CA1317972C - 2-nitro-5-(substituted phenoxy) benzohydroximic acid derivatives - Google Patents

Abstract

Abstract of the Disclosure A compound of the formula ... (I) in which each of X and Y represents a halogen atom, R
represents a hydrogen atom, a lower alkyl group or an agronomically acceptable soluble salt ion, R1 represents a lower alkyl group, R2 represents a hydrogen atom or a lower alkyl group, and Z represents an oxygen or sulfur atom. This compound is useful as herbicide.

Description

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This invention relates to novel 2-nitro-5-(substituted phenoxy)benzohydroximic acid derivatives having herbicidal activity, and more specifically, to compounds of the formula:
ORl R2 H3C X C=NOCHC-Z-R

y--- ~ o ~\( ~ N~2 (I) in which each of X and Y represents a halogen atom, R
represents a hydrogen atom, a lower alkyl group or an ion forming an agronomically acceptable soluble salt, Rl represents a lower alkyl group, R~ represents a hydrogen atom or a lower alkyl group, and Z represents an oxygen or sulfur atom, processes for producing these compounds; herhicides con~aining these compounds as active ingredients; and methods of contro].ling weeds by using these compounds.
The r,ovel benzohydroximic acid derivatives of formula ~I) have very superior herbicidal a~tivity a~ainst weeds, and exhibi~ their ef~ects in the pre-emergence period and in the growth period after emergence, most strongly in the growth period of weeds.

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~: B

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- la - 67566-1103 European Patent Applica~ion ~P-A-155613 discloses diphenyl ether oxime ester derivatives of the followiny general formula ~A) as herbicidally active compounds.
Rl z ( R ) n C = N-0-~2-C_Q

~0 y (A) ~.~..................... ~
~B~

, , , ;

..

, ~ :; ~ , , ~7~72 In the general formula (A), X repre~ents CH or N; Y represents a nitro group, a halogen atom, or a cyano group; Z represents an oxygen or sulfur a~om; R r2-presents a halogen atom, or a nitro, cyanoS alkyl, haloalkyl, alkylthio, haloalkylthio~ alkoxy, haloalkoxy, sulfonamide, dialkylsulfonamide, alkylsulfonyl, haloalkylsulfonyl~ alkylsulfinyl or haloalkylsulfinyl group; Rl represents a hydroyen or haloqen atom, or a cyano, alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, cyanoalkoxy, alkylthio, haloalkylthio, cyanoalkylthio, mono- or di-alkylamino, alkylthioalkyl, or mono- or di-alkylaminoalkyl groupS R2 represents a Cl-C6 alkylene group or an alkenyl group which may be substi-tuted by a haloalkyl, cyanoalkyl or hydroxyl group; n represents 1, 2 or 3; Q represent~ ~oR3 or -SR3; R3 repre~ents an alkoxyalkyl group, a thioalkyl group, a cyanoalkyl group, a cycloalkyl group, a hydroxyalkyl group, a carbalkoxyalkyl group~ an alkylthioalkyl g~oup, an aralkyl group, a sulfonamide group, a 4- to 6-membered heterocyclic group containing not more than 3 he~o atoms in the ring, or an alkyl group substitu~ed by a heterocyclic group containing not more than 3 hetero atoms.
In the de~inition of Q in formula (A~ The group R3 in ~he group -oR3 or -SR3 doe~ not include unsubstituted alkyl yroups, nor does it embrace hydrogen and a salt ion~ Clearly, therefore, formula ~A) does not encompass the compounds of the present invention re-presented by ormula (I).
~hen in formula (A3, CH is selec~ed as X and two halogen atoms and one alkyl group ~n=3) are ~elected as R, the substituted phenoxy moie~y of formula (A~ could overlap the substi~uted phenoxy moiety o~ the compound of formula ~I). EP-A-155613, bowever, totally fails to refer to the selection of su~h substituent It only describes compounds having a combination of a halogen ~3~7~'~2 atom and a trifluoromethyl group as a preferred group of compounds of formula ~A] with regard to ~he group R. ~s a specific example of ~ynthesizing these compounds, EP-A-155613 only shows the preparation of a 2-chloro-4 trifluoromethylphenoxy derivative. When an alkoxy group is selected as Rl in formula tA) in EP-A-155613, it can overlap the group -ORl in the compound of formula ~I) provided by ~his invention~ The above EP-A, howevery does not a~ all de~cribe such a selection, and ~hows only a compound of formula (A) in which Rl is a methyl group in a ~pecific example of synthe~is~ It only discloses compounds of formula ~A) in which Rl is an alkyl or haloalkyl group as a preferred geoup of compounds o~
formula (A).
Thus, although EP-~-155613 describes diphenyl ether oxime es~er derivatives of for~ula (A) which can encompass a very large number of compounds, and generally states that they have herbicidal activity, it cannot embrac~ the compounds of formula (I) in accordance with this invention and gives no disclosure which can suggest the combinations of the groups in the compounds of formula ~I~. Accordingly~ it naturally does not at all suggest the excellent herbicidal activity of the com-pounds o~ formula ~I).
Use of herbicides is essential to the protec-tion of imp~r~ant crops includin~ corn, soybean, wheat, rice, cotton, beet~ rapeseed and sunflower from weeds and to increa~e the amount of crop harve~t. The herbicides are desirably those of the foliage-con~acting type which can be applied after emergence according to the type and amount of weeds to be controlled and in reduced dosages in contrast to those of the soil-treating type which are applied before emergence~
The foliage-treating type herbicide~ are re-quired to have very high sel~c ivity because they al80 make contact with crops~ Thus~ very few foliage~treating :: :

