NZ232181A - Arylthiomethylbenzene acrylic acid derivatives and fungicidal compositions thereof - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £32181 232181 NO DRAWINGS Priority Oa^s): Complete Specification Filed: Class: J..Lji^iu..^r3.^3y( Pu&!;cafion Date: .1..?.. Ml.

P.O. Journal, No: ... la.afe.-.

O Patents Form No. 5 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION SULFUR-CONTAINING ACRYLIC ESTERS AND FUNGI CI CONTAINING THEM WE, BASF AKTIENGESELLSCHAFT, a company organised and existing under the laws of the Federal Republic of Germany, of 6700 Ludwigshafen, Federal Republic of Germany, hereby declare the invention, for which We pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: (followed by page la) 23*181 O.Z. 0050/40504 Sulfur-containing acrylic esters and fungicides containing them The present invention relates to novel acrylic ester derivatives, methods of preparing them, fungicides containing them, and their use as 5 fungicides.

The use of acrylic esters, for example methyl a-(2-[4-chlorophenylthio-methyl]phenyl)-p-methoxyacrylate (EP 226 917) and methyl a-(2-[3-chloro-phenylthiomethyl]phenyl)-p-methoxyacrylate (EP 278 595), as fungicides has 10 been disclosed.

We have now found that substituted acrylic ester derivatives of the general formula where R* and r2 are hydrogen or Cj-Cs-alkyl, X is S, SO or SO2, R^ is phenyl, naphthyl or phenanthrenyl, these radicals being unsubstituted or substituted by halogen, cyano, nitro, formyl, Ci~Cio~alkyl, Cj-C^alkoxy, Ci"C2"haloalkyl, aryl or Ci-C4-alkoxycarbonyl, with the exception of compounds in which R^ is phenyl, 3-chlorophenyl, 4-chlorophenyl, 20 2,4-dichlorophenyl or methylphenyl, have a fungicidal action superior to that of the abovementioned prior art compounds.

The radicals listed in formula I may for example have the following meanings: R* and are identical or different and denote for instance hydrogen, Cj-C5~alkyl, methyl, ethyl, propyl, isopropyl, butyl and pentyl; methyl is preferred.

X may be S, SO or SO2; S is preferred. r3 may for example be phenyl, naphthyl and phenanthrenyl, the rings being unsubstituted or substituted by from one to five of the following radicals: halogen (e.g., fluorine, chlorine, bromine), cyano, nitro, formyl, Cl-Ci0~alkyl (e.g., methyl, ethyl, n- or isopropyl; n-, iso-, sec.- or tert.-butyl; n-, iso-, sec.-, tert.- or neopentyl; hexyl, heptyl, octyl, nonyl, decyl), C]-C2-haloalkyl (e.g., difluoromethyl, trifluoromethyl, I 40 -la- (followed by page 2) r 232 1 2 O.Z. 0050/40504 chloromethyl, dichloromethyl, trichloromethyl, pentafluoroethyl), Ci-C4-alk°xy (e.g., methoxy, ethoxy, n- or isopropoxy; n-, iso-, sec.- or tert.-butoxy), aryl (e.g., phenyl, naphthyl) and Cj-C^alkoxycarbonyl (e.g., methoxycarbonyI, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl).

The novel compounds of the formula I may, because of the C=C double bond, be present both as E and Z isomers. Both the individual isomeric compounds and mixtures thereof are encompassed by the invention and may be used as fungicides.

The novel compounds of the general formula I (X = S) may for example be prepared by reacting a thiol of the formula II with a benzyl bromide of the general formula III.

R1, R2 and R3 have the meanings given in claim 1.

The reactions to give compounds of the formula I may be carried out for instance in inert solvents or diluents (e.g., acetone, acetonitrile, dimethyl sulfoxide, dioxane, dimethylformamide, N-methy1pyrrolidone, 20 N,N'-dimethy1propyleneurea and pyridine) using a base (e.g., sodium carbonate, potassium carbonate). It may also be advantageous to add a catalyst, e.g., tris-(3,6-dioxoheptyl)-amine (J. Org. Chem. 50 (1985) 3717), to the reaction mixture.

Alternatively, the compounds of the general formula II may also be converted first with a base (e.g., sodium hydroxide or potassium hydroxide) into the corresponding sodium or potassium salts, which are then reacted in an inert solvent or diluent (e.g., dimethylformamide) with the benzyl bromide of the formula III to give the corresponding compounds of 30 the general formula I.

The thiols of the general formula R3-SH (R3 having the above meanings) are either known or may be prepared by methods analogous to known methods.

Such manufacturing methods are disclosed for instance in Houben-Weyl, 35 Methoden der organischen Chemie VI/3, p. 54 et seq. (1955).

