DE1259135B - Agents for combating phytopathogenic fungi and / or bacteria - Google Patents

Description

Agents for controlling phytopathogenic fungi and / or bacteria The present invention relates to agents for controlling phytopathogenic fungi and / or bacteria, characterized by a content of a compound of the general formula as an active ingredient. where R is an F, Cl or Br atom, a methyl, methoxy or methylthio radical, a - CF: 3-, - NO-, - CN-, - SCN- or the N (CH: 3) o- Radical means, 11 is 1 or 2 and X is oxygen or sulfur.

The compounds of the general formula (1) have a pronounced Effect against fungi and bacteria that cause plant diseases.

In particular, show those compounds of the general formula (1) in which X means sulfur, an excellent effect against phytopathogens Mushrooms.

Furthermore, the effect of the compounds mentioned is against certain phytopathogenic bacteria, such as. B. the genus Corynebacterium should be emphasized. A particularly pronounced antibacterial effect is shown by z. B. the compound of formula which in a concentration of 0.001 ppm still has an inhibiting effect, such as. B. the dilution test with a culture of Staphylococcus aureaus in glucose broth shows.

It is of particular importance that the compounds mentioned also their effectiveness against phytopathogenic in the presence of surface-active substances Do not lose microorganisms.

As examples of the application of the compounds of general Formula (1) in plant protection is the treatment of plant seeds and of whole or partially developed plants as well as the soil in which the plants grow called the harmful microorganisms.

It proves to be particularly advantageous that these compounds versus crops at the concentrations required for the antiparasitic Use are required, have no toxic side effects.

The compounds of the general formula (1) can be per se known processes.

You can z. B. proceed so that a compound of the general formula in which X stands for 0 or S, with a compound of the general formula NW-R in which R has the meaning given above for the general formula (1), or that a compound of the general formula is reacted with one of the general formula RN = C = X in which R and X have the meanings given above.

So is used in the preparation of the compounds of the general formula (1) e.g. B. the 3,5-bis-trifluoro- methylphenyl isocyanate or isothiocyanate with the following Compounds implemented: - with the radicals R [cf. Formula (1)], substituted anilines, such as B. p-chloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,5-dichloroaniline, 3-chloro-4-bromoaniline, 3-chloro-4-methoxyaniline, 3-chloro-4-methylaniline, 3-trifluoromethylaniline, 2-chloro-5-trifluoromethylaniline, 3-trifluoromethyl-4-chloroaniline, 3,5 - bis - trifluoromethylaniline, 4-bromoaniline, 2,4-dichloroaniline, 4-rhodananiline, 3-bromoaniline, 4-chloro-3-methylaniline. 4-chloro-2-methylaniline.

In place of the isocyanates, corresponding carbonic acid derivatives, such as the 3,5-bis-trifluoromethylphenyl carbonic acid phenyl ester, the 3,5-bis-trifluoromethylphenyl carbonic acid chloride or the 3,5-bis-trifluoromethylphenylurea can be used with similar success according to the following scheme can be used.

By reacting the 3,5-bis-trifluoromethylphenyl isothiocyanate The corresponding thioureas are formed in place of the 3,5-bis-trifluoromethylphenyl isocyanate. On the other hand, by desulfurizing the thioureas by known processes the correspondingly built ureas are obtained. Or one uses 3,5-bis-trifluoroaniline with phenyl isocyanates or phenyl isothiocyanates to, for. B. with those who have a or contain several nitro groups, such as the 4-nitro phenyl isocyanate, the 3-nitro or 2-nitrophenyl isocyanate, 4-methyl-3-nitrophenyl isocyanate, 4-chloro-3-nitrophenyl isocyanate, the 2-nitro-4-chlorophenyl isocyanate or the 2,4-diniftophenyl isocyanate or the corresponding isothiocyanates.

