IE44653B1 - Substituted alkyl ethers of phenoxyphenols,their preparation and herbicidal compositions containing them - Google Patents

Abstract

The herbicide contains a compound of the formula I in which the individual substituents have the meaning given in Patent Claim 1. It has a broad spectrum of action against grass weeds and is tolerated by dicotyledon crop plants and various cereal species.

Description

This invention relates to herbicidally active compounds and to herbicidal compositions containing them.

The present invention provides herbicidal compositions comprising a carrier and, as active substance, a compound of the general formula Y—CHCH2—z in which each R is a halogen atom or a CF^, CH^ or C2Hg group? each is a halogen atom or a CF^ group; R2 is a hydrogen atom or a (C^-cp-alkyl group; n is 1 or 2,- is 0, 1 or 2; each of X and Y is 0 or S? and Z is -OH, -SH, -F, -Cl, -Br. -I or a group of the formula Ii -O-C-OR„ 0 . R^ II / 4 -O-C-N , / 4 \ -o-so£n 2 V II —0-C—R . -O-SO_-R_ or -O-SO.-R 2 6 3 7 in which R3 is a (C^-C^Jalkyl, (C3-Cg)cycloalkyl, (c2~c^0^ alkenyl, (C.-C,.) cycloalkenyl, (C -C.)alkynyl, phenyl or benzyl 5 o Jo group which may carry one or more substituents selected from halogen atoms and CFy N02, CN, (c^-C4) alkyl, (C^-cpalkylthio, (C.-C.) alkoxy, -OH, -NH , (C,-C.)alkylamino, di-(C-CJ alkylamino 14 - · £. 1 Ό lb and (C _-C.) aIkoxycarbonyl groups; i o R4 is a hydrogen atom or a (Cj-C^alkyl, (C2~C4)alkenyl, cyclopentyl, cyclohexyl, (C^-C^alkoxy or phenyl group which may carry one or more substituents selected from halogen atoms and CF3, N02, CN, (Cj-C^alkyl, (Cj-Cj)alkylthio, (C.^)alkoxy, OH, NH_, (C.-CM alkylamino, di-(C,-Cc)alkylamino and (C.-Cc)alkoxy2 1b lb l b carbonyl groups; is a halogen atom or a (C^-C^alkyl group, or R4 and Rg together with the nitrogen atom to which they are attached form a saturated heterocycle having from 2 to 5 carbon atoms and which may contain an oxygen or sulphur atom or a group of the formula NRg,· Rg has the meanings given for R^ or is a phenoxy-(C^-C^)-alkyl group the phenyl group of which may carry from 1 to 3 substituents selected from F, Cl and Br atoms and methyl groups; 4) R is a hydrogen atom or a (C.-C,)alkyl group or cat ; and eat is the cation of an inorganic or organic base, or Z is a group of the formula The present invention also provides the compounds of the general formula I with the proviso that, when Z is OH or -OCORg in which R, is a (C,-C_)alkyl group and X and Y are both oxygen, b X □ 4 6 5 3 then (R)^ cannot be a halogen atom in the 4-position.

The alkyl, alkenyl and alkynyl groups represented by to R? may be straight-chained or branched.

Preferred compounds of the general formula I are those in which (R)^ is one to two -Cl and/or -Br atoms and/or -CF^ groups, especially 4-Cl, 2,4-Cl, 2-Cl-4-Br, 4-CF3 and 2-Cl-4-CF3? n is 0 or (R ) is Cl or Br in the 2-position to Y; 1 Πχ R2 is CH3, X, Y are both 0, Z is -OH, -Cl, -Br? the group of the formula II; in which (R) n and have the preferred meanings given above? and the groups R -0-C \ V in which R^ is a hydrogen atom or a (C-C )alkyl, phenyl, halophenyl, methylphenyl or trifluoromethylphenyl group, and R^ has the meaning given above; -O-SOyRy in which R3 is a CHy phenyl, methylphenyl or chlorophenyl group; θ —0—SO -R , in which R is a (C.-C.)alkyl group or cat ; / 7 1 4 I -O-C-R , in which R& is a (CyCg)alkyl or (CyC^) chloroalkyl group, a phenoxy-(Cy Chalky 1 group the phenyl group of which may carry one or two substituents selected from halogen atoms and methyl groups, a (CyC,.)alkenyl group or a phenyl group which may carry one or two substituents selected from -Cl, -Br, -NOy -CHy -CF3 and -OCHy· and ++, h3n+c2h5, h3n+ch2ch2oh, h2n+ eat® is Na+, K+, NH4+, 1/2 Ca {W2' V+CH3' fe2Z v 0 or HN+ (CH2CH2OH)3.

Especially preferred, owing to their biological properties, are those compounds in which Z is -OH, -O-CO-NH. or -O-CO-R,. 6 The compounds of the general formula I can be prepared from phenoxyphenols of the formula or the corresponding phenolates, by many methods generally known in the art. Thus, compounds of the formula III can be reacted in a known manner with compounds of the formula B-C-CH -Z IV I 2 H in which B is a halogen atom or a sulpho-ester group, for example 2-bromopropane, 2-bromo-l-chloropropane or 2-bromopropanol, optionally in the presence of an acid-binding agent, and then converted into further compounds of the formula I by conventional reactions, especially by esterification of the resulting propanols The following are preferred methods for preparing the compounds of the general formula I. 1. Alcohols of the formula I (Z = OH) can be obtained, as described above, by the reaction of compounds of the formula III 46 53 •with haloalcohols of the formula IV, by hydrolysis of the corresponding haloalkyl compounds (Z = halogen) or by reduction of the corresponding carboxylic acid esters of the formula II preferably with metal hydrides, for example lithium aluminium hydride. When i*2 is a hydrogen atom, alcohols of the formula I can also be obtained by reacting a compound of the formula III or, preferably, an alkali metal salt thereof, with ethylene oxide. 2. Halocompounds of the formula I (Z = halogen) can be prepared by reacting the corresponding alcohols with halogenating IQ agents, for example thionyl chloride. 3. Mercaptans of the formula I (Z = SH) are obtained, for example, from the corresponding halocompounds of the formula I .(Z = halogen) by reaction with metal hydrogen sulphides, preferably alkali metal hydrogen sulphides or xanthates or by reaction with thiourea and subsequent alkaline cleavage of the resulting isothiouronium salts. 4. Esters are prepared, for example, by the reaction of alcohols of the formula I (Z = OH) in the presence of acidbinding agents (bases) with the appropriate acid halides, prefer20 ably acid chlorides, or acid anhydrides, preferably in inert organic solvents, or by direct esterification in the presence of acid catalysts and solvents which form azeotropes with water or in the presence of water-binding agents. As acid halides, preferably chlorides, there may be used those of monobasic acids, for example alkane carboxylic acids, benzoic acids, and benzenesulphonic acids, or those of polybasic acids such as carbonic acid, sulphuric acid, dicarboxylic acids,in which then the other acid group or groups are, for example, esterified or amidated, for example, by ester groups OR. or amide groups o R, ‘5 - 7 Carbonate esters can be obtained by reacting compounds of the formula I (Z = OH) with appropriate carbamic acid halides in the presence of acid-binding agents or by reaction with isocyanates of the formula R^NCO.