II III I •o -7i n i £ D L I c I O.Z. 0050/40504 a-Bromomethylphenylaerylie esters of the general formula III are known from European Patent 226917.

The novel compounds of the general formula I (where X = SO or SO2) are 5 obtained by oxidation of the corresponding thioethers of the general formula I (where X = S). Oxidation may be carried out for instance with peroxo compounds such as meta-chloroperbenzoic acid in an inert solvent such as toluene.

RS-'S^CH R102 I (X = S) r2 R102 i (X = SO) jT^) R3^-VCH2^Y^ Rl02O-S>^0R2 I (X = S02) (see e.g. Houben-Weyl, Methoden der Org. Chemie IX, 213, 228 (1955)) Examples The following directions illustrate the manufacture of the novel active 15 ingredients.

Example 1 Methyl a-(2-naphthylthiomethylphenyl)-0-methoxyacrylate (compound 2, 20 Table 1) 8 g of methyl cc-(2-broinoiiiethylphenyl)-0-methoxyacrylate, 4.5 g of 2-thio-naphthol, 4.4 g of potassium carbonate and 100 mg of potassium iodide are refluxed for 20 hours in 200 ml of acetone. 200 ml of water is then added 25 and extraction is carried out three times with methylene chloride. The organic phases are dried over Na£S04 and evaporated down. The oil which remains is chromatographed on silica gel using a mixture of n-hexane and ethyl acetate. There is obtained 8.19 g of slightly yellow crystal is of melting point 52-58°C.

I 10 Hay,n AY'99l„,, v,<r- <> Vv o ■'/ •---/• / vf" 232181 4 O.Z. 0050/40504 Example 2 Methyl a-(2-naphthylsulfoxymethylphenyl)-j3-methoxyacrylate (compound 2, Table 2) and methyl a-(2-naphthylsulfonemethylphenyl)-J3-methoxyacrylate 5 (compound 2, Table 3) .91 g of the methyl a-(2-naphthylthiomethylphenyl)-p-methoxyacrylate obtained according to Example 1 are stirred for 18 hours at room temperature in 100 ml of toluene. 50 ml of ethyl acetate is added, and the mix-10 ture is extracted by shaking twice with sodium bicarbonate solution, dried and evaporated down. The oil which remains is chromatographed on silica gel using a mixture of n-hexane and ethyl acetate. There is obtained 660 mg of compound 2 (Table 3) as a colorless solid (m.p. 130-134°C) and 3.72 g of compound 2 (Table 2) as an oil.