Other methods, e.g. B. the implementation of reactive carbonic acid or thiocarbonic acid derivatives, e.g. B. carbon disulfide, urea, phenyl carbonates and phosgene with the correspondingly substituted aromatic amines lead to the concerned Compounds of the general formula (I). To represent a symmetrically built Compound is also the reaction of 3,5-bis-trifluoromethylphenyl isocyanate with the necessary amount of water z. B. in an inert solution medium, such as acetonitrile, suitable. The manufacture of the active ingredients is not protected in this context.

The compounds of the general formula (1 can be used on their own or together with other pesticides and / or the other at the outset mentioned additives who used the.

As a pesticide. which in the invention Agents other than the compounds of the general formula (1) can be present. are for example: 3, 4-dichlorobenzyl alcohol, ammonium compounds. how z. B. Diisobutylphenoxyäthoxyäthyldimethylbenzylammoniumchlorid, Cetylpyridiniumchlorid, Cetyltrimethylammonium bromide, halogenated dioxydiphenylmethane.

Tetramethylthiuramide sulfide, 2,2 '- thio - bis - (4,6 - dichlorophenyl), 2-nitro-2-furfuryl iodide, salicylan ilide.

Dichlorosalicylanilide, dibromosalicylanilide, tribromo salicylanilide. Dichlorocyanuric acid, tetrachlorosalicyl anilide, aliphatic thiuram sulfide, »Hexachloro phen "(2,2'-dihydroxy-3,5,6,3 ', 5', 6'-hexachlorodiphenylmethane).

The agents according to the invention, which the connec tions of the general Containing formula (1) can be in a wide variety of application forms. z. B. as pastes, powders, emulsions, super sions, solutions or sprays.

For the production of directly sprayable solving conditions come z. B. Mineral oil fractions from high to medium boiling range, such as diesel oil or kerosene, also coal tar oils and oils of vegetable or animal origin and hydrocarbons. like alkylated Naphthalenes. Tetrahydronaphthalene ir consideration, if necessary using before Xylene mixtures, cyclohexanols, ketones, other chlorinated hydrocarbons. like tetrachlor itI0iIi. olllIlyIell or tri- and tetrachlorobenzenes.

Aqueous application forms are made from emulsion concentrates and pastes or wettable spray powders by adding water. A emulsifying or Dispersants are non-ionic products, e.g. B. Condensation Products of aliphatic alcohols, amines or carboxylic acids with a long-chain hydrocarbon radical of about 10 to 30 carbon atoms with ethylene oxide, like the condensation product of octadecyl alcohol and 25 to 30 moles of ethylene oxide or that of technical Oleylamine and 15 moles of ethylene oxide or that of dodecyl mercaptan and 12 moles Ethylene oxide Among the anionic emulsifying agents that can be used, the sodium salt of the dodecyl alcohol sulfuric acid ester, the sodium salt, should be mentioned of dodecylbenzenesulfonic acid, the potassium or triethanolamine salt of ulic acid or de abietic acid or mixtures of these acids. or the sodium salt of a petroleum sulfonic acid As a cationic dispersant, rectangular ammonium compounds such as this are used Cetylpyridi niumbromid, or Dioxyäthylbenzyldodecylammoniumchlorid into consideration.

Solid carriers can be used for the production of litter and dust Talc, kaolin, bentonite, calcium carbonate, calcium phosphate, but also coal, cork flour and wood flour and other materials of vegetable origin can be used.

It is also very useful to manufacture the preparations in granulated form Shape. The various application forms can in the usual way by adding Substances, which the distribution, the adhesive strength, the rain resistance or improve penetration. be provided; such substances may be mentioned Fatty acids. Resins, glue, casein or e.g. B. also alginates.

