GB1579201A

GB1579201A - D their herbicidal and fungicidal compositions 2-(4-phenoxyphenoxy) propionic acid esters and nitriles an

Info

Publication number: GB1579201A
Application number: GB26312/77A
Authority: GB
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1976-06-24
Filing date: 1977-06-23
Publication date: 1980-11-12
Also published as: OA05687A; AT354803B; DE2628384A1; PT66708B; ATA438977A; AU510762B2; AU2639677A; GR74113B; DE2628384C2; HU179483B; ES459862A1; IE45009L; FR2355799A1; PT66708A; KE3220A; EG12743A; IE45009B1; FR2355799B1; IT1080655B; JPS6113458B2

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. <IMAGE>

Description

(54) 2- [4-PHENOXYPHENOXY] PROPIONIC ACID ESTERS AND NITRILES AND THEIR HERBICIDAL AND FUNGICIDAL COMPOSITIONS (71) We, HOECHST AKTIENGESELLSCHAFT, a body corporate organised according to the laws of the Federal Republic of Germany, of D-6230 Frankfurt/,' Main 80, Postfach 80 03 20, Federal Republic of Germany, do 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:- This invention provides a compound of the general formula

in which n and n1, which may be the same or different, each represents 0 or an integer from 1 to 3, R and R, each represents a halogen atom or a (C1-C4)-haloalkyl, (C1-C4) alkyl, nitro, (C1-C@)-alkoxy or (C1-C4)-alkylthio group, and any two or more of the R and R1 moieties may be the same or different, X represents -O- or -CH2-, Y represents -0-, -S- or -NH- and Z represents a cyanoethyl group or a radical of the general formula

in which A represents a methylene group which may be unsubstituted or substituted by -CH@, -C2H@, -COCH3 or by a radical of the general formula -COOR@' or a

radical in which the phenylene ring is bonded to Y, or a phenylene radical which may be unsubstituted or substituted in the ring by one or two of the same or different substituents selected from halogen atoms and (C1-C4)-alkyl and nitro groups, and R@ and R.', which may be the same or different, each represents a (C1-C4)-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=l or 2. n,=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, B-Br or 4-CF3, n1 = 0 and X and Y represent oxygen atoms. Z preferably represents a cyanoethyl group, e.g. the 2-cyanoethyl group, or a radical of the general formula -A-COOR,, in which A=-CH2-, -CH(CH8)- or -CH ( C2H3 ) - and R, represents a methyl or ethyl group.

The invention also provides a process for the preparation of a compound of the general formula I, which comprises a) reacting a compound of the general formula

in which n, nl, R, R1, 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 com pound of the general formula II, with a compound of the general formula Hal-Z (III) in which Z has the meaning given above and Hal represents a halogen atom, or b) reacting a compound of the general formula

in which n, n,, R, Rl, X and Hal have the meanings given above, with a compound of the general formula HYZ (V) 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 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 grass (Alopecurus), rye-grass (Lolium) and bristle-grass, hen-grass and crab-grass (Setaria, Echinocloa and Digitaria), in dicotyledonous crop plants.

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

Even when high doses are applied, soya beans, peanuts, dwarf beans, 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, foxtailgrass, rye-grass and millet-grass, the compounds of the present invention may be used in fields strongly affected by weeds in preference to a number of the successful known herbicidal agents such as, for example, Alachlor, Monolinuron, Linuron, Pyrazon, Phenmedipham, sodium 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 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 Helminthosponum graminenm.

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.

For use 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-S 0% 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 the 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 in the form of a wettable powder, emulsifiable concentrate, sprayable solution, dusting agent or granulate.

A mettable 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 a polyethoxylated 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 fluorochloro-hydrocarbons and/or carbon dioxide.

A granulate may be prepared either by spraying the active substance on to adsorptive granulated inert material. or bv 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 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 may vary according to the formulation. In a wettable powder, the concentration of active sub stance may vary, for example, from 10 to 80%. the remainder consisting of the abovementioned 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 in the case of a wettable powder or emulsifiable concentrate. Dusting agents, granulated preparations and spray able 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 andjor soil insecticides.

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)-phenoxy]-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 200C the inorganic salts were filtered off. The acetone was distilled off from the filtrate and the residue was distilled in vacuo.