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type herbicides have been developed although many herbi~
cides of the soil-treating type have been synthesized.
Foliage-treating type herbicides now used in soybean farms include, for exa~ple, 3-isopropyl~

2,1,3-benzothiadiazin~4)-3H-one~2,2-aioxide ~bentazone~
which is of the diazine type and sodium 5-~2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate (acifluorfen sodium) which is of the diphenyl ether type. The~e herbicides, however, have not proved to be entirely satisfactory in herbicidal activity and herbicidal spectrum, and it has been desired to develop more effective foliage-treati~g type herbicides.
Examples of foliage-~reating type herbicides used in rapeseed farms are 3,~-dichloropicolic acid (clopyra~id) of the pyridine t~pe, and 4-chloro-2-oxobenzothiazolin-3-ylacetic acid (benazolin) of the benzothiazoline-typeO The herbicidal activities and herbicidal spectra of the~e co~pounds are ~ot satis-factoryO There is no foliage-treating typ~ daphenyl ether herbicide ~hich has a high lev~l of selectivi~y or rapeseed and p~actical utility~ -The present inventors made extensive invest~-gations in order to develop diphenyl ether-type herbi-cides which would overcome the aforesaid technical problems of diphenyl ether-type herbicides of the foliage-treating type, be applicable at reduced ra es of application, and have a broad herbicidal spectrum and good selectivity in post-emergence application to u~eful crops.
These inves~igations have led to the discovery that novel herbicidally active compounds of formula (I) given above can be synthesized,o that these compounds can overcome the technical problems of the prior art and sho~s a broad range o~ herbicidal activity and excellent selec-tive herbici~al activity in reduced dosage; and that these herbicidal compounds can eæhibit their excellent .
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characteristics in, for example, soil treatmen$ and folia~ treatment, particularly the latter.
It is an object of this invention therefore to provide 2 nitro-5-(substituted phenoxy)benzohydroximic acid derivatives of formula (I) given above.
Another object of this invention is to provide processes for producing the compounds of formula ~I).
S~ill another object of this inventisn is to pro~ide a herbicide comprising a compound of formula ~I) as an active ingredient.
The diphenyl ether derivatives of formula (I) provided by this invention are novel compounds not de-scribed in the literature. They are characterized in that the hydroximic acid moiety specified in formula 5I) which is different from that in the known compounds is attached to the ni~ro group-containing phenyl ring ~to be ometimes referred to as the B ring) of ~he diphenyl ether ~erivatives of formula (I) at a position ortho to the nitro group. A further characteri~tic i~ tha~ two halogen atoms (X, Y) are bonded to both methyl group of ~he methyl group containing phenyl rihng ~o be sometimes referred to as ~he A ring) in the ~ ether deriva-tive. This struc ural characteristic is believed ~o con~ribute to the excellent herbicidal activity of the diphenyl ether derivatives of formula ~I).
