TITLE NOVEL BIS-(HYDROXIMIDOYL CHLORIDE) DERTVATTVES AS AGRICULTURAL FUNGICIDES CRQSS-REFERENCE TO REIATOP APPMCATJQN

This application is a continuation-in-part of U.S. application Serial No. 07/563,839, filed August 6, 1990.

BACKGROUND OF THE INVENTION Bellina U.S. 3,819,700 claims compounds of Formula i as fungicides for crop protection.

Hubele CH 66-16,259 claims compounds of Formula ii as fungicides for crop protection.

Compounds of Formula iii are disclosed in the patent Hterature as antidotes for herbicides in U.S. 4,416,686, U.S. 4,426,221, U.S. 4,453,969, U.S. 4,453,974 and U.S. 4,475,945.

X = halogen iii

Compounds of Formula iv are disclosed in EP 293,667 A as fungicides for crop protection.

iv

Compounds of Formula v are disclosed in U.S. 3,954,992 as fungicides for crop protection.

SUMMARY OF THE INVENTION This invention pertains to compounds of Formula I including all geometric and stereoisomers, agricultural compositions containing them and their use as fungicides

wherein:

A and A are independently O, NH,— CH2O— , — CH2CH2O— or a direct bond; G and Gl are independently C(=0)NR1R2, C(=0)OR3,C(=0)R ⁴ ,

S(0) _n R ⁵ , S02NR1 2 or CN;

X and χl are independently SO2R ⁶ , Cl or Br;

Rl and R* ^** ' are independently H; C1-C4 alkyl; C2-C4 alkoxyalkyl; or

R*** and R***' can be taken together along with the nitrogen atom to which they are attached to form an azetidino, pyrrolidino, piperidino, homopiperidino or morpholino group, each optionally substituted with 1-2 methyl; R ³ is C1-C4 alkyl, C1-C4 haloalkyl or C2-C4 alkoxyalkyl;

R ⁴ is C1-C4 alkyl; C1-C4 haloalkyl; C2-C4 alkoxyalkyl; or phenyl optionally substituted with 1-2 substituents selected from the group consisting of halogen, methyl, methoxy, cyano and nitro; 5 is C1-C4 alkyl; C1-C4 haloalkyl; C2-C4 alkoxyalkyl; or phenyl optionally substituted with 1-2 substituents selected from the group consisting of halogen, methyl, methoxy, cyano and nitro; R is Ci-Cg alkyl; Cj-Cg haloalkyl; C2-Cg alkoxyalkyl; or phenyl or benzyl, said phenyl or benzyl groups being optionally substituted with methyl, trifluoromethyl, methoxy, cyano, nitro or 1-3 halogen; Q is Ci-Cg alkylenyl optionally substituted with 1-2 methyl; C2-C6 alkenylenyl; C2-Cg alkynylenyl; phenylenyl optionally substituted with R^; naphthalenyl optionally substituted with

R?; CQ-CQ cycloalkylenyl optionally substituted with 1-2 methyl; 1-methylpyrrolyl optionally substituted with R9; 1-methylimidazolyl optionally substituted with R*^; a 5- to 10-membered heteroaromatic or fused heteroaromatic ring system wherein the heteroatoms consist of: i) 1-4 nitrogen atoms, ii) 1-2 nitrogen atoms with 1 oxygen or 1 sulfur atom, or iii) 1-2 oxygen or sulfur atoms, said heteroaromatic or fused heteroaromatic rings being optionally substituted with R^; NH; or

Z is O, CH ₂ , S(0) _n , C(=0), NR!0, HC=CH, CH ₂ CH ₂ , CsC, phenylenyl or a direct bond; R' is 1-4 substitutions selected from the group consisting of halogen, methyl, methoxy, cyano and nitro; R* is H, halogen, methyl or methoxy; R is selected from 1-2 halogen, cyano, methyl or methoxy; Rl° is H or C1-C4 alkyl; and n is 0, 1 or 2; provided that: i) when A or Al is — CH2O — or — CH2CH2O — , the carbon atom of these groups is bonded to Q; ii) when A and Al are NH, is not cyclopropylene optionally substituted with 1-2 methyl; iii) when Q is C2-Cg alkenylenyl or C2-Cg alkynylenyl, A and Al are — CH2O — , — CH2CH2O — or a direct bond; and iv) when Q is NH, A and Al are a direct bond.

In the above recitations, examples of "heteroaromatic rings" include pyridine, pyrimidine, pyridazine, pyrazine, furan, thiophene, pyrrole, 1-methylpyrrole, pyrazole, 1-methylpyrazole, l-methyl-l,2,3-triazole, l-methyl-l,2,4-triazole, oxazole, isoxazole, and thiazole. Examples of "fused heteroaromatic rings" include qumoline, isoquinoline, cinnoline, quinazoline, quinoxaline, indole, 1-methylindole, benzimidazole, 1-methylbenziιnidazole, indazole, 1-methylindazole, isoindole, benzo[b]furan and benzo[b]thiophene.

The term "alkyl", used either alone or in compound words such as "haloalkyl" denotes straight chain or branched alkyl, especially methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl, hexyl, heptyl or octyl isomers.

Examples of "alkenylenyl" particularly include CH=CH, CH ₂ CH=CHCH2, CH=CHCH CH2, CH ₂ CH*=CHCH2, CH=CHCH=CH. Examples of "alkynylene" particularly include CsC and

CH ₂ CsCCH2.

"Cycloalkylenyl" particularly includes cyclopropylene, cyclobutylene, cyclopentylene, and cyclohexylene.

The term "halogen", either alone or in compound words such as "haloalkyl", denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl", said alkyl may be partially or ully substituted with halogen atoms which may be the same or different. Examples of "haloalkyl" particularly include F3C, CICH2,

CF3CH2 and CF3CF2* The total number of carbon atoms in a substituent group is indicated by the "Ci-Cj" prefix where i and j are numbers from 1 to 6. For example, "C2 alkoxyalkyl" designates CH3OCH2, "C3 alkoxyalkyl" designates CH3OCH2CH2 and CH3CH2OCH2. Other examples of

"alkoxyalkyl" include CH3CH2CH2OCH2 and CH3CH2OCH2CH2. Preferred F-τph" <*τ- ^s

Preferred for ease of synthesis and/or increased fungicidal activity are:

1) Compounds of Formula I wherein:

A and Al are independently NH, — CH2O — , or a direct bond; and Q is Cj-Cg alkylenyl optionally substituted with 1-2 methyl;

C2-C6 alkenylenyl; C2-Cg alkynylenyl; NH; or Q is selected from the group consisting of

CHq

wherein designations such as:

indicate that substitution at any position on either ring is permissible.

2) Compounds of Preferred 1, wherein: A and A--- are the same; G and G ¹ are both C(=0)NR ¹ R ² ; X and X ¹ are both SO ₂ R ⁶ or Cl; is Ci-Cg alkylenyl optionally substituted with 1-2 methyl; U2-C alkenylenyl; C2-Cg alkynylenyl; or Q is selected from the group of

CHc

R6 is phenyl optionally substituted with methyl, trifluoromethyl, methoxy, cyano, nitro or 1-3 halogen.

3) Compounds of Preferred 2, wherein: A and A are both NH or a direct bond.

4) Compounds of Preferred 3 wherein: Q is selected from the group consisting of:

Specifically preferred for greatest fungicidal activity and/or ease of synthesis are:

1) N,N'-[l,3-phenylenebis(carbonyloxy)]bis[2-dimethylamino)- 2-oxoethanimidoyl chloride];

2) N,N'-[l,3-phenylenebis(ύnmocarbonyloxy)]bis[2-dimethyl amino)-2-oxoethanimidoyl chloride; and

3) N,N'-[2,5-thiophenediylbis(carbonyloxy)]bis[2-dimethyl- am_ino)-2-oxoethanimidoyl chloride].

DETAILED DESCRIPTION OF THE INVENTION

Synthesis

The compounds of Formulae I-III can be prepared from compounds of Formulae IV and/or V and an appropriate electrophilic reagent of Formula VI in an inert solvent with a base used either as a catalyst or acid scavenger. Suitable solvents include polar aprotic solvents such as acetonitrile or dimethylformamide; ethers such as tetrahydrofuran, dimethoxyethane or diethyl ether; ketones such as acetone or 2-butanone;

hydrocarbons such as toluene or benzene; or halogenated hydrocarbons such as dichloromethane, chloroform, or carbon tetrachloride. Appropriate bases include fllkfll-i metal alkoxides, such as sodium methoxide or potassium tert-butoxide, inorganic bases such as sodium hydride or potassium carbonate, or tertiary amine bases such as triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo- [5.4.0]undec-7-ene (DBU), or l,4-diazabicyclo[2.2.2]octane (DABCO). The reaction temperature can vary between 0°C and 150°C for periods of 1 to 96 hours, depending on the choice of base, solvent, temperature, and substrates.

IV V VI

π o o

G-C=NOC-Q-NHCON=C-G ¹

X ^x m

wherein:

R and R ¹ may be independently = NCO, COC1, COBr; X and χl may be independently = Cl; Br or SO2R ⁶ ; and where G and G may be independently equal to the definitions outlined above, and where Q represents any one of the above defined cyclic, alicyclic, or unsaturated systems.

Compounds of Formulae I, II and HI can be prepared by combining an appropriate electrophilic reagent of Formula Vla-c with oximes of Formulae IV and/or V by several processes which are summarized in the following equations:

G-C=NOH + X(0 ^* =)C-Q- =0)X-->G-C-=NO(0=Xϊ-Q-C(-=OJX + G ^■ .l ^x -_.rCfeu ^* N-- OH- X X X ¹

Y Sfe JS.

I

Y IV us IQ

The herein claimed compounds may also be made by the following sequential processes following hterature cited below. Compounds of Formula I where X and X* are not the same, may be made as shown:

YE

VH + N-bromosuccinimide (NBS)

Alternatively, the substituted hydroximidoyl chlorides or bromides of Formula I can be prepared from the corresponding aldoximes of Formulae VH and VEH with halogens (H. Metzger, Herstellung von Oximen, Houben-Weyl, Methoden der Organische Chemie, E. Miller, editor, Vol. 10(4), 4th ed., p. 98, Thieme, Stuttgart, 1968):

YΠ Cl or Br)

vm

or N-chlorosuccinimide (see K C. Liu, B. R. Shelton, R. KHowe, J. Org. Chem., 1980, 45:3916), or N-bromosuccinimide (see C. Grundman and R. Richter, J. Org. Chem., 1968, 23:476).

Compounds of Formula II can be made as shown below, or by following the procedure given by Kaminski, Polish J. Chem., 1981, 55(3):665:

IY a

Compounds of Formula II may be made following the methods given in the Hterature above.

VIb

Compounds of Formula II can be made by an alternate synthetic scheme. Compound X can be made following a procedure given by L. Grehn, K Gunnarsson and U. Ragnarsson, Acta Chem. Scand. B, 1987, 41:18.

A novel method of preparation of compounds of Formulae II and HI comprises sequential preparation of the novel chloroformate XI by reaction of compounds of Formulae IV and V with phosgene in the presence of organic bases such as N,N-diethylaniline and pyridine.

2L ZL

Compounds of Formulae I, H, and IH can be prepared from compounds of Formulae IV and V and a carboxyhc acid Vld in the

presence of a coupling auxiliary reagent such as, but not limited to, N,N-dicyclohexylcarbodϋmide (DCC)

DCC G-C ^s NOH + HOC^R ^{* *} - G-C-sNOCXs- JR'

X X

Y YM

where R' can represent any appropriate embodiment of the above defined Q groups.

Compounds described by Formula IH can be made easily from compounds of Formula IV, V and Vld as shown below:

π: __ JU

Compounds described by Formula IH may be made using an intermediate (XH1) which can be made following the method given by K Mai et al., J. Org. Chem., 1986, ≤1:3545.

XIa XIII XIΪ

Compounds of the Formula IH can also be prepared via the route given below. Phosgene substitutes may also be used (e.g., diphosgene, triphosgene) according to the Hterature of H. Eckert, B. Forster, Angew. Chem, Int. Ed., Eng., 1987, 2£:894; and KKumita, Y. Iwakura, Org. Synth., 1980, 5J):195.

V Y

HBr HOAc O C0C1 ₉ ^G II

XV ■* ^■ ^ - _/ >=NOC-Q-NCO

X

XVI

ιγ m

Compounds of Formula IH may also be prepared following the sequence below:

xi XYΠ

xn. in

Another route to compounds of Formula HI is shown below:

Compounds of Formulae I, H and/or IH may additionally be made through the reaction sequence shown below. Intermediates may be made following methods common in the Hterature.

n may be independently 0 or 1.