The following compounds may be obtained in a similar manner: I 40 23 2 1 81] O.Z. 0050/40504 o fable 1: x = S No. r3 r1 r2 IR (cnfl) (1 1 1-naphthyl CH3 CH3 2 2-naphthyl CH3 CH3 52- 58 °C 3 3-phenanthrenyI CH3 CH3 4 2-chlorophenyl CH3 CH3 97- 99 °C 2-bromophenyl CH3 CH3 121-127 °C 6 3-bromophenyl CH3 ch3 84- 86 °C 7 4-bromophenyl ch3 CH3 84- 91 °C 8 2-fluorophenyl ch3 CH3 00 ■P- 1 00 00 O O 9 3-fluorophenyl CH3 ch3 77- 82 °C 4-fluorophenyl CH3 ch3 50- 54 °C 11 2-ethylphenyl CH3 ch3 12 3-ethylphenyl CH3 ch3 13 4-ethylphenyl CH3 CH3 14 2-i sopropy1pheny1 ch3 ch3 3-i sopropy1pheny1 CH3 CH3 16 4-i sopropyIpheny1 CH3 ch3 17 2-tert-buty1pheny1 CH3 CH3 18 3-tert-buty1pheny1 ch3 ch3 19 4-tert-buty1phenyI CH3 ch3 4-butylphenyl ch3 CH3 21 4-hexylphenyl CH3 CH3 22 4-nonylphenyl CH3 CH3 23 4-decylphenyl CH3 CH3 24 2-methoxypheny1 CH3 CH3 77- 85 °C 3-inethoxy phenyl CH3 CH3 52- 58 °C 26 4-methoxypheny1 CH3 CH3 70- 72 °C 27 2-tr i f1uoromethy1pheny1 CH3 CH3 28 3-trifluoromethylphenyl CH3 CH3 29 4-tr i f1uoromethyIphenyI CH3 CH3 4-formylphenyl CH3 CH3 31 2-nitrophenyl CH3 CH3 32 3-nitrophenyl CH3 CH3 33 4-nitrophenyl CH3 CH3 34 2,5-dichlorophenyl CH3 ch3 69- 73 °C 2,6-d i c h1oropheny1 CH3 CH3 113-116 °C 36 3,4-dichlorophenyl CH3 CH3 99-104 °C 37 2,3-dichlorophenyI CH3 CH3 38 3,5-dichlorophenyl CH3 CH3 39 2,3,4-trichlorophenyl CH3 CH3 40 2,4,5-trichlorophenyl CH3 CH3 41 2,4,6-trichlorophenyl CH3 CH3 42 2,3,4,6-tetrachlorophenyl CH3 CH3 232181 O.Z. 0050/40504 Table 1: X = S (contel.) O no. r3 r1 r2 43 2,3,4,5,6-pentachlorophenyl ch3 CH3 44 2,3,4,5-tetraf1uoropheny1 CH3 CH3 45 2,3,5,6-tetraf1uoropheny1 ch3 ch3 46 2,3,4,5,6-pentaf1uoropheny1 CH3 CH3 47 2-chloro, 4-fluoropheny1 ch3 ch3 48 3-chloro, 4-fluoropheny1 CH3 CH3 49 2-chloro, 6-methylphenyl CH3 CH3 50 4-chloro, 2-methylphenyl ch3 CH3 51 2,4-dichloro, 5-methyIphenyl ch3 CH3 52 4-chloro, 2,5-dimethylphenyl CH3 CH3 53 4-bromo, 3-methylphenyl ch3 ch3 54 3,5-b i str i f1uoromethy1pheny1 CH3 CH3 56 2,5-dimethylphenyl ch3 CH3 57 2,4-di methylpheny1 CH3 CH3 58 2,5-di methylphenyl CH3 CH3 59 2,6-d i methy1pheny1 CH3 CH3 60 3,4-d i met hy 1 pheny 1 CH3 CH3 61 3,5-dimethylphenyl CH3 CH3 62 2,4,5-trimethylphenyl CH3 CH3 63 2,6-diethylphenyl ch3 CH3 64 2,4-d i-tert.-buty1pheny1 CH3 ch3 65 2,5-dimethoxyphenyl ch3 CH3 66 3,4-dimethoxypheny1 ch3 CH3 67 2-methyl, 4-tert.-butylphenyI CH3 CH3 68 2-methoxycarbony1pheny1 CH3 CH3 69 2-ethoxyc arbonyIpheny1 CH3 CH3 70 2-propoxycarbony1phenyI CH3 CH3 71 2-butoxyc arbony1phenyI ch3 CH3 72 2-cyanophenyl CH3 CH3 73 3-cyanophenyl CH3 CH3 74 4-cyanophenyl CH3 CH3 75 phenyl CH3 Et 76 phenyl Et CH3 77 phenyl CH3 n-Bu 78 phenyl n-Bu n-Bu IR (cm~l) (mp.) 145-150 °C 80- 83 °C 1708,1634,1486, 1435,1283,1256, 1197,1126,1093, 768 57- 62 °C 1708,1633,1487, 1434,1283,1256, 1192,1126,1095, 768 232181 O.Z. 0050/40504 Table 2: (X = SO) r3 No. 1 2 3 4 6 7 8 9 11 12 13 14 16 17 18 19 21 22 23 24 26 27 28 29 31 32 33 34 1-naphthyl 2-naphthyl 3-phenanthrenyl 2-chlorophenyl 2-bromophenyl 3-bromopheny1 4-bromophenyl 2-fIuoropheny1 3-fluoropheny1 4-fluoropheny1 2-ethyIphenyl 3-ethylphenyl 4-ethylphenyl 2-i sopropy1pheny1 3-i sopropy1pheny1 4-i sopropy1pheny1 2-tert-buty1pheny1 3-tert-buty1pheny1 4-tert-buty1pheny1 4-butylphenyl 4-hexyIphenyl 4-nonylphenyl 4-decylphenyl 2-methoxy phenyI 3-methoxypheny1 4-methoxyphenyI 2-tr i f1uoromethy1pheny1 3-tr i f1uoromethy1phenyI 4-tr i f1uoromethy1pheny1 4-formylphenyI 2-nitrophenyl 3-nitrophenyl 4-nitrophenyl 2,5-dichlorophenyl r1 CH3 CH3 CH3 CH3 ch3 CH3 CH3 CH3 CH3 ch3 ch3 ch3 CH3 CH3 ch3 CH3 CH3 CH3 CH3 ch3 CH3 ch3 ch3 ch3 ch3 CH3 CH3 CH3 CH3 CH3 CH3 ch3 CH3 CH3 R2 ir (cm 1) (mp.) CH3 CH3 CH3 ch3 CH3 CH3 CH3 ch3 ch3 CH3 CH3 CH3 ch3 ch3 ch3 ch3 ch3 ch3 ch3 ch3 ch3 ch3 ch3 ch3 ch3 ch3 ch3 ch3 ch3 ch3 ch3 ch3 ch3 ch3 1705,1632, 1285, 1258,1197,1126, 1091,1067,1044, 771 112-117 <>C 75- 80 °C 1706,1633,1594, 1481,1285,1252, 1198,1126,1092, 1042,772 Table 2: (X = SO) (contd.) 232 181 O.Z. 0050/40504 NO.

