N-HALOALKYL THIOBENZANILIDES, PRODUCTION THEREOF, COMPOSITIONS CONTAINING THEM AND THEIR USE AS FUNGICIDES

Abstract: N-haloalkyl thiobenzanilide compounds having the for­ mula in which R is hydrogen, C₁-C₅ alkyl, preferably C₁-C₃ alkyl, C₁-C₃ haloalkyl, preferably -CF₃, halogen including -F, -Cl, -Br, and I, -NO₂, C₁-C₂ alkoxy, R₁ is -H or -C≡N, X and Y are either -Cl or -F but not identical when R₁ ist H and X and Y are -Cl when R₁ is -C≡N have fungicidal activity being effective as systemic toxicants. The may be prepared by reaction of a compound of the formula with Cl-S- Cl- CIF.

Description: TITLE N-Haloalkyl Thiobenzanilides, Production Thereof, Compositions Contai-niflq Them and Their use as Fungicides This invention relates to certain novel N-haloalkyl thiobenzanilides, to the production thereof, to compositions containing them and to their use as fungicides. The present invention provides as new compounds having fungicidal activity, compounds of the general formula: EMI1.1 in which R is hydrogen, C1-C5 alkyl, preferably C1-C3 alkyl, C1-C3 haloalkyl, preferably -CF3, halogen including -F, -Cl, -Br, and -I, -NO2, C1 to C2 alkoxy, R1 is -H or -C=N, and X and Y are either -C1 or -F but not identical when R1 is -H and, X and Y are -C1 when R1 is -C9N. Although the compounds of the invention are generally active as fungicides, it has been discovered that they are also effective as systemic toxicants and this ancillary feature greatly increases their usefulness and versatility in treating fungus-infected food crops. As those skilled in the art are aware, a systemic biocide is taken up internally by the organism to which it is applied and lodges in the tissues while still retaining toxicological properties. When used to protect food crops systemic toxicants are not subject to weathering since they are confined within the interstices of the plan tissues which are thereby internally immunized against the attack of harmful fungi, blights and similar pesticidal microorganlsms. The compounds of the present invention are prepared by the following general reaction. Reaction No. 1 EMI1.2 Generally a mclar amount of the substituted benzoyl chloride reactant, dissolved in benzene, is added to a mixture of the are reactant and a slight molar excess of an XC1 acceptor such as trierhyl- mir.e. The mixture is refluxed for 1/2 hour and then cooled. The solid reaction product is diluted with a solvent such as ethyl acetate or chloroform and washed with water twice ard salt solution once. The fungi product is dried over MgSO4, filtered and evaporated. Reaction No. 2 EMI2.1 Under a dry nitrogen atmosphere a molar amount of the reaction product from Reaction No. 1 is dissolved in dry tetrahydrofuran (THF). Next, a slight molar excess of NaR is added with stirring. The mixture is refluxed for 1 hour and cooled. Reaction No. 3 EMI2.2 A molar amount of EMI2.3 in TEF is added dropwise to the reaction mixture of Reaction No. 2. The mixture is refluxed for 2 1/2 hours and a large amount of CH2C12 is added to the solid reaction product. The product is washed twice with water, dried over 3S04 and evaporated. The EMI2.4 is prepared as outlined below: EMI2.5 An equimolar mixture of Reagent I and Reagent II is irradiated under a U V lamp (at 80C to 60 C) for 3 to 5 hours. The product III is isolated and purified by distillation under reduced pressure (40 mm Hg to 50 mm Hg). Preparation of compounds of this rrention is illustrated by the following examples. EXAMPLE I Preparation of 2-iodobenzoyl anilide EMI3.1 43.2 g. (0.464 moles) aniline and 46.9 g. triethylamine are mixed in 930 ml. benzene by stirrin. A solution of 123.7 g. (0.464 moles) 2-iodobenzoyl chloride in 450 ml. benzene is added to the first mixture through a dropping funnel. An exothermic reaction takes placed After the addition is finished, the mixture is refluxed for 1/2 hour. The mixture is cooled and the product soldifies. The product is filtered, added to water, and stirred to dissolve triethylamine hydrochloride. The product is filtered 2gain and dried to yield 146.8 g. - of the desired product. (98p yield) m.p. 141-1440C. EXAMPLE II EMI3.2 8.075 O (0.025 moles) of the amide reaction product of Example I is dissolved in 60 ml. of dry IEP under a dry nitrogen atmosphere. 