. Amines of the formula I (Z = NR^R^) are obtained by reaction of the corresponding halides, preferably chlorides, of the formula I (Z = halogen, preferably chlorine) with amines HNR^Rg in known manner.

The starting compounds of the formula III can be prepared by methods in themselves known, for example, in a manner analogous to the processes described in German Offenlegungsschriften 1,668,896 and 2,433,067.

The compounds of the formula I have a wide spectrum of action against weed grasses, but are well tolerated by dicotyledonous crop plants and by various types of cereals, and can therefore be used for selectively combating weed grasses in crop plants.

The present invention therefore also provides a method for selectively combating weed grasses in an area of crop plants, which comprises applying to said area a herbicidal composition as described above.

The compositions of the present invention generally contain from 2 to 95% by weight of the active substance of the formula Ϊ. They may be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusting preparations or granulates.

Wettable powders are preparations capable of being dispersed uniformly in water, which contain, in addition to the active substance and a diluent or inert substance, wetting agents, for example, polyoxethylated alkyl-phenols, polyoxethylated oleyl30 or stearyl-amines, alkylsulphonates or alkylphenylsulphonates and dispersing agents, for example, sodium lignum sulphonate, sodium 2,2'-dinaphthylmethane-6,6'-disulphonate, sodium di4 46 53 - 8 naphthylmethane disulphonate or sodium oleylmethyl-taurinate.

Emulsifiable concentrates are obtained by dissolving the active substance in an organic solvent, for example, butanol, cyclohexanone, dimethylformamide, xylene or a high boiling aromatic compound and adding to a non-ionic wetting agent, for example, a polyoxethylated alkylphenol or a polyoxethylated oleyl- or stearyl-amine.

Busting preparations are obtained by grinding the active substance with finely divided solid substances, for example, talcum, natural clays, such as kaolin, bentonite, pyrophyllite or diatomaceous earths.

Sprayable solutions, which are often marketed in spraying cans, contain the active substance dissolved in an organic solvent, as well· as, for example, a mixture of fluorochlorohydrocarbons as a propellant.

Granulates can be prepared either by spraying the active substance onto an absorptive granulated inert material or by applying concentrates of the active substance by means of adhesives, for example, polyvinyl alcohol, sodium polyacrylate or mineral oils, onto the surface cf carrier substances, such as sand, kaolinites, or of granulated inert material. Also suitable active substances may be formulated in the manner usual for producing fertiliser granules, if desired in admixture with fertilisers.

In the herbicidal compositions, the concentrations of the active substances in the ordinary commercial formulations may vary. In wettable powders the concentration of active substance varies, for example, between about 10% and 95%, the remainder consisting of the formulation additives mentioned above. In the case of emulsifiable concentrates the concentration of active substance is about 10% to 80%. Dusting formulations contain generally from 5 to 20% of active substance, and sprayable solutions contain about 2 to 20%. In the case of granulates, the content of active substance depends in part on whether the active compound is present in liquid or solid form and on what granulating auxiliaries, fillers, etc. are used.

For use, the ordinary commercial concentrates may be diluted in the usual manner, for example, with water in the case of wettable powders and emulsifiable concentrates. Dusting and granulated preparations and sprayable solutions are not diluted with further inert substances before use. The quantities required for use vary with the external conditions such as temperature and humidity. They may vary within wide limits, for example, between 0.1 and 10.0 kg of an active substance per hectare, but preferably between 0.5 and 5 kg per hectare.

The active substances of the invention may be combined with other herbicides and soil insecticides.

The following Examples illustrate the invention.

FORMUIATING EXAMPLES Example A An emulsifiable concentrate is obtained from parts by weight of active substance parts by weight of cyclohexanone as solvent and 10 parts by weight of oxyethylated nonyl-phenol (10 EO) as emulsifier.

Example B A wettable powder easily dispersible in water is obtained bymixing together parts by weight of active substance parts by weight of kaolin-containing quartz as inert substance parts by weight of potassium lignin sulphonate 1 44653 and 1 part by weight of sodium oleylmethyl-taurinate as wetting and dispersing agent and ground in a rod mill.

Example C A dusting preparation is obtained by mixing together parts by weight of active substance and 90 parts by weight of talcum as inert substance and pulverised in a hammer mill Example D A granulate consists, for example, of about 2-15 parts by weight of active substance 98-85 parts by weight of inert granulate materials such, for example, as atapulgite, pumice, and quartz sand.

PROCEDURAL EXAMPLES Example 1 2-Γ 41-(2 , 4-Dichlorophenoxy)-phenoxy] -propanol 28.6 grams (0.75 mol) of lithium aluminium hydride are introduced into 2 litres of absolute ether. 354.3 grams (1 mol) of 2-[4(2,4-dichlorophenoxy)-phenoxy]-propionic acid ethyl ester dissolved in 500 ml of absolute ether are added dropwise while stirring, in a manner such that the reaction mixture is maintained at the boil. After the addition, the mixture is further stirred for 1 hour at the boiling temperature. After the addition of one litre of water and one litre of sulphuric acid of 10% strength, the ether phase is separated and the aqueous phase is extracted by agitation twice with 300 ml of ether each time. The combined ether phases are washed neutral with water and dried. After removing the ether, the residue that remains behind is distilled in vacuo. By distillation there are obtained 303 grams (96.7% of theory) of 2-[4‘-(2,4-dichlorophenoxy)44653 phenoxy]-propanol of Βρ.θ 181°c.