R3 r* r2 ir (cm 1) (mp.) -~N 2,6-dichloropheny1 CH3 ch3 36 3,4-dichlorophenyl CH3 CH3 97-102 °C 37 2,3-dichlorophenyl ch3 CH3 38 3,5-dichlorophenyl ch3 CH3 39 2,3,4-trichIorophenyl CH3 ch3 40 2", 4,5-tr ichl oropheny 1 ch3 CH3 41 2,4,6-trichlorophenyl ch3 CH3 42 2,3,4,6-tetrachlorophenyI CH3 CH3 43 2,3,4,5,6-pentachlorophenyl ch3 ch3 44 2,3,4,5-tetraf1uoropheny1 CH3 CH3 45 2,3,5,6-tetraf1uoropheny1 CH3 CH3 46 2,3,4,5,6-pentaf 1 uoropheny 1 CH3 ch3 47 2-chloro, 4-fluoropheny1 ch3 ch3 48 3-chloro, 4-fluoropheny1 ch3 ch3 49 2-chloro, 6-methyIphenyl ch3 ch3 50 4-chloro, 2-methylphenyl ch3 CH3 51 2,4-dichloro, 5-methylphenyl CH3 CH3 52 4-chloro, 2,5-dimethylphenyI CH3 CH3 53 4-bromo, 3-methylphenyl ch3 ch3 54 3,5-bistrifluoromethylphenyl CH3 CH3 56 2,5-dimethylphenyl CH3 CH3 57 2,4-dimethylphenyl CH3 CH3 58 2,5-dimethylphenyl CH3 ch3 59 2,6-dimethylphenyl CH3 CH3 60 3,4-dimethylphenyl CH3 ch3 61 3,5-dimethylphenyI CH3 ch3 62 2,4,5-trimethylpheny1 ch3 CH3 63 2,6-d i ethy1pheny1 CH3 ch3 64 2,4-d i-tert.-butyIphenyI CH3 CH3 65 2,5-dimethoxyphenyI CH3 CH3 66 3,4-dimethoxyphenyI CH3 CH3 67 2-methyl, 4-tert.-butylphenyl ch3 CH3 68 2-methoxyc arbony1pheny1 ch3 CH3 69 2-ethoxycarbonyIpheny1 ch3 CH3 70 2-propoxyc arbony1pheny1 CH3 CH3 71 2-butoxyc arbony1pheny1 CH3 CH3 72 2-cyanophenyl CH3 CH3 73 3-cyanophenyl CH3 ch3 74 4-cyanophenyl ch3 CH3 232 1 81; o Table 2: (X = SO) (contd.) O.Z. 0050/40504 No.

