IE45009B1 - 2-(4-phenoxyphenoxy) propionic acid esters and nitriles and their herbicidal and fungicidal compositions - Google Patents

Abstract

The herbicide contains, as active substance, a compound of the formula I. The herbicide is prepared by mixing the carrier with a compound of the formula I. The compound of the formula I can be obtained by reacting a compound of the formula II with a compound Hal-Z or a suitably substituted phenoxypropionyl halide with a compound HYZ. The substituents in the compounds have the meanings given in patent claim 2.

Description

This invention provides a compound of the general formula in which n and n^, which may be the same or different, each represents 0 or an integer from I to 3, R and R^ each represents a halogen atom or a (C-haloalkyl, (C^-C^)-alkyl, nitro, (C^-C^)-alkoxy or (C^-C^)alkylthio group, and any two or more of the R and moieties may be the same or different, X represents =0- or -CH2~, Y represents =0-, -S- or -NH- and Z ' represents a cyanoethyl group or a radical of the general formula -A-c-OR., I! 3 in which represents a methylene group which may be unsubstituted or substituted by -CH^, -CjHj, -COCH3 or by a radical of the general formula -COOR'j, or a radical in which the phenylene ring is banded to Y, or a phenylene radical which may be unsubstituted or substituted in in the ring by one - 2 4ΰ0θ9 or two of the same or different substituents selected from halogen atoms and (C^-C^J-alkyl and nitro groups, and Rg and R'g, which may ba the same or different, each represents a (Cj-C^J-alkyl group.

Preferred compounds of the general formula I are those in which halogens are chlorine and/or bromine, alkyl groups or moieties are those having 1 or 2 carbon atoms, n = 1 or 2, n.j B 0 and Y represents an oxygen atom.

Especially preferred are compounds in which (R)n represents 4-Cl, 2,4-Cl, 4-Br, 2-Cl,4~Br or 4-CPg, n. = 0 and X and Y represent oxygen atoms. Z preferably represents a cysnoethyl group, e.g, the 2~eyancsthyl group, ©r a radical of the general formula -A-COORg, in which A == -CH^-, -CH(CHg)or -CH(C2H5)- ana Rg represents a methyl or ethyl group.

The invention also provides a process fox the preparation of a compound of the general formula I, which comprises (a) reacting a compound of the general formula (11) in which η, , R, R^, X and Y have the meanings given above in the presence Of an acid-binding.agent, or, reacting an alkali metal or ammonium salt of a compound of the general formula XI, with - 3 I • 4500 a compound of the general formula Hal-Z . (IH) in which z has the meaning given above and Hal represents a halogen atom, or h) reacting a compound of-the general formula (IV) in which n, n^, R, , X and Hal have the meanings given above, with a compound of the general formula HYZ (V) rt in which Y and Z have the meanings given above, in the presence of an acid-binding agent, or with an alkali metal or ammonium salt of a compound of the general- formula V.

In the formulae II and III, Hal preferably represents a 15 chlorine or bromine atom.

Compounds of.the general formula I have herbicidal properties, exhibiting a good action against a broad spectrum of weeds in both pre-emergence and post-emergence treatment.

Thus, compounds of this invention may be used to combat, for example, grass-type weeds such as oat grass (Avena), foxtail - 4 grass (Alopecurus), rye-grass (Lolium) and bristle-grass, hen-grass and crab-grass (Setaria, Echinocloa and Digitaria), in dicotyledonous crop plants.

With some of t|ie compounds it is possible to control selectively even grass-type weeds in cereals.

Even when high doses are applied, soya beans, peanuts, dwarf bean3, field beans, peas, lucerne, flax, cabbage, rape, cucumber, sunflower, tobacco, carrots, celery and sugar beet are generally not damaged.

As a result of their specific action against weeds, especially wild oats, foxtail-grass, rye-grass and milletgrass, a compound of the present invention may ba used in fields strongly affected by weeds in preference to a number of the successful known herbicidal agents such as, for example, Alachlor, Mondlinuron, Linuron, Fyrazon, Phenmedipham, sodiuin trichloroacetate, Fluorodifen and Mecoprop.

Further, the quantity necessary for the complete destruction of the weeds is generally far lower than in the case of the above-mentioned known herbicides.

An additional advantage of compounds of the present invention is their low toxicity to warm-blooded animals.

Accordingly, the present invention provides a method’ of combating weed grasses, which comprises applying the compound of the invention to the weed grass or to the area or soil infested with, or liable to infestation by, a weed grass.

Surprisingly, compounds of the formula I also exhibit good action against harmful fungi on commercially valuable - 5 4ΰ009 materials as well as against phytopathogenic fungi, such as, for example, Piricularia oryzae. rust fungus, Botrytis cinerea, Plasmopara viticola, Phytophthora infestans. true types of mildew, Rhizoctonia solani, Septoria nodorum, Ustilago nuda, Phoma betae, Pythium ultimum and Helminthosporium qramineum.

