WO1992002491A1

WO1992002491A1 - Novel bis-(hydroximidoyl chloride) derivatives as agricultural fungicides

Info

Publication number: WO1992002491A1
Application number: PCT/US1991/005579
Authority: WO
Inventors: Joseph Eugene Drumm, Iii
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 1990-08-06
Filing date: 1991-08-06
Publication date: 1992-02-20
Anticipated expiration: 1993-02-06
Also published as: CN1059713A; IL99078A0; AU8326391A

Abstract

Fungicidally active compounds of formula (I) are disclosed.

Description

TITLE

NOVEL BIS-(HYDROXIMIDOYL CHLORIDE) DERIVATIVES AS AGRICULTURAL FUNGICIDES CROSS-REFERENCE TO RELATED APPLICATION

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 literature 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.

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

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 A¹ are independently O, NH,— CH₂O— ,— CH₂CH₂O— or a direct bond;

G and G¹ are independently C(=O)NR¹R², C(=O)OR³,C(=O)R⁴,

S(O)_nR⁵, SO₂NR¹R² or CN;

X and X¹ are independently SO₂R⁶, Cl or Br;

R¹ and R² are independently H; C₁-C₄ alkyl; C₂-C₄ alkoxyalkyl; or

R¹ and R² 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;

R³ is C₁-C₄ alkyl, C₁-C₄ haloalkyl or C₂-C₄ alkoxyalkyl;

R⁴ 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; R⁵ 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; R⁶ is C₁-C₆ alkyl; C₁-C₆ haloalkyl; C₂-C₆ 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 C₁-C₆ alkylenyl optionally substituted with 1-2 methyl; C₂-C₆ alkenylenyl; C₂-C₆ alkynylenyl; phenylenyl optionally substituted with R⁷; naphthalenyl optionally substituted with R⁷; C₃-C₆ cycloalkylenyl optionally substituted with 1-2 methyl; 1-methylpyrrolyl optionally substituted with R⁹;

1-methylimidazolyl optionally substituted with R⁸; 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 R⁹; NH; or

Z is O, CH₂, S(O)_n, C(=O), NR10, HC=CH, CH₂CH₂, C≡C,

phenylenyl or a direct bond;

R⁷ is 1-4 substitutions selected from the group consisting of halogen, methyl, methoxy, cyano and nitro;

R⁸ is H, halogen, methyl or methoxy;

R⁹ is selected from 1-2 halogen, cyano, methyl or methoxy;

R¹⁰ is H or C₁-C₄ alkyl; and

n is 0, 1 or 2;

provided that:

i) when A or A¹ is— CH₂O— or— CH₂CH₂O— , the carbon atom of these groups is bonded to Q;

ii) when A and Al are NH, Q is not cyclopropylene optionally

substituted with 1-2 methyl;

iii) when Q is C₂-C₆ alkenylenyl or C₂-C₆ alkynylenyl, A and A¹ are— CH₂O— ,— CH₂CH₂O— or a direct bond; and

iv) when Q is NH, A and A¹ 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, 1-methyl-1,2,3-triazole, 1-methyl-1,2,4-triazole, oxazole, isoxazole, and thiazole. Examples of "fused heteroaromatic rings" include quinoline, 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,

CH₂CH=CHCH₂, CH=CHCH₂CH₂, CH₂CH=CHCH₂, CH=CHCH=CH.

Examples of "alkynylene" particularly include CsC and

CH₂C≡CCH₂.