R3 R1 r2 ir (cm-*) (mp.) 75 76 77 78 phenyl phenyl phenyl phenyl CH3 Et Et CH3 CH3 n-Bu n-Bu n-Bu O o 232181 O.Z. 0050/40504 Table 3: (X = S02) No. R3 O 1 2 3 4 6 7 8 9 11 12 13 14 16 17 18 19 21 22 23 24 26 27 28 29 31 32 33 34 36 37 38 1-naphthyl 2-naphthyl 3-phenanthrenyI 2-chlorophenyl 2-bromophenyl 3-bromophenyl 4-broroophenyl 2-fluorophenyl 3-fluorophenyl 4-fluoropheny1 2-ethylphenyl 3-ethylphenyl 4-ethylphenyl 2-i sopropyIpheny1 3-i sopropy1pheny1 4-i sopropyIpheny1 2-tert-buty1pheny1 3-tert-buty1pheny1 4-tert-buty1pheny1 4-butylphenyl 4-hexylphenyl 4-nonylphenyl 4-decylphenyl 2-methoxyphenyl 3-methoxyphenyl 4-methoxypheny1 2-tr i f1uoromethy1pheny1 3-tr i f1uoromethy1phenyI 4-tr i f1uoromethy1phenyI 4-formylphenyl 2-nitrophenyl 3-nitrophenyl 4-nitrophenyl 2.5-dichlorophenyl 2.6-dichloropheny1 3.4-dichlorophenyl 2, 3-dichlorophenyl 3.5-dichlorophenyl R1 R2 IR (cm-1) (mp.) CH3 CH3 CH3 CH3 130-134 °C CH3 CH3 CH3 ch3 CH3 CH3 CH3 CH3 CH3 CH3 168-173 °C CH3 CH3 CH3 ch3 CH3 CH3 140-145 °C CH3 CH3 ch3 ch3 CH3 ch3 CH3 ch3 CH3 ch3 CH3 ch3 CH3 ch3 CH3 CH3 CH3 ch3 CH3 CH3 CH3 CH3 CH3 ch3 CH3 ch3 CH3 ch3 CH3 CH3 1698,1627,1296, 1255, 1142,1126, 1096 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 ch3 CH3 CH3 CH3 CH3 163-167 °C CH3 CH3 CH3 ch3 232181 11 O.Z. 0050/40504 o 1o. r3 r1 r2 39 2,3,4-trichloropheny1 ch3 CH3 40 2,4,5-trichlorophenyl CH3 CH3 41 2,4,6-trichloropheny1 ch3 ch3 42 2,3,4,6-tetrachloropheny1 ch3 CH3 43 2,3,4, 5,6-pentachlorophenyl ch3 ch3 44 2,3,4,5-tetraf1uoropheny1 ch3 CH3 45 2,3,5,6-tetrafluoropheny1 ch3 CH3 46 2,3,4,5,6-pentafluoropheny1 ch3 CH3 47 2-chloro, 4-fluorophenyI ch3 CH3 48 3-chloro, 4-fluorophenyI ch3 CH3 49 2-chloro, 6-methylphenyl ch3 CH3 50 4-chloro, 2-methylphenyI ch3 ch3 51 2,4-dichloro, 5-methyIphenyl ch3 CH3 52 4-chloro, 2,5-dimethylphenyl ch3 CH3 53 4-bromo, 3-raethylphenyl ch3 CH3 54 3,5-bistrifluoromethylphenyl ch3 CH3 56 2,5-dimethylphenyl ch3 CH3 57 2,4-dimethylphenyl ch3 ch3 58 2,5-dimethylphenyl ch3 CH3 59 2,6-dimethylphenyl ch3 CH3 60 3,4-dimethylphenyl ch3 CH3 61 3,5-dimethylphenyI ch3 CH3 62 2,4,5-trimethylpheny1 ch3 CH3 63 2,6-diethylphenyl ch3 CH3 64 2,4-d i-tert.-buty1pheny1 ch3 CH3 65 2,5-dimethoxyphenyl CH3 CH3 66 3,4-dimethoxyphenyl ch3 CH3 67 2-methyl, 4-tert.-butylphenyl ch3 CH3 68 2-methoxycarbony1pheny1 ch3 CH3 69 2-ethoxyc arbony1phenyI ch3 CH3 70 2-propoxyc arbonyIpheny1 ch3 CH3 71 2-butoxyc arbony1pheny1 ch3 ch3 72 2-cyanophenyl ch3 CH3 73 3-cyanophenyl ch3 CH3 74 4-cyanophenyl ch3 CH3 75 phenyl ch3 Et 76 phenyl Et ch3 77 phenyl ch3 n-Bu 78 phenyl n-Bu n-Bu R2 ir (cm 1) (mp.) 232 181 12 O.Z. 0050/40504 Generally speaking, the novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the Asco-mycetes and Basidiomycetes classes. Some of them have a systemic action and can be used as foliar and soil fungicides.

The fungicidal compounds are of particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in 10 vegetables such as cucumbers, beans and cucurbits.

The novel compounds are particularly useful for controlling the following plant diseases: Erysiphe graminis in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in vines, Puccinia species in cereals, Rhizoctonia species in cotton and lawns, ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Botrytis cinerea (gray mold) in strawberries and grapes, Cercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Fusarium and VerticiIlium species in various plants, Plasmopara viticola in grapes, Alternaria species in fruit and vegetables.

The compounds are applied by spraying or dusting the plants with the 35 active ingredients, or treating the seeds of the plants with the active ingredients. They may be applied before or after infection of the plants or seeds by the fungi.

The novel substances can be converted into conventional formulations such 40 as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application forms depend entirely on the purposes for which they are intended; they should at all events ensure a fine and uniform distribution of the active ingredient. The formulations are produced in known manner, for example by extending the active ingredient with solvents and/or ■ ' ■ ' 23 2 1 13 O.Z. 0050/40504 carriers, with or without the use of emulsifiers and dispersants; if water is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics (e.g., xylene), chlorinated aromatics (e.g., chloro-5 benzenes), paraffins (e.g., crude oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g., cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), and water; carriers such as ground natural minerals (e.g., kaolins, aluminas, talc and chalk) and ground synthetic minerals ^ (e.g., highly disperse silica and silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) ; and dispersants such as lignin, sulfite waste liquors and methylcellulose.