Accordingly, the present invention also provides a method of combating fungal infections, which comprises applying a compound of the invention to the fungus or to an object, material or area infected with, or liable to infection with, a fungus.

For application as fungicide to a commercial substrate, the compound may be used, for example, as an additive to lacquers, varnishes and paints.

Foruse as a protective agent for plants the compound may be formulated as a dust, spray powder, dispersion or emulsion concentrate. The total content of active substance is generally, depending on the formulation, from 2-80 % by weight.

In addition they may contain the usual adhesives, wetting agents, dispersing agents, fillers and carriers. They may also be mixed with other fungicides.

The invention therefore also provides a herbicidal and/or fungicidal preparation, which comprises a compound of fhe general formula I and a suitable carrier therefor.

The herbicidal or fungicidal preparation may contain one or more customary formulation auxiliaries and inert substances and generally contains from 2 to 95 % by weight of the active substance of formula I. The preparation may, for example, be - 6 45009 in the form of a wettable powder, emulsifiable concentrate, sprayable solution, dusting agent or granulate.

A wettable powder is a preparation uniformly dispersible in water, and in addition to the active substance contains, apart from a diluent or inert substance, a wetting agent, for example apolyethoxylated alkyl phenol, a polyethoxylated oleyl or stearyl amine, or an alkyl or alkylphenyl sulphonate and a dispersing agent, for example the sodium salt of ligninsulphonic acid, 2,2'-dinaphthylmethane-6,6'-disulphonic acid or of oleoylmethyltaurine acid.

An emulsifiable concentrate may be obtained by dissolving the active substance in an organic solvent, for example, butanol, cyclohexanone, dimethylformamide, xylene or an aromatic substance having relatively high boiling point.

A dusting agent or sprayable powder may be obtained by grinding the active substance with a finely divided solid substance, for example talcum or a natural clay, such as kaolin, bentonite, pyrophyllite or diatomaceous earth.

A sprayable solution, used widely in spray cans, contains the active substance dissolved in an organic solvent, and in addition, for example,as propellant, a mixture of fluorochlorohydrocarbons and/or carbon dioxide.

A granulate may be prepared either by spraying the active substance on to adsorptive, granulated inert material, or by applying the active substance concentrate by means of an adhesive, for example polyvinyl alcohol, or the sodium salt of polyacrylic acid, or a mineral oil, to the surface of a carrier 4ΰ009 substance, e.g. sand, kaolinite or granulated inert material. Alternatively, suitable active substances may be formulated in the manner usual for the production of manure granules, if desired in admixture with manure.

The concentration of. the active substance in the herbicidal preparation m^y vary according to the formulation. Xn a wettable powder, the concentration of active substance may vary, for example, from 10 to SO %, the remainder consisting of the above-mentioned formulation additives. In an emulsifiable concentrate, the concentration of active substance may be from 10 to 80 %. A dusting agent usually contains from 5 to 20 % of active substance, and a sprayable solution from 2 to 20 %, The content of active substance in a granulate depends to some • extent on whether the active compound is liquid or solid and on the choice of granulating auxiliary, filler and other material For application, the commercially customary concentrate may, if necessary, be diluted in the usual manner, for example by means of water iii the case of a wettable powder or emulsifiable concentrate. Ousting agents, granulated preparations and sprayable solutions are generally not diluted with further inert substances before use. The quantity required for application varies depending on the external conditions such as temperature and humidity, and may vary, for example, from 0.1 kg/ha to 10 kg/ha of active substance, but is preferably from 0.1 to 3 kg/ha.· The active substance according to the invention may be combined with one or more other herbicides and/or soil insecticides. - 8 43009 The following Examples illustrate the invention. PREPARATION EXAMPLES Example 1 2-[4'(4-Chlorophenoxy)-phenoxy]-propionyllactic acid methyl . ester A solution of 81 grams of 2-[4’-{4-chlorophenoxy)~ phenoxyj-propionic acid and 48 grams of 2-bromopropionic acid methyl ester in 160 ml of acetone was heated at the boil for 8 hours, while stirring, with 40 grams of potassium carbonate.

After cooling to 20°C the inorganic salts were filtered off.

The acetone was distilled off from the filtrate and the residue was distilled in vacuo. grams (87 % of the theoretical yield) of the following compound having a Βρθ : 190° - 191°C were obtained.

Example 2 2-[4'-(2,4-Dichlorophenoxy)-phenoxy]-propionylglycolic acid methyl ester grams of 2-[4’-( 2,4''-dichlorophenoxy)-phenoxy ]20 propionic acid and 24 grams of chloracetic acid methyl ester were dissolved in 200 ml of butanone. After adding 26 grams of potassium carbonate, the mixture was heated at the boil for 8 hours while stirring. The reaction mixture was cooled to °c and the inorganic salts were filtered off. The butanone in the filtrate was distilled off and the ester formed was t purified by vacuum distillation. grams (90.0 % of the theoretical yield) of the following compound having a BP0>05 5 207° - 208°C were obtained.