A number of urea derivatives are listed in Table 1 below. which are suitable as active ingredients in the agents according to the invention: Table 1 Table 1 1.) ½ NH C -7; I. 1. <jl CF3 O Cl M.p .: 927 C CF3 ¼ 2. NH C NH CF3 0 CF3 M.p .: 253 to 356-C CF 3.) ½ NH C-NH CF3 0 CF3 M.p .: 165 to 167 ° C CF 4. y½ NH -C NH OCH3 CF3 ° Cl M.p .: 188-190-C CF 5.) ½NH \ t> NH - N0 5. 4 O C1 CF3 Cl M.p .: 211 to 212 ' CF3 ¼ 6. ~ NH-C NH ½ lt CH3 CF3 0 NO2 M.p .: 215 to 217 ° C CF3 CF3 CI 7.tNU - NH-No 15. y½ NH-C- - NH CF3 0 CF3 0 CF3 M.p .: 220 to 225 C m.p .: 225 to 226 C CF, ro CF3 S.>; ½ \ NH 9 16.> NHCNH ß 3 Cl CF3 0 NO2, 5 CF3 CI 15th M.p .: 230 to 232 C m.p .: 192 to 194 C C F3 CF3 Cl 9. 43 -C1-NHa 20 17. 4 3 NH-C- X Ii NH CF3 O NO2 CF3 O Cl M.p .: 204 to 206 "C 25 m.p .: 225.5 to 227 C CF3 CF3 10. ag NH-C-NH <Br 18. C NH-C-NH <% CF3 Õ CF3 ° Cl M.p .: 224 to 225.5 "C m.p .: 175 to 176; C CF, CF3 11 7NH - C - NH 19. Cl 19.> NH-C1- NH ¼) CF3 0 40 CF3 0 Br M.p .: 214.5 to 215.5 "C. M.p .: 174 to 175C CF3 Cl CF3 12. / - \ NH-CN 20. F3 NH-C-NHCH3 II NH - C - II CF3 0 Cl M.p .: 219 to 21950C M.p .: 50 CF, to CH3 M.p .: 185.5 to 186.5 ° C CF3 CF3 13. 4bNH -F - NH 21st y½ 21st NH CF3 Õ F 55 Cl CI M.p .: 213 to 214 "C 60 m.p .: 222.5 to 223.5'C CF CF3 14. - C - NHCHS 22. 9 Õ - 22. - N CF30 Cl CF3 0 M.p .: 230 to 2310C; MP .: 204 to 205 ° C CF3 23. <A <NH - C - NH My CN w II CF3 O M.p .: 252 to 253 "C CF3 24. NH-C1-NH 2 CF3 ° S-CH3 M.p .: 158 to 159 "C CF3 25. 7NH-C-NH7CH3 - II CF3 M.p .: 227 "C CF3 26. NH- {1-NH CF3 O CF3 M.p .: 177 to 178 "C The following table 2 lists a number of thiourea derivatives which are suitable as active ingredients in the agents according to the invention: CF3 table 2 1. <NH-C-NH <Cl 1 C II = f CF3 S Cl M.p .: 138-139 "C CF3 2.> NH-C-NH <Cl CF3 S CF3 M.p .: 138.5 to 139 "C CF3 3. <'<NHCNH < II CF3 S CF3 M.p .: 133 to 134 "C CF3 4. to NH - C - NH Br - II CF3 M.p .: 163 to 164 "C CF3 CF3 5. X NHCNH CF3 5 CF3 M.p .: 184.5 to 186 "C CF 6. NHCNH <CI CF3 s M.p .: 150 to 151 "C CF CH3 7.;) \ NH - C - NH N CF3 S CH3 M.p .: 167.5 to 1700C CF 8. A NHCNH 4 r S < CF3 5 S-CH3 M.p .: 125 to 127 "C CF 9.) ½ NH -C-NHS-C = -N 9 C II CF3 M.p .: 1220C The invention is described in more detail in the following examples. The temperatures are given in degrees Celsius; Parts mean parts by weight, percentages mean percentages by weight.

