl
2.53 Me 2,5-dimethyIphenyl
2.54 Me 3,4-dimethylphenyl
2.55 Me 3,5-dimethylphenyl
2.56 Me 2-methoxyphenyl
2.57 Me 3-methoxyphenyl
Ex. No. R 3 R4 Phys. Data
2.58 Me 4-methoxyphenyl Oil
2.59 Me 3,4-dimethoxyphenyl Oil
2.60 Me 3,5-dimethoxyphenyl
2.61 Me 3,4-methylenedioxyphenyl
2.62 cyclopropyl 3,4-methylenedioxyphenyl
2.63 SMe 3,4-methylenedioxyphenyl
2.64 OMe 3,4-methylenedioxyphenyl
2.65 Me 3,4-ethylenedioxyphenyl
2.66 cyclopropyl 3,4-ethylenedioxyphenyl
2.67 Me 2,2-difluoro-5-benzodioxolyl
2.68 Et 2,2-difluoro-5-benzodioxolyl
2.69 Me 3-difluoromethoxyphenyl
2.70 Me 4-difluoromethoxyphenyl
2.71 Me 3-difluorobromomethoxyphenyl
2.72 Me 3-difluorochloromethoxyphenyl
2.73 Me 3-(2,2,2-trifluoroethoxy)phenyl
2.74 Me 3-(1 ,1 ,2,2-tetrafluoroethoxy)phenyl
2.75 Me 3-(1 ,1 ,2,3,3,3-hexafluoropropoxy)phenyl
2.76 Me 4-(2,2,2-trifluoroethoxy)phenyl
2.77 Me 4-(1 ,1 ,2,2-tetrafluoroethoxy)phenyl
2.78 Me 3-(1 ,1 ,2,2- tetrafluorobromoethoxy)phenyl
2.79 H 3-trifluoromethoxyphenyl
2.80 Me 3-trifiuoromethoxyphenyl m.p. 89-90°C
2.81 Et 3-trifluoromethoxyphenyl m.p. 88-91 °C
2.82 cyclopropyl 3-trifluoromethoxyphenyl
2.83 CN 3-trifluoromethoxyphenyl
2.84 OMe 3-trifluoromethoxyphenyl
2.85 SMe 3-trifluoromethoxyphenyl
2.86 CH 2 OMe 3-trifluoromethoxyphenyl
2.87 Me 2-trifluoromethylphenyl
2.88 Me 4-trifiuoromethylphenyl
2.89 H 3-trifluoromethylphenyl
Ex. No. R 3 R 4 Phys. Data
2.90 Me 3-trifluoromethylphenyl m.p. 122°C
2.91 Et 3-trifluoromethylphenyl
2.92 cyclopropyl 3-trifluoromethylphenyl
2.93 CN 3-trifluoromethylphenyl
2.94 OMe 3-trifluoromethylphenyl
2.95 SMe 3-trifluoromethylphenyl
2.96 CH 2 OMe 3-trifluoromethylphenyl
2.97 Me 3,5-bis(trifluoromethyl)phenyl
2.98 Me 4-F,3-CF 3 -phenyl
2.99 cyclopropyl 4-F,3-CF 3 -phenyl
2.100 Me 2-CI,5-CF 3 -phenyl
2.101 Me 3-acetylphenyl
2.102 Me 4-acetylphenyl
2.103 Me 3-carboxyphenyl
2.104 Me 4carboxyphenyl
2.105 Me 3-carbethoxyphenyl
2.106 Me 4-carbethoxyphenyl
2.107 Me 2-cyanophenyl
2.108 Me 3-cyanophenyl
2.109 Me 4-cyanophenyl
2.110 Me 3-OCN-phenyl
2.111 Me 4-OCN-phenyl
2.112 Me 3-cyanomethylphenyl
2.113 Me 4-cyanomethylphenyl
2.114 Me 3-cyanomethoxyphenyl
2.115 Me 4-cyanomethoxyphenyl
2.116 Me 4-cyclohexyIphenyl
2.117 Me 4-biphenylyl
2.118 Me 2-fluorenyl
2.119 Me 3-benzyloxyphenyl
2.120 Me 4-benzyloxyphenyl
2.121 Me 3,5-dibenzyloxyphenyl
2.122 Me 4-bromo-2-fluorophenyl
Ex. No. R 3 R 4 Phys. Data
2.123 Me 4-bromo-3-methylphenyl