91 grams (87% of the theoretical yield) of the following compound having a Bpo 1:1900-1910C were obtained.

Example 2.

2- [4'- ( 2",4"-Dichlorophenoxy) -phenoxy] -propionylglycolic acid methyl ester.

61 grams of 2-[4,-(2,,,4"-dichlorophenoxy)-phenoxyj-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 200C and the inorganic salts were filtered off. The butanone in the filtrate was distilled off and the ester formed was purified by vacuum distillation.

67 grams (90.0% of the theoretical yield) of the following compound having a Bp" " . :207 208 C were obtained.

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 400C, 156 grams of 2-[4'-(2",4"-dichlorophenoxy)- phenoxyl-propionic acid chloride, dissolved in 150 ml of toluene, and 48 grams of dry triethylamine, dissolved in 50 ml of toluene, were added dropwise simultaneously.

The mixture was then stirred for 2 hours at 400 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 following compound having a Bp 2:230-2320C were obtained.

Example 4.

2- [4'- ( 4"-Bromophenoxy) -phenoxy] -prop ionic acid 2-cyanoethyl ester.

30 grams of 3-hydroxypropionic acid nitrile were dissolved in 150 ml of toluene.

At a temperature of 20 to 40 C, 143 grams of 2-[4'-(4"-bromophenoxy)-phenoxy]- proDionic 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 400 C, cooled to 200 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 (88% of the theoretical yield of the following compound having a Bp@@:208 -210 C.

Example 5.

2 - [4' - (4" - Trifluoromethylphenoxy) - phenoxy] - propionic acid 4 - methoxy carbonvlphenyl ester.

23 grams of 4-hvdroxvbenzoic acid methyl ester and 17 grams of drv triethylamine were dissolved in 120 ml of toluene. At 20 to 400C a solution of 52 grams of 2 - 4' - (4" - trifluoromethvlphenoxy) - phenoxy] - propionic acid chloride in 80 ml of toluene was added dropwise. After the mixture had been stirred at 400C for 2 hours, it was cooled to 200 C, triethylamine chlorohydrate was filtered off with suction and the toluene was distilled off from the filtrate. The oil obtained was recrystallised from n-hexane.

64 grams (92% of the theoretical yield) of the following compound having a melting point of 780-790C were obtained.

Example 6.

2 - [4' - (2",4" - Dichlorophenoxy) - phenoxy] - propionyloxy (2 - acetoacetic acid methyl ester).

70 grams of the sodium salt of 2-[4'-(2",4"-dichlorophenoxy)-phenoxy]-proplonic acid were suspended in 300 ml of benzene and 32 grams of 2-ehloracetoaeetic 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 by distillation.

76 grams of yellow oil having a refractive index of nn25 = 1.5593 were obtained.

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

TABLE 1

I: A - -CH(CH3)

Example No. R(n) R1(n) R3 Bp( C) 7 2,4-Cl H CH3 Bp0.01: 188 - 190 8 3,4-Cl H CH3 Bp0.1 : 196 - 198 9 4-Br h CH3 Bp0.1 : 195 - 196 10 2-Cl, 4-Br H CH3 Bp0.05 : 198 - 200 11 4-CF3 H CH3 Bp0.01 : 182 - 185 12 2-Cl, 4-CF3 H CH3 Bp0.05 : 187 - 189 13 4-NO2 H CH3 Bp0.05 : 193 - 196 14 3-CF3 H CH3 Bp0.01 : 174 - 176 15 3-CF2, 4-Cl H CH3 Pb0.05 : 182 - 184 16 2-CH3, 4-Cl H CH3 Bp0.05 : 186 - 187 17 2-Cl H CH3 Bp0.05 : 183 - 185 18 3-Cl, 4-CH3 H CH3 Bp0.1 182 - 184 19 4-Cl 3-CH3 CH3 Bp0.1 : 190 - 191 20 2,4-Cl 3-CH3 CH3 Bp0.05 : 194 - 196 21 4-Cl H C2H5 Bp0.1 : 194 - 196 22 2,4-Cl H C2H5 Bp0.1 198 - 200 23 2-Cl, 4-Br H C2H5 Bp0.1 199 - 200 24 2-Cl, 4-CF3 H C2H5 Bp0.05 : 185 - 187 25 4-CF3 H C2H5 Bp0.1 : 186 - 188 26 4-Br H C2H5 Bp0.2 : 204 - 206 27 3,4-Cl H -C2H5 Bp0.1 : 201 - 202 28 2-Cl H -C2H5 Bp0.05 : 194 - 195 CH3 29 4-Cl H -CH Bp0.2 183 - 184 CH3 TABLE 1 (Continued)