The bridging groups, Q, which are not commercially available, may be prepared by one skilled in the art following methods described in the following comprehensive organic chemistry tests:

Advances m HeterocvcHc h*--""-?^. Academic Press, NY; The Ch mistry of HeterocvcHc Pnm ni- s, JohnWiley & Sons, NY, 1982;

Comprehensive HeterocvcHc Cha-mis-hry. Katritskyand Rees,

Pergamon Press, Oxford, 1984; !hem ^* iRtτγ _τ Barton and OlHs, Pergamon Press, Oxford, 1979; HeterocvcHc Cn-m mirnjiB. Elderfield, John Wiley & Sons, NY, 1967;

Rodd's Chft-miR-hr of Carbon Cn-mpm-i-n s, 2nd Ed., Elsevier, 1976; and Vogel's Textbook of Practical O ga-ni r,bp.*m ^* is* rv _τ Δth TC _τ Longman Inc., NY, 1978.

The carboxamide and carboxyhc acid ester compounds shown below can be prepared by the methods taught in, and including the references cited within U.S. Patents 3,557,089, 3,557,190 and 3,560,555.

G is C^ON - ^* * ² , -CO^ ³ , C(=0)R ⁴ or S(0) _n R ⁵

The thiocarboxamide and thioketone compounds shown below can be prepared from the carboxamide or ester compounds, respectively, by methods described elsewhere (see S. Scheibye, E. S. Pedersen and S. O. Lawesson, Bull. Soc. Ch-im T-teljx 1978, £7, 229 and G. Lajore, F. Lepine, L. Maziak and B. BeUeau, Tet Letters. 1983, 24:3815).

Compounds of Formulae IV and V can also be prepared by conversion of other compounds of Formulae IV and V by standard methods of organic reactions, recognizable by those skilled in the art, such as, but not limited to, reduction and oxidation.

The -chloroaldoximes of Formulae IV and V can be prepared by treating amines of Formula XIX with sodium nitrite and hydrochloric acid (see G. S. Skinner, J. Am Chem Soc.. 1924, ϋ:731).

NaN0 ₂

G-CH2NH ₂ »- G-C=NOH

H ₂ 0 I

HC1 ^X

S Y

The α-chloroaldoximes of Formulae IV and V can also be prepared from aldoximes of Formula XX by treatment with N-cUorosucdnimide (see K E. Larsen and K B. G. Torsell, Tetrahedron. 1984, £:2985) or t-butylhypochlorite (see C. J. Peake and J. H. Strickland, fiynfo _r ζ ^~ tm.. 1986.1&763).

X = C1

Some α-haloaldoximes of Formulae IV and V may be prepared from amide oximes XXI by treatment with sodium nitrite in hydrohaHc acid solution (see M. Kocevar, S. Polanc, M. Sollner, M. Tisler and B. Vercek, Svnth On-m-m , 1988,l_g:1427).

HX

The α-haloaldoximes of Formulae IV and V can be prepared from trihalomethyl compounds of Formula XXH by basic hydrolysis in the presence of hydroxylamine (see A P. Kozikowski and M. Adamczyk, J. Org. Chem.. 1983, 4g:366).

NH ₂ OH

X xxπ IV and V

The α-haloaldoximes of Formulae IV and V can be prepared by the reaction of nitrile N-oxides of Formula XXiπ with hydrohaHc acids (see C. Grundmann, V. Mini, J. M. Dean, and H. -D. Frommeld, Justis Liebigs A ^* n ^* n. h ^* m _τ 1965, £S2:191).

G-OsN-0 < ^■ *- G-C=NOH

X

∑ m lϊandY

The nitrile N-oxides of Formula XXIV can be prepared by several methods well known in the chemical art (for a summary of methods, see T. Shimizu, Y. Hayashi, and K Taramura, vJI, ftføc, Chem. Jpn.. 1984, £1:2531). The most familiar method involves treating an α-chloroaldoxime of Formula Va with an inorganic base such as sodium hydroxide or sodium carbonate or an organic base such as triethylamine foHowed by trapping the nitrile N-oxide of Formula XXIV with a hydrohaHc acid. A new α-haloaldoxime of Formula V is produced.

+ .

∑a XXffl V

The carboxamide and carboxyhc acid ester compounds of Formula V can be prepared by the procedures taught in the U.S. Patents 3,557,089, 3,557,190, and 3,560,555.

The cyano compound of Formula V can be prepared by methods already reported (see A. P. Kozikowski and M. Adamczyk, J. Org. Chem., 1983, 42:366).

NC-C=NOH

X

X = C1

The ketone compounds of Formula V can be prepared from halomethyl ketones of Formula XXV by treatment with an alkyl nitrite and hydrochloric acid (see N. Levin and W. H. Hartung, Org. Synthesis. 1944, 24:25).

XXV x = cι = cι

The ketone compounds of Formula V can also be prepared from halomethyl ketones of Formula XXV by treatment with dimethyl sulfide to afford compounds of Formula XXVI, which are then treated with sodium nitrite and hydrochloric acid (see Y. Ofsuji, Y. Tsuju, A Yoshida and E. Imoto, Bull Chem Soc. Japan. 1971, 44:223).

XXV xxy∑ X = C1

The ketone compounds of Formulae IV and V can be prepared from β-ketosulfoxides of Formula XXVH by treatment with sodium nitrite in hydrohaHc acid solution (see Y. Otsuji, Y. Tsuju, A Yoshida and E. Imoto, Bull. Chem Soc. Japan. 1971, :219).

XXVII

The ketone compounds of Formulae IV and V can also be prepared from compoτmds of Formula XX by treatment with chlorine gas (see

G. Casnati and A- Ricca, Tet. Letters. 1967:327 and Y. H. Chiang, J. Org. ^' CJISBL, 1971, :2146).

The thioalkyl and thioaryl compounds of Formulae IV and V can be prepared from dmaloformaldoxime XXVIII (see D. Chiarino, M. Napoletano and A. Sala, fiyn-fti, Qηnrι, , 1988, I&1171 and D. M. Vyas, Y. Chiang and T. W. Doyle, Tet. Letters. 1984, 25:487) by

reaction with thiols and one equivalent of an organic base such as triethylamine (see M. H. Benn, Can. J. Chem.. 1964, 42:2393).

The sulfoxide and sulfone compounds of Formulae IV and V can be prepared from compounds of Formulae IV and V (G = R*-*S) by oxidation using one or two equivalents, respectively, of oxidants such as hydrogen peroxide or organic per acids, such as peracetic acid.

[O]

The sulfone compounds of Formulae IV and V can also be prepared from compounds of Formula XXIX (G=R*->S02) according to methods already reported (see P. A. Wade and H. R. Hinney, J. Am, Chem. Soc.. 1979, 101:1319).

X XXIX V

G = R ⁵ S0 ₂ X = Br

Alternatively, the sulfonylcarbohydroximidoyl chlorides of Formulae IV and V can be prepared from α-diazosulfones of Formula XXX and nitrosyl chloride (see J. C. Jagt, I. van Buuren, J. Strating and A M. Van Leusen, fiγpthi C- T- ™. ! 1974, 4:311).

NOX

^GCH 2 ^N 2 G-C ^* =NOH

X = C1 j

X

G=R ⁵ S0 ₂ , X = C1

The following are representative of the methods used for the preparations of the included examples. EXA P E l

NJST-ri.3-phenvlenebis(carbonvloxvTbisr2- 6.04 g of 2-(dimethylam_mo)-2-oxoethanimidoyl chloride was dissolved in 250 mL THF. 4.06 g of isophthaloyl chloride was added. 5.6 mL of triethylamine was dissolved in 30 mL THF, and this solution was added, while cooling the reaction mixture to 0°C. The mixture was stirred at room temperature for 5 hours after completion of the addition. The soHd was filtered, washed with ethyl acetate, and discarded. The filtrate was stripped to a solid, which was recrystallized by dissolving in a mixture of 1-chlorobutane and methylene chloride, and heating on a steam bath. A soHd crystallized, which was suspended in hexanes and filtered. The soHd was washed with hexanes. 8.27 g of Compound #5 was obtained after drying. m.p. 122-124°C.

EXAMPLE ? N.N'-ri.3-phenvlenebis(irn*i*n^?r^n*nγlnvγ) ^" {- bisr2- dimfith l-^ηr'iτ ^ι f> -?- ^{y fit} ^ ^flτ '^ ^ττ1 ^oy chloride ⁽ Compound #6 ⁾

1.51 g of 2-(dimethylamino)-2-oxoethanimidoyl chloride was dissolved in 100 mL THF. 0.80 g of 1,3-phenylene dusocyanate was added, foUowed by 3 drops of DBU. The mixture was stirred overnight at room temperature under nitrogen. The next day the mixture was stripped to a gum which was sequentially treated with acetone, 1- chlorobutane and hexane. The resulting solution was stripped dry to a soHd. The soHd was suspended in hexanes, filtered, and washed with hexanes. m.p. 176-180°C.

EXAMPLE 3

N N'-r2 _r S-th-ϊ^phenediylbis-(carbonyloxy)bis- r2-di ^* methv1fl ^* m ^* i-nn)-2-OXOetbfl ^* nirn-i nyl chloride Compound #42)

1.51 g of 2-(dimethylan ^* rino)-2-oxoethanimidoyl chloride was dissolved in 75 mL THF. 1.05 g of 2,5-bis-thiophenecarbonyl chloride

[prepared by reaction of the disodium salt in refluxing thionyl chloride

(m.p. 41-44°C)] was added, followed by the dropwise addition of 1.4 mL of triethylamine. The mixture was stirred overnight at room temperature.

The foUowing day, 20 mL of ethyl acetate was added and the mixture was filtered. The soHd was washed with ethyl acetate and was discarded.

The filtrate was stripped to a soHd. This solid was suspended in 1- chlorobutane containing enough CH2CI2 to cause dissolution. Hexanes were then added to cause a soHd to form. The soHd was filtered and washed with hexanes. mp. 157-159°C.

Using the procedures and examples shown above, the compounds in Tables 1-28 and Index Tables A, B, C and D can be prepared.

TABLE 1

G. G ¹

C(-O)pyrrolidino

C (*0) 2,6-diTnethylmorphollno

C(-=0)piperidino C(-0)N(Me) ₂

C(=0)pyrrolidino C(=0) iperidino C(=0)NH-i-Bu C(=0) omopiperidino C(-ON(Me) ₂

C(*=0)pyrrolidino

C(>=0)piperidino

C(=0)NH-i-Bu

C(=0) omopiperidino C(=0)N(Me) ₂

C(=0)pyrrolidino

C(-=0)piperidino

C(«0)NH-i-Bu

C(*=0)homopiperidino

C(=0)N(Me) ₂

C(=0)piperidino C(-=0)N(Me) ₂

¹ X- χ ^J

1-methyl-l,2-ethanediyl 1-methyl-l,3-propanediyl

2-methyl-l,3-propanediyl 2-methyl-l,4-butanediyl

1-methyl-l,4-butanediyl

1-methyl-l,5-pentanediyl

2-methyl-l,5-pentanediyl 3-methyl-l,5-pentanediyl

1-methyl-l,6-hexanediyl

2-methyl-l,6-hexanediyl 3-methyl-l,6-hexanediyl

1,2-cyclobutanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl 1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,4-cyclohexanediyl