-OH In an analogous manner there were prepared: Example Compound of the formula I Bp (°C) 168-172/0,05 Torr 164/0,02 Torr 140/0,05 Torr 156/0,07 Torr 165/0,02 Torr 446 53 CH. .o-c-ch2-oh 133/0,02 Torr Example 8 2-Γ4 (4-Trifluoromethylphenoxy)-phenoxy] -1-chloro-propane 31.2 grams (0.1 mol) of the alcohol obtained in Example (4) are introduced into 150 ml of toluene together with 7.9 grams (0.1 mol) of pyridine, and the mixture is cooled to -5°C, To the mixture are added dropwise 13.1 grams (0.11 mol) of thionyl chloride in a manner such that the temperature does not exceed 10°C. After the addition, the mixture is further stirred for % an hour, and the temperature is slowly raised to 110°C. and maintained at that temperature for 2 hours. The mixture is cooled, about 150 ml of hydrochloric acid of 20% strength are added and the mixture is stirred for % an hour. The toluene phase is separated off and the aqueous phase is extracted by agitation twice with 100 ml of toluene each time. The combined toluene extracts are washed neutral with water and dried. The toluene is distilled off and the residue that remains is distilled. By the distillation there are obtained 31.3 grams (94.6% of theory) of 2-[4'-(4-trifluoromethylphenoxy)-phenoxy] -120 chloropropane Bp^ 182°C., which solidifies after 4 days and has an Mp. of 38°-39°C.

In an analogous manner there were prepared: - 13 Example No.

Cl Bp. ( C) C Br.

Compound of the formula I Example 12 Benzoic acid 2-Γ4*-(4-chlorophenoxy)-phenoxvl -prop-l-yl) ester grams (0.083 mol) of the alcohol obtained in Example (2) are dissolved together with 9.3 grains (0.092 mol) of triethylamine in 50 ml of toluene, and is added dropwise in the course of 15 minutes to a prepared solution at room temperature of 11.7 grams (0.083 mol) of benzoyl chloride in 150 ml of toluene. After the addition, during which the solution heats up to about 40°c. it is stirred for 2 hours, and washed twice with 200 ml of water each time to remove the triethylamine hydrochloride. The toluene phase is dried, and the toluene is distilled off. Drying the residue yields 31.4 grams (99% of theory) of benzoic acid<2-[4'(4-chlorophenoxy)-phenoxy]-prop-l-yl ester, which becomes solid after 3 days and has a Bp. of 68.5°C. 446 5 3 With the use of the appropriate acid components there were prepared in an analogous manner: Example Compound of the formula I n^/Mp. no2 4 6 5 3 Example No.

Cl.

Cl.

Compound of the formula I Cl n CP Mp. : 61-63 CH, nD/Mp.

(°C) D 1.5861 Cl.

°' C Oti ( ) \- 0-C-CH2-0-C-(CH2)g-ffl3 \_7 H CH, 0 I 3 II o_ k_o-c-ch2-o-c-ch2-ch2-ch3 H % = 1.5212 1D ’ 1.5374 % ! 11.5628 24.5 ’D : 1.5846 Mp. : 97-97.5 Mp. : 56-56.5 46 33 - 16 Example Compound of the formula I No. . ' Mp.: 79-80 nD : 1.5884 Mp.: 73.5 nD24: 1.5822 η ι 1.5608 CH 0 I 3 II 0-C-CH -0-C-CHC1, I 2 nQ : 1.5680 - 17 44653 Example No.

Compound of the formula I n^/Mp. (°c) c ch3 o ch3 o-|-cH2-o44-o-/QVo-yQ\ ci n?3: 1.5891 H W \_Z ’d 34 ci II 23 CH„-O-C-CH2-CH2-CH3nD : 1·5489 24.5. 3 1.5076 nQ : 1.5414 37 4 653 Mp.: 38-40 Cl CH.

F3C. u.

J II CH2-0-C-CH2-CH2-CH3 1.5008 44633 Example Compound of the formula I n/Mp. (°C) No. 17 Example 50 2,2-Dichloropropionic acid < 2— Γ4' — (2,4-dichIorophenoxy)-phenoxyprop-l-yl > ester 31.3 grains (0.1 mol) of the alcohol obtained in Example (1) are boiled under reflux for 6 hours with 21.5 grams (0.15 mol) of dichloropropionic acid, 50 ml of chloroform and 1 ml of concentrated sulphuric acid. The water of reaction formed is distilled off azeotropically. The mixture is cooled and washed three times with 60 ml of water each time, neutralised with bicarbonate solution, washed with 100 ml of water, dried and distilled to dryness. The oily residue that remains behind is distilled in vacuo. By the distillation there are obtained 39.1 grains (91% of theory) of 2,2dichloropropionie acid< 2-[4‘-(2,4-dichlorophenoxy)-phenoxy]prop-1-yl > ester Bp. θ s 204° to 206°C.; 1.5602. 44633 Cl CH 0 Cl 3 !> 1 0-C-CH_-0-C-C-CH. | 2 , 3 H Cl In an analogous manner there were obtained Example Compound of the formula I nj/Bp (°C) nD23: 1.5525 nD23: 1.5525 Bp.193-97/0.1 Torr n„ ; 1.5225 D Example 55 l-Methylaminocarbonyloxy-2-r4 1 - (2-chloro-4 -trifluoromethyIphenoxy) 10 phenoxyl -propane grams (0.043 mol) of the alcohol obtained in Example (7) are maintained for 7 hours at 100°C. with 6.3 grams (0.11 mol) of methyl isocyanate and 1 ml of triethylamine in 150 ml of toluene.

The mixture is cooled, washed with 100 ml of water, dried and the toluene is distilled off in vacuo. The residue that remains behind is dried at 100°C. in vacuo. By drying there are obtained 17,1 grams (98.5% of theory) of l-methylaminocarbonyloxy-2-[4’-(215 chloro-4-trifluoromethylphenoxy)-phenoxy]-propane Mp. 64°-65°C.