The fungicidal agents generally contain from 0.1 to 95, and preferably 15 from 0.5 to 90, wt% of active ingredient. The application rates are from 0.02 to 3 kg or more of active ingredient per hectare, depending on the type of effect desired. The novel compounds may also be used for protecting materials, for example against Paecilomyces variotii.

The agents and the ready-to-use formulations prepared from them, such as solutions, emulsions, suspensions, powders, dusts, pastes and granules, are applied in conventional manner, for example by spraying, atomizing, dusting, scattering, dressing or watering.

Examples of formulations are given below. 1. 90 parts by weight of compound no. 2 (Table 1) is mixed with 10 parts by weight of N-methyl-a-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

II. 20 parts by weight of compound no. 4 (Table 1) is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene- sulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.

III. 20 parts by weight of compound no. 25 (Table 1) is dissolved in a 40 mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and finely distributing it therein, an aqueous dispersion is obtained. 232181 14 O.Z. 0050/40504 IV. 20 parts by weight of compound no. 34 (Table 1) is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280°C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.

V. 80 parts by weight of compound no. 2 (Table 1) is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic 10 acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in water, a spray liquor is obtained.

VI. 3 parts by weight of compound no. 4 (Table 1) is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.

VII. 30 parts by weight of compound no. 25 (Table 1) is intimately mixed 20 with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

VIII. 40 parts by weight of compound no. 34 (Table 1) is intimately mixed with 10 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stable aqueous dispersion. Dilution in water gives an aqueous dispersion.

IX. 20 parts by weight of compound no. 2 (Table 1) is intimately mixed with 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate 35 and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.

In these application forms, the agents according to the invention may also be present together with other active ingredients, for example herbicides, 40 insecticides, growth regulators, and fungicides, and may furthermore be mixed and applied together with fertilizers. Admixture with other fungicides frequently results in an increase in the fungicidal spectrum.

