CA1229345A - Herbicidal diphenyl ethers and their use for controlling undesirable plant growth - Google Patents

Abstract

Abstract of the Disclosure: Diphenyl ethers of the for-mula

Description

aye --I 0050/3~813 Herbic1dal diphenyl ethers and their use for controlling undesirable plant growth The present invention relates to diphPnyl ethers, - herbicides which contain these compounds as active in-gradients and -their use for controlling undesirable plant growth Various herbicidal active ingredients which belong to the class consisting of diphenyl ethers and carry a substituted aminosulfonyl radical ortho to the vitro group have been disclosed in the literature German Laid-Open Applications DOS 2,261,918 and DOS 2,833,021).
We have found that diphenyl ethers of the formula I

z2 SNEEZER
n it Ox em where z1 and z2 independently of one another are each hydrogen, halogen, vitro, cyan, carboxyl, C1-C4-alkyl~
C1-C4-haloalkyl or C1-C4-alkoxy, Z3 is halogen, vitro, Sweeney C1-C4-alkY~ C1-c4-haloalkyl~ C1-C4-alkoxy~
C1-C~,-haloalkoxy, C1-C4-alkylmercapto, C1-C4-halo-alkylmercaPto~ C1-C4-alkylsulfinyl, C1-C4-haloalkylsul-final, C1-C4-alkylsulfonyl or c1-C4-haloalkylsulfonyl, X is hydrogen C1-C4-alkyl, unsu~stituted or halogen-substituted azalea of not more than 7 carbon atoms, an alkali metal ion or an unsubstituted or alkyl-substituted ammanium ion, R is C1-C20-alkyl, C1-C12-haloalkyl, an unsubstituted or halogen-substituted araliphatic radix eel of 7 to 20 carbon atoms, cycloalkyl of 3 to 12 carbon atoms, unsubstituted or substituted phenol, amino, C1-C4-alkylamino or di-C1-C~-alkYlamino~ and n and m indepen-deftly of one another are each 00 1 or 2, have a total or selective herbicidal action, depending on the formulation and dosage.
In formula I, z1 and z2 independently of one another are each hydrogen, halogen, vitro, cyan, carboxyl, I

- 2 - OOZE. 0050/36813 C1-C4-alkyl, C1-C4-haloalkyl or C~-C4-alkoxY, ego foreign, chlorine, bromide, iodine, methyl, ethyl, n-pro-pow isopropyl, n-butyl, tert.-butyl~ trifluoromethyl, dip fluoromethyl, fluoromethyl, trichloromethyl, dichloro-methyl, chloromethyl, difluorochloromethyl, 1-chloroethyl, 2-chloroethyl, 1-fluoroethyl, 2-fluoroethyl, Roy-chloroethyl, 2,2,2-trifluoroethyl, 1,1,2,Z-tetrafluoro-ethyl, 1,1,2-trifluoro-2~chloroethyl~ spinet fluoroethyl, methoxy, eighth, n-propoxy, isopropoxy or ter~.obutoxy, Z3 is halogen, vitro, cyan, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, c1-C4-haloalkoxY~
C1-C4-alkylmercapto, Cl-C4-haloalkylmercapto, Cluck-alkylsulfinyl, C1-C4-haloalkylsuLfinyl" C1-G4-alkYlsul-phenol or C1~C4-haloalkylsulfonyl~ ego fluorine, chlorine, bromide, iodine, methyl, ethyl, n-propyl, isopropyl, n-bottle, tert.-butyl, trifluoromethyl, difluoromethyl, fluoromethylO trichloromethyl~ dichlorome~hyl, sheller methyl, difluoromethyl, 1-chloroethyl, 2Ochloroethyl, 1-fluoroethyl, floral, 2,2,2-trichloroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, trifler-2 chloroethyl, 1,1,Z,2,2-pentafluoroethyl, methoxy, ethics, n-propoxy~ isopropoxy, tert~-butoxy, trichloromethoxy, in-fluoromethoxy, 1-chloroethoxy, 2-chloroethoxy, flyer-ethics, 2-fluoroethoxy, 2,2,2-trichloroethoxy, try-Z5 fluoroethoxy, 1,1,2,2-tetrafluoroethoxy, punt-fluoroethoxy, methylmercapto, ethylmercapto, trichloro-methylmercapko, trifluoromethylmercapto, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl or trifler-methylsulfonyl, X is hydrogen, C1-C4-alkyl, ego methyl, ethyl, n-proPyl, propel, n bottle or tert.-butyl, us-substituted or halogen-substituted azalea of not more than 7 carbon atoms, ego acutely, pronely, chloroacetyl, dip chloroacetyl or bouncily, an alkali metal ion, ego sodium or potassium, or an unsubstituted or alkyl~substituted ammonium ion, ego ammonium, methylammonium, dim thylammon-sum, trimethylammonium, ~etramethylammonium, ethylammonium, diethylammonium, triethylammonium or n-butylammonium~ and