"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 fully 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 "C_i-C_j" 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 Embodiments

Preferred for ease of synthesis and/or increased fungicidal activity are: 1) Compounds of Formula I wherein:

A and A¹ are independently NH,— CH₂O— , or a direct bond; and

Q is C₁-C₆ alkylenyl optionally substituted with 1-2 methyl;

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

wherein designations such as:

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

2) Compounds of Preferred 1, wherein:

A and A¹ are the same;

G and G¹ are both C(=O)NR¹R²;

X and X¹ are both SO₂R⁶ or Cl;

Q is C₁-C₆ alkylenyl optionally substituted with 1-2 methyl;

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

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

3) Compounds of Preferred 2, wherein:

A and A¹ 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'-[1,3-phenylenebis(carbonyloxy)]bis[2-dimethylamino)- 2-oxoethanimidoyl chloride];

2) N,N'-[1,3-phenylenebis(iminocarbonyloxy)]bis[2-dimethyl amino)-2-oxoethanimidoyl chloride; and

3) N,N'-[2,5-thiophenediylbis(carbonyloxy)]bis[2-dimethylamino)-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 alkali 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 1,4-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.

wherein:

R and R¹ may be independently = NCO, COCl, COBr;

X and X¹ may be independently = Cl; Br or SO₂R⁶;

and where G and G¹ 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 III 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: α >

The herein claimed compounds may also be made by the following sequential processes following hterature cited below. Compounds of Formula I where X and X¹ are not the same, may be made as shown:

Alternatively, the substituted hydroximidoyl chlorides or bromides of Formula I can be prepared from the corresponding aldoximes of Formulae VII and VIII 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):

or N-chlorosuccinimide (see K C. Liu, B. R. Shelton, R. K Howe, J. Org. Chem., 1980, 45:3916), or N-bromosuccinimide (see C. Grundman and R. Richter, J. Org. Chem., 1968, 33:476).

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:

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

m

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 III 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.

Compounds of Formulae I, II, and III can be prepared from

compounds of Formulae IV and V and a carboxylic acid Vld in the presence of a coupling auxiliary reagent such as, but not limited to, N,N-dicyclohexylcarbodiimide (DCC) O

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

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

Y

Compounds described by Formula III may be made using an intermediate (XIII) which can be made following the method given by K Mai et al., J. Org. Chem., 1986, 51:3545.

Compounds of the Formula III can also be prepared via the route given below. Phosgene substitutes may also be used (e.g., diphosgene, triphosgene) according to the literature of H. Eckert, B. Forster, Angew. Chem, Int. Ed., Eng., 1987, 26:894; and K Kumita, Y. Iwakura, Org. Synth., 1980, 59:195.

X / v

V

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

Another route to compounds of Formula III is shown below:

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

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 in Heterocyclic Chemistry, Academic Press, NY;

The Chemistry of Heterocyclic Compounds, JohnWiley & Sons, NY, 1982;

Comprehensive Heterocyclic Chemistry, Katritskyand Rees,

Pergamon Press, Oxford, 1984;

Comprehensive Organic Chemistry Barton and Ollis, Pergamon Press, Oxford, 1979;

Heterocyclic Compounds, Elderfield, John Wiley & Sons, NY, 1967;

Rodd's Chemistry of Carbon Compounds, 2nd Ed., Elsevier, 1976; and

Vogel's Textbook of Practical Organic Chemistry, 4th Ed.,

Longman Inc., NY, 1978.

The carboxamide and carboxylic 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. R

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. Chim Belg., 1978, 87, 229 and G. Lajore, F. Lepine, L. Maziak and B. Belleau, 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 α-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, 46:731).

X

The α-chloroaldoximes of Formulae IV and V can also be prepared from aldoximes of Formula XX by treatment with N-chlorosuccinimide (see K E. Larsen and K B. G. Torsell, Tetrahedron. 1984, 40:2985) or t-butylhypochlorite (see C. J. Peake and J. H. Strickland, Synth. Comm., 1986.16:763).

Some α-haloaldoximes of Formulae IV and V may be prepared from amide oximes XXI by treatment with sodium nitrite in hydrohalic acid solution (see M. Kocevar, S. Polanc, M. Sollner, M. Tisler and B. Vercek, Synth. Comm., 1988,18:1427).

The α-haloaldoximes of Formulae IV and V can be prepared from trihalomethyl compounds of Formula XXII by basic hydrolysis in the presence of hydroxylamine (see A P. Kozikowski and M. Adamczyk, J. Org. Chem., 1983, 48:366).