2.124 Me 6-(2,2-difluoro-1 ,4-benzodioxanyl)
2.125 Me 6-(2,2,3-trifluoro-1 ,4-benzodioxanyl)
2.126 Me pentafluorophenyl
2.127 Me 3-F,5-CF 3 -phenyl
2.128 Me 3-OMe,5-CF 3 -phenyl
2.129 Me 3-N0 2 ,5-CF 3 -phenyl
2.130 Me 4-Br,3-CF 3 -phenyl
2.131 Me 4-tert-butylphenyl
2.132 Me 4-sec-butylphenyl
2.133 Me 4-butylphenyl
2.134 Me 4-butoxyphenyl Oil
2.135 Me 3-F,4-OMe-phenyl Oil
2.136 Me 3-CI,4-OMe-phenyl
2.137 Me 3-CI,4-Me-phenyl
2.138 Me 4-CI,2-Me-phenyl
2.139 Me 4-CI,3-Me-phenyl
2.140 Me 5-Cl,2-Me-phenyl
2.141 Me 4-CI,3-N0 2 -phenyl
2.142 Me 5-indanyl
2.143 Me 3,5-dinitrophenyl
2.144 Me 2-nitrophenyl
2.145 Me 3-nitrophenyl
2.146 Me 4-nitrophenyl
2.147 Me 2-ethylphenyl
2.148 Me 3-ethylphenyl
2.149 Me 4-ethylphenyl
2.150 Me 3-ethoxyphenyl
2.151 Me 4-ethoxyphenyl Oil
2.152 Me 4-ethynylphenyl
2.153 Me 4-propylphenyl
2.154 Me 4-isopropylphenyl
2.155 Me 4-propyn-1 -yl
Ex. No. R 3 R 4 Phys. Data
2.156 Me 3-F,4-CH 3 -phenyl
2.157 Me 4-F,3-N0 2 -phenyl
2.158 Me 4-CI,3-CF 3 -phenyl
2.159 Me 3-hydroxyphenyl
2.160 Me 4-hydroxyphenyl
2.161 Me 3-hydroxy-4-methoxyphenyl
2.162 Me 4-hydroxy-3-methylphenyl
2.163 Me 4-hydroxy-3-nitrophenyl
2.164 Me 4-isopropylphenyl
2.165 Me 3-iodophenyl
2.166 Me 4-iodophenyl
2.167 Me 3-mercaptophenyl
2.168 Me 4-mercaptophenyl
2.169 Me 3-SFs-phenyl
2.170 Me 4-SF 5 -phenyl
2.171 Me 2-(NH 2 C (S))-phenyl
2.172 Me 3-(NH 2 C(S))-phenyl
2.173 Me 4-(NH 2 C(S))-phenyl
2.174 Me 3-methylmercaptophenyl
2.175 Me 4-methylmercaptophenyl
2.176 Me 2-methylthio-5-CF 3 -phenyl
2.177 Me 4-CH 3 ,3-N0 2 -phenyl
2.178 Me 4-CH 3 ,2-N0 2 -phenyl
2.179 Me 2-CH 3 ,4-N0 2 -phenyl
2.180 Me 2-CH 3 ,5-N0 2 -phenyl
2.181 Me 4-methoxy,3-N0 2 -phenyl
2.182 Me 4-(4-morpholino)phenyl
2.183 Me 3-phenoxyphenyl
2.184 Me 4-phenoxyphenyl
2.185 Me 3-methanesulfinylmethyl-4-OMe-phenyl
2.186 Me 4-sulfamoylphenyl
2.187 Me 4-OMe,3-CH 3 SCH 2 -phenyl
2.188 Me 3-trifluoromethylsulfonylphenyl
Ex. No. R 3 RA Phys. Data
2.189 Me 3-thiocyanophenyl
2.190 Me 4-thiocyanophenyl
2.191 Me 3-thiocyanomethylphenyl
2.192 Me 4-thiocyanomethylphenyl
2.193 Me 3-prop-1 -en-3-yloxyphenyl
2.194 Me 3-prop-1 -yn-3-yloxyphenyl
2.195 Me 2-cyclopropylmethoxyphenyl
2.196 Me 2,3,4,5-tetrafluorophenyl
2.197 Me 2,3,5,6-tetrafluorophenyl
2.198 Me 2,3,4-trimethoxyphenyl
2.199 Me 5,6,7,8-tetrahydro-1 -naphthyl
2.200 Me 2,3-dihydrobenzofur-5-yl
2.201 Me 2,3-dihydrobenzofur-6-yl
2.202 Me 3-trimethylsilylphenyl
2.203 Me 4-trimethylsilylphenyl