- 3 - OOZE. 0050/36813 R is C1~C20-alkyl, preferably C1-C7-alkYl, in portico-far C~-C4-alkyL, ego methyl, ethyl, n propel, isopropyl, n-butyl, tertl-butyl or the isometric ponytail, Huxley or hop-twill radicals C1-C12-haloalkyl, preferably C1-C~-5 haloalkyl, ego chloromethyl, trichloromethyl, sheller ethyl, 2-fluoroethyl, sheller n-propyl or chlorine-bottle, an unsubstituted or halogen-substituted araliphatic radical of 7 to 20, in particular 7 to 9, carbon atoms, ego bouncily 4-chlorobenzyl, 2~4-dichlorobenzyl, phenethyl 1û or phenylpropyl, or cycloalkyl of 3 to 1Z, preferably 3 to 6, and in particular 5 or 6, carbon atoms, ego cycle-propel, cyclobutyl, cyclopentyl or cyclohexyl, or is pie-nil which is unsubstitu~ed or substituted by halogen, such as fluorine, chlorine or bromide, by C1-C4-alkyl, such as methyl or ethyl, by C1-C4-alkoxy, such as methoxy or ethics, by C1-C4-haloalkyl, such as trifluoromethyl, by vitro or by cyan, or is amino, C1-C4-alkylamino or di-C1-C4-alkylamino, ego methyl amino, ethyl amino, n-propylamino, iso~ropy~amino, n-butylamino, dimethylamino, diethylamino, di-n-propylamino, diisopropylamino or din-butylamino.
The preferred diphenyl ethers are compounds of the formula I where z1, zZ and Z3 independently ox one another are each hydrogen, halogen, Cook haloalkyl or C1-C4-haloalkylmercapto, X is hydrogen, C1-C4-alkyd or an alkali metal ion, R is C1-C20-alkyl or C1-C1~-haloalkyl or is phenol which is unsubstituted or substituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, c1-C4-haloalkyl, vitro or cyan, n is 0, 1 or 2 and 3û m is I Diphenyl ethers of the formula I where to Jo hydrogen, ZZ is chlorine and Z3 is trifluoromethyl are particularly preferred especially those of the formula I which contain a 2-chloro-4-trifluoromethylphenoxy radical.
Diphenyl ethers of the formula I are obtained by reacting a sulfonyl halide of the formula issue Al 4 OOZE Owe 3~0~J~)2 ( I I ) Z Shoal where z1, I Z3 and n have the above meanings and Hal is halogen, with not Less than an equimolar amount of a compound of the formula ~12NS-~, ( I I I
em where R and m have the above meanings, in an inert organic solvent and in the presence or absence of an acid acceptor at from -20 to ~150C, in particular from 0 to 120C.
The reaction can be carried out bushes or continuously, under atmospheric or supera~mospheric pressure.
The process for the preparation of the diphenyl ethers of the formula I can be represented, by way of example, by the following equation:

F3C 2 H2NS2C~3 _ F3 0 No Of Sol Of S-NHso2cH3 US The starting materials are employed in about stoichiometric amounts to. from 0.9 to 1.1 moles of starting material III are employed per mole of II. If necessary an acid acceptor can be added to complete the reaction. Furthermore, the hydrogen halide formed during the reaction can be expelled by passing in an inert gas, ego nitrogen Advantageously, the process is carried out as follows: a solution of the sulfonyl halide II in an inert organic solvent is run, if appropriate simultaneously with an equimolar amount of an acid acceptor, into a soul-ton of the starting material III in an inert organic sol-vent at from ~20 to ~150C, preferably from 0 to +120C.
To complete the reaction, stirring is continued ~2~93~S
- 5 - OOZE. 0~50/36R13 for from 0.5 to 48, preferably from Z to 1Z, hours at from 0 to 60C. The reaction mixture is filtered and evaporated down, and the desired end products can be is fated by reprecipitation or recrysealli2ation or by stir-ring with water. If necessary, they can be purified by chromatography.
The diphenyl ethers of the formula I are also ox-twined by reacting a sulfonamide of the formula Al Z3 ~12 (IV) Z S NH
n O X
n where z1~ z2, z3~ X and n have the above meanings and Hal is halogen with not less than an equimolar amount of a compound of the formula Claus-I where R and m have the above meaning sin an inert organic solvent and in the presence or absence of an acid acceptor at from -20 to ~150C, in particular from 0 to 120C.
The reaction can be carried out bushes or continuously, under atmospheric or super atmospheric pressure.
The diPhenyl ethers of the formula I in which m and n are each 1 or Z can also be obtained by oxidation of a compound of the formula I in which m and n are each 0, by means of a suitable oxidizing agent.
Compounds of the formula I where X is hydrogen can subsequently be converted into compounds of the formula Z5 I where X is alkyd, unsubstituted or halogen substituted assailed an alkali metal ion or an ammonium ion by using the conventional alkylation, acylation or neutralization reactions.
The process for the preparation of the diphenyl ethers of the formula I by reacting a compound of the formula IV with a compound of the formula V can be 3t3~5 - 6 - OOZE. 0050/36813 represented by Jay of example, by the hollowing equation:

F~C 0 No I CLASSIC -MCi~ Fur 0 2 C l N~12 C l S-NH-50 The starting materials are employed in about stoichiometric amounts, to. from 0.9 to 1.1 moles of S starving material V are employed per mole of IVY If necessary, an acid acceptor can be added to complete the reaction. Furthermore, the hydrogen halide formed during the reaction can be expelled by passing in an inert gas, ego nitrogen Advantageously, the process is curried out as follows: a solution of the sulfonyl halide V in an inert organic solvent is run, if appropriate simultaneously with an e~ui~olar amount of an acid acceptor, into a soul-lion of the starting material IV in an inert organic sol-vent, at from -20 to ~150C, preferably from 0 to +120C.
To complete the reaction, stirring is continued for prom 0.5 to 48, preferably from 2 to 1Z, hours, the temperature being kept at from 0 to 60C. The reaction mixture is then evaporated down, and the end products of the formula I can be isolated by reprecipitation or no-crystallization or by stirring with water. If necessary, they can be purified by chromatography.
For both processes, organic solvents which are in-oft under the particular reaction conditions are used.
Examples of suitable solvents are halo hydrocarbons, in Particular chlorohydrocarbons, ego tetrachloroethylene, 1,1,2,2- or 1~1,1,2-tetrachloroethane, dichloropropane, ethylene chloride, dichlorobutane, chloroform, sheller-naphthalene, dichLoronaphthalene, carbon tetrachloride, 1,1~1- or 1,1,2-trichloroe~hane, trichloroethylene, punt chloroethane, o-, m- or p-difluorobenzene, 1,2-dichloro-ethanes 1,1~dichloroethane, 1,2-cis-dichloroethylene, chLorobenzene, ~luorobenzene, bromobenzene, iodobenzene, o-, p- or m-dichloroben2ene, o-, p- or m-dibromobenzene, owe m- or p-chlorotoluene or 1,2,4-trichlorobenzene, ~2293D~5 ` - 7 - OOZE. 0050/36813 ethers ego ethyl propel ether, methyl tert.-butyl ether, n-butyl ethyl ether, d;-n-butyl ether, diisobutyl ether, dismal ether, diisopropyL ether, anisole, finitely, cyclohexyl methyl ether, deathly ether, ethylene glycol dip methyl ether, tetrahydrofuran~ Dixon, thioanisole or I '-dichlorodiethyl ether, nitrohydrocarbons, such as nitromethane, nitroethane, nitrobenzene, o-, my or p-chloronitrobenzene or o-nitrotoluene~ nitrites, ego asset-nitrite, butyronitrile, isobutyronitrile, benzonitrile or m~chlorobenzonitrile, aliphatic and cycloaliphatic hydra-carbons, ego Hutton, inane, nonage, o-, m- or p-cymene, gasoline fractions boiling within a range from 7û Jo 190C, cyclohexane, methylcyclohexane, decline, petrol Lomb ether, hexane, naphtha, 2,2,4-trimethylpentane, 2,2,3-tr;methylpentane, 2,3,3-trimethylpentane or octane, ester, ego ethyl acetate, ethyl acetoacetate or isobutyl acetate, asides, ego formamide, methylformam;de or dip methylformam;de, kittens, ego acetone or methyl ethyl key tone, and mixtures of these. Advantageously, the solvent is used in an amount of from 100 to 2,000, preferably prom 200 to 7U0~ % by weight, based on the starting materials.
Suitable acid acceptors are all conventional acid acceptors. These preferably include tertiary amine, alkaline earth metal compounds, ammon;um compounds alkali metal compounds and mixtures of these, but zinc compounds can also be used. Examples of suitable basic compounds are potassium hydroxide, sodium hydroxide, potassium car-borate, sodium carbonate, lithium hydroxide, lithium car-borate, sodium bicarbonate, potassium bicarbonate, calcium hydroxide, calcium oxide, barium oxide, magnesium hydroxide magnesium oxide, barium hydroxide, calcium carbonate, Meg noisome carbonate, magnesium bicarbonate, magnesium ace-late, zinc hydroxide zinc oxide, zinc carbonate, zinc bicarbonate, zinc acetate, sodium format, sodium acetate, trimethylamine, triethylamine, tripropylamine, triisopropyl~mine, tributylamine, triisobutylamine~ in-sec.-butylamine, tri-tert.-butylamine, tribenzylamine, ~;~293~;
.
- 8 - 0.Z. 0~50/36813 tricyclohexylam;ne, triamylamine~ d;;sopropylethylamine, ~rihexylam;ne, N,N-dimethylanil;ne, N,~J-diethylaniline, N,N-diprouylaniline, NUN dimethyltoluidine, N,N-diethyl-Teledyne, NUN dipropyltoluidine, N,N-dimethyl-p-am;no-pardon, N,N-diet-hyl-p~aminopyridine, NON-dipropyl-p-aminopyridine, N-methylpyrrolidone, N-ethylpyrrolidone, N-methylD;peridine, N-ethylpiperidine, N-methylpyrroli-dine, N-ethylpyrrolidine, N-methylimidazole, N-ethylimi-dazzle, N-methylpyrrole, N-ethylpyrrole, N-methylmorpho-10 line, N ethylmorpholine, N-methylhexamethyleneimine, N-ethylhexamethyleneimine, pardon, quinoline, ~X-picoline, î~p;coline, ~-picoline, isoquinoline~ pyrimidine, acrid dine, N,N,N',NI-tetramethylethyLenediamine, N,N,N',N'-tetraethylethylenediamine, quinoxaline, quinazoline, N-propyldiisoPropylamine, N~N'-dimethylcyclohexylamine, letdown, letdown, trifurylamine and triethylene-Damon The starting compounds are prepared by methods known from the literature. For example, the ethers of the 20 formulae II and IV are obtained by the procedures desk cried in German Laid-Open Applications DOS 2,833,021 and DOS 3,21Z,1~5. The compounds of the formulae III
and V are available generally, or can likewise be prepared by methods known from the literature.
The Examples which follow illustrate the prepare-lion of the compounds of the formula I by the above pro-cusses. Parts by weight bear the same relation to parts by volume as that of the kilogram to the liter.