P3C NH-CH, \_y h In an analogous manner there were obtained (see the Table): Example No.

Compound of the Formula I nD/Mp ( C) C CH, 0 I 3 II O-C-CH.-O-C-NH-CH, I 2 3 H 0^- O-C-CH2-O-I-NH-C3H7 (n) Cl Mp.: 76-77 nD24: 1.5488 Cl.

CH, 0 I 3 II C-CH--O-C-NH, I 2 \_/ \_/ H Mp.: 68-69 Cl.

Cl MP.: 76 C 60 Cl. \_Z . / H Cl I , > n Ο-|-ΟΗ2-Ο-Ο-ΝΗ_/θ\_ Cl si 1.6006 D i-/o>“oXo)>-otch2o^nhX9 \ / \ / ι \_Z 7 H Cl nD : 1.5935 C CH 0 I 3 II -C-CH2-O-C-NH-CH3 H ηβ : 1.5690 4 6 5 3 Ρ3, .0. 4-36S3 Example 74 l-Dimethylaminocarbonyloxy-2-Γ4 ' -(2 ,4-dichlorophenoxy)-phenoxy] propane grams (0.08 mol) of the alcohol in Example (1) are heated under reflux with 21.5 grams (0.2 mol) of dimethylcarbamic acid chloride and 20 grams (0.198 mol) of triethylamine in 150 ml of toluene, until no starting material can be detected in the thin layer chromatogram. The mixture is filtered off while hot, and after cooling washes with 150 ml of water and dried. The toluene is distilled off in vacuo. The residue remaining behind is purified by column chromatography over aluminium oxide neutral with ethyl acetate as eluting agent. By distilling off the ethyl acetate there are obtained 26.6 grams (86.4% of theory) of 1-dimethylaminocarbonyloxy-2-[41 -(2 ,4-dichlorophenoxy)-phenoxy] -propane having 24 an nQ : 1.5609.

Cl In an analogous manner were prepared: Example Compound of the formula I n_ No.

Calc. 59.5 5.3 3.7 Fnd. 59.4 5.2 3.4 Example 78 l-Ethoxycarbonyioxy^-f 4'-(2,4-dichlorophenoxv)-phenoxy)-propane 31.3 grams (0.1 mol) of the alcohol obtained in Example (1) are heated at the boil with 15.9 grams (0.105 mol) of a-ehlorocarbonic acid ethyl ester and 16.6 grams (0.12 mol) of potassium carbonate in 100 ml of acetone. A slight splitting off of carbon dioxide takes place. After 18 hours, the salt constituent is filtered off and the acetone is distilled off. The residue is purified by column chromatography with aluminium oxide and ethyl acetate as eluting agent. The eluting agent is split off and the residue is dried in vacuo. After drying, 18.5 grams (48% of theory) of l-ethoxycarbonyloxy-2-[4‘—(2,4-dichloro44633 - 25 24 phenoxy)-phenoxy]-propane having an n : 1.5516 is obtained.

Example 79 Methanesulphonic acid < 2-Γ4(4-trifluoromethylphenoxy)-phenoxy]prop-l-yl> ester. grams (0.08 mol) of the alcohol obtained in Example (4) are dissolved with 10.1 grams (0.1 mol) of triethylamine in 50 ml of toluene, and the solution is introduced dropwise in the course of 10 minutes into a solution of 9.2 grams (0.08) of methane sulphonyl chloride in 140 ml of toluene. After the addition, the mixture is further stirred for 2 hours and washed three times with 150 ml of water each time. Drying is carried out, and the toluene is distilled off in vacuo. Drying in vacuo of the residue remaining behind yields 29 grams (92.7% of theory) of methane sulphonic acid < 2-[4'-(4-trifluoromethylphenoxy)-phenoxy]-prop1-yl >ester.

Analys is : Calculated: Found: C 52.3%; H 4.4%; S 8.2% C 52.0%; H 4.3%; S 8.0% In an analogous manner were prepared: Example Compound of the formula I No. nD/Mp. (°C) 23.5 1.5412 46 5 3 Example Compound of the formula I No. nD/Mp. (°C) CH I 3 O-C-CH-I 2 H O3¾.

Mp.: 56-58 Example 84 l-N-Piperidlno-2~r41 - (2 , 4-dichlorophenoxy)-phenoxvl -propane 27.5 grams (0.083 mol) of the chloride in Example (10) are 10 maintained at 140°C. in an autoclave with 150 ml of piperidine for hours. After cooling, the product is taken up in 400 ml of methylene chloride and washed neutral with water. Methylene chloride is distilled off and the residue remaining behind is dried in vacuo. After the drying, 28.5 grams (90.4% of theory) of l-N-piperidino-2-[4'-(2,4-dichlorophenoxy)-phenoxy]-propane, 22 are obtained: n : 1.5688.

Cl In an analogous manner were prepared. 44633 Example Compound of the formula I nQ No.

Example 90; 1-Απά·ηοο3^3οην1οχν-2-Γ4'- (4-trif luoromethylphenoxy) -phenoxvl -propane 31.2 grams (0.1 mol) of the alcohol obtained in Example (4) were introduced with 13 grams (0.2 mol) of sodium cyanate into 200 ml of methylene chloride, and 24 grams of trifluoroacetic acid were added dropwise, while stirring, in the course of one hour. After the addition, the mixture is heated at the boil (about 2 days) until no starting material is detected by thin layer chromatography. The mixture is cooled and stirred into 400 ml of water, the organic phase is separated and washed neutral with water. The methylene chloride is distilled off, and the residue'remaining behind is recrystallised from ethanol/ water. After recrystallisation there are obtained 27.2 grains (80.4% of theory) of l-aminocarbonyloxy-2-[4'-[4-trifluoromethylphenoxy) -phenoxy] -propane melting at 80°r82°C.

Example 95: Sodium 2-Γ4'-(4-trifluoromethylphenoxy)-phenoxy] -propyl sulphate 13.4 grams (0.115 mol) of chlorosulphonic acid are cautiously mixed with about 15 ml of diethyl ether, the mixture is cooled to -1O°C. and 31.2 grams (0.1 mol) of 2-[4'-(4-trifluoromethyl-phenoxy)-phenoxy]-propanol-(1) are added dropwise.