2.204 Me benzyl
2.205 Me 3-CF 3 -benzyl
2.206 Me 4-chlorobenzyl
2.207 Me 3-CF 3 ,4-chlorobenzyl
2.208 cyclopropyl 3-CF 3 ,4-chlorobenzyl
2.209 Me phenoxymethyl
2.210 Me 3-chlorophenoxymethyl
2.211 Me 3-CF 3 -phenoxymethyl
2.212 Me 2-methoxy-5-benzodioxolyl
2.213 Me 2-methyl-5-benzodioxolyl
2.214 Me 2-phenyl-5-benzodioxolyl
2.215 Me 3-methoxycarbonylphenyl
2.216 Me 4-methoxycarbonylphenyl
2.217 Me 3-methoximinomethylphenyl
2.218 Me 3-ethoximinomethylphenyl
2.219 Me 4-methoximinomethylphenyl
2.220 Me 2-pyrazinyl
2.221 Me 5-chloro-2-pyrazinyl
Ex. No. R 3 R 4 Phys. Data
2.222 Me 3,5-dimethylpyrazin-2-yl
2.223 Me 3-ethoxypyrazin-2-yl
2.224 Me 5-CONHCH 3 -pyrazin-2-yl
2.225 Me 2-pyrimidinyl
2.226 Me 4-pyrimidinyl
2.227 Me 4-chloropyrimidin-2-yl
2.228 Me 4-ethoxypyrimidin-2-yl
2.229 Me 4-methoxypyrimidin-2-yl
2.230 Me 4-(2,2,2-trifluoroethoxy)pyrimidin-2-yl
2.231 Me 2-SCH 3 -pyrimidin-4-yl
2.232 Me 4-isopropoxypyrimidin-2-yl
2.233 Me 4,6-dimethylpyrimidin-2-yl
2.234 Me 4-Me,6-cyclopropylpyrimidin-2-yl
2.235 Me 4,6-diethoxypyrimidin-2-yl
2.236 Me 4-Me,6-OMe-pyrimidin-2-yl
2.237 Me 4-Me,6-CF 3 -pyrimidin-2-yl
2.238 Me 2-pyridyl
2.239 Me 3-pyridyl
2.240 Me 4-pyridyl
2.241 Me 5,6-dichloro-3-pyridyl
2.242 Me 2,6-dichloro-4-pyridyl
2.243 Me 2-chloro-3-pyridyl
2.244 Me 5-chloro-3-pyridyl
2.245 Me 6-chloro-3-pyridyl
2.246 Me 2-chloro-4-pyridyl
2.247 Me 2-quinolinyl
2.248 Me 6-quinolinyl
2.249 Me 7-quinolinyl
2.250 Me 5-lsoquinolinyl
2.251 Me 2-benzimidazolyl
2.252 Me 2-benzoxazolyl
2.253 Me 2-benzothiazolyl
2.254 Me 3,4-benzocoumarin-6-yl
Ex. No. R 3 R 4 Phys. Data
2.255 Me 2-thienyl
2.256 Me 2-benzothienyl
2.257 Me 3-methylbenzo(b)thien-2-yl
2.258 Me 5-chlorothien-2-yl
2.259 Me 5-bromothien-2-yl
2.260 Me 2-methoxycarbonyl-3-thienyl
2.261 Me 2-furyl
2.262 Me benzo(b)fur-2-yl
2.263 Me benzo(b)fur-3-yl
2.264 Me 1 -methylpyrrol-2-yl
2.265 Me 4-methylthien-2-yl
2.266 Me 5-methylfur-2-yl
2.267 Me 6-bromo-2-pyridyl
2.268 Me 4-trifluoromethyl-2-pyridyl
2.269 Me 4-ethoxypyrimidin-2-yl
2.270 Me 5-chloro-2-pyridyl
2. 271 Me 5-bromo-2-pyridyl
2.272 Me 6-trifluoromethyl-2-pyridyl
2.273 Me 6-quinoxalinyl
2.274 Me 2-quinoxaIinyl
2.275 Me 6-chloro-2-quinoxalinyl
2.276 Me 2-thiazolyl
2.277 Me 5-trifluoromethyl-2-pyridyl
2.278 Me 2,1 ,3-benzothiadiazol-5-yl
2.279 Me 2,1 ,3-benzoxadiazol-5-yl
2.280 Me 5-methylisoxazol-3-yl
2.281 Me 4-methyl-1 ,2,3-thiadiazol-5-yl
2.282 Me 3-benzisoxazolyl m.p. 162°C