0.66 g. (0.0275 moles) NaH is added to the mixture with stirring. the mixture is refluxed for one hour and then cooled. EXAMPLE III N-1,1,2-trichloro-2,2-difluoromethylthio-o-iodobenzariiide EMI3.3 (0.025 moles) of ClSCCl2CF2Cl dissolved in 12 ml. THF is added dropwise to the cooled reaction mixture of Example II. The mixture is then refluxed for 2-1/2 hours. Next 150 ml. CE2C12 is added, the mixture is washed twice with water, dried over ggS04 and evaporated to yield the desired product. EXAMPLE IV Preparation of 2-iodobenzoyl anilide EMI4.1 43.2 g. (0.464 moles) aniline and 46.9 g. triethylamine are mixed in 930 ml. benzene by stirr¯n. A solution of 123.7 g. (0.464 moles) 2-iodobenzoyl chloride in 450 ml. benzene is added to the first mixture through a dropping funnel. An exothermic reaction takes place. After the addition is finished, the mixture is refluxed for 1/2 hour. The mixture is cooled and the product soldifies. The product is filtered, added to water, and stirred to dissolve triethylamine hydrochloride. The product is filtered again and dried to yield 146.8 g. of the desired product. (98% yield) m.p. 141-1440C. EXAMPLE V EMI4.2 8.075 g. (0.025 moles) of the amide reaction product of Example I is dissolved in 60 ml. of dry THF under a dry nitrogen atmosphere. 0.66 g. (0.0275 moles) NaH is added to the mixture with stirring. The mixture is refluxed for one hour and then cooled. EXAMPLE VI N-2-fluorotetrachlo roethylthio-o-iodo-p -cyanobenzanilide EMI4.3 (0.025 moles) of ClSCCl2CCl2F dissolved in 12 ml. THF is added dropwise to the cooled reaction mixture of Example II. The mixture is then refluxed for 2-1/2 hours. Next 150 ml. CH2C12 is added, the mixture is washed twice with water, dried over MgSO4 and evaporated to yield the desired product. The following is a ta'ole of certain selected compounds tat are preparable according to the procedure described herein. Compound nur1ers are assigned to each compound and are used throughout the remainder of the application. TABLE I EMI5.1 Compound Physical Constants Number R R1 X Y m.p. or np30 1 2-I H Cl F glassy solid 2 A H C1 F semi-solid 3 A H H F Cl 1.5772 4 2-CF3 H F C1 1.5345 5 2-CF3 H Cl F 1.5410 6 2-1 H F C1 1.6034 7 2-CCH3 H F Cl 1.5698 8 2-1 C-N Cl Cl 98-100.5 C Foliar Fungicide Evaluation Tests A. Evaluation for Preventive Action 1. Bean Rust Test: Pinto bean plants (Phaseolus vulgaris L.) approximately 10 centimeters (cm.) tall are transplanted into sandy loam soil in three-inch clay pots. The plants are then inverted and dipped for two to three seconds in 50-50 acetone/water solution of the test cca1. Test concentrations range from 1000 ppm downward. After the leaves are dried they are inoculated with a water suspension of spores of the bean rust fungus (Urumyces phaseoli Arthur) and the plants are placed in an environment of 100% humidity for 24 hours. The plants are then removed from the humidity chamber and held until disease pustules appear on the leaves. Effectiveness is recorded as the lowest concentra- tion, in ppm, which will provide 75% or greater reduction in pustule formation as compared to untreated, inoculated plants. These values are recorded in Table II. 2. Bean Powdery Mildew Test: A candidate chemical is prepared and applied in the same manner as for the bean rust test. After the plants are dry, the leaves are dusted with spores of the powder mildew furtis (Erysiphe polygon De Candolle) and the plants are retained in the greenhouse until the fungal growth appears on the leaf surface. Effectiveness is recorded as the lowest concentration, in ppr, which will provide 75p or greater reduction in irycelial formation as compared to untreated, incoulated plants. These values are recorded in Table II. 3. Tomato Early Blight: A candidate compound is dissolved in an appropriate solvent and diluted with a 50-50 acetone water solution. Four week old tomato (Lycocersicon esculentum) plants are then sprayed with the solution to the point of runoff. Test concentrations range from 1000 ppm downward. When the leaves are dry, they are inoculated with a water-suspens'on of spores of the early blight fungus (Alternaria solar Ellis and rtin) and placed in an environment of 100% humidity for 48 hours. The plants are then removed from the humidity chamber and held until disease lesions appear on the leaves. Effectiveness is recorded as the lowest concentration, in ppm, which will provide 75% or greater reduction in the number of lesions formed as compared to untreated, inoculated plants. These values are recorded in Table I1. 