The following list of fungicides with which the novel compounds may be combined is intended to illustrate possible combinations but not to impose any restrictions. 232 181 O.Z. 0050/40504 Examples of fungicides which may be combined with the novel compounds are: sulfur, dithiocarbamates and their derivatives, such as 5 ferric dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethyIenebi sdi thiocarbamate, manganese zinc ethylenediaminebisdithiocarbamate, tetramethylthiuram disulfides, ammonia complex of zinc N,N'-ethylenebisdithiocarbamate, ammonia complex of zinc N,N'-propylenebisdithiocarbamate, zinc N,N'-propylenebisdithiocarbamate and N,N'-polypropylenebis(thiocarbamyl) disulfide; nitro derivatives, such as d i n i tro(1-methy1heptyI)-pheny1 c rotonate, 2-sec-buty1-4,6-dinitrophenyI 3,3-dimethy1aery1ate, 2-sec-butyl-4,6-dinitrophenyl isopropylcarbonate and 20 diisopropyl 5-nitroisophthalate; heterocyclic substances, such as 2-heptadecylimidazol-2-yl acetate, 2,4-d i c h1oro-6-(o-c h1oroan i1i no)-s-tr i az i ne, 0,0-diethyl phthaliraidophosphonothioate, -amino-l-[-bis-(dimethylamino)-phosphinyl]-3-phenyl-l,2,4-triazole, 2,3-d i cy ano-1,4-d i th i oanthraqu i none, 2-thio-l, 3-dithio[4,5-b]quinoxaline, methyI 1-(buty1carbamy1)-2-benz i mi dazo1ec arbamate, 30 2-methoxycarbony1aminobenzimidazo1e, 2-(fur-2-y1)-benz imidazole, 2-(thiazol-4-yl)benzimidazole, N—(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide, N-trichloromethylthiotetrahydrophthalimide, 35 N-trichloromethyIthiophtha1imide, N-dichlorofIuoromethylthio-N*,N'-dimethyl-N-phenylsulfuric acid diamide, 5-ethoxy-3-trichloromethyl-l, 2,3-thiadiazole, 2-th i ocyanatomethyIth i obenzoth i azole, 40 l,4-dichloro-2,5-dimethoxybenzene, 4-(2-c hIorophenyIhydrazono)-3-methyI-5-i soxazo1one, 2-thiopyridine 1-oxide, 8-hydroxyquinoline and its copper salt, 2,3-dihydro-5-carboxani1ido-6-methyl-l, 4-oxathiyne, 2,3-dihydro-5-carboxanilido-6-methyl-l,4-oxathiyne 4,4-dioxide, 232181 16 O.Z. 0050/40504 2-methyIfuran-3-carboxaniIide, 2,5-d i methy1furan-3-carboxan i1i de, 2,4, 5-trimethylfuran-3-carboxani1ide, 2.5-d imethy1-N-cyc1ohexy1 f uran-3-c a rboxamide, N-cyclohexyl-N-methoxy-2,5-diethylfuran-3-carboxamide, 2-methylbenzanilide, 2-i odobenzan i1i de, N-formyl-N-morpholine-2,2,2-trichloroethylacetal, piperazine-l,4-diylbis-(l-(2,2,2-trichloroethyl)-formamide), 10 1—(3,4-dichloroanilino)-l-formylamino-2, 2, 2-trichloroethane, 2.6-dimethyl-N-tridecylmorpholine and its salts, 2,6-dimethyl-N-cyclododecylmorpholine and its salts, N-[3-(p-tert.-buty1pheny1)-2-methy1propy1]-c i s-2,6-d imethyImorpholi ne, N-[3-(p-tert.-butyIpheny1)-2-methylpropyl]-piperidine, 15 l-[2-(2,4-dichlorophenyl)-4-ethyl-l,3-dioxolan-2-ylethyl]-lH-l,2,4--triazole, l-[2-(2,4-dichlorophenyl)-4-n-propyl-l, 3-dioxolan-2-ylethyl]-lH-l,2,4--triazole, N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazolyl-urea, 20 l-(4-chlorophenoxy)-3,3-dimethyl-l-(lH-1,2,4-triazol-l-yl)-butan-2-one, l-(4-chlorophenoxy)-3,3-dimethyl-l-(lH-l,2,4-triazol-l-yl)-butan-2-ol, 1-(4-phenylphenoxy)-3,3-dimethyl-l-(lH-l,2,4-triazol-l-yl)-2-butanol, a-(2-c h1orophenyI)-a-(4-c hIorophenyl)-5-pyrimidi nemethano1, -buty1-(2-d imethyIami no-4-hydroxy-6-methy 1pyrimi d i ne, 25 bis-(p-chlorophenyl)-3-pyridinemethanol, 1,2-b i s-(3-ethoxyc arbonyI-2-th i oure i do)-benzene, 1,2-b i s-(3-methoxyc arbony1-2-th i oure ido)-benzene, and various fungicides, such as 30 dodecylguanidine acetate, 3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]-glutaramide, hexac h1orobenzene, DL-methy1-N-(2,6-d i methy1pheny1)-N-fur-2-y 1 a1anate, methy1 DL-N-(2,6-diraethy1pheny1)-N-(2 *-methoxyacety1)-alanate, 35 N—(2,6-dimethylphenyI)-N-chloroacetyl-DL-2-aminobutyrolactone, methy1 OL-N-(2,6-d i methy1phenyI)-N-(pheny 1acetyI)-a1anate, 5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-l, 3-oxazolidine, 3-[3,5-dichlorophenyl]-5-methyl-5-methoxymethyl-l,3-oxazolidine-2,4-dione, 3-(3,5-dichlorophenyl)-l-isopropylcarbamylhydantoin, 40 N-(3,5-dichlorophenyl)-l,2-dimethy1eyelopropane-1,2-dicarboximide, 2-cyano-[N-(ethylaminocarbony1)-2-methoximi no]-acetami de, 1-[2-(2,4-dich1oropheny1)-penty1]-1H-1,2,4-1riazo1e, 2,4-difluoro-a-(lH-l,2,4-triazol-l-yImethyl)-benzhydryl alcohol, N-(3-ch1oro-2,6-d i n i tro-4-tr i fIuoromethy1pheny1)-5-tr i f1uoromethy1-3-chloro-2-aminopyridine, and 1-((bis-(4-fluorophenyl)-methylsilyI)-methyl)-lH-l,2,4-triazole. 2 A a J 0 17 O.Z. 0050/40504 Use examples The compounds methyl a-(2-[3-chlorophenylthiomethyl]-phenyl)-p-methoxy-acrylate (A) disclosed in EP 278,595 and methyla-(2-[4-chlorophenylthio-5 methyl]-phenyl)-p-methoxyacrylate (8) disclosed in EP 226,917 were used as comparative active ingredients.