After the addition, the temperature is maintained for 2 hours and then the mixture is warmed up to room temperature. The ether is removed in vacuo, and to the free acid so obtained is added dropwise a solution of 9 grams (0.225 mol) of sodium hydroxide in 50 ml of water. Immediately on the addition of salt precipi5 tates out, it is filtered off with suction, washed well with water and then dried. 36.6 grams (95.7% of theory) of sodium 2-[41-(4-trifluoromethylphenoxy)-phenoxy] -propyl sulphate melting at 235.50°C (with decomposition), are obtained. 226-7 (decomp.) 446s3 Example Mp (°C) 101 102 I 3 θ «ΓΛ O-C-CH.-O-SO. NH. 0 136-137 (d) η 3 viz 104 Cl. 105 C 106 Cl. 107 F I 3 O-C-CH -0-S0, NH 0 127-128 (d) i 2 J . 2 \y CH | J θ £ ο O-C-CH -0-S0. K 215 (d.) I 2 3 H OH • 3 Θ O-C-CH -Q-SO- fiH_ O 112-113“(d.) A 2 3 \!/ 108 F yo^yy-0CH.

I 3-\k_7/--^_CH2~° S°3 ^4 137°(d.) In a manner analogous to that in Example 12 the following further compounds were prepared: - 31 Example ηβ or Bp ( c) 109 Cl Cl nD24: 1.5645 111 F3C CH, 0 3 » CH2-0-C-CH=CH2 Bp.170 /0.003 mm CH.

CH.

CH.

Bp.170 /0.02 mm 113 F3C.

CH I 3 O-C-CH.-O-C-CH I 2 /7*2 nD25: 1.5142 114 F3C CH, Cl CH, 0 CH, I 3 II I 3 o-c-ch2-o-c-ch- Cl n 24.5, D 1.5452 115 F3C CH, 0 I 3 II O-C-CH -O-C-CH-CH. I 2 ι 3 H n s 1.5202 Br The following further compounds can be prepared by the process 10 described 44®s3 ί as under Example - 33 as under Example Cl Cl Cl ’3C-<0> ° CH I 3 O-C-CH.-OH I 2 H Cl as under Example 4 6 5 3 as under Example O-^-CH2-Cl H H3C CH t 3 O-C~CH„-Cl I H ?H3 G-C-CH.-Cl I 2 H 44®s3 as under Example I *4653 - 37 as under Example CH, 0 I 3 I O-£-CH2-O-C-CH2-CH3 H Cl CH, 0 CH, I 3 » I 3 O-C-CH,-O-C-C-H I 2 I H CH, Cl.

O-C-CH,-O-C-CH=CH„ I 2 2 H f3 or 51 Cl oa3 o O-C-CH -O-I-CH=CH-CH, 12 or 51 I * «3 Cl.

CH 0 I 3 II O-C-CH,-O-C-CH=C H 2 X ZCH3 CH, Cl.

CH I 3 O-C-CH, I 2 H -oX CH-CH, I 3 Br Cl.

O-C-CH,-O-C-CH I 2 CH, CH.

Cl Cl.

O-Cjl-CHyO-C-CHyO CH I 3 .Cl 12 4653 as under Example CH, 0 CH I 3 HI3 0-C-CH,-0-C-CHI 2 H Cl H - 39 Cl.

CH, 0 I 3 I O-C-CH -O-C-CH=CH I 2 2 H or 51 ?“3 f O-C-CH,-O-C-CH=CH-CH, I 2 3 H or 51 Cl - 40 as under Example Cl Cl Cl Cl Cl CH, 0 CH, I 3 II | 3 0-C-CH -O-C-CH-O i 2 H Cl Cl 4 6 5 3 - 41 as under Example CH I 3 -C-CH,I 2 H 4 6 5 3 as under Example - 42 Cl or 51 Cl or 51 CI 0 ,CH0 « /\ 2 .Cl Cl » O-C-CH2-O-C 44633 as under Example CH, Cl CH, O-C-CH,-0-C I 2 Cl 4 6 3 3 - 44 -as under Example Cl Cl CH3 0 o-A-ch2-o-c(ch2)3-o_^Q' ci - 45 as under Example CH. 0 CH.

I 3 HI3 O-C-CH2-O-C-CH-O. z x z x ?H3 xOaoaO/~°i’ch'’’0' H Cl 12 Λ-Cl 12 Cl 12 Cl CH. 0 CH.

I 3 II I 3 O-C-CH.-O-C-CH-O. I 2 H Cl 12 CP3 12 P3C O-C-CH,-O-C-CH.-CH, I 2 2 3 CH.

II H 4653 as under Example . or 51 - 47 as under Example Cl <16 3 3 as under Example Cl Br as under Example ci CH, 0 I 3 II O-C-CH -O-C-CH, 12 I 2 3 H Cl 4653 as under Example 4 6 5 3 - 51 as under Example Cl 4 6 3 3 - 52 BIOLOGICAL EXAMPLES Example 1: The seeds of grasses were sown in pots and the preparations of the invention formulated as scatterable powders were sprinkled at various dosages onto the surface of the soil. The pots were then placed in a greenhouse for 4 weeks. The result of the treatment (as also in the case of the following Examples) was assessed by the method of evaluation according to the system of Bolle (Nachrichteriblatt des Deutsehen Pflanzenschutzdienstes 16, 1964, - 94): Value Percentage degree of damage number Weeds Crop plants 100 θ 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 37.5 9 0 to 35 :.5 67.5 60 100 The procedure was the same with the herbicidal agents used for comparison, fluorodifen (4-nitrophenyl-(2'-nitro-4'-trifluoromethylphenyl) ether) and mecoprop (2- (4 chloro-2 '-methy Iphenoxy)propionic acid). The results collated in Table I show that the claimed compounds are on the average more active against grasses than the two herbicides for comparison. A similar action against grasses is shown, also by the claimed compounds according to Examples 2, 9, 10, 12, 13, 14, 15, 21, .26, 27, 28, 36, 37, 38, 39, 40, 41, 57, 59, 60, 61, 63, 68, 69, 71, 74 and 80.