Example CH 30 2,4-Cl H -CH cH 185 - 186 CU3 CH3 31 3,4-Cl H -CH/ Bpo,: :191 - 194 CH3 CH3 32 2-Cl, 4-Br H CH CU3 Bpo,: 201 - 203 CU3 33 4-Br H -CH Bp01 :198 - 199 CU: CH3 34 4-CF3 H -CH Bp0.1 : 18? - 188 CU3 CH, 35 2,4-Cl 3-CH3 CHCH3 Bp0.1 :188 - 189 CH3 36 4-Cl H -CH2-CH Bpo :195 - 197 CH3 ,CH, 37 2,4-Cl H -CH,-CH CU3 Bp0 : 202 - 204 CH3 38 4-Br H -CH,-CH CU3 05: 199 - 201 CU3 39 2-Cl, 4-Br H -CH2-CH Bp0.1 : 207 - 208 CU3 CU, 40 4-CF3 H -CU2-CH Bop0.1 :186 - 188 CU, CH, 41 2,4-Cl 3-CH3 -CU2-CH Bp0.0, : 204 - 206 CH3 TABLE 1 (Continued) II: A = -CH2

Example No. R(n) Rl(nl) R2 Bp./Mp. (OC) 42 4-Cl H -CH3 Hip0,0, :190 - 192 43 4-Br H -CII, Bp001 : 193 - 194 44 4-CF3 H -CU3 Bpoos 175 - 177 45 2-Cl, 4-Br H - CH3 Bpo : 205 - 207 CH3 46 4-Cl H CH~ C Bpoel : 201 - 203 CII3 47 4-Br H -CH2-CII3 Bpoos : 202 - 204 48 4-CF3 H II3-CU, Bpoos : 178 - 179 ,CH, 49 2,4-Cl H -CII2-CU CU, Bpoos : 212 - 214 CH3 99 - L 01 /CH, 50 2-Cl, 4-Br H --CH Bpo,l : 207 - 209 CII3 Mp.94-95

Example No. I R(n) Rl(nl) R3 Bp./Mp. (OC) 51 4-Cl II -CII, Bpo os- 186 - 187 52 4-Br H - CH3 Hp0.05 :155 - 190 53 4-CF, H -CH, Bpo :178 54 2,4-Cl H -CII, Bp,,,: 195 - 196 55 2-Cl, 4-Br H - CH3 Bp,, : 205 - 208 C 56 4-Cl H -CH,-CH Bpo.l:: 195 Hp,,1: I CII3 57 4Hr H -CH,-CH, Hp0,1 :194 - 197' ,CH, CII% Hp,.,,: 176 - 177 CII3 59 2,4-Cl H -CH2-CH3 Bpo l - 198 60 2-Cl, 4-Br H -CH,-CH, Hp0,05 : 204 - 205 TABLE 2

Example No. (R)n Z Bp.( C) 61 4-Cl -CH2Ch2C#N Bp0.1 : 200 - 203 62 2,4-Cl " Bp0.1 : 214 - 216 63 2-Cl, 4-CF3 " Bp0.05 : 190 - 192 64 4-Cl -CH(CH3)C#N Bp0.1 : 196 - 198 65 2,4-Cl " Bp0.1 : 200 - 202 66 4-Br " Bp0.05 : 194 - 195 67 4-CF3 " Bp0.1 : 184-186 68 2-Cl, 4-Br " Bp0.1 : 206 - 209