CH, 3 O-CH-C-O~CH„-C-0CH, il 2 II 3 O 0 ci Example 3 2= [4' - (2 , 4-Dichlorophenoxy)-phenoxy]-propionylthioglycolic acid methyl ester 48 grams of thioglycolic acid methyl ester were dissolved in 200 ml of toluene. At a temperature of 20 to 40°C, 156 grams of 2-[4’-(2,4-dichlorophenoxy)phenoxy]-propionic acid chloride· ..dissolved in 150 ml of toluene, and 48 grams of dry triethylamine, dissolved in 50 ml of toluene, were added drop15 wise simultaneously.' The mixture was then stirred for 2 hours at 40°C - The triethylamine chlorohydrate formed was suction filtered. The toluene in the filtrate was distilled off and the residue was purified by distillation at 0.2 torr. 180 grams (96 % of the theoretical yield) of the follow20 ing compound having a Βρθ 2 s 230° - 232°C were obtained.

Cl - 10 43000 Example 4 2-[4*-(4~Bromophenoxy)-phenoxy]-propionic acid 2-cyanoethyl ester grams of 3-hydroxypropionic acid nitrile were dissolved 5 in 150 ml of toluene. At a temperature of 20 to 40°C, 143 grams of 2-[4i-(4-bromophenoxy)-phenoxy]-propionic acid chloride, dissolved in 100 ml of toluene, and 40 grams of dry triethylamine, dissolved in 50 ml of toluene, were simultaneously added dropwise. The mixture was then stirred for 2 hours at 40°C, cooled to 20°C, suction filtered and the toluene was distilled off from the filtrate. 151 grams of residue were obtained. Distillation of the residue yielded 138 grams (83 % of the theoretical yield) of the following compound having a Βρθ s 208° - 210°C.

Example 5 2-[41-(4“-Trifluoromethylphenoxy)-phenoxy]-propionic acid 4-methoxycarbonylphenyl ester grams of 4-hydroxybenzoic acid methyl ester and 17 grams of dry triethylamine were dissolved in 120 mi of toluene. At 20 to 40°C a solution Of 52 grams of 2-[4'-(4-trifluoromethylphenoxy) -phenoxy )-propionic acid chloride in 80 ml of toluene was added dropwise. After the mixture had been stirred at 40°G for 2 hours, it was cooled to 20°C, triethylamine - 11 4ΰΟθ9 chlorohydrate was filtered off with suction and the toluene was distilled off from the filtrate. The oil obtained was recrystallised from n-hexane. grams (92 % of the theoretical yield) of the following 5 compound having a melting point of 78° - 79°C were obtained.

CH3 o o Example 6 2-[4'-(2,4-Dichlorophenoxy)-phenoxy]-propionyloity (2-acetoacetic acid methyl ester) 70 grams of the sodium salt of 2-[4'~{2,4-dichlorophenoxy) phenoxyj-propionic acid were suspended in 300 ml of bensene and 32 grams of 2-chloracetoacetic acid methyl ester were added. Stirring was carried out at 80°C for 8 hours then the mixture was cooled and sodium chloride was filtered off. The toluene was removed b^ distillation. grams of yellow oil having a refractive index of 25 nD =« 1.5593 were obtained.

The compounds listed in the following Tables were prepared 20 in accordance with the processes in Examples 1 to 6.