4. Blue Grass Leaf Spot: A candidate chemical is prepared and applied in the same manner as the tomato early blight test except that four week old Kentucky Bluegrass (Poa pratensis) plants are utilized 2s the host plant. When the leaves are dry, they are inoculated with a water suspension of spores of the blue grass leaf spot fungus (Helminthosporium sativum) and placed in an environment of 100% humidity for 48 hours. The plants are then removed from the humidity chamber and held until disease lesions appear on the leaves. Effectiveness is recorded as the lowest concentration, in ppm, which will provide 75% or greater reduction in number of lesions formed as compared to untreated, inoculated plants. These values are recorded in Table II. : Evaluation for Eradicant Action 1. Bean Rust Test: Untreated bean plants (Fhaseolus vulganis .) are incoluated with spores of the bean rust fungus (Uromyces phaseoli Ar+hur) and placed in an environment with 100% humidity for 24 hours. The plants are then removed fran the humidity chamber and held -in the greenhouse for two days to allow the disease to become established. A candidate chemical is then prepared and applied in the same manner as in the bean rust test in "Evaluation for Preventive Action??. Eradicative effectiveness is recorded as the lowest concentration, in ppm, which will provide a 75% or greater reduction in number of pustules appearing on the leaves as compared to untreated inoculated plants. These values are recorded in Table II. 2. Eean Powdery Mildew Test: Untreated pinto bean plants are dusted with spores of the powdery mildew fugus (Erysiphe polygon re Car,dolle) and maintained in the greenhouse until mycelial growth appears in the leaf surface. A candidate chemical is then prepared and applied in the same manr.er as for the bean rust test. Four days later the leaves are examined for inhibition of further mycelial growth. Eradicative effectiveness is recorded as the lowest concentration, in pan, which will provide a 75% or greater inhibition of viable, sporulating mycelium as compared to untreated inoculated plants. These values are recorded in Table II. TABLE II Preventive Action Compound 3ean Bean Powdery Tomato Early Blue Grass Number Rust Mildew Blight Leaf Spot 1 10 100 100 25 2 25 50 .50 25 3 50 50 25 25 4 25 100 50 50 5 10 100 50 100 6 10 100 50 * 7 50 50 50 100 8 100 > 1000 20 20 5 No control at 1000 ppm and not tested at higher concentrations. Eradicant Action 1 1 > 50 2 > 50 > 50 3 > 50 > 50 4 0.5 50 5 0.5 (50) 6 0.5 > 50 7 -. - ( ) Indicates partial control. The compounds of this invention are generally embodied into a form suitable for convenient application. For ex-ple, the compound can be embodied into a pesticidal composftion which is provided in the form. of emulsions, suspensions, sclutions, dusts and aerosol sprays. Tr, general, such corsositions will contain, in addition to the active compound, the adjuvants which are found noramily in pesticide preparations In these compositions the active compound of this invention can be employed as the sole pesticide component or it can be used in admixture with other compounds having similar uility. The pesticide compositions of this invention can contain, as adjutants, organic solvents, such as sesame oil, xylene range solvents heavy petroleum, etc.; water; emulsifying agents; surface active agents; talc; pyrophylllte; diatomite; gypsum; clays, propellants, such as dichlorodifluoromethanne, etc. It desired, however, the active compound can be applied directly to feedstuffs, seeds, etc., upon which the pests feed. When applied in such a manner, it will be acvsntageous to use 2 compound which is not volatile. In connection with the activity of the presently disclosed pesticidal compound, it should be fully understood that it is not necessary that they be active as such. The purposes of this invention will be fully served if the compound is rendered active by external influences, such as light or by scme physiological action which occurs when the compound is ingested into the body of the pest. The precise manner in which the pesticidal compositions of h-s invention are used in any particular instance will be readily apparent to a person skilled in the art. Generally, the active pesticide compund will be embodied in the form of a liquid composition; for example, an emulsion, suspension, or aerosol spray. While the concentration of the active pesticide in the present compositions can vary within rather wide limits, ordinarily the pesticide compund will comprise not more than about 15.0,Wo by weight of the composition. Preferably, however, the pesticide compositions of this invention will be in the form of solutions or suspensions containing about 0.1 to 1.0% by weight of the active pesticide compound.