The α-haloaldoximes of Formulae IV and V can be prepared by the reaction of nitrile N-oxides of Formula XXIII with hydrohalic acids (see C. Grundmann, V. Mini, J. M. Dean, and H. -D. Frommeld, Justis Liebigs Ann. Chem., 1965, 687:191).

x

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, Bull. Soc. Chem. Jpn.. 1984, 57:2531). 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 followed by trapping the nitrile N-oxide of Formula XXIV with a hydrohalic acid. A new α-haloaldoxime of Formula V is produced.

The carboxamide and carboxylic 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, 48:366).

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).

x 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).

The ketone compounds of Formulae IV and V can be prepared from β-ketosulfoxides of Formula XXVII by treatment with sodium nitrite in hydrohalic acid solution (see Y. Otsuji, Y. Tsujii, A Yoshida and E. Imoto, Bull. Chem Soc. Japan. 1971, 44:219).

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. Chem., 1971, 36:2146).

The thioalkyl and thioaryl compounds of Formulae IV and V can be prepared from dihaloformaldoxime XXVIII (see D. Chiarino,

M. Napoletano and A. Sala, Synth. Comm., 1988, 18:1171 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 = R⁵S) by oxidation using one or two equivalents, respectively, of oxidants such as hydrogen peroxide or organic per acids, such as peracetic acid.

The sulfone compounds of Formulae IV and V can also be prepared from compounds of Formula XXIX (G=R⁵SO₂) according to methods already reported (see P. A. Wade and H. R. Hinney, J. Am, Chem. Soc., 1979, 101:1319).

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, Synth. Commun., 1974, 4:311). *

The following are representative of the methods used for the preparations of the included examples.

EXAMPLE 1

N,N'-[1,3-phenylenebis(carbonyloxy]bis[2- (dimethylamino)-2-oxoethanimidoyl chloride (Compound #5)

6.04 g of 2-(dimethylamino)-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 solid 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 solid crystallized, which was suspended in hexanes and filtered. The solid was washed with hexanes. 8.27 g of Compound #5 was obtained after drying. m.p. 122-124°C.

EXAMPLE 2

N,N'-[1,3-phenylenebis(iminocarbonyloxy)]- bis[2-(dimethylamino)-2-oxoethanimidoyl 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 diisocyanate was added, followed 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 solid. The solid was suspended in hexanes, filtered, and washed with hexanes. m.p. 176-180°C.

EXAMPLE 3

N,N'-[2,5-thiophenediylbis-(carbonyloxy)bis- [2-dimethylamino)-2-oxoethanimidoyl chloride (Compound #42)

1.51 g of 2-(dimethylamino)-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 following day, 20 mL of ethyl acetate was added and the mixture was filtered. The solid was washed with ethyl acetate and was discarded.

The filtrate was stripped to a solid. This solid was suspended in 1-chlorobutane containing enough CH₂Cl₂ to cause dissolution. Hexanes were then added to cause a solid to form. The solid 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.

79

97

101

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 Dispersible Granules

Oil Suspensions, 5-50 40-95 0-15

Emulsions, Solutions,

(including Emulsifiable

Concentrates)

Aqueous Suspensions 10-50 40-84 1-20 Dusts 1-25 70-99 0-5

Granules and Pellets 1-95 5-99 0-15

High Strength 90-99 0-10 0-2

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", Chemical 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'-[1,3-phenylenebis-(carbonyloxy)]bis- [2-(dimethylammo)-2-oxoethanimidoyl

chloride] 80%

sodium alkylnapthalenesulfonate 4%

sodium ligninsulfonate 2%

synthetic amorphous silica 1%

kaolinite 13%

The ingredients are blended, hammermilled, re-blended and packaged. EXAMPLE B

High Strength Concentrate

N,N-[1,3-phenylenebis-(carbonyloxy)]bis- [2-(dimethylamino)-2-oxoethanimidoyl

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'-[1,3-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. Phytophthora infestans, Peronospora tabacina, Pseudoperonospora cubensis, Pythium aphanidermatum, Alternaria brassicae, Septorianodorum, Cercosporidium personatum, Cercospora arachidicola,