4.95 parts by weight of metnanesulfonamide and 3.95 parts by weight of pardon are added simultaneously to a solution of 19.Z parts by weight of sheller'-trifluoromethylphenoxy~-6-nitrophenylsulfenyl chloride in 200 parts by volume of absolute tetrahydrofuran, after US which the reaction mixture is stirred for 2 hours at 40C, cooled stirred into 500 parts by volume of water and then acidified with 2 N hydrochloric acid. The precipitate ~LZ~:93~Si 9 Oat I 0050/36813 is filtered off under suction and recrystallized from 1,Z-dichLoroethane to give 18.1 parts by weight ~82% yield) of3-C2'-chloro-4'-trifluoromethylphenoxyl-6-n;tropheenyl-N-methanesuLfonylsuLfenamide of melting point 215-~18C
(compound No. 1).

8 parts by weight of sheller trifler-methylphenoxy~-6-nitrophenyl~N~methanesulfonylsulffenamide and 3.25 parts by weight of 30X strength sodium methyl ate are suspended in 100 parts by volume of absolute Matthew not, and the suspension is heated to the reflex tempera-lure. It is then evaporated down under reduced pressure to give 8~37 parts by weight (100X yield) of the sodium salt of 3-C2'-chloro-4'-trifluoromethylphenoxy~-6-nitro-PhenyL-N-methanesulfonylsulfenamide of melting point 188-191C (compound No. I

A solution of 3.8 parts by weight of sheller-4'-trifluoromethylphenoxy~-6-nitrophenyl-N-me~haneesulfonyl-Z0 sulfonamide and 3~85 parts by weight of 85X strength m-chloroperbenzoic acid in 150 parts by volume of chloroform is stirred at room temperature for 12 hours, after which the reaction mixture is extracted with dilute sodium ho-dioxide solution and water, dried with magnesium sulfate, filtered and evaporated to dryness. 8 parts by weight (87% yield) of 3-C2'-chloro-4'-trifluoromethylphenoxy~-6 nitrophenyl-N-methanesulfonylsulfinamide of melting point 178-18?C are obtained compound No. I

A solution of 8.8 parts by weight of 3-C2 '-sheller-4'-trifluoromethylphenoxy~-6-nitrophenyl-N-methaneesulfonyl-sulfonamide and 9.36 parts by weight of 85% strength m-chloroperbenzoic acid in 150 parts by volume of chloroform is stirred at 40C for 4 hours, after which the reaction 35 solution is extracted with dilute sodium hydroxide solution and water, dried with magnesium sulfate filtered and evaporated to dryness. 9 parts by weight (95% yield) of ~22~L5 - 10 - OOZE. OOZE
3-C2'-chloro-4'-erifluoromethylphenoxy]-6-nitropheenyl-N-methanesulfonylsuLfonamide of refractive index n2D5 1.5469 are obtained compound No. 4).

A mixture of 10 parts by weight of sheller 4'~trifluoromethylphenoxy]-6-nitrophenyl-N-methaneesulfo nylsulfenamide, I parts by weight of dim ethyl sulfate and 3~2 parts by weight of potassium carbonate in 100 parts by volume of acetone is stirred for 2 hours at 64C, after which the mixture is filtered and the reaction soul-lion is evaporated to dryness. Recrystallization fromdiisopropyl ether gives 7 parts by weight t69X yield) of 3-C2'-chloro-4'-trifluoromethylphenoxy]-6-nitropheenyl-N-methyl-N methanesulfonylsulfenamide of melting Point 128-130C compound No. 5).

3.9 parts by weight of benzenesulfonamide are added, a little at a time Jo a solution of 9.1 parts by weigh of 3-C2'-chloro-4'-trifluoromethylphenoxyJ-6-nitro-phenylsulfenyl chloride in So parts by volume of pardon.
The reaction mixture is stirred for 3 hours at 40C, after which it is stirred into water and acidified with 3 N ho-drochloric acid, and the precipitate which separates out is filtered off under suction and recrystallized from 1,Z-dichloroethane to give 7 parts by weight t77X yield) of 25 3-~2'-chloro~4'-trifluoromethylphenoxy]-6-nitropheenyl-N-benzenesulfonylsulfenamide of molting point 170-178C
compound No. 6).
For instance the following compounds of the formula Of S - N - S
n n on X em may be obtained analogously.