2.283 Me 4-fluoro-3-benzisoxazolyl
2.284 Me 5-fluoro-3-benzisoxazolyl
2.285 Me 6-fluoro-3-benzisoxazolyl
2.286 Me 7-fluoro-3-benzisoxazolyl
2.287 Me 5-chloro-3-benzisoxazolyl
Ex. No. R 3 R 4 Phys. Data
2.288 Me 6-chloro-3-benzisoxazolyl
2.289 Me 5-methyl-3-benzisoxazolyl
2.290 Me 6-methyl-3-benzisoxazolyl
2.291 Me 7-methyl-3-benzisoxazolyl
2.292 Me 5-CF 3 -3-benzisoxazolyl
2.293 Me 6-CF 3 -3-benzisoxazolyl
2.294 Me 5-methoxy-3-benzisoxazolyl
2.295 Me 6-methoxy-3-benzisoxazolyl
2.296 Me 3-benzisothiazolyl
2.297 Me 4-fluoro-3-benzisothiazolyl
2.298 Me 5-fluoro-3-benzisothiazolyl
2.299 Me 6-fluoro-3-benzisothiazolyl
2.300 Me 7-fluoro-3-benzisothiazolyl
2.301 Me 5-chloro-3-benzisothiazolyl
2.302 Me 6-chloro-3-benzisothiazolyl
2.303 Me 5-methy-3-benzisothiazolyll
2.304 Me 6-methyl-3-benzisothiazolyl
2.305 Me 7-methyl-3-benzisothiazolyl
2.306 Me 5-CF 3 -3-benzisothiazolyl
2.307 Me 6-CF 3 -3-benzisothiazolyl
2.308 Me 5-methoxy-3-benzisothiazolyl
2.309 Me 6-methoxy-3-benzisothiazolyl
2.310 Me 1-methyl-3-indazolyl
2.311 Me 1 -methyl-4-fluoro-3-indazolyl
2.312 Me 1 -methyl-5-fluoro-3-indazolyl
2.313 Me 1 -methyl-6-fluoro-3-indazolyl
2.314 Me 1 -methyl-7-fluoro-3-indazolyl
2.315 Me 1 -methyl-5-chloro-3-indazolyl
2.316 Me 1 -methyl-6-chloro-3-indazolyl
2.317 Me 1 ,5-dimethyl-3-indazolyl
2.318 Me 1 ,6-dimethyl-3-indazolyl
2.319 Me 1 -methyl-5-CF 3 -3-indazolyl
2.320 Me 1 -methyl-6-CF 3 -3-indazolyl
Ex. No. R 3 R 4 Phys. Data
2.321 Me 1 -methyl-5-methoxy-3-indazolyl
2.322 Me 1 -methyl-6-methoxy-3-indazolyl
2.323 Me isoxazolo(4,5-b)-3-pyridyl
2.324 Me isoxazolo(4,5-c)-3-pyridyl
2.325 Me isoxazolo(5 ,4-b)-3-pyridyl
2.326 Me isoxazolo(5,4-c)-3-pyridyl
2.327 Me 4-CN-2-pyridyl
2.328 Me 5-bromo-3-pyridyl
2.329 Me 6-methyl-3-pyridyl
2.330 Me 1 -moφholinyl
2.331 Me 1 -(2,6-dimethylmoφholinyl)
2.332 Me 1 -(2-mefhylmoφholinyl)
2.333 Me 1 -piperidinyl
2.334 Me 1 -piperazinyl
2.335 Me methyl
2.336 Me ethyl
2.337 Me propyl
2.338 Me isopropyl
2.339 Me cyclopropyl
2.340 cyclopropyl cyclopropyl
2.341 Me ethoxy
2.342 Me methylthio
2.343 CN 2-methoxyprop-2-yl
2.344 Me 2-n-butoxyprop-2-yl
2.345 CN 2-methylthioprop-2-yl
2.346 CN isopropyl
2.347 CN cyclopropyl
2.348 CN phenyl
2.349 CN 2-n-propoxyprop-2-yl
2.350 cyclopropyl 4-methoxyphenyl
2.351 Me 4-propoxyphenyl
2.352 Me 4-isopropoxyphenyl
2.353 Me 4-sec-butoxyphenyl
2. Formulation examples for active ingredients of the formula I (% = per cent by weight