1,4-cyclohexanediyl 1,4-cyclohexanediyl 1,4-cydohexanediyl

^{1 J}

-lH-pyrrole-2,3-diyl -lH-pyrrole-2,3-diyl -lH-pyrrole-2,3-diyl

-lH-pyrrole-2,3-diyl

-lH-pyrrole-2,3-diyl ^' -lH-pyrrole-2,3-diyl

-lH-pyrrole-2,3-diyl

-lH-pyrrole-2,3-diyl -lH-pyrrole-2,3-diyl

-lH-pyrrole-3,4-diyl -lH-pyrrole-3,4-diyl

-lH-pyrrole-3,4-diyl

-lH-pyrrole-3,4-diyl

-l-methyl-lH-pyrrole-3,4-diyl

-l-methyl-lH-pyrrole-3,4-diyl -l-methyl-lH-pyrrole-3,4-diyl

-l-methyl-lH-pyrrole-3,4-diyl

-l-methyl-lH-pyrrole-3,4-diyl -l-methyl-lH-pyrrole-3,4-diyl

-l-methyl-lH-pyrrole-3,4-diyl

-l-methyl-lH-pyrrole-2,5-diyl

-l-methyl-lH-pyrrole-2,5-diyl

-1-methyl-lH pyrrole-2,5-diyl

-l-methyl-lH-pyrrole-2,5-diyl

-l-methyl-lH-imidazole-4,5-diyl -l-methyl-lH-imidazole-4,5-diyl

g, G ¹ X, x ³

-l-methyl-lH-imidazole-4, 5-diyl

-l-methyl-lH-imidazole-4, 5-diyl

-l-methyl-lH-imidazole-4, 5-diyl -l-methyl-lH-imidazole-4, 5-diyl

-l-methyl-lH-imidazole-4, 5-diyl

-lH-imidazole-1, 5-diyl

-lH-imidazole-1, 5-diyl -lH-imidazole-1, 4-diyl

-lH-imidazole-1, 4-diyl -1H-1, 2, 3-triazole-4, 5-diyl

-1H-1, 2, 3-triazole-4, 5-diyl -1H-1, 2, 3-triazole-l, 5-diyl

-1H-1, 2, 3-triazole-l, 5-diyl

-1H-1, 2, 3-triazole-l, 4-diyl -1-methyl-lH-l, 2, 3-triazole-4, 5-diyl

-1-methyl-lH-l, 2, 3-triazole-4, 5-diyl

-1-methyl-lH-l, 2, 3-triazole-4, 5-diyl

-1-methyl-lH-l, 2, 3-triazole-4, 5-diyl 2, 6-naphthalenediyl

2, 6-naphthalenediyl

2, 3-dihydro-lH-indene-2, 6-diyl

2, 3-dihydro-lH-indene-2, 6-diyl 2, 3-dihydro-lH-indene-2, 6-diyl

^{1 1}

2, 3-dihydro-lH-indene-l, 6-diyl

2, 3-dihydro-lH-indene-l, 7-diyl

-1,2,3,4-tetrahydro-l,8-naphthalenediyl

-1,2,3,4-tetrahydro-l,8-naphthalenediyl

-1,2,3,4-tetrahydro-l,8-naphthalenediyl

-1,2,3,4-tetrahydro-l,8-naphthalenediyl -5,6,7,8-tetrahydro-l,7-naphthalenediyl

-5,6,7,8-tetrahydro-l,7-naphthalenediyl

-1,2,3,4-tetrahydro-l,5-naphthalenediyl

-1,2,3,4-tetrahydro-l,5-naphthalenediyl

-1,2,3,4-tetrahydro-l,7-naphthalenediyl

-1,2,3,4-tetrahydro-l,7-naphthalenediyl -1,2,3,4-tetrahydro-2,7-naphthalenediyl

-1,2,3,4-tetrahydro-2,7-naphthalenediyl -benzo[b]thiophene-2,6-diyl

-benzo[b]thiophene-2,6-diyl

-benzo[b]thiophene-2,6-diyl -benzo[b]thiophene-2,6-diyl

-2,5-benzofurandiyl-

-2,5-benzofurandiyl-

-2,5-benzofurandiyl-

-2,5-benzofurandiyl- -2,5-benzofurandiyl-

-2,7-benzofurandiyl-

-2,7-benzofurandiyl- -2,7-benzofurandiyl-

¹

-2,7-benzofurandiyl -2,7-benzofurandiyl -2,6-benzofurandiyl -2,6-benzofurandiyl -2,6-benzofurandiyl

2,3-quinolinediyl 2,3-quinolinediyl 2,3-quinolinediyl

2,3-quinolinediyl 3,6-quinolinediyl

3,6-quinolinediyl 3,7-quinolinediyl

3,7-quinolinediyl 2,4-isoquinolinediyl

2,4-isoquinolinediyl

2-chloro-3,7-quinolinediyl 2-chloro-3,7-quinolinediyl

6-fluoro-3,7-quinolinediyl

6-fluoro-3,7-quinolinediyl -2-methoxy-3,7-quinolinediyl

-2-methoxy-3,7-quinolinediyl

-2-methoxy-3,7-quinolinediyl -2-methoxy-3,7-quinolinediyl

-lH-pyrazole-1,5-diyl

-lH-ρyrazole-1,5-diyl -3-methyl-lH-pyrazole-l,4-diyl

-3-methyl-lH-pyrazole-l, 4-di -lH-pyrazole-3, 5-diyl

-lH-pyrazole-3, 5-diyl

-lH-pyrazole-3, 5-diyl

-lH-pyrazole-3, 5-diyl

-lH-pyrazole-3, 5-diyl 4-chloro-lH-pyrazole-3, 5-diyl

4-chloro-lH-pyrazole-3, 5-diyl 4-chloro-lH-pyrazole-3, 5-diyl l-methyl-lH-pyrazole-3, 5-diyl l-methyl-lH-pyrazole-3, 5-diyl l-methyl-lH-pyrazole-3, 5-diyl l-methyl-lH-indole-3, 5-diyl l-methyl-lH-indole-3, 5-diyl l-methyl-lH-indole-3, 5-diyl -lH-indole-1, 2-diyl

-lH-indole-1, 2-diyl

-lH-indole-1, 2-diyl -lH-indole-1, 2-diyl

-Bu ) Ph -lH-indole-1 , 2 -diy 1

-lH-indole-2, 6-diyl

-lH-indole-2, 6-diyl 5-methoxy-l -methy 1-lH-indole-

2, 3-diyl

5-methoxy-l-methyl-lH-indole-

2, 3-diyl lH-indazole-1, 7-diyl lH-indazole-1, 7-diyl

¹

lH-indazole-1,7-diyl lH-indazole-1,3-diyl lH-indazole-1,3-diyl lH-indazole-1,3-diyl lH-indazole-1,5-diyl lH-indazole-1,5-diyl lH-indazole-3,5-diyl lH-indazole-3,5-diyl lH-benzimidazole-1,2-diyl lH-benzimidazole-1,2-diyl lH-benzimidazole-1,2-diyl lH-benzimidazole-1,5-diyl lH-benzimidazole-1,5-diyl lH-benzimidazole-1,5-diyl lH-benzimidazole-1,6-diyl lH-benzimidazole-1,6-diyl lH-benzimidazole-1,6-diyl 2-amino-lH-benzimidazole-l,2-diyl

2-amino-lH-benzimidazole-l,2-diyl lH-benzimidazole-2,5-diyl lH-benzimidazole-2,5-diyl lH-benzimidazole-2,4-diyl lH-benzimidazole-2,4-diyl

-l-methyl-lH-benzimidazole-2,5-diyl -l-methyl-lH-benzimidazole-2,5-diyl -l-methyl-lH-benzimidazole-2,5-diyl

G. G X ^*1

-l-methyl-lH-benzimidazole-2,5-diyl methylenedi-4,1-phenylene methylenedi-4,1-phenylene methylenedi-4,1-phenylene methylenedi-4,1-phenylene methylenedi-4,1-phenylene

1,2-ethanediylbis(4,1-phenylene)-

1,2-ethanediylbis(4,1-phenylene)-

1,2-ethanediylbis(4,1-phenylene)- 1,2-ethanediylbis (4,1-phenylene)-

1,2-ethanediylbis (4,1-phenylene)

1,2-ethenediylbis(4,1-phenylene)-

1,2-ethenediylbis(4,1-phenylene)- 1,2-ethenediylbis(4,1-phenylene)- ethynediylbis(4,1-phenylene)- ethynediylbis(4,1-phenylene)- ethynediylbis(4,1-phenylene)- -carbonyldi-4,1-phenylene-

-carbonyldi-4,1-phenylene-

-carbonyldi-4,1-phenylene- methyliminobis-(4,1-phenylene)- methyliminobis-(4,1-phenylene)- -iminodi-4,1-phenylene

-iminodi-4,1-phenylene -iminodi-4,1-phenylene

-N0 ₂ )Ph -oxydi-4,1-phenylene -oxydi-4,1-phenylene

-oxydi-4,1-phenylene

oxymono(3,1-phenylene)mono(4,1-phenylene)- oxymono(3,1-ρhenylene)mono(4,1-phenylene)- oxymono(3,1-phenylene)mono(4,1-phenylene)- oxymono(3,1-phenylene)mono(4,1-ρhenylene)

-oxydi-3,1-phenylene

-oxydi-3,1-phenylene -oxydi-3,1-phenylene -oxydi-3,1-phenylene

oxymono(2, -phenylene)mono(4,1-phenylene)- oxymono(2,1-phenylene)mono(4,1-phenylene)- oxymono(2,1-phenylene)mono(4,1-phenylene)- oxymono(2,1-phenylene)mono(4,1-phenylene)- -thiodi-4,1-phenylene

-thiodi-4,1-phenylene -thiodi-4,1-phenylene

-thiomono(3,1-phenylene)mono(4,1-phenylene

-thiomono(3,1-phenylene)mono(4,1-phenylene

-thiomono(3,1-phenylene)mono(4,1-phenylene thiodi-3,1-phenylene thiodi-3,1-phenylene thiodi-3,1-phenylene -sulfinyldi-4,1-phenylene -sulfinyldi- ,1-phenylene

X ¹ Ω

sulfinylmono(3,1-phenylene)mono(4,1-phenyle sulfinylmono(3,1-phenylene)mono(4,1-phenyle sulfonyldi-4,1-phenylene sulfonyldi-4,1-phenylene sulfonyldi-4,1-phenylene sulfonyldi-4,1-phenylene

sulfonylmono(3,1-phenylene)mono(4,1-phenylen sulfonylmono(3,1-phenylene)mono(4,1-phenylen sulfonylmono(3,1-phenylene)mono(4,1-phenylen -4,5-thiazolediyl

-4,5-thiazolediyl -3,4-cinnolinediyl-

-3,4-cinnolinediyl-

-3,4-cinnolinediyl- -2,3-quinoxalinediyl

-2,3-quinoxalinediyl -6-chloro-2,3-quinoxalinediyl

-6-chloro-2,3-quinoxalinediyl -1-methyl-lH-l, 2,4-triazole-3,5-diyl

-1-methyl-lH-l,2,4-triazole-3,5-diyl 3-chlorobenzo[b]thiophene-2,5-diyl

3-chlorobenzo[b]thiophene-2,5-diyl

3-chlorobenzo[b]thiophene-2,5-diyl -[1,1' :4',l"-terphenyl]-4, "-diyl -[1,1' :4',l"-terphenyl]-4,4"-diyl

-[1,1• :4 ^« ,l"-terphenyl]-4,4"-diyl -[1,1' : •,l"-terphenyl]-4,4"-diyl

-[1,1•:2•,l"-terphenyl]-3,3"-diyl

-[1,1' :2*,l"-terphenyl]-3,3 ^« -diyl imino i ino imino imino imino imino imino

-[1,1'-biphenyl]-4,4'-diyl

-[1,1'-biphenyl]-3,3'-diyl

-[1,1'-biphenyl]-3,3'-diyl

-[1,1'-biphenyl]-3,3'-diyl

-[1,1'-biphenyl]-3,3'-diyl benzo[b]thiophene-2,3-diyl benzo[b]thiophene-2,3-diyl benzo[b]thiophene-2,3-diyl benzo[b]thiophene-2,3-diyl benzo[b]thiophene-2,3-diyl ethyne-1,2-diyl ethyne-1,2-diyl 2-butyne-l,4-diyl

2-butyne-l, -diyl

-1,3-phenylenebis(methylenoxy)- -1,3-phenylenebis (methylenoxy)-

¹

-1,3-phenylenebis(methylenoxy)-

-1,3-phenylenebis(methylenoxy)- 3, -furandiyl

3,4-furandiyl

3,4-furandiyl

3,4-furanidyl

3,4-furandiyl

3, -furandiyl 3,4-furandiyl

-2,6-naphthalenediylbis(methylenoxy) -2,6-naphthalenediylbis(methylenoxy)

__£___Z

G. G ¹ x _r X ^J

C(-0)pyrrolidino

C(-0)2,6-dimethylmorpholino

C(-0)piperidino

C( ^« 0)N(Me) ₂

C(- )pyrrolidino

C(-=0)piperidino

C(«0)NH-i-Bu

C(-0)homopiperidino

C(-0)N ⁽ Me) ₂

C(<=0)pyrrolidino

C(-0)piperidino

C{-=0)NH-i-Bu

C(-O)homopiperidino

C( ^* =0)N(Me) ₂

C("O)pyrrolidino

C(=-0)piperidino

C(«0)NH-i-Bu

C(-0)homopiperidino

C( ^« 0)N(Me) ₂

C(-0)piperidino C(=0)N(Me) ₂

1-methyl-l,2-ethanediyl 1-methyl-l,3-propanediyl

2-methyl-l,3-propanediyl 2-methyl-l,4-butanediyl

1-methyl-l,4-butanediyl

1-methyl-l,5-pentanediyl

2-methyl-l,5-pentanediyl 3-methyl-l,5-pentanediyl

1-methyl-l,6-hexanediyl

2-methyl-l,6-hexanediyl 3-methyl-l,6-hexanediyl

1,2-cyclobutanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl 1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,4-cyclohexanediyl