-I ~22~5 No. n m X R Mop. C~; n25;
wavelength of a band in the infrared spectrum ..
7 0 2 acutely . methyl 8 o 2 ammonium methyl 9 0 2 dimethylammonium methyl 10 0 2 ethyl methyl 11 1 2 methyl methyl 12 2 2 methyl methyl 13 2 2 sodium methyl 250 (decomposition) 14 1 2 sodium methyl 240 15 o 2 H ethyl 16 0 2 sodium ethyl 17 0 2 methyl ethyl 18 1 2 H ethyl 19 2 2 H ethyl 20 1 2 sodium ethyl 21 2 2 sodium ethyl 22 0 2 H n propel 23 0 2 sodium n-propyl 24 1 Z H n-propyl 25 2 2 H n-propyl 26 1 2 sodium n-propyl 27 2 2 sodium n-propyl I 0 2 H i-propyl 29 1 2 H i-propyl 30 2 2 H i-propyl 31 0 2 sodium i-propyl 32 1 2 sodium i-propyl 33 2 2 sodium i-propyl 34 0 2 methyl i-propyl 35 0 2 H n-butyl 36 1 2 H n-butyl 37 2 2 H n-butyl 38 0 2 sodium n-butyl 39 1 2 sodium n-butyl 40 2 2 sodium n-butyl 41 0 2 H chloromethyl 42 1 2 H chl~romethyl 43 2 2 H chloromethyl 44 0 2 sodium chloromethyl 45 1 2 sodium chloromethyl o O

~2293~S

- 12 - OOZE. Allah No. n m .X R Mop. C]; nD5;
wavelength ox a band in the infrared spectrum . . . . . _ .
46 2 2 sodium chloromethyl 47 0 2 H bouncily 48 0 2 sodium bouncily 49 0 2 H chlorobenzyl 50 0 2 sodium chlorobenzyl 51 0 2 sodium phenol 150 (decomposition) 52 1 2 H phenol 70-75 53 2 2 H phenol 90-92 54 0 2 methyl phenol 145-148 55 1 2 sodium phenol 56 2 2 sodium phenol 57 n 2 H 4~chlarophenyl 168 - 170 58 0 2 sodium 4-chloropheny} 145 (decomposition) 59 0 2 methyl 4-chlorophenyl 128-132 60 0 2 ethyl 4-chlorophenyl 61 1 2 H 4-chlorophenyl 75-B2 62 2 2 H 4-chlorophenyl 75-80C
63 0 2 H 2-chlorophenyl 110-113 64 0 2 sodium 2-chlorophenyl 100 (decomposition) 0 2 methyl 2-chlorophenyl 130-140 66 1 2 H 2-chlorophenyl 67 2 2 H 2-chlorophenyl 170-174 68 0 2 H 4-~luorophenyl 115-120 69 û 2 sodium 4 Pluorophenyl 70 (decomposition) 70 0 2 methyl 4-tluorophenyl 1.6141 71 1 2 H 4-~luorophenyl oil 72 2 2 H 4-~luorophenyl oil 73 0 2 H 4-bromophenyl 145-150 74 0 2 sodium 4-bromophenyl }60 (decomposition) 75 0 2 methyl 4-bromophenyl 64-66 76 1 2 H ,4-bromophenyl 240 77 2 2 H 4-bromophenyl ' oil 78 0 2 H 2,6-dlchlorophenyl 168 - 172 79 0 2 sodium 2,6-dlchlorophenyl 8û 0 2 methyl 2,6-dichlorophenyl 81 0 2 H 2,4-dichlorophenyl 82 0 2 sodium 2,4 dichlorophenyl 83 0 2 H sheller nitrophenyl 84 0 2 sodium 4-chloro-3-nitrophenyl ' O

~2~93~S
- 13 w OOZE. 0050/36B13 No. n m X R Mop. okay; nD5;
wavelength ox a band in the infrared spectrum 85 0 2 methyl 4-ohloro-3-nitrophenyl 86 0 2 H 2-nitrophenyl 87 0 2 sodium 2-nitrophenyl 88 0 2 H 4-nitrophenyl 89 o 2 sodium 4-nitrophenyl 90 o 2 methyl 4-nitrophenyl 91 a 0 H ~-nitrophenyl 92 1 0 H 4-nitrophenyl 93 2 0 H 4-nitrophenyl 94 1 1 H 4-nltrophenyl 95 2 1 H 4-nitrophenyl 96 2 2 H 4-nitrophenyl 97 0 2 H 4-cyanophenyl 98 0 2 sodium 4-cyanophenyl 99 0 2 H 4-methylphenyl 198 - 202 100 0 2 sodium 4-methylphenyl 85 (decomposition) 101 0 2 methyl 4-methylphenyl 106-110 102 0 2 H 3-nitrophenyl 148-152 103 0 2 sodium 3-nitrophenyl 105 (decomposition) 104 0 2 methyl 3-nitrophenyl 128-134 105 0 2 H 4-methoxyphenyl 165-172 106 0 2 sodium 4-methoxyphenyl 90 107 û 2 methyl 4-methoxyphenyl 98-106 108 1 2 H 4-methoxyphenyl 192-196 (decomposition) 109 2 2 H 4-m0khoxyphenyl 110 0 2 H 4-trlfluoromethoxyphenyl 111 0 2 H 4-trl~luoroethylphenyl 112 0 2 sodium 4-trifluoromethylphenyl 113 0 2 H 3-trifluoromethylphenyl 114 0 2 sodium 3-trifluoromethylphenyl 115 o 2 H 2,2,2-tri~luoroethyl 116 0 2 sodium 2,2,2-tri~luoroethyl 117 2 2 H 2,2,2-trifluoroethyl 118 0 2 H methyl amino 119 0 2 H ethyl amino 120 0 2 H propylamino 121 0 2 H isopropyl amino 122 2 2 H 4-methylphenyl 56-60 123 1 2 H 4-Methylphenyl 165-170 decomposition 124 2 2 H 3-Nitrophenyl oil 125 1 2 H 3-Nitrophenyl 65-70 126 2 2 sodium 2-chlorophenyl 93-98 O
S