2.1. Wettable powders a) b) c)
Active ingredient from Tables 1-2 25 % 50 % 75 % Sodium lignosulfonate 5 % 5 % -
Sodium lauryl sulfate 3 % - 5 %
Sodium diisobutylnaphthalenesulfonate - 6 % 10 % Octylphenol polyethylene glycol ether 2 % - (7-8 mol of ethylene oxide) Highly-disperse silica 5 % 10 % 10 %
Kaolin 62 % 27 % .
The active ingredient is mixed thoroughly with the additives and the mixture is ground thoroughly in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.
2.2. Emulsion concentrate
Active ingredient from Tables 1-2 25 %
Castor oil (36 mol of ethylene oxide, 6 % alcohol-free)
Calcium dodecyl benzenesulfonate 4 %
(alcohol-free)
Cyclohexanone 5 %
Soya oil (39 mol of ethylene oxide) 5 %
Triethanolamine 5 %
Xylene/toluene mixture 50 %
Emulsions of any desired dilution can be prepared from this concentrate by diluting it with water.
2.3. Dusts a) b)
Active ingredient from Tables 1-2 5 % 8 %
Talc 95 %
Kaolin - 92 %
Ready-to-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill.
2.4. Wettable powder d) Active ingredient from Tables 1-2 25 % Sodium lignosulfonate 5 % Kieselguhr 25 % Na 2 C0 3 5 % Disodiuml -benzyl-2-heptadecyl- benzimidazol-X,X'-disulfonate
(incl. 15-30 % Na 2 S0 4 ) 5 %
Champagne limestone 35 %
The active ingredient is mixed with the additives, and the mixture is ground and moistened with water. This mixture is extruded and subsequently dried in a stream of air.
2.5. Coated granules
Active ingredient from Tables 1 -2 3 %
Polyethylene glycol (MW 200) 3 %
Kaolin 94 % (MW = molecular weight)
In a mixer, the finely ground active ingredient is applied uniformly to the kaolin which has been moistened with polyethylene glycol. This gives dust-free coated granules.
--.9—
2.6. Suspension concentrate
Active ingredient from Tables 1 -2 40 %
Ethylene glycol 10 %
Nonylphenol polyethylene glycol ether 6 %
(15 mol of ethylene oxide)
Sodium lignosulfonate 10 %
Carboxymethylcellulose 1 %
37% aqueous formaldehyde solution 0.2 %
Silicone oil in the form of a 75% aqueous emulsion 0.8 %
Water 32 %
The finely ground active ingredient is mixed intimately with the additives. This gives a suspension concentrate from which suspensions of any desired dilution can be prepared by diluting it with water.
3. Biological examples
In Examples B-1 to B-15 which follow, active ingredients according to the invention are very effective against fungus infestation.