Table 1 - 13 (continued) 4ΰ009· TABLE 1 (Continued) Example No.R(n)Rl(ni)R3 Bp (°C) 40 4-CF3 H -CH2-CH<“33Bp0.1 : 186-188 .CH 41 2,4-Cl 3-CH3 -CH,-CH< CH3Bp0.05 : 204-206 II: A = -ch2- Example No.R(n) ‘'llnjR3 Bp./Mp (°C) 42 4-C1 H -ch3 ®p0.'05 = 190-192 43 4-Br H -ch3Bp0.01 : 193-194 44 4-CF3 H -ch3Bp0.05 : 175-177 45 2-Cl,4-Br H -ch3 Βρθ 3 : 205-207 45 4-C1 H CH, -CH<; 'ch3 Βρθ L : 201-203 47 4-Br H -ch2-ch3Bp0.05 = 202204 43 4-CF3 H -ch2-ch3Bp0.05 5 178-179 49 2,4-Cl H -CH,-CHL ά ΓΗBp0.05 ! 212-214 50 2-Cl,4-Br H ΖΗ3 3 Mp. 99 - 101 Bp0.1 : 207-209 — Mp. 94 - 95 * TABLE 1 (Continued) CH_-CH_ I 2 J III: A = -CH- Example No. — R(n) ί R1 (¾)R3 - Bp./Mp. (°C) 51 4-Cl H -ch3Bp0.05 186-187 52 4-Br H-CH3Bp0.05 188-190 53 4-CF3 H ~CH3Bp0,l 178 54 2,4-Cl H -CH- 3Bp0.05 195-196 55 2-Cl,4-Br H -CH3Bpo.i 205-208 56 4-Cl H -CH,-^3Xch3Bpo.i 193-195 57 58 4-Br 4-CF3 H H -ch2-ch3- /CH -CH/' 3 ^h3Bp0.1 Bp0.05 194-197 176-177 59 2,4-Cl ' H -ch2-ch3Bpo.i 197-198 60 2-Cl,4-Br , H -CH2CH3Bp0.05 204-205 TABLE 2 (R)n Example No.(R)n Z Bp.(°C) 61 4-Cl -CH2CH2CsN Βρθ T : 200-203 62 2,4-Cl II Βρθ χ : 214-216 63 2-Cl,4-CF3 IIBp0.05 S 19°-192 - 16 TABLE 2 (Continued) •O-CH-C-O-Z CH (H)„ ., qO® Example No. <R)n Z Mp. (°C) 69 4-Cl ~O~^°cH3 64-66 70 2,4-Cl 85-87 71 4-Cl _^_jO-CH2-CH3 Cl 44-47 72 4-CF. ' 3 I > gO-CH3 91-92 73 2,4-Cl ~^^-och2-ch3 67-70 74 2,4-Cl _/)V.C=C-C-OCH- W 1 II 3 Η H 0 102-104 75 2,4-Cl - XC-O-CH. ί 3 101-103 76 4-Cl 81-82 77 2,4-Cl KO2 H^-|-och3 N02 104-106 Example No.R(n) R< hn,)R3 Bp. (°C) 78 4-C1 H -ch3 CH,Bp0.2* 220 - 22?. 79 4-C1 H z 3 -CH ch3 CH,Bp0.05: 214 ·· 216 8b 4-C1 H / 3 ..ch2-ch ch3Bp0.05! 223 - 224 81 2,4-Cl H -ch2-ch3 /CH3 Bp0>1: 234 - 236 82 2,4-Cl fl H CHjBp0.1! 237 - 239 834CF3H -ch, CH,Bp0.2: 194 - 197 84 4-CF3 H Ζ ύ -CH2-CH CH3Bp0.1! 207 - 210 — iS 43009 Example 85 2-[4'-(2,4-Dichlorobenzyl)-phenoxy]-propionyllactic acid methyl ester ‘ grams of 2~[4-(2,4-dichlorobenzyl)-phenoxy]“ propionic acid, 27 grams of 2-bromopropionic acid methyl ester, grams of anhydrops potassium carbonate and 100 ml of acetone were stirred at 60°C for 8 hours. After cooling to 20°G the inorganic salts were filtered off. The acetone was distilled off from the filtrate and the residue was distilled in vacuo. 51 grams (91.6 % of the theoretical yield) of the follow» ing compound having a Βρθ θ5 : 165° - 166°C were obtained.

CH,’ CH, I 3 I 3 O-CH-C-O-CH-C-OCH, II II 3 ο ο ci Example 85 2-[4·-(4-Chlorophenoxy)-phenoxy]-propionyltartronic acid 15 diethyl ester grams of thi sodium salt of 2-[4'-(4~chlorophenoxy)phenoxyj-propionie acid, 27 g of bromomalonic acid diethyl ester, 1 ml of dimethylformamide and 150 ml of toluene were stirred at 80°c for 18 hours. After filtering off the sodium bromide with suction, the toluene and the excess of bromomalonic acid diethyl ester were distilled off from the filtrate, grams of light yellow oil (96.0 % of the theoretical - 20 = yield) were obtained. nD : 1.5300.

CH„ O-CH-C-C-CH ^/00002¾ COOC2H5 Example 87 2-[4'-(2,4“-Dichlorophenoxy)~phenoxy]-propionyltartronic acid diethyl ester g of the sodiuin salt of 2-[4'~(2,4-dichlorophenoxy)phenoxy]-propionic acid, 27 grams of bromomalonic acid diethyl ester, 1 ml of dimethylformamide and 150 ml of toluene were stirred at SO°C for 18 hours. After cooling to 20°C and fil4,0 tering off the sodium bromide with suction, the toluene and the excess bromomalonic acid diethyl ester were distilled off from the filtrate. grams of ligh£ yellow oil (97 % of the theoretical . 25 yield; were obtained. nQ : 1.5337.