Pseudocercosporella herpotrichoides, Cercospora beticola, Botrytis cinerea. Monilinia fructicola, Pyricularia oryzae, Podosphaera leucotricha, Venturia inaequalis, Puccinia recondita, Puccinia gramminis, Hemileia vastatrix, Puccinia striiformis, Puccinia arachidis, 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 minimum 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: Fungicides

methyl 2-benzimidazolecarbamate (carbendazim)

tetramethylthiuram disulfide (thiuram)

n-dodecylguanidine acetate (dodine)

manganese ethylenebisditbiocarbamate (maneb)

1,4-dichloro-2,5-dimethoxybenzene (chloroneb)

methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate

(benomyl)

2-cyano-N-ethylcarbamoyl-2-methoxyimmoacetamide

(cymoxanil)

N-trichloromethylthiotetrahydrophthalamide (captan)

N-trichloromethylthiophthalimide (folpet)

dinιethyl 4,4'-(o-phenylene)bis(3-thioallophanate)

(thiophanate-methyl)

2-(thiazol-4-yl)benzimidazole (thiabendazole)

aluminum tris(O-ethyl phosphonate)(phosethyl aluminum)

tetrachloroisophthalonitrile (chlorothalonil)

2,6-dichloro-4-nitroaniline (dichloran)

N-(2,6-dimethylphenyl)-N-(methoxyacetyl)alanine methyl

ester (metalaxyl)

cis-N-[1,1,2,2-tetrachloroethyl)thio]cyclohex-4-ene- 1,2-dicarbioximide (captafol) 3-(3,5-dichlorophenyl)-N-(1-methylethyl)-2,4-dioxo-1- imidazolidine carboxamide (iprodione)

3-(3,5-dichlorophenyl)-5-ethenyl-5-methyl-2,4-oxazolidinedione (vinclozolin)

kasugamycin

O-ethyl-S,S-diphenylphosphorodithioate (edifenphos) 4-(3-(4-(1,1-dimethyl-ethyl)phenyl)-2-methyl)propyl- 2,6-dimethylmorpholine (fenpropimorph)

4-(3-4(1,1-dimethyl-ethyl)phenyl)-2-methyl)propylpiperidine (fenpropidine)

1-(4-chlorophenoxy)-3,3-dimethyl-1-1H-1,2,4-triazol-1- yl)butanone (triadimefon)

2-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-ylmethyl)- hexanenitrile (myclobutanil)

a-[2-(4-chlorophenyl)ethyl]-alpha-(1,1-dimethylethyl)- 1H-1,2,4-triazole-1-ethanol (tebuconazol)

3-chloro-4-[4-methyl-2-(1H-1,2,4-triazol)-1-ylmethyl)- 1,3-dioxolan-2-yl]phenyl-4-chlorophenyl ether

(difenoconazole)

1-[2-(2,4-dichlorophenyl)pentyl]1H-1,2,4-triazole (penconazole)

(+a-(2-fluorophenyl-V-(4-fluorophenyl)-1H-1,2,4- triazole-1-ethano (flutriafol)

1-[[bis(4-fluorophenyl)methylsilyl)methyl]-1H-1,2,4- triazole (flusilazol)

1-N-propyl-N-[2(2,4,6-trichlorophenoxy) ethyl]- carbamoylimidazole (prochloraz)

1-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2- yl]methyl]-1H-1,2,4-triazole (propiconazole) a-(2-chlorophenyl)-a-(4-chlorophenyl)-5-pyridinemethanol (fenarimol)

copper oxychloride methyl N-(2,6-dimethylphenyl)-N-(2-furanylcarbonyl)-DL-alaninate (furalaxyl)