Example No. (R)n z Mp. (0C) Qc- 4-CI C 0 CH3 69 4-Cl U 646 a 70 2,4-Cl 4 g 0 - C--dCH3 85-87 0 71 4-Cl tÓ~a2g2- Ct3 44-47 C, 72 4-CF3 < Cz 91-92 cO-CH,3 0 73 2,4C1 tC~oCHzC//g 67-70 74 2,4-Cl e | -Cl- C=c1-c1-ocH 102-104 H HO 75 2,4-Cl < 101-103 c-o-cH3 a 76 4-Cl 9o 81-82 AI02 77 2,4C1 U ~ c//, 104-106 N02

Example No. R(n) Rl(nl) R3 Bp. (QC) 78 4-Cl H -CII, Bop,,, : 220 - 222 CII, 79 4-Cl H -CH Bpo.o,5: 214 - 216 CII, -,,,,CH, 80;' 4cl H CH,-CH Bpozos :223-224 81 2,4-Cl H -CH,-CH, Bposl : 234 - 236 ,,,,,CH, 82 2,4-C1 H -CH Bpoe : 237 - 239 CII, 83 4-CF, H -CII, Bpo.2 :194 - 197 -,,,CH, 84 4-CF3 H -CH,-CH ~ BpoXl 207 - 210 Example 85.

2-[4'-(2",4"-Dichlorobenzyl)-phenoxy]-propionyllactic acid methyl ester.

44 grams of 2 - [4' - (2",4" - dichlorobenzyl) - phenoxy] - propionic acid, 27 grams of 2-bromopropionic acid methyl ester, 21 grams of anhydrous potassium carbonate and 100 ml of acetone were stirred at 60 C for 8 hours. 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 51 grams (91.6% of the theoretical yield) of the following compound having a Bp,,,,:1650--1660C were obtained.

Example 86.

2- [4'-(4"-Chlorophenoxy)-phenoxy] propionyltartronic acid diethyl ester.

32 grams of the sodium salt of 2- [4'-(4"-chlorophenoxy)-phenoxy] -propionic 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 dis tilled off from the filtrate.

43 grams of light yellow oil (96.0% of the theoretical yield) were obtained. nD25:1.5300.

Example 87.

2- [4'- (2",4"-Dichlorophenoxy) -phenoxyl -propionyltartronic acid diethyl ester.

35 g of the sodium 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 80 C for 18 hours. After cooling to 200C and filtering off the sodium bromide with suction, the toluene and the excess bromomalonic acid diethyl ester were distilled off from the filtrate.

47 grams of light yellow oil (97% of the theoretical yield) were obtained. nD26: 1.5337.

Example 88.

2- 4'- ( 2",4"-Dichlorophenoxy) -phenoxy] -propionylglycine methyl ester.

At a temperature of 10015CC a solution of 24 grams (0.076 mole) of 2-[4' (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 220C. The resulting glycine methyl ester chlorohydrate was filtered off with suction. The toluene was distilled off in vacuo from the filtrate.

30 grams of light yellow oil, nD26:1.5652 were obtained.

There should also be mentioned 2-[4'-(4"-chlorophenoxy)-phenoxy]-proplonyl- thioglycolic acid methyl ester.

BIOLOGICAL EXAMPLES.

HERBICIDES.

In these Examples, results were determined by evaluation according to Bolle's scheme (Nachrichtenblatt des Deutschen Pflanzenschutzdienstes 16, 1964, 92-94). Evaluation scheme

Percentage damage to Numerical value Weeds 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 < 65 > 35 to 67.5 9 0 to < 32.5 > 67.5 to 100 Example I: 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 the 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 examole 0.15 kg of active substance/ha. Fluorodifen and Mecoprop are substantially weaker in their action against grasses.

TABLE A Weed evaluation number in the case of pre-emergence treatment Compound Types of plant according Dosage to Example (Kg/ha A S) 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 9 2.5 1 1 1 1 0.6 1 3 1 2 10 2.5 2 1 1 1 0.6 2 2 1 1 11 2.5 1 1 1 1 0.6 2 2 2 1 12 2.5 2 1 1 1 0.6 4 2 1 1 25 2.5 2 1 1 1 0.6 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 1 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 1 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 1 1 53 2.5 1 1 1 1 0.6 2 1 1 1 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 TABLE A (Conti;ued) Weed evaluation number in the case of pre-emergence treatment Compound Types of plant according Dosage to Example (Kg 'ha A S) AL SA LO EC 56 2.5 2 1 1 1 0.6 3 2 2 7 62 2.5 I 1 1 1 0.6 2 3 2 1 64 5.0 - - 1 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 87 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 Mecoprop 2.5 4 3 5 3 0.6 7 6 8 7 0.15 8 8 9 8 AL = Alopecurus SA Setaria LO = Lolium EC = Echinocloa AS = Active substance Example ll: 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 MecoDrop were used as a comparison.