TABLE I Example Dosage Type of plants No. (kg/ha A.S.) AL SL LO EC 1 2.5 2 1 1 2 0.6 3 2 1 2 4 2.5 1 1 1 1 0.6 1 1 1 1 8 2.5 1 1 2 1 0.6 2 2 2 2 22 2.5 3 1 1 1 0.6 4 2 2 2 30 2.5 1 1 1 1 0.6 3 2 1 1 29 2.5 2 1 1 1 0.6 3 1 1 1 24 2.5 4 2 2 2 0.6 5 4 3 2 62 2.5 4 3 1 3 0.6 4 5 4 5 70 2.5 1 1 1 1 0.6 2 1 1 1 79 2.5 2 2 1 1 0.6 5 3 3 3 fluoro- 2.5 7 1 1 4 difen 0.6 8 5 8 8 Mecoprop 2.5 4 3 5 3 0.6 7 6 8 7 AL = Alopecurus myosuroides, SA = Setaria lutescens, LO = Lolium multiflorum, EC = Echinochloa crus-galli.

Example 11: The seeds of grasses were sown in pots and grown in a green house. 3 weeks after sowing the preparations of the invention formulated as scatterable powders were sprinkled at different dosages on the plants and the effect of the preparations were - 54 evaluated after a period of 4 weeks in the greenhouse. Also in this case fluorodifen and mecoprop served as herbicidal agents for comparison. The claimed compounds in this method of applica tion did indeed have a somewhat weaker action than in the preemergence method described in Example 1, but had a better action against grasses than the two agents for comparison (Table II).

A similar action against grasses were exhibited by the claimed compounds according to Examples 2, 10, 24, 36, 37, 39 and 41.

TABLE II Evaluation numbers against weeds in post-emergence.

Example Dosage Type of plants No. (kg/ha A. S.) AL SA LO EC 1 2.5 5 1 1 1 0.6 8 2 1 1 4 2.5 1 1 1 1 0.6 2 1 2 1 8 2.5 1 1 2 1 0.6 2 2 2 2 22 2.5 8 3 2 1 0.6 9 3 5 1 30 2.5 3 2 2 1 0.6 9 4 3 1 29 2.5 2 1 1 1 0.6 7 2 2 2 70 2.5 4 1 1 1 0.6 6 2 6 1 Eluoro- 2.5 8 2 6 4 difen 0.6 8 3 8 6 Mecoprop 2.5 8 7 8 8 0.6 9 8 9 9 Example 111; The seeds for a large number of crop plants were inserted in pots. Some of the pots were placed in a greenhouse for 2 to 3 weeks for germination and sprouting, and treated with the substances of the invention after the plants had developed 2 to 3 true leaves. The other pots were sprinkled immediately after being sown in the same manner as is given in Example II. The - 55 result was ascertained 4 to 4¾ weeks after the treatment, and is given in Table III. In particular, the results show that almost all dicotyledonous crop plants at the highest dosage (2.5 kg per hectare) tolerate very well the preparations of the invention both in pre-emergence and post-emergence. As the effective dosage is about 0.6 kg per hectare, the active substances of the invention have a good selectivity in these crops Ω. -Π Ω to +j ω £ co o Ω g $ t-« co co to g « ro ro Ω 0 0 H H ro c β 0 β ro 5* ro ro β Ό ro ro* ro rt I-· 0* 3 (+ P 0 ro cn 0 0 β H· (+ ro Η· ro ro rt K ro ro ro (+ X ro ro* ro ro β 1-. f+ ro <+ th » it ro H 0 rt 0 (+ 0 Oi κ 3. Η· ro c ro H (+ ro rt ω 0 ro ro* ro σ* rtl Ω Q Ω 0 0 ro* ro ro ro Ω ro £ O' 0 ro ro rt Q PL ro (+ ro s c g rt ro ro ro1 rt ro (Q © J_I f-* to ι_ι to 1-. W W Η ω η» ι-» to to to ϋΐ Φ ro to w to ω to to ω to }_l t_4 f* f-» }-l t-l }_J t-1 t-j t-J t·* η H ω oj Η* η ω ω η Cn to Η H to K h-J Η H t-» Η H to W H OJ OJ to to to H W H h-> H H t-* H· Η· Η Η· Η» t-j j-» to to to to to cn t-u oj to to Η Η Η Η O OS to OJ Η t-» H to ω H ro to tn p σ< to Ul O OS to tn W I I o OS to on H t-1 H O Os $ ro ro to TABLE III tJ O tn rt* ro *8 ro ro o to rt· ro to 4s.

CO 4653 - 57 Example IV Seeds of maize and rice and of a few weed grasses that occur in these crops were sown in pots and allowed to germinate in a greenhouse for 3 weeks. The preparations formulated in accordance with the invention as scattering powders and the agents for comparison were then sprinkled on the plants in various dosages, and after 4 weeks the effect of the preparations was ascertained.

As agents for comparison the following compounds were used: A = 2-4'-(2,4-dichlorophenoxy)-phenoxy-propionic acid methyl ester (DT-OS 22 23 894) B = 2-4'~(4-chlorophenoxy)-phenoxy-propionic acid isobutyl ester (DT-OS 22 23 894) C = 2-[4'-(4-trifluoromethylphenoxy)-phenoxy]-propionic acid methyl ester (DT-CS 24 33 067) The claimed compounds showed, as compared with the herbicides used for comparison, a distinctly better tolerability by maize and/or rice. At the dosages which did not, or only very slightly, damage the crop plants, they were outstandingly effec20 tive against the weed grasses tested. On the other hand, the compounds for comparison were not selective in maize and rice. - 58 TABLE IV Evaluation numbers in post-emergence treatment. Dose Crop plants Weed grasses Compound (kg/ha) }feize Rice EV SA 5 1 2.5 6 3 1 1 O.S 3 3 1 2 0.15 , 1 1 5 3 2 2.5 6 7 1 1 0.6 2 3 2 1 10 0.15 - 1 2 6 2 4 2.5 8 - 1 1 0.6 3 - 1 1 0.15 1 - 6 8 22 2.5 - 3 1 - 15 0.6 - 1 1 - 0.15 - 1 6 - A 2.5 8 8 1 1 0.6 7 7 1 1 0.15 6 6 3 1 20 B 2.5 9 8 1 1 0.6 9 7 1 1 0.15 8 4 2 7 C 2.5 9 - 1 1 0.6 9 - 1 1 25 Example V 0.15 9 3 1 In a further test the compounds 8, 45. 90 and 111 were used together with the comparison compound C at post-emergence in a manner corresponding to that in Example I.