Example B-1 : Activity against Phytophthora infestans in tomatoes
a) Curative action
Tomato plants cv. "Roter Gnom" are grown for three weeks and then sprayed with a zoospore suspension of the fungus and incubated in a cabin at 18 to 20° and saturated atmospheric humidity. The humidification is interrupted after 24 hours. After the plants have dried, they are sprayed with a mixture which comprises the active ingredient, formulated as a wettable powder, at a concentration of 200 ppm. After the spray coating has dried on, the plants are returned into the humid chamber for 4 days. Number and size of the typical foliar lesions which have formed after this time are used as an assessment scale for the efficacy of the test substances.
b) Preventive-systemic action
The active ingredient, formulated as a wettable powder, is applied at a concentration of 60 ppm (based on the soil volume) to the soil surface of three-week-old tomato plants cv. "Roter Gnom" in pots. After a waiting period of three days, the underside of the leaves is sprayed with a zoospore suspension of Phytophthora infestans. They are then kept for 5 days in a spray cabinet at 18 to 20°C and saturated atmospheric humidity. After this time, typical foliar lesions are formed, whose number and size are used to assess the efficacy of the test substances.
While untreated, but infected control plants show an infestation level of 100%, the use of the active ingredients of the formula I as shown in one of Tables 1 or 2 reduces the infestation level in both tests to 20% or less. A particularly sustained activity is shown by compounds of sub-group Ib.
Example B-2: Activity against Plasmopara viticola (Bert, et Curt.) (Berl. et DeToni) in grapevines
a) Residual-preventive action
Grapevine cuttings cv. "Chasselas" are grown in the greenhouse. Three plants in the 10- leaf stage are sprayed with a mixture (200 ppm of active ingredient). After the spray coating has dried on, the plants are infected uniformly on the underside of the leaves with the spore suspension of the fungus. The plants are subsequently kept in a humid chamber for 8 days. After this time, the control plants show marked disease symptoms. Number and size of the infection sites in the treated plants are used as an assessment scale for the efficacy of the test substances.
b) Curative action
Grapevine cuttings cv. "Chasselas" are grown in the greenhouse and, in the 10-leaf stage, infected on the underside of the leaves with a spore suspension of Plasmopara viticola. After the plants have remained in a humid chamber for 24 hours, they are sprayed with a mixture of the active ingredient (200 ppm of active ingredient). The plants are subsequently kept for a further 7 days in the humid chamber. After this time, the disease symptoms
emerge on the control plants. Number and size of the infection sites in the treated plants are used as an assessment scale for the efficacy of the test substances. In comparison with the control plants, the plants which have been treated with active ingredients of the formula I show an infestation level of 20 % or less. A particularly sustained activity is shown by the compounds No. 2.58, 2.151 and others.
Example B-3: Activity against Pythium debaryanum in sugar beet (Beta vulgaris)
a) Action following soil application
The fungus is grown on sterile oat kernels and admixed with a soil/sand mixture. This infected soil is filled into floweφots, and sugar beet seeds are sown. Immediately after sowing, the test preparations, formulated as wettable powders, are poured on the soil in the form of an aqueous suspension (20 ppm of active ingredient based on the soil volume). The pots are then placed in a greenhouse at 20-24°C for 2-3 weeks. The soil is always kept uniformly moist by gently spraying on water. When evaluating the tests, the emergence of the sugar beet plants and the proportion of healthy and diseased plants are determined.
b) Action following seed-dressing
The fungus is grown on sterile oat kernels and admixed with a soil/sand mixture. This infected soil is filled into flowerpots, and sugar beet seeds are sown which had been treated with the test preparations formulated as seed-dressing powders (1000 ppm of active ingredient based on the weight of the seeds). The pots together with the seeds are placed in a greenhouse at 20-24°C for 2-3 weeks. The soil is kept uniformly moist by gently spraying on water.
In the evaluation, the emergence of the sugar beet plants and the proportion of healthy and diseased plants are determined.
After treatment with active ingredients of the formula I, over 80% of the plants emerge and are healthy in appearance. In the control pots, only a few plants with diseased appearance were observed. Particularly good effects were shown by compounds of sub-group Ib.
Example B-4: Residual-protecive action against Cercospora arachidicola in groundnuts Groundnut plants 10 to 15 cm in height are sprayed to drip point with an aqueous spray mixture (0.02% of active ingredient) and, 48 hours later, infected with a conidia suspension
of the fungus. The plants are incubated for 72 hours at 21 ° and high atmospheric humidity and subsequently placed in a greenhouse until the typical foliar lesions appear. The activity of the active ingredient is assessed 12 days after infection basd on the number and size of the foliar lesions.