Cl 7-CH-C-O-CH· I! o CHg , COOC2H5 'C00C2Hs Example 88 2- [4' - (2 , 4 -Dichlorophenoxy)-phenoxy]-propionylglycine methyl ester At a temperature of 10°C - 15°C a solution of 24 grains A©°°9 (Ο.076 mole) of 2- [ 41 - (2 , 4-dichlorophenoxy)-phenoxy]propionic acid chloride in 40 ml of toluene were added dropwise over a period of 30 minutes to 14 grams (0.152 mole) of glycine ester, freshly released from glycine methyl ester chlorohydrate, dissolved in 80 ml of toluene. The mixture was then stirred for 2 hours at 15 to 22°C. The resulting glycine methyl ester chlorohydrate was filtered off with suction. The toluene was distilled off in vacuo from the filtrate grams of light yellow oil, nQ : 1.5652 were obtained.

Cl There should also be mentioned 2-[4'-(4-chlorophenoxy)phenoxy]-propionylthioglycolic acid methyl ester.

BIOLOGICAL EXAMPLES HERBICIDES Xn these Examples, results were determined by evaluation according to Bolle's scheme (Nachrichtenblatt des Deutsehen Pflansenschutzdienstes 1.6, 1964, 92 - 94').

«SQOg Evaluation scheme Numerical value Percentage damage to Weeds j Crops 1 100 0 2 97.5 to < 100 > 0 to 2.5 3 95 to <, 97.5 \ / 2.5 to 5 4 90 to < 95 > 5 to 10 5 85 to < 90 ) 10 to 15 6 75 to < 85 ) 15 to 25 7 65 to < 75 ) 25 to 35 8 32.5 to < S5 > 35 to 67.5 9 0 to < 32.5 67.5 to 100 —_J---,--Example X : Pre-emergence treatment Seeds of various grasses were sown in pots and spray powders or emulsion concentrates of a number of compounds of the invention were sprayed in different doses on to fhe soil surface. Fluorodifen and Mecoprop were used as comparison agents. The pots were then placed in a greenhouse for 4 weeks and the results determined by evaluation according to Bolle's scheme. The results are shown in Table A. As can be seen, the compounds according to the invention listed in Table A exhibit a very good action against weed grasses. For most types of grass this is true even at very low dosages, for example 0.15 kg of active substance/ha. Fluorodifen and Mecoprop are substantially weaker in their action against grasses - 23 4S009 Table A; Weed evaluation number in the case of pre-emergence treatment Compound according to Example Dosage (Kg/ha A S) Types of plant AL SA LO EC 1 2.5 2 2 3 1 0.6 3 3 5 2 2 2.5 3 1 1 1 0.6 4 2 1 2 7 2.5 3 1 1 2 0.6 3 2 2 3 2.5 1 1 1 1 0.6 1 3 1 2 10 2.5 2 1 0.6 2 2 ί 1 11 2.5 1 1 1 1 0.6 2 2 2 1 12 • 2.5 2 1 1 1 O.S 4 2 . 1 1 25 2.5 2 1 1 1 O.S 2 2 1 1 ' 36 2.5 1 1 1 1 0.6 3 2 3 3 37 2.5 1 1 1 0.6 3 _ 3 4 40 2.5 i 1 1 1 0.6 3' 1 1 1 42 2.5 2 1 1 1 0.6 3 2 1 2 43 2.5 1 1 1 1 0.6 1 2 4 1 46 2.5 2 1 1 1 0.6 4 2 2 3 •52 2.5 1 1 1 1 0.6 1 2 ί 1 53 2.5 1 1 1 1 0.6 2 1 1 1 ·· 24 TABLE A (Continued) 4 3009 Weed evaluation number in the case of pre-emergence treatment Compound according to Example Dosage (Kg/ha A S) Types of plant AL SA L0 EC 54 2.5 1 1 1 1 0.6 2 1 1 1 55 2.5 3 1 1 1 0.6 4 2 1 1 55 2.5 2 1 1 1 0.6 3 2 2 2 62 2.5 1 1 1 1 O.S 2 3 2 1 54 5.0 1 e. 1.2 - 2 65 5.0 1 1.2 - 2 66 5.0 1 <*. 1.2 1 70 2.5 2 3 1 1 0.6 3 6 3 3 71 2,5 4 2 1 2 0.6 6 4 2 3 57: 2.5 3 1 1 3 0.6 4 1 3 4 Fluorodifen 2.5 7 1 1 4 0.6 8 5 8 8 0.15 8 7 8 9 2.5 4 3 5 3 Mecoprop 0.6 7 6 Θ 7 0.15 8 8 •3 8 AL = Alopecurus SA = Setaria LO = Lolium EC = Echinochloa AS = Active substance Example II: Post-emergence treatment Seeds of various grasses were sown in pots and cultivated in the greenhouse. 3 weeks after sowing, a number of compounds of the invention were· applied in different doses On to the plants in the form of spray powders or emulsion concentrates, and after standing for 4 weeks in the greenhouse the action of the compounds was evaluated according to Bolle's scheme. Fluorodifen and Mecoprop were used as a comparison.