As can be seen from the results listed in Table B, compounds of the invention exhibit a good to verv good action against the weed grasses, and are superior to the known agents Fluorodifen and Mecoprop Example Lilt: Post-emergence treatment.

Using the same method as in Example II (post-emergence treatment), various crop plants were spraved 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, neanuts. 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 B Weed evaluation numbers in the case of post-emergence treatment Compound Type of plant according Dosage to Example (kg/ha A S) AL SA LO EC AV 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 - 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 1 1 1 0.6 2 1 1 1 11 2.5 1 1 1 1 0.6 1 1 1 1 12 -2.5 1 1 1 1 0.6 1 1 1 1 25 2.5 1 1 1 1 0.6 1 1 1 1 36 2.5 3 2 - 1 0.6 4 4 - 1 37 2.5 - 1 3 1 0.6 - 4 5 1 40 2.5 1 1 1 1 0.6, 1 1 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 46 2.5 - 1 2 2 0.6 - 6 6 2 52 2.5 1 1 1 1 0.6 1 1 1 1 53 2.5 1 1 1 1 0.6 1 1 1 1 54 2.5 1 1 1 1 0.6 1 1 1 1 55 2.5 1 1 1 0.6 - 1 1 1 TABLE B (Continued) Weed evaluation numbers in the case of post-emergence treatment Compound Types of plant according Dosage to Example (Kg/ha A S) AL SA LO EC AV 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 4 2.5 - - 3 1 0.6 - - 6 1 65 2.5 1 1 - 1 0.6 1 3 - 1 66 2.5 - 4 1 1 0.6 - 5 6 1 87 2.5 1 1 1 1 0.6 2 1 2 4 Fluorodifen 2.5 8 2 6 4 8 0.6 8 3 8 6 8 0.15 9 5 9 8 9 Mecoprop 2.5 8 7 8 8 8 0.6 9 8 9 9 9 0.15 9 9 9 9 9 AV = Avena AL = Alopecurus SA = Setaria LO = Lolium EC -- Echinochloa BIOLOGICAL EXAMPLES.

FUNGICIDES.

In these Examples, the following were used as comparison agents: A=Combination of 5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide and nmethoxyethyl Hg silicate B =Manganese ethylene-1,2-bis-dithiocarbamate D=Tetramethylthiuram-disulphide (TMTD) E=S-ethyl-N-(3-dimethylaminopropyl)-thiolcarbamate hydrochloride (Prothio carb).

Example IV: Barley seeds infected with Ustilago 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 infected with Ustlago 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.

TABLE C

Effect in % of 1 g of dressing agent per Compound 100 kg of seed according to Example 250 200 100 50 25 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 Us tila go nuda Example V: Summer barley seeds naturally infected with Helminthosporium gramineum, 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 were sown in trays which were subsequently placed in a greenhouse. Later, both the plants infected with Helminthosporium gramineum and those that were sound were counted, the 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

Effect in % of 1 g of dressing agent Dressing agent per 100 kg of seed according to Example 300 250 200 100 65 (50% strength) @ 100 80 A (50% strength) 100 95 B (80% strength) 75 60 untreated infected plants 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 mercury-free comparison agent B and the mercury-containing comparison agent A.

Example VI: Sugar beet seeds naturally infected with Phoma betac with a degree of infection of approximately 60%, were dressed with the compound of the invention shown in Table E and with comparison agent D, placed in trays and cultivated at 200C in a greenhouse. 3 weeks after sowing, the sugar beet plants were examined for infection with Phoma betac and the degree of action of the compound of the invention was determined. The results are shown in Table E.

TABLE E

Effect in % of 1 g of active substance Dressing agent per 100 kg of seed according to Example 300 200 100 50 55 (50% strength) - - 100 80 D (80% strength) 100 95 85 75 untreated infected plants 0 Example VII: 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 E for comparison. 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.