Active ingredients of the formula I cause a reduction in foliar lesions to below approximately
10% of the leaf area. In some cases, the disease is contained completely (0-5% infestation level).
Example B-5: Activity against Puccinia graminis in wheat a) Residual-protective action
6 days after sowing, wheat plants are sprayed to drip point with an aqueous spray mixture (0.02% of active ingredient) and, 24 hours later, infected with a uredospore suspension of the fungus. After an incubation time of 48 hours (conditions: 95 to 100 per cent relative atmospheric humidity at 20°), the plants are placed in a greenhouse at 22°. The rust pustule development is assessed 12 days after infection.
b) Systemic action
5 days after sowing, an aqueous spray mixture (0.006% of active ingredient based on the soil volume) is poured next to wheat plants. Care is taken that the spray mixture does not come into contact with aerial parts of the plants. 48 hours later, the plants are infected with a uredospore suspension of the fungus. After an incubation time of 48 hours (conditions: 95 to 100 per cent relative atmospheric humidity at 20°), the plants are placed in a greenhouse at 22°. The rust pustule development is assessed 12 days after infection. Compounds of the formula I cause a marked reduction in fungus infestation, in some cases down to 10-0%, for example the compounds No. 2.80, 2.82, 2.83, 2.90 and others.
Example B-6: Activity against Pyricularia oryzae in rice a) Residual-protective action
Rice plants are grown for two weeks and then sprayed to drip point with an aqueous spray mixture (0.02% of active ingredient) and, 48 hours later, infected with a conidia suspension of the fungus. The fungus infestation is assessed 5 days after the infection, during which a relative atmospheric humidity of 95 to 100 percent and a temperature of 22° are maintained.
b) Systemic action
An aqueous spray mixture (0.006% of active ingredient based on the soil volume) is poured next to rice plants which are 2 weeks old. Care is taken that the spray mixture-does not come into contact with aerial parts of the plants. The pots are then filled with water to such an extent that the bottommost parts of the rice plant stalks are submerged. After 96 hours, the plants are infected with a conidia suspension of the fungus and kept for 5 days at a relative atmospheric humidity of 95 to 100 percent and a temperature of 24°C.
To a large extent, compounds of the formula I prevent the onset of the disease in the infected plants. Particularly marked effects are achieved with the compounds No. 2.80,
2.83, 2.90 and others.
Example B-7: Residual-protective action against Venturia inaequalis in apples
Apple cuttings having fresh shoots 10 to 20 cm in length are sprayed to drip point with a spray mixture (0.02% of active ingredient) and, 24 hours later, infected with a conidia suspension of the fungus. The plants are incubated for 5 days at a relative atmospheric humidity of 90 to 100 percent and for a further 10 days in a greenhouse at 20 bis 24°. The scab infestation is assessed 15 days after infection.
Most of the compounds of the formula I from one of Tables 1 or 2 have a sustained action against scab diseases.
Example B-8: Activity against Erysiphe graminis in barley a) Residual-protective action
Barley plants approximately 8 cm in height are sprayed to drip point with an aqueous spray mixture (0.02% of active ingredient) and, 3 to 4 hours later, dusted with conidia of the fungus. The infected plants are placed in a greenhouse at 22°. Fungus infestation is assessed 10 days after the infection.
b) Systemic action
An aqueous spray mixture (0.002% of active ingredient, based on the soil volume) is poured next to barley plants approximately 8 cm in height. Care is taken that the spray mixture does not come into contact with aerial parts of the plants. 48 hours later, the plants are dusted with conidia of the fungus. The infected plants are placed in a greenhouse at 22°. The fungus infestation is assessed 10 days after the infection.
Compounds of the formula I are generally capable of reducing the disease level to less than 20%, in some cases also completely (for example compounds of sub-group Ic).
Example B-9: Activity against Podosphaera leucotricha in apple shoots
Residual-protective action
Apple cuttings which have fresh shoots of approximately 15 cm length are sprayed with a spray mixture (0.06% of active ingredient). After 24 hours, the treated plants are infected with a conidia suspension of the fungus' and placed in a controlled-environment cabinet at a relative atmospheric humidity of 70% and 20°C. The fungus infestation is assessed 12 days after the infection.
After treatment with active ingredients of the formula I, the disease level is less than 20%.
The disease level of the control plants is 100%.