Example 1 a) 10 g of the active ingredient described in Table 2 under 1 and 2 g of sulphite cellulose waste liquor are mixed with 100 ccm of water. This mixture is subjected to intensive grinding, creating a finely divided, stable dispersion arises, which can be diluted in any way with water. b) 7.5 parts from Ninol Inc., Chicago, under the brand name »Toximul MP« Brought emulsifier are dissolved in 72.5 parts of butanol. Be in this mixture 20 parts of the compound described in Table 2 under 1. solved.

The solution can be diluted with water in any way. c) Tomato and celery plants are sprayed with a 0.20% solution of the dispersions prepared analogously a) or b), 2 days after the spraying, the tomato plants with a spore suspension of Alternaria solani or Phytophthora infestans and the celery plants with a Septoria appi spore suspension infected. After infection, the plants are placed in the incubation chamber at 95 to 1000 / o relative humidity and 22 to 25 ° for 2 days. The result for the celery plants is evaluated about 15 to 18 days, that for the tomato plants 6 to 8 days after infection: Fungicidal effect in% Active ingredient C1 NH-C-NH 9 Cl 95 85 100 CF, ; ½NH -CN Br 76 83 97 II II CF3 S CF ) ½ NH -C-NH 96 0 90 CF3 5 - CF3 CF 9 S 9 93 100 100 CF3 Cl The compounds of the formulas also show the equally good action against the fungi mentioned The other compounds described in Table 2 also have a pronounced action against the above-mentioned plant disease-causing fungi. The compounds listed in Table 1 under 1., 3., 10., 11., 22. and 24. should also be emphasized in their action against the fungi mentioned under the test conditions described above.

Example 2 The fungicidal effect and the phytotoxicity of the following compounds according to the present invention Table 1, No. 1, 2, 3, 4, 7, 10, 13, 20, 22 and 23 Table 2, Nos. 1, 2, 4, 5, 7 and 9 compared to the known fungicide zinc ethylene bis dithiocarbamate.

The compounds were each in the form of an aqueous spray liquor, prepared analogously to Example 1, containing 0.20 / 0 of the active ingredient, applied. as Test plants were courgettes and beans. The plants were grown 2 days after treatment infected with the spray liquors in question with spores of Erysiphe cichoriacearum. The effect was noted 12 days after the treatment.

The following table shows the result. Active ingredient fungicidal effect phytotoxicity in ° / 0 courgettes, beans Invention: Table 1, No. 1 .................................... 80 to 85 practically none Table 1, No. 2 .................................... 85 to 90 practically none Table 1, No. 3 .................................... 95 to 100 practically none Table 1, No. 4 .................................... 75 to 80 practically none Table 1, No. 7 .................................... 70 to 75 only insignificant leaf damage to beans Table 1, No. 10 ................................... 70 to 75 practically none Table 1, No. 13 ................................... 75 to 80 practically none Table 1, No. 20 ................................... 85 to 90 practically none Table 1, No. 22 ................................... 70 to 75 practically none Table 1, No. 23 ................................... 70 to 75 practically none Table 2, No. 1 .................................... 90 to 95 practically none Table 2, No. 2 .................................... 95 to 100 practically none Table 2, No. 4 .................................... 70 to 75 practically none Table 2, No. 5 .................................... 95 to 100 practically none Table 2, No. 7 .................................... 70 to 75 practically none Table 2, No. 9 .................................... 70 to 75 practically none Zinc-ethylene-bis-dithiocarbamate ........................ 25 to 30 practically none From the above results it follows that the agents according to the present invention have an equally low or only insignificantly higher phytotoxicity compared to ZINEB, but at the same time a significantly stronger fungicidal effect.

Claims (1)

Claim: Agent for combating phytopathogenic fungi and / or bacteria, characterized by a content of a compound of the general formula as an active ingredient, in which R is an F, Cl or Br atom, a methyl, methoxy or methylthio radical, a - CF3-, - NO2-, - CN-, - SCN- or the - N (CH.i) 2 radical means, 1 is 1 or 2 and X is oxygen or sulfur.