1,4-cyclohexanediyl 1,4-cyclohexanediyl 1, -cyclohexanediyl

G _r G X, X ³

G. G ³ X. X ^J

C(=0)N(Me) ₂ Cl 1,3-butadien-l,4-diyl

C(=0)pyrrolidino Cl 1,3-butadien-l,4-diyl

C(=0)piperidino Cl 1,3-butadien-l,4-diyl C(=0)N(Me) ₂ Cl 2,4-furandiyl

C(=0)pyrrolidino Cl 2,4-furandiyl

C(=0)piperidino Cl 2,4-furandiyl

C(-=0)azetidino Cl 2,4-furandiyl

C(=0)homopiperidino Cl 2,4-furandiyl C(=0)OCH ₂ CF ₃ Cl 2,4- urandiyl

C(=0)N(Me) 2 Cl 2,5-furandiyl

C(=0)piperidino Cl 2,5-furandiyl C(=0)NHCH ₃ Cl 2,5-furandiyl

C(=0)OEt Cl 2,5-furandiyl

C(=0)pyrrolidino S0 ₂ (4-Me)Ph 2,5-furandiyl

CN Cl 2,5-furandiyl

C(=0 ⁾ N(Me) ₂ Cl 2,3-furandiyl

C(=0)N(CH ₂ CF ₃ ) ₂ Cl 2,3-furandiyl

C(=0)piperidino Cl 2,3-furandiyl C(=0)N(Me) ₂ Cl 4,5-oxazolediyl

C(=0)homopiperidino Cl 4,5-oxazolediyl

C(=0)4-CN)Ph Cl 4,5-oxazolediyl

C(=0)N(Me) ₂ Cl 2,5-oxazolediyl

C(=0)piperidino Cl 2,5-oxazolediyl

3,4-isoxazolediyl

3,4-isoxazolediyl

3, -isoxazolediyl

3,4-isoxazolediyl

3,4-isoxazolediyl 3,4-isoxazolediyl

3-methyl-4,5-isoxazolediyl

3,5-oxazolediyl

3,5-oxazolediyl

3,5-oxazolediyl

3,5-oxazolediyl 3,5-oxazolediyl

3,5-oxazolediyl

2,5-pyrazinediyl

2,5-pyrazinediyl

2,5-pyrazinediyl 2,6-pyrazinediyl

2,6-pyrazinediyl

2,6-pyrazinediyl 2,3-pyrazinediyl

2,3-pyrazinediyl 2,3-pyrazinediyl

4,6-pyrimidinediyl

4,6-pyrimidinediyl 4,6-pyrimidinediyl

-lH-pyrrole-3, 4-diyl -lH-pyrrole-3, 4-diyl

-lH-pyrrole-3, 4-diyl

-lH-pyrrole-3, 4-diyl

-l-methyl-lH-pyrrole-3, 4-diyl

-l-methyl-lH-pyrrole-3, 4-diyl -l-methyl-lH-pyrrole-3, 4-diyl

-l-methyl-lH-pyrrole-3, 4-diyl

-l-methyl-lH-pyrrole-3, -diyl -l-methyl-lH-pyrrole-3, 4-diyl

-l-methyl-lH-pyrrole-3, 4-diyl -l-methyl-lH-pyrrole-2, 5-diyl -l-methyl-lH-pyrrole-2, 5-diyl -1-methyl-lH pyrrole-2, 5-diyl -l-methyl-lH-pyrrole-2, 5-diyl

-l-methyl-lH-imidazole-4, 5-diyl -l-methyl-lH-imidazole-4, 5-diyl

^{1 3}

-l-methyl-lH-imidazole-4, 5-diyl

-l-methyl-lH-imidazole-4, 5-diyl

-1-methyl-lH-imJ dazole-4, 5-diyl -l-methyl-lH-imidazole-4, 5-diyl

-l-methyl-lH-imidazole-4, 5-diyl

-1H-1, 2, 3-triazole-4, 5-diyl

-1H-1, 2, 3-triazole-4, 5-diyl -1-methyl-lH-l, 2, 3-triazole-4, 5-diyl -1 -methyl -1H-1, 2, 3-triazole-4, 5-diyl

-1-methyl-lH-l, 2, 3-triazole-4, 5-diyl

-1-methyl-lH-l,2,3-triazole-4,5-diyl 2,6-naphthalenediyl

2,6-naphthalenediyl

2,3-dihydro-lH-indene-2,6-diyl

2,3-dihydro-lH-indene-2,6-diyl 2,3-dihydro-lH-indene-2,6-diyl

¹

2,3-dihydro-lH-indene-l,5-diyl 2,3-dihydro-lH-indene-l,7-diyl -1,2,3,4-tetrahydro-l,8-naρhthalenediy -1,2,3,4-tetrahydro-l,8-naphthalenediy

-1,2,3,4-tetrahydro-l,8-naphthalenediy

-1,2,3,4-tetrahydro-l,8-naphthalenediy -5,6,7,8-tetrahydro-l,7-naphthalenediy

-5,6,7,8-tetrahydro-l,7-naphthalenediy

-1,2,3,4-tetrahydro-l,5-naphthalenediy

-1,2,3,4-tetrahydro-l,5-naphthalenediy

-1,2,3,4-tetrahydro-l,7-naphthalenediy

-1,2,3,4-tetrahydro-l,7-naphthalenediy -1,2,3,4-tetrahydro-2,7-naphthalenediy

-1,2,3,4-tetrahydro-2,7-naphthalenediyl -benzo[b]thiophene-2,6-diyl

-benzo[b]thiophene-2,6-diyl

-benzo[b]thiophene-2,6-diyl -benzo[b]thiophene-2,6-diyl

-2,5-benzofurandiyl-

-2,5-benzofurandiyl-

-2,5-benzofurandiyl-

-2,5-benzofurandiyl- -2,5-benzofurandiyl-

-2,7-benzofurandiyl-

-2,7-benzofurandiyl- -2,7-benzofurandiyl-

G. G ³ X. X

-2,7-benzofurandiyl -2,7-benzofurandiyl -2,6-benzofurandiyl -2,6-benzofurandiyl -2,6-benzofurandiyl

2,3-quinolinediyl 2,3-quinolinediyl 2,3-quinolinediyl

2,3-quinolinediyl 3,6-quinolinediyl

3,6-quinolinediyl 3,7-quinolinediyl

3,7-quinolinediyl 2,4-isoquinolinediyl

2,4-isoquinolinediyl

2-chloro-3,7-quinolinediyl 2-chloro-3,7-quinolinediyl

6-fluoro-3,7-quinolinediyl

6-fluoro-3,7-quinolinediyl -2-methoxy-3,7-quinolinediyl

-2-methoxy-3,7-quinolinediyl

-2-methoxy-3,7-quinolinediyl i-Bu) h -2-methoxy-3,7-quinolinediyl

-lH-pyrazole-3, 5-diyl -lH-pyrazole-3, 5-diyl

-lH-pyrazole-3, 5-diyl

-lH-pyrazole-3, 5-diyl

-lH-pyrazole-3, 5-diyl 4-chloro-lH-pyrazole-3, 5-diyl

4-chloro-lH-pyrazole-3, 5-diyl 4-chloro-lH-pyrazole-3, 5-diyl l-methyl-lH-pyrazole-3, 5-diyl l-methyl-lH-pyrazole-3, 5-diyl l-methyl-lH-pyrazole-3, 5-diyl l-methyl-lH-indole-3, 5-diyl l-methyl-lH-indole-3, 5-diyl l-methyl-lH-indole-3, 5-diyl -lH-indole-2, 6-diyl

-lH-indole-2, 6-diyl 5-methoxy-l-methyl-lH-indole-

2, 3-diyl

C (=0) OEt Cl 6-methoxy-l-methyl-lH-indole- 2, 3-diyl

___ ■Λ ., Λ

lH-indazole-3,5-diyl lH-indazole-3,5-diyl lH-benzimidazole-2,5-diyl lH-benzimidazole-2,5-diyl lH-benzimidazole-2,4-diyl

C(-0)3-methylpiperidino Cl lH-benzimidazole-2,4-diyl

C(«0)N(Me) ₂ Cl -l-methyl-lH-benzimidazole-2,5-diy

C(-S)N(Me) ₂ Cl -l-methyl-lH-benzimidazole-2,5-diy

C(HD)pyrrolidino Cl -l-methyl-lH-benzimidazole-2,5-diy

¹ x ^α

-l-methyl-lH-benzimidazole-2,5-diyl methylenedi-4,1-phenylene methylenedi-4,1-phenylene methylenedi-4,1-phenylene methylenedi-4,1-phenylene methylenedi-4,1-phenylene

1,2-ethanediylbis(4,1-phenylene)-

1,2-ethanediylbis(4,1-phenylene)-

1,2-ethanediylbis(4,1-phenylene)- 1,2-ethanediylbis(4,1-phenylene)-

1,2-ethanediylbis(4,1-phenylene)

1,2-ethenediylbis(4,1-phenylene)-

1,2-ethenediylbis(4,1-phenylene)-

1,2-ethenediylbis(4,1-phenylene)- ethynediylbis(4,1-phenylene)- ethynediylbis(4,1-phenylene)- ethynediylbis(4,1-phenylene)- -carbonyldi-4,1-phenylene-

-carbonyldi-4,1-phenylene-

-carbonyldi-4,1-phenylene- methyli inobis-(4,1-phenylene)- methyliminobis-(4,1-phenylene)- -iminodi-4,1-phenylene

-iminodi-4,1-phenylene -iminodi-4,1-phenylene

¹

-N0 ₂ )Ph -oxydi-4,1-phenylene -oxydi-4,1-phenylene

-oxydi-4,1-phenylene

oxymono(3, -phenylene)mono(4,1-phenylene) oxymono(3,1-phenylene) ono(4,1-phenylene) oxymono(3,1-phenylene) ono(4,1-phenylene) oxymono(3,1-phenylene)mono(4,1-phenylene)

-oxydi-3,1-phenylene

-oxydi-3,1-phenylene -oxydi-3,1-phenylene -oxydi-3,1-phenylene

oxymono(2,1-phenylene)mono(4,1-phenylene)- oxymono(2,1-phenylene)mono(4,1-phenylene)- oxymono(2,1-phenylene) ono(4,1-phenylene)- oxymono(2,1-phenylene)mono(4,1-phenylene)- -thiodi-4,1-phenylene

-thiodi-4,1-phenylene -thiodi-4,1-phenylene

-thiomono(3,1-phenylene)mono(4,1-phenylene

-thiomono(3,1-phenylene)mono(4,1-phenylene

-thiomono(3,1-phenylene)mono(4,1-phenylene thiodi-3,1-phenylene thiodi-3,1-phenylene thiodi-3,1-phenylene -sulfinyldi-4,1-phenylene -sulfinyldi-4,1-phenylene

sulfinylmono(3,1-phenylene)mono(4,1-phenyle sulfinylmono(3,1-phenylene)mono(4,1-phenyle sulfonyldi-4,1-phenylene sulfonyldi-4,1-phenylene sulfonyldi-4,1-phenylene sulfonyldi-4,1-phenylene

sulfonylmono(3,1-phenylene)mono(4,1-phenyle sulfonylmono(3,1-phenylene)mono(4,1-phenyle sulfonylmono(3,1-phenylene)mono(4,1-phenyle -4,5-thiazolediyl

-4,5-thiazolediyl -3,4-cinnolinediyl-

-3,4-cinnolinediyl-

-3,4-cinnolinediyl- -2,3-quinoxalinediyl

-2,3-quinoxalinediyl -6-chloro-2,3-quinoxalinediyl

-6-chloro-2,3-quinoxalinediyl -l-methyl-lH-1,2,4-triazole-3,5-diyl

-1-methyl-lH- 1,2,4-triazole-3,5-diyl 3-chlorobenzo[b]thiophene-2,5-diyl

3-chlorobenzo[b]thiophene-2,5-diyl

3-chlorobenzo[b]thiophene-2,5-diyl -[1,1' :4',l"-terphenyl]-4,4"-diyl -[1,1' : ',l"-terphenyl]-4,4"-diyl

G. G ^J X. X ³

-[1,1':4',l"-terphenyl]-4,4"-diyl -[1,1': •,l"-terphenyl]-4,4"-diyl

-[1,1•:2',l"-terphenyl]-3,3"-diyl

-[1,1 ^» :2',l"-terphenyl]-3,3"-diyl imino imino imino imino imino imino

C (-0) 0CH ₃ Cl imino C (=0)N (Me) ₂ S0 ₂ (2,4-Cl)Ph -[1,1 ^« -biphenyl]-4,4 ^« -diyl C (-=0)N (Me) ₂ Cl -[1,1'-biphenyl]-3,3'-diyl C ( ^* =S) N (Me) ₂ Cl -[1,1 ^• -biphenyl]-3,3 ^• -diyl