Example B-10: Activity against Botrytis cinerea in apple fruits. Residual-protective action Artificially damaged apples are treated by dropwise application of a spray mixture (0.02% of active ingredient) to the sites of damage. The treated fruits are subsequently inoculated with a spore suspension of the fungus and incubated for one week at high atmospheric humidity and approximately 20°C. The fungicidal activity of the test substance is deduced from the number of sites of damage where rot has started.
Active ingredients of the formula I from Table 1 or 2 are capable of preventing the rot from spreading, in some cases completely.
Example B-11 : Activity against Helminthosporium gramineum
Wheat kernels are contaiminated with a spore suspension of the fungus and left to dry. The contaiminated kernels are treated with a suspension of the test substance (600 ppm of active ingredient based on the weight of the seeds). After two days, the kernels are placed on suitable agar dishes, and after a further four days the development of the fungal colonies around the kernels is assessed. Number and size of the fungal colonies are taken into consideration for assessing the test substance.
Some of the compounds of the formula I have a good action, i.e. inhibit the fungal colonies.
Example B-12: Activity against Colletotrichum laαenarium in cucumbers Cucumber plants are grown for 2 weeks and then sprayed with a spray mixture (concentration 0.002%). After 2 days, the plants are infected with a spore sus ension of the fungus (1.5 x 10 5 spores/ml) and incubated for 36 hours at 23°C and high atmospheric humidity. The incubation is then continued at normal atmospheric humidity and approximately 22-23°C. 8 days after the infection, the fungus infestation is assessed. Untreated, but infected control plants have a fungus infestation of 100 %. Some of the compounds of the formula I cause almost complete inhibition of the incidence of disease.
Example B-13: Activity against Fusarium nivale in rye
Using a mixing roll, rye cv. Tetrahell which was naturally infected with Fusarium nivale was treated with the test fungicide, the following concentrations being used: 20 or 6 ppm of a.i. (based on the seed weight).
Using a seed drill, the infected and treated rye is sown in October in the open in plots of 3 m length and 6 seed rows. 3 replications per concentration.
Until the infestation is assessed, the test field is grown under normal field conditions (preferably in a region with closed snow cover during the winter months).
To assess the phytotoxicity, seed emergence is scored in autumn and plant density/tillering in spring.
To determine the activity of the active ingredient, the percentage of Fusarium-infested plants is counted immediately after the snow has melted. In the present case, the number of treated plants was less than 5%. Those plants which had emerged were healthy in appearance.
Example B-14: Activity against Septoria nodorum in wheat
Wheat plants in the 3-leaf stage are sprayed with a spray mixture (60 ppm of a.i.) prepared from a wettable powder of the active ingredients (2.8:1).
After 24 hours, the treated plants are infected with a conidia suspension of the fungus. The plants are then incubated for 2 days at a relative atmospheric humidity of 90-100% and placed for a further 10 days in a greenhouse at 20-24°C. 13 days after infection, the fungus infestation is assessed. Less than 1 % of the wheat plants were infested. The compounds No. 2.80 and 2.90 had a particularly sustained action.
Example B-15: Activity against Rhizoctonia solani in rice Protective local soil application:
Rice plants which are 10 days old are watered with a suspension (spray mixture) prepared from a formulated test substance without contaminating aerial parts of the plants. Infection takes place three days later by placing a stem of barley straw which is infected with Rhizoctonia solani between the rice plants of each pot. After 6 days, incubation in a controlled-environment cabinet at a daytime temperature of 29°C and a nighttime temperature of 26°C and 95 % relative atmospheric humidity, the fungus infestation is assessed. Less than 5% of the rice plants were infested. The plants were healthy in appearance.
Protective local foliar application:
Rice plants which are 12 days old are sprayed with a suspension prepared from a formulated test substance. Infection takes place one day later by placing a stem of barley straw which is infected with Rhizoctonia solani between the rice plants of each pot. After 6 days' incubation in a controlled-environment cabinet at a daytime temperature of 29°C and a nighttime temperature of 26°C and 95 % relative atmospheric humidity, the plants are scored. Untreated, but infected control plants show a fungus infestation of 100%. Compounds of the formula I cause inhibition of the incidence of disease, in some cases almost completely.
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