Use Example 1 Action on wheat brown rust Leaves of pot-grown wheat seedlings of the "Kanzler" variety were dusted with spores of brown rust (Puccinia recondita). The pots were then placed for 24 hours at 20 to 22°C in a high-humidity (90 - 95%) chamber. During 15 this period the spores germinated and the germ tubes penetrated the leaf tissue. The infected plants were then sprayed to runoff with aqueous liquors containing (dry basis) 80% of active ingredient and 20% of emulsifier. After the sprayed-on layer had dried, the plants were set up in the greenhouse at 20 to 22°C and a relative humidity of 65 to 70%. The 20 extent of rust fungus spread on the leaves was assessed after 8 days.

The results show that active ingredients 4 and 34 (Table 1), applied as 0.025wt% spray liquors, have a better fungicidal action (94%) than prior art active ingredients A (65%) and B (80%).

Use Example 2 Action on Pyricularia oryzae Leaves of pot-grown rice seedlings of the "Bahia" variety were sprayed to runoff with aqueous emulsions containing (dry basis) 80% of active ingredient and 20% of emulsifier, and inoculated 24 hours later with an aqueous spore suspension of Pyricularia oryzae. The plants were then set up in a climatic cabinet at 22-24°C and a relative humidity of 95-99%. The 35 extent of fungus spread was determined after 6 days.

The results show that active ingredients 2, 4, 25 and 34 (Table 1), applied as 0.05% spray liquors, have a better fungicidal action (94%) than prior art comparative active ingredients A (65%) and B (55%). 40 232181 alle Lander auper ZA 18 O.Z. 0050/40504

Claims (12)

WHAT WE CLAIM IS:

1. Acrylic esters of the formula 15 jO R102C^S>^OR2 and 5 where R* and R2 are hydrogen or Cj-Cs-allcyl, X is S, SO or S02,/r3 is phenyl, naphthyl or phenanthrenyl, these radicals being unsubstituted or substituted by halogen, cyano, nitro, formyl, Ci-Cio~alkylr cl_c4~ alkoxy, Ci-C2~haloalkyl, aryl or Cj-C^alkoxycarbonyl, with the exception of compounds in which R3 is phenyl, 3-chlorophenyl, 4-chloro-10 phenyl, 2,4-dichlorophenyl or methylphenyl.

2. A process for combating fungi, wherein the fungi, or the materials, plants, seed or soil threatened by fungus attack are treated with a fungicidally effective amount of an acrylic ester of the formula XI R3^X^CH; R102C^SJ-^OR2 and where R* and R2 are hydrogen or Cj-Cs-alkyl, X is S, SO or SO2,/R^ is phenyl, naphthyl or phenanthrenyl, these radicals being unsubstituted or substituted by halogen, cyano, nitro, formyl, Ci-Cio~3lkyl, C1-C4-alkoxy, Ci-C2~haloalkyl, aryl or Ci~C4-alkoxycarbonyl, with the ex-20 ception of compounds in which R3 is phenyl, 3-chlorophenyl, 4-chloro-phenyl, 2,4-dichlorophenyl or methylphenyl.

3. A fungicide containing an inert carrier and a fungicidally effective amount of an acrylic ester of the formula 25 R3^xm:H9> i and where R* and R2 are hydrogen or Cj-Cs-alkyl, X is S, SO or S02,/R^ is phenyl, naphthyl or phenanthrenyl, these radicals being unsubstituted or substituted by halogen, cyano, nitro, formyl, Ci-Cio~a^yl» cl"c4" alkoxy, Ci-C2~haloalkyl, aryl or Ci-C^-alkoxycarbon^ with the ex-30 ception of compounds in which R3 is phenyl, 3-c hi oropheny 1^4^-chl oropheny 1, 2,4-dichlorophenyl or methylphenyl. 232 181 alle Lander auper ZA 19 O.Z. 0050/40504

4. A compound as set forth in claim 1, where R* and R2 are methyl, X is S and R3 is 2-naphthyl.

5. A compound as set forth in claim 1, where R* and R2 are methyl, X is S 5 and R3 is 2-chlorophenyl.

6. A compound as set forth in claim 1, where R* and R2 are methyl, X is S and R3 is 2, 5-dichlorophenyl. 10

7. A compound as set forth in claim 1, where R1 and R2 are methyl, X is S and R3 is 2-bromopheny1.

8. A compound as set forth in claim 1, where R* and R2 are methyl, X is S and R3 is 3-bromophenyl. 15

9. Acrylic esters as claimed in claim 1, substantially as herein described in any one of the ccxnpound examples. 20 io.

A process as claimed in claim 2, substantially as herein described.

11. A fungicide as claimed in claim 3, substantially as herein described. 25

12. A fungicide as claimed in claim 3, substantially as herein described in any one of the formulation examples. 30 o BASF ACTIENOyKT ,T .SCHAFT by their attorneys Baldwin, Son & Carey LA. AwdlteUO 35 40 | l9j*N199ol J