C (-0) pyrrolidino Cl -[1,1'-biphenyl]-3,3'-diyl

C ( ^« 0) piperidino Cl -[1,1'-biphenyl]-3,3•-diyl C ( ^« 0) N (Me) ₂ Cl benzo[b]thiophene-2,3-diyl

C (-0) NHll-Bu Cl benzo[b]thiophene-2,3-diyl

C (=0) N (Me)β-Bu Cl benzo[b]thiophene-2,3-diyl

C(=0)pyrrolidino Cl benzo[b]thiophene-2,3-diyl

C("O)piperidino Cl benzo[b]thiophene-2,3-diyl C(=0)N(Me) ₂ Cl ethyne-1,2-diyl

C(=0)piperidino Cl ethyne-1,2-diyl C(=0)N(Me) ₂ Cl 2-butyne-l,4-diyl

C(=0)piperidino Cl 2-butyne-l,4-diyl

G. G ¹

C(=0)N(Me) ₂

C (=0) azetidino

C (=0) pyrrolidino

C (=0) piperidino

C (=0) homopiperidino

C(=0) NH-i-Bu C(=0)N(Me) ₂

G. G ¹ X- X ¹

1-methyl-l,2-ethanediyl 1-methyl-l,3-propanediyl

2-methyl-l,3-propanediyl 2-methyl-l,4-butanediyl

1-methyl-l,4-butanediyl

1-methyl-l,5-pentanediyl

2-methyl-l,5-pentanediyl 3-methyl-l,5-pentanediyl

1-methyl-l,6-hexanediyl

2-methyl-l,6-hexanediyl 3-methyl-l,6-hexanediyl

1,2-cyclobutanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl 1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,3-cyclohexanediyl

1,4-cyclohexanediyl

1,4-cyclohexanediyl 1,4-cyclohexanediyl 1,4-cyclohexanediyl

G, G X, X ³ fi

G. G-- X. X ^A

C (=0) N (Me) ₂

C(=0)pyrrolidino

C(-=0)piperidino

C(=0)N(Me) ₂

C(«=0)azetidino C(=0)N(Me) ₂ C(-ON(Me) ₂ C(*=0)pyrrolidino C(-0)piperidino C(=0)azetidino

C(=0)homopiperidino C(=0)0CH ₂ CF ₃

C(=0)N(Me) ₂

C(=0)piperidino C(=0)NHCH ₃

C(=0)0Et

C(=0)pyrrolidino

CN

C(=0)N(Me) ₂

C( ^* =0)N(CH ₂ CF ₃ ) ₂

C(=0)piperidino C(=0)N(Me) ₂

C(=0)homopiperidino C(=0) (4-CN)Ph C(-0)N(Me) ₂

C(=0)piperidino Cl 2,5-oxazolediyl

¹ fi

3,4-isoxazolediyl

3,4-isoxazolediyl

3,4-isoxazolediyl

3,4-isoxazolediyl

3,4-isoxazolediyl 3,4-isoxazolediyl

3-methyl-4,5-isoxazolediyl

3,5-oxazolediyl

3,5-oxazolediyl

3,5-oxazolediyl 3,5-oxazolediyl 3,5-oxazolediyl

3,5-oxazolediyl 2,5-pyrazinediyl 2,5-pyrazinediyl

2,5-pyrazinediyl 2,6-pyrazinediyl

2,6-pyrazinediyl

2,6-pyrazinediyl 2,3-pyrazinediyl

2,3-pyrazinediyl ² r3-pyrazinediyl

4,6-pyrimidinediyl

4,6-pyrimidinediyl ,6-pyrimidinediyl -IH-pyrrole-l,3-diyl

³ x- x ¹

-lH-pyrrole-1, 3-diyl

-lH-pyrrole-1, 3-diyl -lH-pyrrole-1, 3-diyl

-lH-pyrrole-1, 3-diyl

-lH-pyrrole-1, 3-diyl -lH-pyrrole-1, 2-diyl

-lH-pyrrole-1, 2-diyl

-lH-pyrrole-1, 2-diyl -lH-pyrrole-1, 2-diyl

-lH-pyrrole-3, 4-diyl -lH-pyrrole-3, 4-diyl

-lH-pyrrole-3, 4-diyl

-lH-pyrrole-3, 4-diyl

-l-methyl-lH-pyrrole-3, 4-diyl

-l-methyl-lH-pyrrole-3, -diyl -l-methyl-lH-pyrrole-3, 4-diyl

-l-methyl-lH-pyrrole-3, 4-diyl

-l-methyl-lH-pyrrole-3, 4-diyl -l-methyl-lH-pyrrole-3, -diyl

-l-methyl-lH-pyrrole-3, 4-diyl

-l-methyl-lH-pyrrole-2, 5-diyl

-l-methyl-lH-pyrrole-2, 5-diyl

-1-methyl-lH pyrrole-2, 5-diyl

-l-methyl-lH-pyrrole-2, 5-diyl

-l-methyl-lH-imidazole-4, 5-diyl -l-methyl-lH-imidazole-4, 5-diyl

___ X, X ^Λ

-l-methyl-lH-imidazole-4 , 5-diyl

-l-methyl-lH-imidazole-4, 5-diyl

-l-methyl-lH-imidazole-4, 5-diyl -1-methyl-lH- i mida zole- , 5-diyl

-l-methyl-lH-imidazole-4, 5-diyl

-lH-imidazole-1, 5-diyl

-lH-imidazole-1, 5-diyl -lH-imidazole-1, 4-diyl

-lH-imidazole-1, 4-diyl -1H-1, 2, 3-triazole-4, 5-diyl

-1H-1, 2, 3-triazole-4, 5-diyl -1H-1, 2, 3-triazole-l, 5-diyl

-1H-1, 2, 3-triazole-l, 5-diyl

-1H-1, 2, 3-triazole-l, 4-diyl -1-methyl-lH-l, 2, 3-triazole-4, 5-diyl

-1-methyl-lH-l, 2, 3-triazole-4, 5-diyl

-1-methyl-lH-l, 2, 3-triazole-4, 5-diyl

-1-methyl-lH-l, 2, 3-triazole-4, 5-diyl 2, 6-naphthalenediyl

2, 6-naphthalenediyl

2, 3-dihydro-lH-indene-2, 6-diyl

2, 3-dihydro-lH-indene-2, 6-diyl 2, 3-dihydro-lH-indene-2, 6-diyl

2,3-dihydro-lH-indene-l,5-diyl 2,3-dihydro-lH-indene-l,7-diyl -1,2,3,4-tetrahydro-l,8-naphthalenediyl -1,2,3,4-tetrahydro-l,8-naphthalenediyl

-1,2,3,4-tetrahydro-l,8-naphthalenediyl

-1,2,3,4-tetrahydro-l,8-naphthalenediyl -5,6,7,8-tetrahydro-l,7-naphthalenediyl

-5,6,7,8-tetrahydro-l,7-naphthalenediyl

-1,2,3,4-tetrahydro-l,5-naphthalenediyl

-1,2,3,4-tetrahydro-l,5-naphthalenediyl

-1,2,3, -tetrahydro-l,7-naphthalenediyl

-1,2,3,4-tetrahydro-l,7-naphthalenediyl -1,2,3,4-tetrahydro-2,7-naphthalenediyl

-1,2,3,4-tetrahydro-2,7-naphthalenediyl -benzo[b]thiophene-2,6-diyl

-benzo[b] hiophene-2,6-diyl

-benzo[b]thiophene-2,6-diyl -benzo[b]thiophene-2,6-diyl

-2,5-benzofurandiyl-

-2,5-benzofurandiyl-

-2,5-benzofurandiyl-

-2,5-benzofurandiyl- -2,5-benzofurandiyl-

-2,7-benzofurandiyl-

-2,7-benzofurandiyl- -2,7-benzofurandiyl-

^{1 3}

-2,7-benzofurandiyl -2,7-benzofurandiyl -2,6-benzofurandiyl -2,6-benzofurandiyl -2,6-benzofurandiyl

2,3-quinolinediyl 2,3-quinolinediyl 2,3-quinolinediyl

2,3-quinolinediyl 3,6-quinolinediyl

3,6-quinolinediyl 3,7-quinolinediyl

3,7-quinolinediyl 2,4-isoquinolinediyl

2, -isoquinolinediyl

2-chloro-3,7-quinolinediyl 2-chloro-3,7-quinolinediyl

6- luoro-3,7-quinolinediyl

6-fluoro-3,7-quinolinediyl -2-methoxy-3,7-quinolinediyl

-2-methoxy-3,7-quinolinediyl

-2-methoxy-3,7-quinolinediyl i-Bu)Ph -2-methoxy-3,7-quinolinediyl

-lH-pyrazole-1,5-diyl

-lH-pyrazole-1,5-diyl -3-methyl-lH-pyrazole-l, -diyl

g, g ¹ x _r x ^J

-3-methyl-lH-pyrazole-l,4-di -lH-pyrazole-3,5-diyl

-lH-pyrazole-3,5-diyl

-lH-pyrazole-3,5-diyl

-lH-pyrazole-3,5-diyl

-lH-pyrazole-3,5-diyl 4-chloro-lH-pyrazole-3,5-diy

4-chloro-lH-pyrazole-3,5-diy 4-chloro-lH-pyrazole-3,5-diy l-methyl-lH-pyrazole-3,5-diy l-methyl-lH-pyrazole-3,5-diy

C(=0)2,6-dimethylmorpholino Cl l-methyl-lH-pyrazole-3,5-diy l-methyl-lH-indole-3,5-diyl l-methyl-lH-indole-3,5-diyl l-methyl-lH-indole-3,5-diyl

-lH-indole-1,2-diyl

-lH-indole-1,2-diyl

-lH-indole-1,2-diyl -lH-indole-1,2-diyl

-lH-indole-1,2-diyl

-lH-indole-2,6-diyl

-lH-indole-2,6-diyl 5-methoxy-l-methyl-lH-indole-

2,3-diyl

6-methoxy-l-methyl-lH-indole-

2,3-diyl lH-indazole-1,7-diyl lH-indazole-1,7-diyl

- ³

lH-indazole-1,7-diyl lH-indazole-1,3-diyl lH-indazole-1,3-diyl lH-indazole-1,3-diyl lH-indazole-1,5-diyl lH-indazole-1,5-diyl lH-indazole-3,5-diyl lH-indazole-3,5-diyl lH-benzimidazole-1,2-diyl lH-benzimidazole-1, -diyl lH-benzimidazole-1,2-diyl lH-benzimidazole-1,5-diyl lH-benzimidazole-1,5-diyl lH-benzimidazole-1,6-diyl lH-benzimidazole-1,6-diyl lH-benzimidazole-1,6-diyl 2-amino-lH-benzimidazole-l,2-diyl

2-amino-lH-benzimidazole-l,2-diyl lH-benzimidazole-2,5-diyl lH-benzimidazole-2,5-diyl lH-benzimidazole-2,4-diyl lH-benzimidazole-2,4-diyl -l-methyl-lH-benzimidazole-2,5-diyl

-l-methyl-lH-benzimidazole-2,5-diyl -l-methyl-lH-benzimidazole-2,5-diyl

³ X ¹

-l-methyl-lH-benzimidazole-2, 5-diyl methylenedi-4,1-phenylene methylenedi-4,1-phenylene methylenedi-4,1-phenylene methylenedi-4,1-phenylene methylenedi-4,1-phenylene

1,2-ethanediylbis(4,1-phenylene)-

1,2-ethanediylbis(4,1-phenylene)- 1,2-ethanediylbis(4,1-phenylene)- 1,2-ethanediylbis(4,1-phenylene)-

1,2-ethanediylbis(4,1-phenylene) 1,2-ethenediylbis(4,1-phenylene)-

1,2-ethenediylbis(4,1-phenylene)-

1,2-ethenediylbis(4,1-phenylene)- ethynediylbis(4,1-phenylene)- ethynediylbis(4,1-phenylene)- ethynediylbis(4,1-phenylene)- -carbonyldi-4,1-phenylene-

-carbonyldi-4,1-phenylene-

-carbonyldi-4,1-phenylene- methyliminobis-(4,1-phenylene)- methyliminobis-(4,1-phenylene)- -iminodi-4,1-phenylene