Bactericides

tribasic copper sulfate

streptomycin sulfate

osytetracycline

Acaricides

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

6-nιethyl-1,3-dithiolo[2,3-b]quinonolin-2-one

(oxythioquinox)

2,2,2-trichloro-1,1-bis(4-chlorophenyl)ethanol

(dicofol)

bis(pentachloro-2,4-cyclopentadien-1-yl)(dienochlor) tricyclohexyltin hydroxide (cyhexatin)

hexakis(2-methyl-2-phenylpropyl)distannoxane

(fenbutin oxide) Nematicides

2-[diethoxyphosphinylimino]-1,3-diethietane (fosthietan) S-metiιyl-1-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)- thioformimidate (oxamyl)

S-methyl-1-carbamoyl-N-(methylcarbamoyloxy)thioformimidate

N-isopropylphosphoramidic acid, O-ethyl-O'-[4-(methylthio)-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, O',O'-dimethyl ester (tetrachlorvinphos)

2-mercaptosuccinic acid, diethyl ester, S-ester with thionophosphoric acid, dimethyl ester (malathion) phosphorothioic acid, O,O-dimethyl, O-p-nitrophenyl ester (methyl parathion)

methylcarbamic acid, ester with a-naphthol

(carbaryl)

methyl N-[[(methylammo)carbonyl]oxy]ethanimidothioate (methomyl)

N'-(4-chloro-o-tolyl)-N,N-dimethylformamidine

(chlordimeform)

O,O-diethyl-O-(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-methylethyl)benzeneacetate (fenvalerate)

(3-phenoxyphenyl)methyl (+)-cis,trans-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate (permethrin) dimethyl N,N'-[thiobis(N-methylimino)carbonyloxy]]- bis[ethanimidothioate] (thiodicarb)

phosphorothiolothionic acid, O-ethyl-O-[4-(methylthio)phenyl]-S-n-propyl ester (sulprofos)

a-cyano-3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2- dimethylcyclopropane carboxylate (cypermethrin) cyano(3-phenoxyphenyl)methyl 4-(difluoromethoxy)- a-(methylethyl)benzeneacetate (flucythrinate)

O,O-diethyl-O-(3,5,6-trichloro-2-pyridyl)phosphorothioate (chlorpyrifos) O,O-dimethyl-S-[(4-oxo-1,2,3-benzotriazin-3-(4H)-yl)- methyl]phosphorodithioate (azmphos-methyl)

5,6-dimethyl-2-dimethylamino-4-pyrimidinyl dimethyl

carbamate (pirimicarb)

S-(N-formyl-N-methylcarbamoylmethyl)-O,O-dimethyl

phosphorodithioate (formothion)

S-2-(ethylthioethyl)-O,O-dimethyl phosphiorothioate

(demeton-S-methyl)

a-cyano-3-phenoxybenzyl cis-3-(2,2-dibromovinyl)- 2,2-dimethylcyclopropane carboxylate (deltamethrin)

cyano(3-phenoxyphenyl)methyl ester of N-(2-chloro-4- trifluoromethylphenyl)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.

TEST B

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 peanut seedlings. The following day the seedlings were inoculated with a spore suspension of Cercosporidium 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.

TEST C

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 spore suspension of Puccinia recondita (the 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.

TEST D

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 Phytophthora infestams (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 of Plasmopara 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 G

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 of Botrytis 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.