"` ~Z29~4S
14 - OOZE. 0050/3681 For example the ~ollowlng diphenyl ethers ox the formula may also be obtained: z1 En. no. Z3~ n m X R Mop. I no - . . . . .
122 2,4-dichlorophenoxy 0 2 H methyl 123 2,4-dlchlorophenoxy 0 2 sodium methyl 124 2,4-dibromophenoxy 0 2 H methyl 125 2,4-dibromophenoxy 0 2 sodium methyl 126 3-chloro-4-tri~luoro- 0 2 H methyl methylphenoxy 127 3-chloro-4-trifluoro- 0 2 sodium methyl methylphenoxy 128 2,6-dichloro-4-tri- 0 2 H methyl ~luoromethylphenoxy 129 2,6-dichloro-4-tri- 0 2 sodium methyl l'luoromethylphenoxy 130 2,6-dichloro-4-tri- 0 2 methyl methyl ~luoromethylphenoxy 1}1 2,6-dichloro-4~tri- 0 2 H isopropyl ~luoromethylphenoxy 132 2,6-dichloro-4-tri- 0 2 H phenol ~luoromethylphenoxy 133 2,6-dichloro-4-tri- 0 2 H 4-chlorophenyl ~luoromethylphenoxy 134 2,6-dichloro-4-tri- 0 2 H 4-tluorophenyl ~luoromethylphenoxy an :

~l22~34S

- 15 - OOZE. 0050/36813 The diphenyl ethers of the formula I, and salts thereof, may be applied for instance in the form of direct-lye spray able solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), 05 dispersions emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of applique-anion depend entirely on the purpose for which the agents are being used, but they must ensure as fine a duster-lo button of the active ingredients according to the invent lion as possible.
For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil free-lions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydra-carbons such as Bunsen, Tulane, xylener paraffin, twitter-hydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, buttonhole, chloroform, carbon tetrachloride, cyclohexanol, cycle-hexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dim ethyl sulfa oxide, and N-methylpyrrolidone, and water are suitable.
Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil disk pensions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by moans of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredienkr wetting agent, adherent, emulsify-in or dispersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyd sulfates, and alkyd sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalene-N
No o go 22~33~5 - 16 - ooze. 0050/36813 sulfonic acid laurel ether sulfate, fatty alcohol sulk fates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, Hyatt decanols, and octadecanols, salts of sulfated fatty Alcoa 05 hot glycol ethers, condensation products of sul~onatednaphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesul-ionic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, elk-lo oxylated octylphenol and ethoxylated nonylphenol f alkyd-phenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyd ethers, ethoxylated polyoxypropylene, laurel alcohol polyglycol ether acutely, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active inure-dints to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, US silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loss, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide ground plastics/ fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
The formulations contain from 0.1 to 95, and prefer-ably 0.5 to 90, I; by weight of active ingredient.
Examples of formulations are given below.