TABLE F

Effect in % of 1 mg of active substance Compound per kg of soil according to Example 200 100 50 25 25 100 100 100 80 E 80 70 60 untreated infected plants 0 Tables E and F show the excellent fungicidal action of the compounds, which is superior to that of the comparison agents D and E.

Our copending application No. 9460/77 (Serial No. 1,563,850) describes and claims compounds of the general formula

in which R, represents a hydrogen or halogen atom, each R2 represents a halogen or (C,-C,)- alkyl group or a CF, group, n represents 1 or 2, R, represents, inter alia, a methyl group, and R4 represents, inter alia, a phenylamino, phenyloxy or phenylthio group, the phenyl group of which carries a carbo-(C1-C2)-alkoxy group and may additionally carry one or more substituents selected from halogen atoms and methyl groups.

Claims

No claim is made herein to any of such compounds, or to processes for their preparation, herbicidal/fungicidal preparations containing them or to methods of combating weed grasses or fungal infections using thern.

Subject to the foregoing disclaimer, WHAT WE CLAIM IS:

1. A compound of the general formula

in which n and n1, which may be the same or different, each represents 0 or an integer from 1 to 3, R and R1 each represents a halogen atom or a halogen-substituted-(C1-C4)-alkyl, (C1-C4)-alkyl, nitro, (C1-C4)-alkoxy or (C1-C4)-alkylthio group, and any two or more of the R and R1 moieties may be the same or different, X represents -O- or -CH2-, Y represents -O-, -S- or -NH- and Z represents a cyanoethyl group or a radical of the general formula

in which A represents a methylene group which may be unsubstituted or substituted by -CH3, -C2H@, -COCH3 or by a radical of the general formula -CO OR',, or represents a

radical in which the phenylene ring is bonded to Y, or a phenylene radical which may be unsubstituted or substituted in the ring by one or two of the same or different substituents selected from halogen atoms and (C1-C4 ) -alkyl and nitro groups, and R. and R,', which may be the same or different, each represents a (C1-C4 ) -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 R(n) represents 4-Cl, 2,4-Cl, 4-Br, 2-Cl, 4-Br or 4-CF3.

4. A compound as claimed in any one of claims 1 to 3, in which n1 =0.

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

6. A compound as claimed in any one of claims 1 to 5, in which X 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-COOR3 in which A=-CH-, -CH(CH@)- or -CH(C@H@)- and R3 represents a methyl or ethyl group.

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

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

10. A compound Rs claimed in claim 1, which has the formula

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

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

13. A compound as claimed in claim 1. which has the formula

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

15. A comnound as claimed in claim 1, which has the formula

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

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

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

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

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 to 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

in which n, n1, R, R1, 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 com pound of the general formula II, with a compound of the general formula Hal-Z (III) in which Z has the meaning given in claim 1 and Hal represents a halogen atom, or b) reacting a compound of the general formula

in which n n1, 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 acidhinding agent, or with an alkali metal or 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 Examoles herein

23. A comnound as claimed in claim 1, whenever prepared by a process as claimed in claim 21 or claim 22. t4. A herbicidal and/or fungicidal preparation which comprises a compound as claimed in anv one of claims 1 to 2n and 23 and a carrier.

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

26. A preparation as claimed in claim 24, which is in 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 comnound 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 combating weed 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 28, wherein the weed grass is Avena, Alopecurus, L@lium, Setaria. Echinocloa or digitaria.

30. A method of combating fungal infections, which comprises applying to the fungus or to an ohiect, 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 comnrises applying the compound or preparation to the fungus or to the crown. crop area. seed or soil.

32. A method as claimed in claim 30 or claim 31, wherein the fungus is Piricularia oryzae, rust fungus, Botrytis cinerea, Plasmopara viticola, Phytophthora infestans, a true type of mildew, Rhizoctonia solani, Septoria nodorum, Ustlago nuda, Phoma betake. Pythium ultimum or Helm in thosporium gramineum.

33. A method as claimed in any one of claims 28, 29, 31 and 32, wherein the crop is soya beans, peanuts, dwarf beans, field beans, peas, lucerne, flax, cabbage, rape, cucumber. sunflower, 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 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.