-iminodi-4,1-phenylene -iminodi-4,1-phenylene

^**

N0 ₂ )Ph -oxydi-4,1-phenylene -oxydi-4,1-phenylene

-oxydi-4,1-phenylene

oxymono(3,1-phenylene)mono(4,1-phenylene)- oxymono(3,1-phenylene)mono(4,1-phenylene)- oxymono(3,1-phenylene)mono(4,1-phenylene)- oxymono(3,1-phenylene)mono(4,1-phenylene)-

-oxydi-3,1-phenylene

-oxydi-3,1-phenylene -oxydi-3,1-phenylene -oxydi-3,1-phenylene

oxymono(2,1-phenylene)mono(4,1-phenylene)- oxymono(2,1-phenylene)mono(4,1-phenylene)- oxymono (2,1-phenylene)mono(4,1-phenylene)- oxymono(2,1-phenylene)mono(4,1-phenylene)- -thiodi-4,1-phenylene

-thiodi-4,1-phenylene -thiodi-4,1-phenylene

-thiomono(3,1-phenylene)mono(4,1-phenylene) -thiomono(3,1-phenylene)mono(4,1-phenylene)

-thiomono(3,1-phenylene)mono(4,1-phenylene) thiodi-3,1-phenylene thiodi-3,1-phenylene thiodi-3,1-phenylene -sulfinyldi-4,1-phenylene -sulfinyldi-4,1-phenylene

^{1 ' 1} fi

sulfinylmono(3,1-phenylene)mono(4,1-phenylene) sulfinylmono(3,1-phenylene)mono(4,1-phenylene) sulfonyldi-4,1-phenylene sulfonyldi-4,1-phenylene sulfonyldi-4,1-phenylene sulfonyldi-4,1-phenylene

sulfonylmono(3,1-phenylene)mono(4,1-phenylene) sulfonylmono(3,1-phenylene)mono(4,1-phenylene) sulfonylmono(3,1-phenylene)mono(4,1-phenylene) -4,5-thiazolediyl

-4,5-thiazolediyl -3,4-cinnolinediyl-

-3,4-cinnolinediyl-

-3,4-cinnolinediyl- -2,3-quinoxalinediyl

-2,3-quinoxalinediyl -6-chloro-2,3-quinoxalinediyl

-6-chloro-2,3-quinoxalinediyl -1-methyl-lH-l,2,4-triazole-3,5-diyl

-1-methyl-lH-l,2,4-triazole-3,5-diyl 3-chlorobenzo[b]thiophene-2, 5-diyl

3-chlorobenzo[b]thiophene-2,5-diyl

3-chlorobenzo[b]thiophene-2,5-diyl -[1,1• :4',l"-terphenyl]-4,4"-diyl -[1,1* :4',l"-terphenyl]-4,4"-diyl

G. G ¹ Xr X ³

-[1,1' :4•,l"-terphenyl]-4,4"-diyl -[1,1' :4',l"-terphenyl]-4,4"-diyl

-[1,1 ^» :2',1"-terphenyl]-3,3"-diyl

-[1,1' :2',l"-terphenyl]-3,3"-diyl imino imino imino imino imino imino imino

-[1,1'-biphenyl]-4,4'-diyl

-[1,1'-biphenyl]-3,3'-diyl

-[1,1'-biphenyl]-3,3*-diyl

-[1,1'-biphenyl]-3,3'-diyl

-[1,1'-biphenyl]-3,3'-diyl benzo[b]thiophene-2,3-diyl benzo[b]thiophene-2,3-diyl benzo[b]thiophene-2,3-diyl benzo[b]thiophene-2,3-diyl benzo[b]thiophene-2,3-diyl ethyne-1,2-diyl ethyne-1,2-diyl 2-butyne-l,4-diyl 2-butyne-l,4-diyl

G. G- ¹

C(=0)N(Me) ₂

C (=0) azetidino

C (=0) pyrrolidino

C (=0) piperidino

C (=0) homopiperidino

C (=0) NH-i-Bu C(=0)N(Me) ₂

____A

CO-t-Bu Cl COEt Cl

0 II CO-t-Bu Cl CO-t-Bu Cl

O 0

II II COCH ₂ CF ₃ Cl COEt Cl

O II

COCH ₂ CH ₂ OCH ₃ Cl COEt Cl

CH ₃ CH ₂ C Cl CH ₃ CH ₂ C Cl

O o

II

C1CH ₂ C Cl C1CH ₂ C Cl

0 O

II II

CH ₃ OCH ₂ CH ₂ C Cl CH ₃ OCH ₂ CH ₂ C Cl

¹

3-OCH ₃ -Ph-C

II

3-OCH ₃ -Ph-C Cl O Cl

2-Me-Ph-C 2-Me-Ph-C II

Cl O Cl

s o

II II

(Me) ₂ -N-C- Cl (Me) ₂ -N-C- Cl

O II NsC- Cl (Me) ₂ "N-C- Cl

S-CH ₃ Cl S-CH ₃ Cl

O O

II II

Ph-S- Cl Ph-S- Cl

Ph-S0 ₂ - Cl Ph-S0 ₂ - Cl

4-Cl-Ph-S0 ₂ Cl 4-Cl-Ph-S0 ₂ Cl

O O

II II

(Me) ₂ -N-C Cl H ₂ N-C Cl

Ph-S Cl Ph-S Cl

O O

II II

(Et) -N-C Br (Et) ₂ -N-C Cl

_XaElE_≥

E ³

79

(Me) ₂ N (Me) ₂ N (Me) ₂ -N

I&B l 3.

x ³

TABLE 7

(Me) ₂ ~N pyrrolidino piperidino (Me) ₂ -N (Me) ₂ -N pyrrolidino piperidino

OEt

O-i-Pr

O-t-Bu OEt

OEt CH ₃

BrCH ₂ - CH ₃ OCH ₂ CH ₂ 0 CF ₃ CH ₂ 0 CH ₃ OCH ₂ -

Ph

Ph

Ph

4-Cl-Ph

4-Cl-Ph

2,4-F-Ph

4-Me-Ph 4-CH ₃ 0-Ph

4-CN-Ph

2,4-F-Ph

Ph 4-N0 -Ph

2 ³

TABLE 8

s ³

E ³

______

Σ £

£

CH ₃ C Cl N0 ₂ CN

TABLE 10

Cl

Cl Cl

Cl

Cl

Cl

Cl

Cl

Cl Cl

Br Cl

Cl

Cl

Cl

Cl

Cl

Br

Cl

Cl

Cl

Cl

Cl Cl

Cl

Cl

Cl Cl

Cl S0 ₂ (2-C1 Ph)

TABLE 11

(Me) ₂ -N C-S Cl pyrrolidino C-S Cl piperidino C-S Cl

(Me) ₂ -N C-S Br

(Me) ₂ -N C-0 Br pyrrolidino C-0 Br piperidino C-0 Br

OEt C-0 Cl

O-i-Pr C-0 Cl

O-t-Bu C-0 Cl

OEt C-0 Cl

OEt C-0 Br

CH3 C-0 Cl

BrCH ₂ - C-0 Cl

CH ₃ OCH ₂ CH ₂ 0 C-0 Cl

CF ₃ CH ₂ 0 C-0 Cl

CH ₃ OCH ₂ - C-0 Cl

Ph C-0 Cl

Ph C-0 Br

Ph C-0 Br

4-Cl-Ph C-0 Cl

4-Cl-Ph C-0 Br

2,4-F-Ph C-0 Cl

4-Me-Ph C-0 Cl

4-CH ₃ 0-Ph C-0 Cl

4-CN-Ph C-0 Cl

2,4-F-Ph C-0 Cl

Ph C-0 Br

4-N0 ₂ -Ph OO Cl

CN Cl

(Me) ₂ -N C-0 S0 ₂ (2-

TABLE 12

97

TABLE 13

£

O II

CH ₃ NHC Cl H

(CH ₃ -OCH ₂ CH ₂ )2NC Cl H

S

II

(Me) ₂ NC Cl H

S

II

(Me) ₂ NC Cl

C

II

COEt Cl H

O

II

-CO-t-Bu Cl H

O

II

CH ₃ OCH C Cl H

O

II

CF ₃ CH ₂ OC- Cl H

£ ^■ Si *ι

o

II

TABLE 14

101

T B E I ^** .

(Me) ₂ -N O Cl (Me) ₂ -N C-0 Cl pyrrolidino C-0 Cl pyrrolidino C-0 Cl piperidino C-0 Cl piperidino C-0 Cl 2,6-di-Me-morpholino C-0 Cl 3,3'-di-Me-piperidino C-0 Cl 3-Me-piperidino C-0 Cl 3-Me-piperidino C-0 Cl 3,3'-di-Me-piperidino C-0 Cl 3,3'-di-Me-piperidino C-0 Cl Me-NH C-0 Cl Me-NH C-0 Cl (Et) ₂ -N C-0 Cl (Et) ₂ -N C-0 Cl

Me,i-Pr-N C-0 Cl Me,i-Pr-N C-0 Cl (MeOCH ₂ CH ₂ ) ₂ -N C-0 Cl (MeOCH ₂ CH ₂ ) ₂ -N C-0 Cl (Me) -N C-S Cl (Me) ₂ -N C-S Cl pyrrolidino C-S Cl pyrrolidino C-S Cl piperidino C-S Cl piperidino C-S Cl

3,3'-di-Me-piperidino C-S Cl 3,3'-di-Me-piperidino OS Cl t-Bu-NH C-O Cl t-Bu-NH C-0 Cl

CF ₃ CH -NH C-0 Cl CF ₃ CH ₂ -NH C-0 Cl

(Me) -N C-0 Br (Me) ₂ -N C-0 Br pyrrolidino C-0 Br pyrrolidino C-0 Br piperidino C-0 Br piperidino C-0 Br

. Σ

TABLE lβ

£

O O

II II

H ₂ NC- Cl Cl H ₂ NC- Cl

O O

II II

H ₂ NC- Cl Cl (Me) ₂ NC Cl

O O

II II

(Me) ₂ NC Br Cl (Me) ₂ NC Cl

O O

II II

(Me) ₂ NC Br Cl (Me) ₂ NC Br

S II

(Me) ₂ N-C Cl Cl (Me) ₂ N-C Cl

S S

II II

(Me) ₂ NC Cl Cl (Me) ₂ NC Cl

O O

II II

COEt Cl Cl COEt Cl

£ •Gl Xi

o

II

CO-t-Bu Cl Cl CO-t-Bu Cl

O O

II II

COCH ₂ CF ₃ Cl Cl COCH ₂ CF ₃ Cl

O o

II II

COCH ₂ CF ₃ Cl COCH ₂ CF ₃ Cl

0

II

COCH ₂ CF ₃ Cl COEt Cl

0

II

COEt Br COEt Br

O 0

II II

CH ₃ OCH ₂ C Cl CH ₃ OCH ₂ C Cl

O

I!

COEt Cl (Me) ₂ -NC Cl

o S

II II COEt Cl (Me) ₂ -NC Cl

NsC Cl NsC- Cl

NsC Br NsC- Br

£ ≤l Xi

O

II

N≡C Cl Br (Me) ₂ NC- Cl

CH ₃ S Cl Br CH ₂ -S- Cl

O O

II II

CH ₃ S- Cl NC CH ₃ -S Cl

CH ₃ S0 ₂ - Cl CH ₃ S0 ₂ - Cl

O

II

(Me) ₂ NC- Cl CH ₃ (Me) ₂ NC Cl

II

(Me) ₂ NC- Cl CH ₃ (Me) ₂ NC Cl

s

II

(Me) ₂ NC- Cl CH ₃ (Me) ₂ NC Cl

H N-C- Cl CH-: H ₂ N-C- Cl

O o

II II

COEt Cl CH ₃ COEt Cl

COEt Cl CH ₃ (Me)2-NC- Cl

£ fii -Xi

NsC Cl CH, NsC Cl

TABLE 17

TABLE 18

(Me) ₂ -N C-0 Cl pyrrolidino C-0 Cl piperidino C-0 Cl

3,3'-di-Me-piperidino C-0 Cl

3-Me-piperidino OO Cl

3,3'-di-Me-piperidino C-0 Cl

Cl Cl

Cl Cl Cl

Cl Cl Cl Cl Cl

TABLE IQ

E

TABLE 111

£

O 0

II II

(Me) ₂ NC Cl H (Me) ₂ NC Cl

o O

II II H NC Cl H H ₂ NC Cl

O O

II II

(Me) ₂ NC Cl H H ₂ NC Cl

O O

II II

H ₂ NC Cl H (Me) ₂ NC Cl

O o II II t-C ₄ H ₉ NH-C Cl H t-C ₄ H ₉ NH-C Cl

O O

II II

COEt Cl H COEt Cl

£ ≤ ³

o

II COEt Cl H (Me) ₂ NC Cl

O O

II II

(Me) ₂ NC Cl H COEt Cl

O II

(Me) ₂ NC Cl H N=C- Cl

0

II

NsC- Cl H (Me) ₂ NC- Cl

O

II

CH ₃ C Cl H CH ₃ C- Cl

CH ₃ S0 ₂ - Cl H CH ₃ S0 ₂ - Cl pyrrolidino-CO Cl H pyrrolidino-CO Cl piperidino-CO Cl H piperidino-CO Cl