o N

93~S
- 17 - OOZE. 0050/36813 I. Jo parts by weight of compound no. 3 is mixed with lo parts by weight of N-methyl-alpha-pyrrolidone. A
mixture is obtained which is suitable fox application in the form of very fine drops.
05 II. lo parts by weight of compound no. 4 is dozily-vied in a mixture consisting of 90 parts by weight of zillion 6 parts by weight of the adduce of 8 to 10 moles of ethylene oxide and l mole of oleic acid-N-monoethanol-aside, 2 parts by weight of the calcium salt of dodecyl-lo benzenesulfonic acid, and 2 parts by weight of the adduce of 40 moles of ethylene oxide and l mole of castor oil.
III. 20 parts by weight of compound no. 5 is dozily-vied in a mixture consisting of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the adduce of 7 moles of ethylene oxide and 1 mole of isooctylphenol, and 5 parts by weight of the adduce of 40 moles of ethylene oxide and l mole of castor oil.
IV. 20 parts by weight of compound no. 106 is disk I solved in a mixture consisting of 25 parts by weight ofcyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduce of I moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly disk tributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.
V. 80 parts by weight of compound no. 1 is well mixed with 3 parts by weight of the sodium salt of dyes-butylnaphthalene-alpha-sulfonic acid, lo parts by weight of the sodium salt of a iignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel, and triturated in a hammer mill.
VI. S parts by weight of compound no. 2 is intimately mixed with 95 parts by weight of particulate kaolin. A dust is obtained containing I by weight of the active ingredient.
I, o - ~%2~3~5 - I - OOZE. ooze VII. 30 parts by weight of compound no. 122 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of 05 this silica gel. A formulation of the active ingredient is obtained having good adherence.
VOW 20 parts of compound no. 13 is intimately mixed with 2 parts of the calcium salt of dodecylbenzene-sulfonic acid, 8 parts of a fatty alcohol polyglycol lo ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a purify phonic mineral oil. A stable oily dispersion is obtained.
The active ingredients, or agents containing them, may be applied pro- or post emergence. If certain crop plants tolerate the active ingredients less well when they are applied post emergence, application techniques may be used in which the herbicidal agents are sprayed from suitable equipment in such a manner that the leaves of sensitive crop plants are if possible not touched, and the agents reach the soil or the unwanted plants growing beneath the crop plants (post-directed, lay-by treatment).
The amount of active ingredient applied depends on the time of the year, the plants to be combated and their growth stage, and varies from 0.025 to 3 kg/ha, but is preferably from 0.05 to l kg/ha.
The herbicidal action of the diphenyl ethers of the formula I is demonstrated in greenhouse experiments.
The vessels employed were plastic flowerpots having a volume of 300 cm3, and which were filled with a sandy loam containing about 1.5% humus. The seeds of the test plants were sown shallow, and separately, according to species.
or the reemergence treatment the active ingredients were applied to the surface of the soil immediately after the seeds had been sown. The compounds were emulsified or suspended in water as vehicle, and sprayed through finely distributing nozzles. The application rate was 3.0 kg of active ingredient per Hector. After the agents had been o :0 w ., 93~
- 19 - OOZE. 0050/36813 applied, the vessels were lightly sprinkler-irrigated to induce germination and growth. Transparent plastic covers were then placed on the vessels until the plants had taken root. The cover ensured uniform germination of the plants, 05 insofar as this was not impaired by the active inure dints.
For the post emergence treatment, the plants were first grown in the vessels to a height of from 3 to 15 cm, depending on growth form, before being treated. The rice lo plants were grown in a peat-enriched substrate. For this treatment, either plants which had been sown directly in the pots and grown there were selected, or plants which had been grown from seedlings and were transplanted to the pots a few days before treatment. the application rates for post emergence treatment were 0.06, 0.25 and 3.0 kg of active ingredient per Hector.
The pots were set up in the greenhouse - species from warmer areas at from 20 to 35C, and species from moderate climates at lo to 25~C. The experiments were run for 2 to 4 weeks. During this period, the plants were tended and their reactions to the various treatments assessed. The scale used for assessment was O to 100, 0 denoting no damage or normal emergence, and loo denoting non emergence or complete destruction of at least the visible plant parts.
The plants used in the experiments were ~maranthus retroflexus, Arachis hypogaea, Arena saliva, Sinatra Cygnus, Chenopodium album, Echinochloa crus-galli, Gallium apron, Ipomoea sup., Ours saliva, Synapse alga, Selenium nigrum, and Triticum aestivum.
On reemergence application, for example compounds nos. 4, 106 and 122 proved to be herbicidally effective, and selective in oats selected as an exemplary cereal.
On post emergence application of for instance 3.0 kg of active ingredient per Hector r compounds nos. 1, 2 r 3 r 4 and 5 had a strong herbicidal action on broad leaved I, I

~22~3~

unwanted plants; compounds nos. 3, 4 and Al and compound no. 13 were also effective on grasses such as barnyard-grass Compounds nos. 1 and 3 are suitable for the select live control of unwanted plants at low application rates OX such as 0~06 or 0.25 kg/ha.
In view of the numerous application methods possible, the compounds according to the invention may be used in a further large number of crops for removing unwanted wild grasses or grassy crop plants growing where they are not lo desired The following crops may be mentioned by way of example:
Botanical name Common name _ 15 Gallium cope onions Bananas comosus pineapples Arachis hypogaea peanuts (groundnuts) Asparagus of~icinalis asparagus Arena saliva oats I Beta vulgarism sup. altissima sugar beets Beta vulgarism sup. nape odder beets Camellia sinensis tea plants Carthamus tinctures safflower Carve illinoinensis pecan trees 25 Citrus lion lemons Citrus maxima grapefruits Citrus reticulate mandarins Citrus sinensis orange trees Coffee Arabic (Coffee conifer, 30 Coffee Liberia coffee plants Cucumis memo melons Cucumis sativus cucumbers Sundown dactyl on Bermuda grass in turf and lawns 35 Caucus karat carrots flats guineensis oil palms E'xagaria vesca strawberries o O
0, 21 - OOZE. 0050/36813 Botanical name Common name Gleason Max soybeans Gossypium hirsutum 05 (Gossypium arboretum cotton Gossyplum herbaceum Gossypium vitifolium) Helianthus annuls sunflowers Helianthus tuberosus Jerusalem artichoke 10 Hove brasiliensis rubber plants Hordeum vulgar barley Cumulus lapels hops Ipomoea batatas sweet potatoes Juglans Regina walnut trees 15 Lens culinaris lentils Linus usitatissimum flax Lycopersicon lycopersicum tomatoes Mauls sup. apple trees Monet esculenta cohesive 20 Medic ago saliva alfalfa (Lucerne) Month paperweight peppermint Muse sup. banana plants Nicothiana tabacum tobacco (N. rustic) 25 Olga europaea olive trees Ours saliva rice Panicum miliaceum millet Fossils lunatus lima beans Fossils mango mungbeans 30 Fossils vulgarism snap beans, green beans, dry beans Pennisetum glaucoma pearl millet Petroselinum crispum parsley Pica abides Norway spruce 35 Boyce alga fir trees Pious sup. pine trees Possum sativum English peas o o z ~93~S
- 22 - ooze. 0050/36813 Botanical name Common name .
Prunes avium cherry trees Prunes domestic plum trees 05 Prunes dualizes - almond trees Prunes Persia peach trees Pyres communist pear trees Robes Sylvester redcurrants Robes uva-crispa gooseberries 10 Rosins communist castor-oil plants Saccharum officinarum sugar cane Scale cereal rye Sesamum indicum sesame Selenium tubexosum Irish potatoes 15 Sorghum buckler (s. vulgar) sorghum Sorghum dochna forgo Spanish oilers spinach Theobroma cacao cacao plants Trifolium pretense red clover I Triticum aestivum wheat Vaccinium corymbosum blueberries Vaccinium vitis-idaea cranberries Viola Ahab tick beans Vegan sinensis TV unguiculata) cow peas 25 Votes vinier grapes Zeta may Indian corn, sweet corn, maize To increase the spectrum of action and to achieve synergistic effects, the diphenyl ethers of the formula I
may be mixed and applied together with numerous represent-natives of other herbicidal or growth regulating active ingredient groups. Examples of suitable mixture components are doziness OH 3,1-benzoxazine derivatives, benzothiadia-intones 2,6-dinitroanilines, N-phenylcarbamates, they'll-carbamates, halocarboxylic acids, treasons, amides,ureas, other diphenyl ethers, triazinones, uracils, buoyancy-Furman derivatives, cyclohexane~l,3-dione derivatives, etc.