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). CMPD

NO. IR

7 3229, 3200, 1787, 1636

40 1778, 1661

41 1774, 1656

66 1779, 1711, 1665

69 3194, 1847, 1762, 1640

87 1808, 1651

90 1766, 1666

TABLE A

CMPD TEST TEST TEST TEST TEST TEST TEST NO. A B C D E F G

1 100 96 96 74 100 100 99

2 100 99 99 29 100 100 97

3 25 0 18 0 44 59 0

4 100 67 89 0 100 98 82

5 100 98 100 85 100 100 99

6 100 98 99 96 97 100! 99

7 100 86 44 0 98 78! 11

8 96 100 43 0 99 90! 2

9 100 100 94 68 100 100! 2

10 100 97 37 0 100 96! 8

11 99 62 25 0 91 38! 0 12 100 29 37 0 93 90! 0

13 79 54 20 0 97 96! 3

14 19 0 NT 0 22 NT 0 15 64 0 NT 0 22 68 0 16 88# 23 NT 0 0 NY 0 17 82 28 NT 0 63 90 0 18 93! 61 42 0 93 79! 0 19 92 0 NT 0 62 64 0 20 100! 96 83 88 100 100! 99 21 100 0 70 0 100 100! 0 22 60 59 97# 0 45# 100# 0 23 9 59 99# 0 24 100# 0 24 0 0 21# 0 0 59# 0 25 76! 73 66 25 89 73! 0 26 45 29 NT 0 47 88! 0 27 83! 92 85 68 92 97! 0 28 45 29 o# 0 25 0# 94# CMPD TEST TEST TEST TEST TEST TEST TEST NO. A B C D E F G

29 7 12 NT NT NT NT NT

30 90! 76 28 0 93 68! 0

31 90! 60 28 0 85 78! 0 32 60 27 NT 0 96 46! 0 33 100! 91 59 93 100 100! 0 34 100! 97 93 95 100 100! 10 35 100! 100 93 99 100 92! 10 36 NT NT NT 0 100 98! 0 37 17 0 NT 17 94 97! 0 38 NT NT 97 98 97 97! 0 39 96! 100 66 92 98 95! 10 40 100! 96 74 67 99 98! 0 41 92! 65 80 0 100 100! 0 42 100! 100 98 99 100 100! 68 43 90! 50 7 0 94 74! 0 44 0! NT 29 0 98 70! 0 45 68 NT NT 0 93 85! 0 46 100! NT 95 98 100 100! 0 47 100! NT 99 99 100 100! 11 48 9 0 NT 0 45 81! 11 49 99! 74 28 28 100 100! 0 50 100! NT 100 100 100 100! 97 51 100! NT 97 98 100 100! 0 55 100! 99 95 93 100 100! 78 56 69! 75 7 79 92 66! 0 57 99! 100 96 98 100 97! 0 58 97! 53 41 31 99 100! 0 CMPD TEST TEST TEST TEST TEST TEST TEST NO. A B C D E F G

59 100! 53 7 0 92 69! 0

60 90! NT 65 0 98 99! 0

61 67 NT NT 0 92 53! 0

62 100! NT 95 100 100 99! 11

63 100! NT 100 100 100 100! 0

64 100! NT 92 96 100 100! 0

65 NT NT 80 76 100 100! 10

66 NT NT 80 7 83 91! 0

67 NT NT 72 0 99 94! 0

68 NT NT NT 0 96 73! 7

69 97! 42 66 79 100 100! 8

70 67! 0 97 98 97 97! 10

71 NT NT 100 98 100 100! 11

72 NT NT 84 56 100 100! 0

73 NT NT 92 98 100 100! 35

74 NT NT 98 97 100 100! 99

75 NT NT 36 0 93 100 0

76 NT NT 36 0 100 100! 0

77 NT NT 62 0 100 100 0

78 NT NT 88 90 98! 100! 0

79 NT NT 88 23 100! 100! 0

80 NT NT 55 0 99 70! 0

81 NT NT 88 54 100! 100! 41

82 NT NT 91 80 99 100! 97

83 NT NT 16 82 99 100! 0

84 NT NT 0 64 92 44! 0

85 NT NT 16 85 97 100! 0

86 NT NT 49 77 99 100! 0

87 NT NT 98 53 99 100! 10 CMPD TEST TEST TEST TEST TEST TEST TEST NO. A B C C E F G

88 NT NT 100 90 100! 100! 0

89 NT NT NT 0 92 74! 0

90 NT NT 92 74 99 100! 0

93 NT NT 0 0 0 0 0

94 NT NT NT 62 100 100! NT

95 NT NT NT 92 NT 99! 0

! = Percent control at 40 ppm, the highest rate tested. # = Tested at 500 ppm.