Ph Cl H Ph Cl

4-OCH ₃ -Ph Cl H 4-OCH3-Ph Cl

Ph Br H Ph Br

PhS0 ₂ - Cl H PhS0 - Cl

(Me)2-N-CO Cl Cl (Me) ₂ -N-CO Cl pyrrolidino-CO Cl Cl piperidino-CO Cl

2,6-di-Me-morpholino-CO Cl Cl 2,6-di-Me-morpholino-CO Cl

3,5-di-Me-piperidino-CO Cl Cl 3,5-di-Me-piperidino-CO Cl

C0 ₂ -i-Pr Cl Cl C0 ₂ -i-Pr Cl

Ph Cl Cl Ph Cl

£

(Et) 2- -CO Cl (Me) ₂ -N-CO Cl

C0 ₂ -Et Cl

Cθ2~Bu Cl

C02-CH ₂ CF ₃ Cl

CH ₃ -CO Cl

Br-CH ₂ -CO Cl

TABLE 21

TABLE 22

TABLE 23

X

H ₂ N (Me) ₂ -N pyrrolidino piperidino (Me) ₂ -N

(Me) ₂ -N pyrrolidino piperidino

OEt

O-i-Pr OEt

OEt CH ₃

BrCH ₂ -

CH ₃ OCH ₂ CH ₂ 0

CF ₃ CH ₂ 0

CH ₃ OCH ₂ -

Ph

Ph

Ph

4-Cl-Ph

4-Cl-Ph

2,4-F-Ph

4-Me-Ph 4-CH ₃ 0-Ph

4-CN-Ph

2,4-F-Ph

Ph 4-N0 -Ph

TABLE ^■ >.&

(Me) ₂ -N OO Cl (Me) ₂ -N C-0 Cl pyrrolidino C-0 Cl pyrrolidino C-0 Cl piperidino C-0 Cl piperidino C-0 Cl

2, 6-di-Me-morpholino C-0 Cl 3,3'-di-Me-piperidino C-0 Cl

3-Me-piρeridino C-0 Cl 3-Me-piperidino C-0 Cl

3, 3 ' -di-Me-piperidino C-0 Cl 3,3'-di-Me-piperidino C-0 Cl

Me-NH OO Cl Me-NH C-0 Cl

(Et) ₂ "N C-0 Cl (Et) ₂ -N C-0 Cl

Me, i-Pr-N C-0 Cl Me,i-Pr-N C-0 Cl

(MeOCH ₂ CH ₂ ) 2-N C-0 Cl (MeOCH ₂ CH ₂ ) ₂ -N C-0 Cl

(Me) 2-N ^' OS Cl (Me) ₂ -N C-S Cl pyrrolidino C-S Cl pyrrolidino C-S Cl piperidino OS Cl piperidino C-S Cl

3,3'-di-Me-piperidino C-S Cl 3,3'-di-Me-piperidino OS Cl t-Bu-NH OO Cl t-Bu-NH OO Cl

CF ₃ CH ₂ -NH OO Cl CF ₃ CH ₂ -NH OO Cl

(Me)2-N C-O Br <Me) -N OO Br pyrrolidino C-0 Br pyrrolidino OO Br piperidino C-0 Br piperidino C=0 Cl

H ₂ N C-0 Cl H ₂ N C-0 Cl

H ₂ N C-S Cl H ₂ N OS Cl

H ₂ N C-S Cl H ₂ N OO Cl

TABLE 2, ^* ?

(Me) ₂ -N C-0 Cl (Me) ₂ -N OO Cl pyrrolidino C-0 Cl pyrrolidino C-0 Cl piperidino C-0 Cl piperidino C-0 Cl

2,6-di-Me-morρholino C-0 Cl 3, 3 ' -di-Me-piperidino C-0 Cl

3-Me-piperidino C-0 Cl 3-Me-piperidino C-0 Cl

3,3'-di-Me-piperidino C-0 Cl 3, 3 ' -di-Me-piperidino OO Cl

Me-NH C-0 Cl Me-NH OO Cl

(Et) ₂ -N C-0 Cl (Et) ₂ -N C-0 Cl

Me,i-Pr-N C-0 Cl Me, i-Pr-N C-0 Cl

(MeOCH ₂ CH ₂ ) ₂ -N C-0 Cl (Me) CH ₂ CH ₂ ) ₂ -N C-0 Cl

(Me) ₂ -N C-S Cl (Me) ₂ -N OS Cl pyrrolidino C-S Cl pyrrolidino OS Cl piperidino C-S Cl piperidino C-S Cl

3,3'-di-Me-piperidino C-S Cl 3, 3 ' -di-Me-piperidino C-S Cl t-Bu-NH C-0 Cl t-Bu-NH OO Cl

CF ₃ CH ₂ -NH C-0 Cl CF ₃ CH ₂ -NH OO Cl

(Me) ₂ -N C-0 Br (Me) ₂ -N C-0 Br pyrrolidino C-0 Br pyrrolidino OO Br piperidino C-0 Br piperidino C-0 Cl

H ₂ N C-0 Cl H ₂ N OO Cl

H ₂ N C-S Cl H ₂ N OS Cl

TABLE 26

TABLE 27

Ph 4-N0 ₂ -Ph

TABLE 28

(Me) 2-N C-0 Cl pyrrolidino C-0 Cl piperidino C-O Cl

2, 6-di-Me-morpholino C-0 Cl

3-Me-piperidino C-0 Cl

3, 3 ' -di-Me-piperidino C-0 Cl

Me-NH C-O Cl

(Et) ₂ ~N C-0 Cl

Me, i-Pr-N C-0 Cl

(MeOCH ₂ CH ₂ ) ₂ -N C-0 Cl

(Me)2-N C-S Cl pyrrolidino C-S Cl piperidino C-S Cl

3,3'-di-Me-piperidino C-S Cl t-Bu-NH C-0 Cl

CF ₃ CH ₂ -NH C-O Cl

(Me)2-N C-0 Br pyrrolidino C-O Br piperidino C-0 Br

H ₂ N C-0 Cl

^■ 2 ^**

H ₂ N H ₂ N (Me) ₂ -N pyrrolidino piperidino (Me) ₂ -N

(Me) ₂ -N pyrrolidino piperidino

OEt

O-i-Pr

O-t-Bu OEt

OEt CH ₃

BrCH ₂ -

CH ₃ OCH ₂ CH ₂ 0

CF ₃ CH ₂ 0

CH ₃ OCH ₂ -

Ph

Ph

Ph

4-Cl-Ph

4-Cl-Ph

2,4-F-Ph

4-Me-Ph 4-CH ₃ OPh

4-CN-Ph 2, -F-Ph

CN Cl CN Cl

Formulations

The compounds of this invention will generally be used in formulation with a liquid or solid diluent or with an organic solvent. Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 1% to 99% by weight of active ingredient(s) and at least one of a) about 0.1% to 20% surfactant(s) and b) about 5% to 99% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:

Percent by Weight

Active Ingredient(s) Diluent(s) Surfactantfs)

Wettable powders 20-90 0-74 1-10 and Water Disper- sible Granules

Oil Suspensions, 5-50 40-95 0-15 Emulsions, Solutions, (including Emulsifiable Concentrates)

Aqueous Suspensions 10-50

Dusts 1-25

Granules and Pellets 1-95

High Strength 90-99 Compositions

Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank ^• mixing. Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, New Jersey, but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide," 2nd Ed.,

Interscience, New York, 1985. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0°C. "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiological growth, etc. Preferably, ingredients should be approved by the U.S. Environmental Protection Agency for the use intended.

The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Water dispersible granules may be produced by agglomerating a fine powder composition (see, for example, B. Cross and H. Scher, "Pesticide Formulations", ACS Symposium Series 371, American Chemical Society, Washington, D.C., 1988, pp. 251-259). Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Che- irpl Engineering.

December 4, 1967, pp. 147ff. and 'Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.

For further information regarding the art of formulation, see for example:

H. M. Loux, U.S. Patent 3,235,361, February 15, 1966, CoL 6, line 16 through Col. 7, line 19 and Examples 10 through 41;

R. W. Luckenbaugh, U.S. Patent 3,309,192, Marchl4, 1967, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;

H. Gysin and E. Knusli, U.S. Patent 2,891,855, June 23, 1959, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4;

G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pp. 81-96; and

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.

Examples of useful formulations of compounds of the present invention are as follows.

EXAMPLE A Wettable Powder

N,N'-[l,3-phenylenebis-(carbonyloxy)]bis- [2-(di ethylammo)-2-oxoethanimidoyl chloride] 80% sodium alkylnapthalenesulfonate 4% sodium ligninsulfonate 2% synthetic amorphous silica 1% kaolinite 13%

The ingredients are blended, ihammermilled, re-blended and packaged.

EXAMPLE S

High Strength Concentrate N, -[l,3-phenylenebis-(carbonyloxy)]bis- [2-(dimethylamino)-2*<)xoethanimidoyl chloride] 98.5% silica aerogel 0.5% synthetic amorphous silica 1.0%

The ingredients are blended and ground in a hammermill to produce a high strength concentrate essentially all passing a U.S.S. No. 50 Sieve (0.3 mm openings). This material may then be formulated in a variety of ways.

EXAMPLE C Solution

N,N'-[l,3-phenylenebis-(carbonyloxy)]bis- [2-(dimethylammo)-2-oxoethanimidoyl chloride] 30%

N-methyl-2-pyrrolidone 70%

The ingredients are combined and stirred to produce a solution, which can be used for low volume applications.

Utility

The compounds of this invention are useful as plant disease control agents. They provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete. Ascomycete. and Oomycete classes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal, and fruit crops. These pathogens include, Plasmopara viticola. Phvtophthora -i ^* nfep ^* .p ^* n« ^g , Peronospora tabacina. Pseudoperonospora cubensis. Pyth- im aphanider ^* m?t. τn , Alternaria brassicae. Septoria τι f>r1nnτm _τ Cercospori iiT-n personatum. Cercospora arachidicola. Pseudocercosporella herpotrichoides. Cercospora beticola. Botrytis cinerea. Monilinia fructicola. Pyricularia oryzae. Podosphaera

leucotricha. Venturia ififlegnfll-is- Puccinia recondita. Puccinia grflm-m-in-is. and other species closely related to these pathogens.

The compounds of this invention can be mixed with fungicides, bactericides, acaricides, nematicides, insecticides or other biologically active compounds in order to achieve desired results with a -m-m-m- -m of expenditure of time, effort and material. Suitable agents of this type are well-known to those skilled in the art. Some are listed below:

iTTiffir-if s; methyl 2-benzimidazolecarbamate (carbendazim) tetramethylthiuram disulfide (thiuram) n-dodecylguanidine acetate (dodine) manganese ethylenebisditbiocarbamate (maneb) l,4-dichloro-2,5-dimethoxybenzene (chloroneb) methyl l-(butylcarbamoyl)-2-benzimidazolecarbamate

(benomyl) 2-cyano-N-ethylcarbamoyl-2-methoxyim oacetamide

(cymoxanil) N-trichloromethylthiotetrahydrophthalamide (captan) N-tricUoromethylthiophthalimide (folpet) dinιethyl 4,4'-(o-phenylene)bis(3-thioallophanate)

(thiophanate-methyl) 2-(tbiazol-4-yl)benzimidazole (thiabendazole) aluminum tris(0-ethyl phosphonateXphosethyl aluminuni) tetrachloroisophthalonitrile (chlorothalonil) 2,6-dichloro-4-nitroaniline (dichloran) N-(2,6-dinιethylphenyl)-N-(methoxyacetyl)alanine methyl ester (metalaxyl) cis-N-[l,l,2,2-tetrachloroethyl)thio]cyclohex-4-ene-

1,2-dicarbioximide (captafol)

3-(3,5-dichlorophenyl)-N-(l-methylethyl)-2,4-dioxo-l- imidazolidine carboxamide (iprodione) 3-(3,5-dichlorophenyl)-5-ethenyl-5-methyl-2,4-oxazoli- dinedione (vinclozolin) kasugamycin 0-ethyl-S,S-diphenylphosphorodithioate (edifenphos) 4-(3-(4-(l,l-dimethyl-ethyl)phenyl)-2-methyl)propyl-