The results given in Table V show that the claimed compounds - 59 are superior to the agents for comparison with regard to tolerability by crop plants (compound 8),and, coupled with the same good tolerability by the soya bean, they exhibit advantageous actions against the weed grasses tested.

TABLE V Evaluation numbers in pre-emergence treatment.

Compound Bose (Jcg/ha) Crop plants Barley Wheat Soya bean Weed grasses AL DI SA EC 8 2.5 1 1 I 2 - 1 1 0.6 1 1 1 4 - 2 4 0.15 1 1 1 7 - 5 5 45 2.5 - - 1 1 1 1 1 0.6 - - 1 2 1 1 2 0.15 - - 1 3 1 2 2 90 2.5 - - 1 1 1 1 1 0.6 - - 1 1 1 1 1 0.15 - - 1 3 1 1 2 111 2.5 - - 1 1 1 1 1 0.6 - - 1 1 1 1 1 0.15 - - 1 3 1 2 3 c 2.5 9 9 1 1 1 1 1 0.6 9 9 1 1 2 1 2 0.15 8 5 1 5 6 4 4 DI = Digitaria sanguinalis Example VI The efficiency of further compounds of the invention in pre-emergence is shown in the following Table. - 60 TABLE VI Evaluation results in pre-emergence treatment against important weed grasses.

Compound Dose (kg/ha) Action against weed grasses AL EC SA DI 2 2.5 1 1 1 -. - 0.6 2 1 3 - 3 2.5 2 1 1 - 0.6 3 1 3 - 10 7 2.5 1 1 1 1 0.6 3 1 2 1 13 2.5 2 1 1 - 0.6 3 1 3 - 14 2.5 2 1 1 - 15 0.6 4 2 3 - 15 2.5 2 1 2 - 0.6 3 3 3 - 1 12 2.5 1 1 - - i 0.6 3 3 - - 20 16 2.5 - 1 1 - 0,6 - 1 3 - 17 2.5 1 1 - 0.6 - 4 4 - 20 2.5 . - 1 1 - 25 0.6 - 3 3 - 21 2.5 3 2 3 - 1 0.6 3 3 4 - i 24 2.5 - 2 2 - 0.6 - 3 4 - | 30 26 2.5 - 2 3 - i 0.6 - 3 4 - t 27 2.5 - 3 - - 0.6 - 4 - - 28 2.5 - 2 3 - - 35 0.6 ‘ - 3 3 - 31 2.5 3 3 2 - 0.6 4 3 3 - 1 32 2.5 2 1 1 - 1 0.6 4 4 4 - 40 33 2.5 1 1 1 1 0.6 4 1 2 1 34 2.5 - 1 - - 0.6 - 3 - - 35 2.5 - 3 - - 45 0.6 - 4 - - 4463 3 Compound Dose TABLE VI Action cont‘d against weed grasses (kg/ha) AL EC SA DI 36 2.5 1 1 1 1 0.6 3 1 1 1 37 2.5 - 1 1 1 0.6 - 1 1 2 38 2.5 - 1 1 1 0.6 - 2 1 1 39 2.5 1 1 1 1 0.6 2 2 2 1 41 2.5 2 1 1 - 0.6 3 1 1 - 42 2.5 1 1 1 - 0.6 2 2 1 - 44 2.5 2 1 1 - 0.6 3 4 3 - 47 2.5 2 2 2 - 0.6 4 6 4 - 46 2.5 1 1 1 - 0.6 3 2 - - 45 2.5 1 1 1 1 0.6 2 2 1 1 51 2.5 3 3 2 0.6 4 4 4 - 53 2.5 1 1 1 - 0.6 1 2 1 - 55 2.5 - 3 - - 0.6 - 5 - - 57 2.5 - 1 3 - 0.6 - 2 4 - 60 2.5 - 2 2 - 0.6 - 3 4 - 61 2.5 - 4 1 - 0.6 - 5 2 - - 62 TABLE VI cont'd.

Compound Dose (kg/ha) Action AL against weed grasses EC SA DI 62 2.5 4 3 3 - 5 0.6 4 5 5 - 63 2.5 - 2 2 - 0.6 - 3 4 - 68 2.5 - 3 2 - 0.6 - 4 3 - 10 69 2.5 - 1 1 - 0.6 - 2 2 - 71 2.5 1 1 1 - 0.6 4 1 2 - 74 2.5 - 2 2 - 15 0.6 - 3 3 - 77 2.5 - 2 1 - 0 .6 '· - 3 3 - 78 2.5 2 2 2 - 0.6 4 4 4 - 20 79 2.5 - 1 2 - 0.6 - 3 3 - 802-5 - 2 1 - 0.6 - 2 4 - 81 2.5 - 1 1 - 25 0.6 - 2 6 - 90 2.5 1 1 1 1 0.6 1 1 1 1 111 2.5 1 1 1 1 0.6 1 1 •1 1 30 112 2.5 1 1 1 - 0.6 2 1 2 - 115 2.5 1 1 1 - 0.6 2 2 1 - 44633 TABLE VI cont'd.