Claims

CLAIMS What is claimed is:

1. Compounds of Formula I including all geometric and stereoisomers thereof

wherein:

A and A¹ are independently O, NH,— CH₂O—,— CH₂CH₂O— or a direct bond;

G and G¹ are independently C(=O)NR¹R², C(=O)OR³, C(=O)R⁴, S(O)_nR5, SO₂NR¹R² or CN;

X and X¹ are independently SO₂R⁶, Cl or Br;

R¹ and R² are independently H; C₁-C₄ alkyl; C₂-C₄ alkoxyalkyl; or R¹ and R² 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;

R³ is C₁-C₄ alkyl; C₁-C₄ haloalkyl or C₂-C₄ alkoxyalkyl;

R⁴ 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;

R⁵ 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; R⁶ is C₁-C₆ alkyl; C₁-C₆ haloalkyl; C₂-C₆ 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 C₁-C₆ alkylenyl optionally substituted with 1-2 methyl;

C₂-C₆ alkenylenyl; C₂-C₆ alkynylenyl; phenylenyl optionally substituted with R⁷, naphthalenyl optionally substituted with R⁷; C₃-C₆ cycloalkylenyl optionally substituted with 1-2 methyl; 1-methylpyrrolyl optionally substituted with R⁹; 1- methylimidazolyl optionally substituted with R⁸, a 5- to 10- membered heteroaromatic or fused heteroaromatic ring system wherein the heteroatoms consist of:

i) 1-4 nitrogen atoms,

Z is O, CH₂, S(O)_n, C(=O), NR¹⁰, HC=CH, CH₂CH₂, C≡C,

phenylenyl or a direct bond;

R⁷ is 1-4 substitutions selected from the group consisting of

halogen, methyl, methoxy, cyano and nitro;

R⁸ is H, halogen, methyl or methoxy;

R⁹ is selected from 1-2 halogen, cyano, methyl or methoxy;

R¹⁰ is H or C₁-C₄ alkyl; and

n is 0, 1 or 2; provided that:

i) when A or A¹ is—CH₂O— or—CH₂CH₂O—, the carbon atom of these groups is bonded to Q;

ii) when A or A¹ are NH, Q is not cyclopropylene optionally substituted with 1-2 methyl;

iii) when Q is C₂-C₆ alkenylenyl or C₂-C₆ alkynylenyl, A and A¹ are—CH₂O—,—CH₂CH₂O— or a direct bond; and

iv) when Q is NH, A and A¹ are a direct bond.

2. Compounds of Claim 1 wherein A and A¹ are independently NH,—CH₂O—, or a direct bond; and Q is C₁-C₆ alkylenyl optionally substituted with 1-2 methyl; C₂-C₆ alkenylenyl; C₂-C₆ alkynylenyl; NH; or Q is selected from the group of

3. Compounds of Claim 2 wherein A and A¹ are the same; G and G¹ are both C(=O)NR¹R²; X and X¹ are both SO₂R⁶ or Cl; Q is either C₁-C₆ alkylenyl optionally substituted with 1-2 methyl, C₂-C₆ alkenylenyl, C₂-C₆ alkynylenyl, or a member selected from the group of

c

4. Compounds of Claim 3 wherein A and A¹ are both NH or a direct bond.

5. Compounds of Claim 4 wherein Q is selected from the group consisting of:

6. Compounds of Claim 1 wherein said compounds are selected from the group N,N'-[1,3-phenylenebis(carbonyloxy)]bis[2-(dimethylamino)-2-oxoethanimidoyl chloride]; N,N'-[1,3-phenylenebis(iminocarbonyloxy)]bis[2-(dimethylamino)-2-oxoethanimidoyl chloride; and N,N'-[2,5-thiophenediylbis-(carbonyloxy)]bis[2-dimethylamino)-2-oxoethanimidoyl chloride].