I
Cal J

- 23 I o. z . Q050/36813 It may also be useful to apply the diphenyl ethers of the formula I, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g., agents for combating pests or footpath-05 genie fungi or bacteria. The compounds may also be mixed with solutions of mineral salts used to remedy nutritional or trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added.

I.
I;

Claims (8)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A diphenyl ether of the formula (I), where Z1 and Z2 independently of one another are each hydrogen, halogen, nitro, cyano, carboxyl, Cl-C4-alkyl, Cl-C4-haloalkyl or C1-C4-alkoxy, Z3 is halogen, nitro, cyano, Cl-C4-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy, C1-C4-haloalkoxy, Cl-C4-alkylmercapto, Cl-C4-haloalkyl-mercapto, Cl-C4-alkylsulfinyl, Cl-C4-haloalkylsulfinyl, Cl-C4-alkylsulfonyl or Cl-C4-haloalkylsulfonyl, X is hydrogen, Cl-C4-alkyl, unsubstituted or halogen-sub-stituted acyl of not more than 7 carbon atoms, an alkali metal ion or an unsubstituted or alkyl-substituted ammonium ion, R is Cl-C20-alkyl, Cl-C12 haloalkyl, an unsubstituted or halogen-substituted araliphatic radical of 7 to 20 carbon atoms, cycloalkyl of 3 to 12 carbon atoms, unsubstituted or substituted phenyl, amino, Cl-C4-alkylamino or di-Cl-C4-alkylamino, and n and m independently of one another are each °r 1 or 2.

2. A diphenyl ether of the formula I as defined in claim 1, where Z1, Z2 and Z3 are in the 2-, 4- and 6-positions and, independently of one another, are hydrogen, halogen, Cl-C4 haloalkyl or Cl-C4-halvalkyl-mercapto, X is hydrogen, C1-C4 alkyl or an alkali metal ion, R is Cl-C20-alkyl, Cl-C4-haloalkyl or phenyl which is unsubstituted or substituted by halogen, Cl-C4-alkyl, Cl-C4-alkoxy, Cl-C4-haloalkyl, nitro or cyano, n is 0, l or 2, and m is 2.

3. A diphenyl ether of the formula I as defined in claim 1, where Z1 is hydrogen, Z2 is chlorine and Z3 is trifluoromethyl.

4. A process for the manufacture of a diphenyl ether of the formula (I) as defined in claim 1, wherein:
either a sulfonyl halide of the formula :

(II) where Z1, Z2, Z3 and n have the meanings given in claim 1 and Hal is halogen, is reacted with not less than an equi-molar amount of a compound of the formula:

(III) where R and m have the meanings given in claim 1, and, if desired, the resulting compound of the formula (I) as defined in claim 1 where X is hydrogen is subsequently alkylated, acylated or neutralized to obtain a compound of the formula (I) where X has another meaning given in claim 1, or a sulfon-amide of the formula:

(IV) where Z1, Z2, Z3, X and n have the meanings given in claim 1 and Hal is halogen, is reacted with not less than an equimolar amount of a compound of the formula:

(V) where R and m have the meanings given in claim 1.

5. A process for the manufacture of diphenyl ethers of the formula (I) as defined in claim 1, where X
is hydrogen, wherein a sulfonyl halide of the formula:

(II) where Z1, Z2, Z3 and n have the meanings given in claim 1 and Hal is halogen, is reacted with not less than an equi-molar amount of a compound of the formula:

( I I I ) where R and m have the meanings given in claim 1.

6. A process for the manufacture of diphenyl ethers of the formula (I) as defined in claim 1, wherein a sulfonamide of the formula:

(IV) where Z1, Z2, Z3, X and n have the meanings given in claim 1 and Hal is halogen, is reacted with not less than an equimolar amount of a compound of the formula:

(V) where R and m have the meanings given in claim 1.

7. A herbicide containing at least one inert additive in combination with a dephenyl ether of the formula (I) as defined in claim 1, 2 or 3.

8. A process for combatting the growth of unwanted plants, wherein the unwanted plants or the area to be kept free from unwanted plant growth are treated with a herbicidally effective amount of a diphenyl ether of the formula (I) as defined in claim 1, 2 or 3.