Claims: Claims: 1. Compounds of the general formula: EMI10.1 in which R is hydrogen, C1-C5 alkyl, C1-C3 haloalkyl, halogen, -NO2, C1-C2 alkoxy, R1 is -H or -C3N, X and Y are either -Cl or -F provided they are not identical when R1 is -H and X and Y are -Cl when R1 is -C#N. 2. A compound as claimed in claim 1 characterised in that R is 2-I, R1 is -H, Xis -C1 and Y is -F. 3. A compound as claimed in claim 1 characterised in that R is -H, R1 is -H, X is -C1 and Y is -F. 4. A compound as claimed in claim 1 characterised in that R is -H, R1 is -H, X is -F and Y is -C1. 5. A compound as claimed in claim 1 characterised in that R is 2-CF3, R1 is -H, X is -F and Y is -C1. 6. A compound as claimed in claim 1 characterised in that R is 2-CF3; R1 is -H, X is -Cl and Y is -F. 7. A compound as claimed in claim 1 characterised in that R is 2-I, R1 is -H, X is -F and Y is -C1. 8. A compound as claimed in claim 1 characterised in that R is 2-OCH3, R1 is -H, X is - F and Y is -C1. 9. A compound as claimed in claim 1 characterised in that R is 2-I, R1 is -C-N, X is -C1 < and Y is -C1. 10. A method of making a compound as claimed in claim 1 wherein a compound of the general formula EMI11.1 in which R and R1 have the meaning given in claim 1, reacted with a compound of the general formula EMI11.2 where X and Y have the meaning given in claim 1. 11. A fungicidal composition comprising a fungicidally effective amount of a compound as claimed in any of claims 1 to 9 or when made by the method of claim 10, in association with an inert diluent carrier and optionally other active compounds. 12. A method of controlling fungi comprising applying thereto or a habitat thereof a fungicidally effective amount of a compound as claimed in any of claims 1 to. 9 or when made by a method as claimed in claim 10, optionally as a composition as claimed in claim 11. Austria Claims: 1. A fungicidal composition comprising a fungicidally effective amount of a compound of the general formula: EMI12.1 in which R is hydrogen, C1-C5 alkyl, C1-C3 haloalkyl, halogen, -NO2, C1-C2 alkoxy, R1 is -H or CaN, X and Y are either -C1 or -F provided they are not identical when R1 is -H and X and Y are -C1 when R1 is -C=N in association with an inert diluent carrier and optionally other active compounds. 2. A composition as claimed in claim 1 characterised in that R is 2-I, R1 is -H, X is -C1 and Y is -F. 3. A composition as claimed in claim 1 characterised in that R is -H, R1 is -H, X is -C1 and Y is -F. 4. A composition as claimed in claim 1 characterised in that R is -H, R1 is -H, X is -F and Y is -C1. 5. A composition as claimed in claim 1 characterised in that R is 2-CF3, R1 is -H, X is -F and Y is -C1. 6. A composition as claimed in claim 1 characterised in that R is 2-CF3, R1 is -H, Xis -C1 and Y is -F. 7. A composition as claimed in claim 1 characterised in that R is 2-I, R1 is -H, Xis -F and Y is -C1. 8. A composition as claimed in claim 1 characterised in that R is 2-OCH3, R1 is -H, X is -F and Y is -C1. 9. A composition as claimed in claim 1 characterised in that R is 2-I, R1 is -C-N, X is -C1, and Y is -C1. 10. A method of making a compound as claimed in claim 1 wherein a compound of the general formula EMI13.1 in which R and R1 have the meaning given in claim 1, reacted with a compound of the general formula EMI13.2 where X and Y have the meaning given in claim 1. 11. A method of controlling fungi comprising-apply- ing thereto or to a habitat thereof a fungicidially effective amount of a compound as defined in any of claims 1 to 9- or when made by a method as claimed in claim 10, optionally as a composition as claimed in any of claims 1 - 9.

Inventors: CHIN, HSIAO-LING MAO, PALLOS, FERENC MARCUS
Applicants: STAUFFER CHEMICAL COMPANY
Application year: 1982
Main classification: C07C145
IPC codes: A01N41, C07C313, A01N37