7. A composition comprising a fungicidally effective amount of any of the compound of Claims 1-6.

8. A method of controlling fungal growth in plants comprising applying to the locus of plants to be protected a compoτind of Formula I including all geometric and stereoisomers thereof

wherein:

A and A¹ are independently O, NH,—CH₂O—,—CH₂CH₂O— or a direct bond;

G and G¹ are independently C(=O)NR¹R², C(=O)OR3, C(=O)R⁴, S(O)_nR⁵, SO₂NR¹R² or CN;

X and X¹ are independently SO₂R⁶, Cl or Br;

R³ is C₁-C₄ alkyl; C₁-C₄ haloalkyl; C₂-C₄ alkoxyalkyl;

R⁴ is C₁-C₄ alkyl; C₁-C₄ haloalkyl or C₂-C₄ alkoxyalkyl; or phenyl optionally substituted with 1-2 substituents selected from the group consisting of halogen, methyl, methoxy, cyano and nitro;

R⁵ is C₁-C₄ alkyl; C₁-C₄ haloalkyl; C₂-C₄ alkoxyalkyl;

R⁶ is C₁-C₆ alkyl; C₁-C₆ haloalkyl; C₂-C₆ alkoxyalkyl;

Q is C₁-C₆ alkylenyl optionally substituted with 1-2 methyl;

C₂-C₆ alkenylenyl; C₂-C₆ alkynylenyl; phenylenyl optionally substituted with R?, naphthalenyl optionally substituted with R⁷; C₃-C₆ cycloalkylenyl optionally substituted with 1-2 methyl; 1-methylpyrrolyl optionally substituted with R⁹; 1- methylimidazolyl optionally substituted with R⁸, a 5- to 10- membered heteroaromatic or fused heteroaromatic ring system wherein the heteroatoms consist of:

i) 1-4 nitrogen atoms,

said heteroaromatic or fused heteroaromatic rings being optionally substituted with R⁹; NH or

Z is O, CH₂, S(O)_n, C(=O), NR¹⁰, HC=CH, CH₂CH₂,C≡C, or

phenylenyl; R⁷ is 1-4 substitutions selected from the group consisting of halogen, methyl, methoxy, cyano and nitro;

R⁸ is H, halogen, methyl or methoxy;

R⁹ is selected from 1-2 halogen, cyano, methyl or methoxy;

R¹⁰ is H or C₁-C₄ alkyl; and

n is 0, 1 or 2;

provided that:

ϋ) when A or Al are NH, Q is not cyclopropylene optionally substituted with 1-2 methyl;

iv) when Q is NH, A and A¹ are a direct bond.

9. The method of Claim 8 wherein A and A¹ are independently

NH,—CH₂O—, or a direct bond; and Q is either C₁-C₆ alkylenyl optionally substituted with 1-2 methyl, C₂-C₆ alkenylenyl, C₂-C₆ alkynylenyl, NH or a member selected from the group of

10. The method of Claim 9 wherein A and Al are the same; G and G¹ are both C(=O)NR¹R²; X and X¹ are both SO₂R⁶ or Cl; Q is either C₁-C₆ alkylenyl optionally substituted with 1-2 methyl, C₂-C₆ alkenylenyl, C₂-C₆ alkynylenyl, or a member selected from the group of

11. The method of Claim 10 wherein A and Al are both NH or a direct bond.

12. The method of Claim 11 wherein Q is selected from the group consisting of:

13. The method of Claim 8 wherein said compounds are selected from the group of N,N-[1,3-phenylenebis(carbonyloxy)]bis[2-(dimethylamino)-2-oxoethanimidoyl chloride]; N,N-[1,3-phenylenebis(iminocarbonyloxy)]bis[2-(dimethylamino)-2-oxoethanimidoyl chloride; and N,N'-[2,5-thiophenediylbis-(carbonyloxy)]bis[2-dimethylamino)-2-oxoethanimidoyl chloride].