Aa can be seen from the results listed in Table B, com10 pounds of the invention exhibit a good to very good action against the weed grasses, and are superior to the known agents Fluorodifen and Mecoprop.

Example III: Post-emergence treatment Using the same method as in Example II (post-emergence 15 treatment), various crop plants were sprayed with suspensions or emulsions of compounds of the invention mentioned in Examples I and II. Even at a high dosage of 2.5 kg/ha, soya beans, peanuts, dwarf beans, field beans, peas, lucerne, flax, cabbage, rape, cucumber, sunflower, tobacco, carrots, celery and sugar beet showed no damage. Barley and wheat showed no reaction to the preparations according to Examples 1, 2, 7, 10, 36, 37, 42, 46, 52, 55 and 56.

Similar results were obtained when the compounds were sprayed on to the soil surface in the pre-emergence method.

Table Β; Weed evaluation numbers in the case of post-emergence treatment Compound according to Example Dosage (Kg/ha A S) Types of plant EC AL SA LO 1 2.5 1 1 1 1 0.6 1 1 4 1 2 2.5 1 1 1 0.6 4 3 1 7 2,5 o. 1 2 1 0.6 - 2 5 3 9 2.5 1 1 1 1 0.6 2 1 1 1 10 2.5 1 I <9 a 1 0.6 2 1 1 1 11 2.5 1 ί 1 1 0.6 1 1 1 1 12 2»5 1 1 1 1 0,6 1 1 1 t 25 2.5 ί 1 1 1 0.6 1 1 1 1 36 2.5 3 s - 1 0.6 4 4 1 37 2,5 1 3 1 0.6 » 4 5 1 40 2,5 1 ί 1 1 0.6 1 'l 2 1 42 2,5 1 1 4 1 0.6 2 2 5 1 43 2.5 1 1 1 1 , 0.6 1 1 1 1 45 2.5 — 1 2 2 0.6 - 6 6 2 52 2 * o 1 1 1 1 0.6 1 1 1 1 53 2.5 t 1 1 1 0.6 1 1 1 1 - 27 'I^ABEE β (Continued) Weed evaluation number s in, the case of post-emergence treatment Compound Dosage · Types of plant according (Kg/ha A S) to Example AL SA LO EC AV ' 54 2.5 1 1 1 1 · 0.6 1 i 1 1 55 2.5 e. 1 1 1 0.6 = 1 1 1 56 2.5 1 1 1 1 0.6 4 1 1 1 62 2.5 1 1 4 1 0.6 4 1 7 1 64 2.5 a. o« 3 1 0.6 6 1 65 2.5 1 1 1 0.6 1 3 - 1 66 2.5 «9 4 1 1 0.6 5 6 1 87 2.5 1 1 1 1 0.6 2 1 2 4 2.5 8 2 6 4 8 Pluorodifen 0.6 8 3 8 6 3 0.15, 9 5 9 8 9 »*/ 2.5 8 7 8 8 8 Mecoprop 0.6 9 8 9 9 9 0.15 9 9 9 9 9 AV = Avena AL = Alopecurus SA = Setaria LO ts Lolium EC ~ Echinochloa 4500a BIOLOGICAL EXAMPLES FUNGICIDES In these Examples, the following were used as comparison agents? A = Combination of 5,6-dihydro-2-methy1-1,4-oxathiin” 3-earboxanilide and methoxyethyl Hg silicate B = Manganese ethylene-1,2-bis-dithiocarbamate D = Tetramethylthiuram-disulphide (TMTD) Ε a S-ethyl-N-v3-dimethylaminopropyl)-thiolcarbamate hydrochloride (Prothiocarb).

Example IV: Barley seeds infected with Ustilaqo nuda (degree of infection 15 %) were dressed with compounds according to the invention in the concentrations given in Table C, sown in pots, and cultivated first at a low temperature and later at higher temperatures (20°C) in a greenhouse. The combination A was used as comparison agent. 10-12 weeks later, the sound stems and the stems infested with Ustilaqo nuda were counted, the degree of infection was determined in each case, and finally the degree of action calculated. The results are shown in Table c. - 29 dSQOS Table Ci Compound according to Example Effect in % of 1 g of dressing agent per 100 kg of seed 50 25 250 200 100 1 (50 % strength) - 100 95 60 - 36 (50 % strength) - - 100 80 86 (50 % strength) - - - 100 90 12 (50 % strength) - - - 100 70 42 (50 % strength) - - 100 70 71 (50 % strength) - 100 95 50 - A (50 % strength) 100 98 90 - - untreated infected plants 0 Table C shows the excellent action, superior to that of the comparison agent A, of compounds of the invention against Ustilaqo nuda.