2,6-dimethylmorpholine (fenpropimorph) 4-(3-4(l,l-dimethyl-ethyl)phenyl)-2-methyl)propylpi- peridine (fenpropidine) l-(4-cMorophenoxy)-3,3-dimethyl-l-lH-l,2,4-triazol-l- yDbutanone (triadimefon) 2-(4-chlorophenyl)-2-(lH-l,2,4-triazol-l-ylmethyl)- hexanenitrile (myclobutanil) a-[2-(4-cMorophenyl)ethyl]-alpha-(l,l-dimethylethyl)- lH-l,2,4-triazole-l-ethanol (tebuconazol)

3-chloro-4-[4-methyl-2-(lH-l,2,4-tria2θl)-l-ylmethyl)- 1 ,3-dioxolan-2-yl]phenyl-4-chlorophenyl ether (difenoconazole) l-[2-(2,4-dichlorophenyl)pentyl]lH-l^,4-triazole (penconazole) '

(+a-(2-fluorophenyl-V-(4-fluorophenyl)-lH-l,2,4- triazole-1-ethano (flutriafol) l-[[bis(4-fluorophenyl)methylsilyl)methyl]-lH-l^,4- triazole (flusilazol) l-N-propyl-N-[2(2,4,6-trichlorophenoxy) ethyl]- carbamoylimidazole (prochloraz) l-[[2-(2,4-dichlorophenyl)-4-propyl-l,3-dioxolan-2- yl]methyl]-lH-l,2,4-triazole (propiconazole) a-(2-chlorophenyl)-a-(4-chlorophenyl)-5-pyridine- methanol (fenarimol) copper oxychloride

methyl N-(2,6-dimethylphenyl)-N-(2-furanylcar- bonyl)-DL-alaninate (furalaxyl)

Bactericides tribasic copper sulfate streptomycin sulfate osytetracycline

Acaricides senecioic acid, ester with2-sec-butyl-4,6- dinitro-phenol (binapacryl)

6-nιethyl-l,3-dithiolo[2,3-b]quinonoliή-2-one

(oxythioquinox) 2,2,2-trichloro-l,l-bis(4-chlorophenyl)ethanol (dicofol) bis(pentachloro-2,4-cyclopentadien-l-yl)(dienochlor) tricyclohexyltin hydroxide (cyhexatin) hexakis(2-methyl-2-phenylpropyl)distannoxane (fenbutin oxide)

Nematicides

2-[diethoxyphosphinylimino]-l ,3-diethietane (fosthietan) S-metiιyl-l-(d__αnethylcarbaιnoyl)-N-(nιethylcarbanιoyl oxy)- thioformimidate (oxamyl) S-methyl-l-carbamoyl-N-(methylcarbamoyloxy)thio- formimidate

N-isopropylphosphoramidic acid, 0-ethyl-0'-[4-(methyl- thio)-m-tolyl]diester (fenamiphos)

Insecticides 3-hydroxy-N-methylcrotonamide(dimethylphosphate)ester (monocrotophos)

methylcarbamic acid, ester with 2,3-dihydro-2,2- dimethyl-7-benzofuranol (carbofuran) 0-[2,4,5-trichloro-a-(chloromethyl)benzyl]phosphoric acid, 0',0'-dimethyl ester (tetracMorvinphos) 2-mercaptosuccinic acid, diethyl ester, S-ester with thionophosphoric acid, dimethyl ester (malathion) phosphorothioic acid, 0,0-dimethyl, 0-p-nitrophenyl ester (methyl parathion) methylcarbamic acid, ester with a-naphthol (carbaryl) methyl N-[[(methylam o)carbonyl]oxy]ethanimidothio- ate (methomyl) N'-(4-cMoro-o-tolyl)-N^-dinιethylfoπnamidine (chlordimeform)

0,0-diethyl-0-(2-isopropyl-4-methyl-6-pyrimidyl)- phosphorothioate (diazinon) octachlorocamphene (toxaphene)

O-ethyl O-p-nitrophenyl phenylphosphonothioate (EPN) cyano(3-phenoxyphenyl)-methyl 4-chloro-a-( 1-methyl- ethyDbenzeneacetate (fenvalerate) (3-phenoxyphenyl)methyl (+)-cis,trans-3-(2,2-dichloro- ethenyl)-2,2-dimethylcydopropanecarboxylate (permethrin) dimethyl NJ^-[thiobis(N-methylimino)carbonyloxy]]- bis[ethanimidothioate] (thiodicarb) phosphorothiolothionic acid, 0-ethyl-O-[4-(methyl- thio)phenyl]-S-n-propyl ester (sulprofos) a-cyano-3-phenoxybenzy! 3-(2,2-dichlorovinyl)-2,2- dimethylcyclopropane carboxylate (cypermethrin) cyano(3-phenoxyphenyl)methyl 4-(difluoromethoxy)- a-(methylethyl)benzeneacetate (flucythrinate) 0,0-diethyl-O-(3,5,6-trichloro-2-pyridyl)phosphoro- thioate (chlorpyrifos)

0,0-dimethyl-S-[(4-oxo-l,2,3-benzotriazin-3-(4H)-yl)- methyl]phosphorodithioate (az phos-methyl) 5,6-diniethyl-2-din ethylamino-4 _^ pyrimidinyl dimethyl carbamate (pirimicarb) S-(N-forιnyl-N-nιethylcarbanιoyb3iethyl)-0,0-diπιethyl phosphorodithioate (formothion)

S-2-(ethylthioethyl)-0,0-dimeΛyl phosphiorothioate (demeton-S-methyl) a-cyano-3-phenoxybenzyl cis-3-(2,2-dibromovinyl)- 2,2-dimethylcyclopropane carboxylate (deltamethrin) < ^* yano(3-phenoxyphenyl)methyl ester of N-(2-chloro-4- trifluoroπιethylphenyl)alanine (fluvalinate)

Application

Disease control is ordinarily accomplished by applying an effective amount of the compound, pre-infection, to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs. The compound may also be applied to the seed, to protect the seed and seedling.

Rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than 10 g ha to 10,000 g ha of active ingredient. Seed and seedlings can normally be protected when seed is treated at a rate of from 0.1 to 10 g per kilogram of seed.

TEST A The test compounds were dissolved in acetone in an amount equal to 3 % of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on apple seedlings. The following day the seedlings were inoculated with a spore suspension of Venturia inaequalis (the causal

agent of apple scab) and incubated in a saturated atmosphere at 20°C for 24 hr, and then moved to a growth chamber at 22°C for 11 days, after which disease ratings were made.

TESTP The test compoτmds were dissolved in acetone in an amount equal to 3 % of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on peanut seedlings. The following day the seedlings were inoculated with a spore suspension nf C**ffrwpft 'faτ ⁿ personatum (the causal agent of peanut late leafspot) and incubated in a saturated atmosphere at 22°C for 24 hr, a high humidity atmosphere at 22°C to 30°C for 5 days, and then moved to a growth chamber at 29°C for 6 days, after which disease ratings were made.

__ __ The test compounds were dissolved in acetone in an amount equal to 3 % of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a causal agent of wheat leaf rust) and incubated in a saturated atmosphere at 20°C for 24 hr, and then moved to a growth chamber at 20°C for 6 days, after which disease ratings were made.

TESTP The test compounds were dissolved in acetone in an amount equal to 3 % of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on rice seedlings. The following day the seedlings were inoculated

with a spore suspension of Pyricularia oryzae (the causal agent of rice blast) and incubated in a saturated atmosphere at 27°C for 24 hr, and then moved to a growth chamber at 30 C for 5 days, after which disease ratings were made.

TEST E

The test compounds were dissolved in acetone in an amount equal to 3 % of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on tomato seedlings. The following day the seedlings were inoculated with a spore suspension of Ph tophthora -mfeRfo-n ^g (the causal agent of potato and tomato late blight) and incubated in a saturated atmosphere at 20°C for 24 hr, and then moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.

TEST F The test compounds were dissolved in acetone in an amount equal to 3 % of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on grape seedlings. The following day the seedlings were inoculated with a spore suspension ofPlasmopara viticola (the causal agent of grape downy mildew) and incubated in a saturated atmosphere at 20°C for 24 hr, moved to a growth chamber at 20°C for 6 days,and then incubated in a saturated atmosphere at 20°C for 24 hr, after which disease ratings were made.

TEST The test compounds were dissolved in acetone in an amount equal to 3 % of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of

run-off on cucumber seedlings. The following day the seedlings were inoculated with a spore suspension ofBotrytis cinerea (the causal agent of gray mold on many crops) and incubated in a saturated atmosphere at 20°C for 48 hr, and moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.

Results for Examples A to G are given in Table A. In the table, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the carrier sprayed controls). NT indicates that no test was performed.

INDEX TABLE A

CMPD NO. G. G ¹ mp f°C)

-1,2-ethanediyl- 148-150

-1,3-benzenediyl- 187-190

-1,3-benzenediyl- 145-147 -1,3-benzenediyl- 122-124

-1,3-butadiene-l,4-diyl 180-183

-1,4-benzenediyl- 177-178

-1,4-benzenediyl- 164-166

-[1,1*-biphenyl]-4,4'-diyl- 233-235

-[1,1*-biphenyl]-4,4*-diyl- 199-200 -2,6-naphthalenediyl- 242-243

-2,6-naphthalenediyl- 222-223

-2,6-naphthalenediyl- 217-218 (dec) -2,6-pyridinediyl- 163-165

-2,6-pyridinediyl- 148-150

-1,2-ethenediyl- 160-164 -1,3-benzenediyl- 253-254 (dec)

-1,4-benzenediyl- 273-274 (dec)

-methylenedi-4,1-phenylene- 230-240 (dec)

-methylenedi-4,1-phenylene- 156-160

-methylenedi-4,1-phenylene- 176-178 -methylenedi-4,1-phenylene- 106-108 -methylenedi-4,1-phenylene- 234-236

(methylenoxy)- 4 C(-0)piperidino Cl -1,3-phenylenebis- 68-72

(methylenoxy)- 6 C(-O)piperidino Cl -3,4-pyridinediyl- oil

CMPD NO. Z S ¹ Σ

7 C(-O)piperidino Cl

8 C(=0)N(Me) ₂ Cl

9 C(=0)piperidino Cl

0 C(=0)N(Me) ₂ Cl benzenediyl- 1 C(=0)piperidino Cl -3,4,5,6-tetrafluoro-1,2- 115-119 benzenediyl- 2 C(=0)pyrrolidino Cl -3,4-furandiyl- 148-150 3 C(=0)homopiperidino Cl -3,4-furandiyl- 132-136 4 C(=0)pyrrolidino Cl -2,6-pyridinediyl- 154-156 5 C(=0)N(Me) ₂ Cl -4,5-dichloro-l,2- 167-169 benzenediyl- 6 C(=0) ipe idino Cl -4,5-dichloro-l,2- 97-99 benzenediyl- 7 C(=0)piperidino Cl -3- luoro-1,2-benzenediyl- oil

CMPD

X _^ x*- mp °C)

Cl -benzo[b]thiophen-2,3-diyl- 100-103

Cl -benzo[b]thiophen-2,3-diyl- oil

S0 ₂ (2-Cl-Ph) -1,2-benzenediyl- 184-185

S0 ₂ (2-Cl-Ph) -1,4-benzenediyl- 175-179 S0 ₂ Ph -1,3-benzenediyl- 85-90

INPEX TABLE P

CMPD

X.X- ¹ Q mp(°C)

-1,3-benzenediyl- 115-120

-1,3-benzenediyl- 176-180

-methylene-di-4,1-phenylene- gum

-methylene-di-4,1-phenylene- 82-83

-methylene-di-4,1-phenylene- 169(dec)

-1,4-benzenediyl- 214-215

-4-methyl-l,3-benzenediyl- 171-178

-4-methyl-l,3-benzenediyl- 103-106

-1,4-benzenediyl- 225-226

-1,4-benzenediyl- 173-179

-1,4-cyclohexanediyl- 186-188

-oxydi-4,1-ρhenylene- 175-177 oxydi-4,1-phenylene- 178-179

-2-methyl-l, 3-benzenediyl- 176-178 -oxydiphenylene-(mono 4,1- 188-193 mono 3,1-)-

INDEX TABLE C

CMPD

NO. £ β ¹ Σ X ¹ Ω. ιτφ t°C)

33 C(-0)N(Me) ₂ C(-0)piperidino Cl -1,3-benzenediyl- 131-136

34 C(-0)N(Me) ₂ C(-0)pyrrolidino Cl -1,3-benzenediyl- 115-118

The following table contains physical property information for those compounds which were not crystallized. In the absence of a melting point, spectral data are given for each compound. Characteristic infrared absorbances are given in wave numbers (reciprocal centimeters).

! = Percent control at 40 ppm, the highest rate tested.

# = Tested at 500 ppm.