Compound Dose (kg/ha) Action AL against weed EC SA grasses DI 113 2.5 1 1 1 - 5 0.6 3 2 1 - 110 2.5 3 3 1 - 0.6 4 4 3 - 109 2.5 3 1 1 - 0.6 4 2 1 - 10 95 2.5 2 2 1 1 0.6 3 4 2 1 100 2.5 1 •Ί 4 - 0.6 3 2 5 - 107 2.5 2 1 1 - 15 0.6 3 2 2 - 108 2.5 1 1 1 - 0.6 3 2 2 - 103 2.5 2 1 1 - 0.6 3 2 2 - 20 104 2.5 1 2 2 - 0.6 3 2 3 - 105 2.5 3 3 2 - 0.6 4 4 3 - 106 2.5 4 3 2 - 25 0.6 4 4 3 - 4 6 5 3

Claims (11)

1. A herbicidal composition comprising a carrier and, as active substance, a compound of the general formula 5 in which each R is a halogen atom or a CF,, CH, or C.H group; 3 3 Z 5 each R| is a halogen atom or a CF 3 group. R 2 is a hydrogen atom or a (CyC^)-alkyl group; n is each Z is 1 or 2; n^ is 0, 1 or 2; of X and Y is 0 or S; and -OH, -SH, -F, -Cl, -Br, -I or a group of the / £\ -N 1 -OCO-OR, \ t *5 3 0 R.-s ,Β.'' II / 4\ Z 4 -O-C-N / -O-SO.-N 1 \ / 2 \ > r' R / 5 5 -O-CO-R,, -O-SO.-R ,6 2 6 or -O-SO 3 -R ? in which R 3 is a (CyC^Jalkyl, (CyCg) cycloalkyl, ( c 2 _c x 0 ) alkenyl, (C-C.) cycloalkenyl, (C,-C n )alkynyl, phenyl or benzyl 15 group which may carry one or more substituents selected from halogen atoms and CFy NOy CN, (CyC^)alkyl, (CyC^) alkylthio, (C,-C.) alkoxy, -OH, -NH_, (0,-0,.)alkylamino, di-(C,-C c )alkylamino 1 4 Z 1 b lb and (C,-C )alkoxycarbonyl groups; 1 b *4853 - 65 R 4 is a halogen atom or a (C^-C^ alkyl, (C^-C^)alkenyl, cyclopentyl, cyclohexyl, (C^-C/alkoxy or phenyl group which may carry one or more substituents selected from halogen atoms and CF 3 , N0 2 , CN, (C^-C^Jalkyl, (C^-C^Jalkyltbio, (Cj-C^ alkoxy, OH, NH,, (C.-C.)alkylamino, di-(C.-C,.) alkylamino and (C.-C)2 s. o ±o io alkoxycarbonyl groups; is a hydrogen atom or a (C^-C^)alkyl group, or and R,_ together with the nitrogen atom to which they are attached form a saturated heterocycle having from 2 to 5 carbon atoms and which may contain an oxygen or sulphur atom or a group of the formula NR^; R has the meanings given for R_ or is a phenoxy-(C -C.)-alkyl b J 14 group the phenyl group of which may carry from 1 to 3 substituents selected from F, Cl and Br atoms and methyl groups; θ R? is a hydrogen atom or a (C^-C^Jalkyl group or cat ,and cat® is the cation of an inorganic or organic base, or 2 is a group of the formula (II) -O-CO-CH-Y

2. A herbicidal composition according to claim 1 in which (R) is one to two chlorine and/or bromine atoms and/or CF groups n j n is 0; R 2 is CH 3 ; X, Y are both oxygen, Z is -OH, Cl, -Br; the group of the formula II, in which (R) and n. have the meanings specified above; or a group of the η l formula -o-c-: in which is a hydrogen atom or a (C^-C^)alkyl, phenyl, halophenyl, methylphenyl or trifluoromethylphenyl group and R has the meaning specified in claim 1; -O-SOg-Rg, in which Rg is a CHg, phenyl, methylphenyl or chlorophenyl group; -O-SOg-R?, in which R ? is a (C^-C^)alkyl group or cat ; I -o-c-r 6 , in which R. is a (C..-C„)alkyl or (C,-C.)chloroalkyl group, a ο x y x 4 phenoxy-(C^-Cg)alkyl group the phenyl group of which may carry one or two substituents selected from F, Cl and Br atoms and methyl groups, a (Cg-Cg) alkenyl group or a phenyl group which may carry one or two substituents selected from -Cl, -Br, -NOg, -CHg, -CFg and OCHg; and cat € is Na + , K + , 1® 4 + , 1/2 Ca ++ , V + CH 2 CH 2 OH, HgN + CHg or HgN + Cft.

3. A herbicidal composition according to claim 2, in which (R) is 4-chloro, 2,4-dichloro, 2-chloro-4-bromo, 4-trin fluoromethyl or 2-chloro-4-tri£luoromethyl, n is zero. Rg IS CHg. X and Y are both oxygen, and Z has the meanings specified in claim 2.

4. A herbicidal composition according to claim 1, in which each of (R) , n,, R_, X, Y, Z, R., R_, R, and R_ has the a 1 2 5 + 6 7 + meaning specified in claim 2 and cat is H„N (CH) , HN (C„H ) , 2 3 2 2 5 3 HN (CHgCHgOH)g or NH„

5. A herbicidal composition according to claim 1, in which (R) n has the meaning specified in claim 3, each of n , Rj, X, Y, Z, R^, R^, Rg and R.^ has the meaning specified in claim 2 and cat® has the meaning specified in claim 4. 5

6. A.herbicidal composition according to claim 2, in which Z is -OH, -Cl, -Br; the group of the formula II in which (R) n and n^ have the meanings specified in claim 3; or a group of the formula -0-C0-N \ R 4 (R) n r R , X, Y, η, 1 2 < in claim 3, and cat *4' © -0-S0 3 - cat or -O-CO-Κθ; R and R have the meanings specified 5, ,6 , Na , K or NH 4 .

7. A herbicidal composition according to claim 1, in which each of Z, (R) , n., R , X, Y, R , R and R, has the n —j. 2 4 5 6 meaning specified in claim 4 and cat is NH, /Ά

8. A herbicidal composition according to claim 1, in which each of (R) , R,, X, Y, Z, R., R,, R,, and cat has the meaning n z 4 5 o specified in any one of claims 2 to 7 and (R^) n^ is a chlorine or bromine atom in the 2-position to Y.

9. A herbicidal composition according to claim 1 substantially as hereinbefore described.

10. A method for selectively combating weed grasses in an area of crop plants, which comprises applying to said area a herbicidal composition according to any one of claims 1 to 5. V»-»

11. A compound as specified in claim 1 with the proviso that, when Z is OH or -OCOR g in which R g is a alkyl group and X and Y are both oxygen, then (R)^ cannot be a halogen atom in the 4-position.