Example V; Summer barley seeds naturally infected with Belminthosporium qramineum, with a degree of infection of 24 %, were dressed in various’ concentrations with 50 % dressing agents containing the agents shown in Table D. The seeds v/ere sown in trays which were subsequently placed in a greenhouse. Later S 0 0 9 both the plants infected with Helminthosporium qramineum and those that were sound were counted, t.he degree of infection in each case was determined, and finally the degree of action was calculated. The .results are given in Table D.

Table D: Dressing agent I Effect in % of 1 g of dressing agent according to j per 100 kg of seed £iACui(|7J.C 300 250 200 100 65 (50 % strength) - 100 80 A (50 % strength) 100 95 - S (80 % strength) 75 ___________ 60 ..... . . untreated infected I plants I 0 The results in Table D show the excellent action of the compound of the invention against Helminthosporium and the superiority of this mercury-free compound over the mercuryfree comparison agent B and the mercury-containing comparison agent A.

Example VI: Sugar beet seeds naturally infected with Phoma betae with a degree of infection of approximately 60 %, were dressed with the compound of the invention shown in Table B and with comparison agent D, placed in trays and cultivated at 20°C in a greenhouse. 3 weeks after sowing, the sugar beet plants - 31 were examined for infection with Phoma betae and the degree of action of the compound of the invention was determined. The results are shown in Table E.

Table E;.

Dressing agent according to Example Effect in % of 1 g of active substance per 100 kg of seed 300 200 100 50 56 (50 % strength) - 100 80 D (80 % strength) i 100 95 85 75 untreated infected plants 0 Example Vlis The compound shown in Table F was uniformly distributed and mixed.-.into a soil uniformly but heavily infected with Pythium ultimum. The soil treated in this manner was introduced into plastic pots and 10 pea seeds were then sown in each pot. The procedure was repeated with agent S for com15 parison. 8 to 10.days after sowing, the evaluation of the experiments was carried out by determining the number of sound plants that had emerged and calculating the degree of action of the compound of the invention. The controls used were pots containing infected, untreated earth. - 32 4 5 0 0 s Table Fi Compound according Effect in % of 1 mg of active substance per kg of soil to Example 200 f wo 50 25 25 100 100 100 80 E 80 70 60 untreated infected plants 0 = Tables E and P show the excellent fungicidal action of the compounds, which is superior to that of the comparison agents D and Ξ.

Claims (36)

1. Patent Specification No. 44423 describes and claims compounds of the general formula iR.,)n in which R^ represents a hydrogen or halogen atom, each R 2 represents' a halogen or (C^-C^l-alkyl group or a CF, group, n represents 1 or 2, represents, inter alia, a methyl group, and R 4 represents, inter alia, a phenylamino, phenyloxy or phenylthio group, the phenyl group of which carries a carbo-(C^-C 2 )-alkoxy group and may additionally carry one or more substituents selected from halogen atoms and methyl groups. No claim is made herein to any of such compounds, or to processes for their preparation, herbicidal/fungicidal preparations containing than or to methods of oonbating weed grasses or fungal infections using than. - 33 4ΰ0θ9 claims (subject to the foregoing dislcaimer): Io A compound of the general formula in which n and n^ R and R^ CD which may be the same or different, each represents 0 -or an integer from 1 to 3, each represents a halogen atom or a halogensubstituted-(c^-C 4 )-alkyl, (C^-C^)-alkyl, nitro, (C^-C^)-alkoxy or (C^-C^)-«alkyl thio group, and. any two or more of the R and R^ moieties may be the same or different, represents -0- or -CH 2 ~, represents -0-, -S- or -NH- and represents a cyanoethvl group or a radical of the general formula -A-C-OR*, I! ? o in which represents a methylene group which may be Unsubstituted or substituted by -CH^, -C^Hg, -COCH^ or by a radical of the general formula -COOR^, or represents a radical in which the phenylene ring is bonded to Y, or a phenylene radical which may «Sooa be unsubstituted or substituted in the ring by one or two of the same or different substituents selected from halogen atoms and (CpC 4 )-alkyl and nitro groups, and and R' 3 , which may be fhe same or different, each represents a (C|-C 4 )-alkyl group.

2. A. compound as claimed in claim 1, in which n = 1 or 2.

3. A compound as claimed in claim 2, in which represents 4-Cl, 2,4-Cl, 4-Br, 2-Cl,4-Br or 4-CF^.

4. A compound as claimed in any one of claims 1 to 3, in which n. ι °·

5. A compound as claimed in any one of claims 1 to 4, in whieh y represents an oxygen atom.

6. A compound as claimed in any one of claims i to 5, in whieh V xt. represents an oxygen atom.

7. A compound as claimed in any one of claims 1 to 6, in which Z represents a cyanoethyl group or a radical of the general formula -A-CCOR, in which A = -CH,-, or --CH(C 2 H 5 3- and R 3 represents a methyl or ethyl group.

8. A compound as claimed in claim i, which has the formula

9. A compound as claimed in claim 1, which has the 35 4S0 09 formula

10. formula

11. formula

12. formula CF, O-CH-C-O-CH-COOCH, CH, CH, I J I J A compound as claimed in claim 1, which has the Cl Cl CH, CH, CH, j -i | O-CH-C-O~CH-C00CH 3 A compound as claimed in claim 1, which has the Cl CH-· CH, j 3 j 3 O-CH-C-O-CH-COOCH 2 CH(CH 3 ) 2 A compound as claimed in claim 1, which hao the CH- CH! 3 J 3 O-CII-C-O-CH-COOCH 2 CH( CH 3 ) 2 Br Cl

13. A compound &s claimed in claim 1, which has the formula CF. O-CH-C-O-CH-COOCH, CH, C,H c ι 3 ι 2 b 4. S009 14. formula

A compound as claimed in claim 1, which has the Cl 15. 5. Formula

A compound as claimed in claim 1, which has the S Cl 16. formula

A compound as claimed in claim 1, which has the 0 17. formula

A compound as claimed in claim 1, which has the

18. formula A compound as claimed in claim 1, which has the - 37 10

19. formula ci O°O CH, I 3 O-CH-C-S-CH 2 -COOCH 3 ο A compound as claimed in claim 1, which has the Br · Cl O-CH-C~O~CH 2 ~COOCH 3 CH,

20. A compound as claimed in claim 1, which is listed in any one of Examples 1, 3 to 10, 12 to 19, 21 to 35, 37, 38, 40 to 44, 46 to 52, 56 to 60, 62, 63 and 65 tO 77 and 79’td 88 herein.

21. A process for the preparation of a compound claimed in claim 1, which comprises a) reacting a compound of the general formula l (n) CH, I 3 0-CH-C-YH I! o (II) in which n, n^, R, Rp X and Y have the meanings given in claim· 1 in the presence of an acid-binding agent or reacting an alkali metal or ammonium salt of a compound of the general formula II, with a compound of the general formula Hal-3 (III) in which Z has the meaning given in claim 1 and Hal 38 4 5 0 0 9 represents a halogen atom, or b) reacting a compound of the general formula in which η, n^, R, R^, and X have the meanings given in claim 1 and Hal has the meaning given above, with a compound of the general formula HYZ (V) in which Y and Z have the meanings given in claim 1, in the presence of an acid binding agent, or with an alkali Sistal off ammonium salt of a compound of the general formula V.

22. A process as claimed in claim 21, which is carried out substantially as described in any one of the Examples herein.

23. A compound as claimed in claim 1, whenever prepared by a process as claimed in claim 21 or claim 22.

24. A herbicidal and/or fungicidal preparation which comprises a compound as claimed in any one of claims 1 to 20 and 23 and a carrier.

25. A preparation as claimed in claim 24, which is in the form of a wettable powder, emulsifiable concentrate, sprayable solution, dusting agent or granulate.

26. A preparation as claimed in claim 24, which is in - 39 the form of a lacquer, varnish or paint.

27. A method of combating weed grasses, which comprises applying to the weed grass or to an area or soil infested with, or liable to infestation by, a weed grass, a compound as claimed in any one of claims 1 to 20 and 23 or a preparation as claimed in claim 24 or claim 25.

28. A method as claimed in claim 27 for combatingweed grasses in crop plants, which comprises applying the compound or preparation to the weed grass or to the crop area or soil.

29. A method as claimed in claim 27 or claim 38, '1 wherein the weed grass is Avena, Alopecurus, Lolium, Setaria, Echinocloa or Digitaria.

30. A method of combating fungal infections, which comprises applying to the fungus or to an object, material or area infected with, or liable to infection with, a fungus, a compound as claimed in any one of claims 1 to 20 and. 23 or a preparation as claimed in any one of claims 24 to 26.

31. A method as claimed in claim 30 for combating fungal infections in crop plants, which comprises applying the compound or preparation to the fungus or to the crop, crop area, seed or soil.

32. A method as claimed in claim 30 or claim 31, wherein the fungus is Piricularia oryzae, rust fungus, BOtrvtis cinerea, Plasmopara viticola, Phytophthora infestans, a true type of mildew, Rhizoctonia solani, Septoria nodorum, Dstilaqo nuda, Phoma betae, Pvthium ultimum or Helminthosporium - 40 gramineum.

33. A method as claimed in any one of claims 27, 29,31 and 32 wherein the crop is soya beans, peanuts, dwarf beans, field ' beans, peas, lucerne, flax, cabbage, rape, cucumber, sunflower, 5 tobacco, carrots, celery or sugar beet.

34. A method as claimed in any one of claims 28, 29,31 and 32, wherein the crop is a cereal.

35. A method as claimed in any one of claims 27 to 34, wherein the compound is applied in an amount of from 0.1 to 0 10 kg/ha.

36. A method as claimed in claim 35, wherein the compound is applied in an amount of from 0.1 to 3 kg/ha.