The compounds of formula ~I) provided by this invention have excellent characteristics th~t canno~ be expected from the prior art. They have selectivity for useful crops including rice~ corn, wheat, barley9 3~ sorghum, rapeseed, and soybean and a broad herbicidal spectrum and can exhibit their herbicidal activity sufficiently in very low dosage as compared wi~h ordinary herbicides~
The term ~lower~, used in the present specifi-cation and the appended claims to qualify a group or acompound, means that the group or compound so qualified ~-.
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~7~72 6 67566~1103 has not more than 6 carbon atoms, preferably not ~ore than 4 carbon atoms.
In the definition~ of the ~ubsti~uents in formula (I~, the ~lower alkyl" may be llnear or branched, and includes, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, n-pentyl, sec-pentyl and n-hexyl.
The ~halogen atom~ includes Eluorine, chlorine, bromine and iodine atoms, and chlorine is preferred.
The "ion f~rming an agronomically acceptable soluble salt may be an ion of any of salts of inorganic and organic bases conventional in the field of agricultural chemicals.
. In the compound~ of formula (I) provided by this invention, X and Y are p~eferably chlor~ne, R i9 preferably methyl, and R2 is preferably hydrogen. R is preferably ~ethyl.
~mong the compounds given in Table 1 herein-below, cQmpounds Nos. l and ~ ar~ preferred, and compound No. l i~ e~pecially preferred~ .
The compounds of formula ~I) have one A~ymmetric carbon atom and may exl6t ln a levorotatory, dextr~-rotatory oe racemlc form. The co~npound~ of formula ~I
include two stereolsomers (~yn-form and anti-for~) of formulae ~I-a) and ~I-b). It should be understood that the ~ormula ~I1 includes both o~ thes~ stereoisomer~

R2 o I
R 0 o~CII-C-Z-~
~l3C X CnN
Y ~ ~ N2 ~I-a) (syn-form) B
... . . . , .. , , 1.. . .

.

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~lo\
tl3C ~ X C8N ~O CH-C~Z-R
Y ~ ~ NO2 ~2 O (I-b) ~anti-form) Hardly any difference is seen in herbicidal activ~ty between the two stereo~somers, but generally syn-form stereoi~omer6 are believed to be preferred.
The compoun~s of formula ~I) may be produced, for example, by the route shown by the following reaction scheme A~
Reaction Scheme A

O R
rl ~
l~3C~ X ~ -N~IOCHC-Z~R
Y ~ ~ 2 + Rl-X' or C~N~
(III ~III) oRl ~2 base~ H3C ~ ~ -NOCHC-Z R
Y~)-O~N02 tI) In the ~ormulae, X, y, ~ l and R2 ~re the 6ame au de~lned abovel and X' repre~ent6 an acld residue such as halogen or the group -OSO2R' ~in which R' representfi a ~ub~tituted or unsubstitu~ed alkyl group7 a phenyl group, or an alkoxy group, preferably methyl ~ub~tltuted methyl or methoxy~.
Acaording to the above proce~sr the compound of formula tI) in accordance w~th this invention can be prepared by reacting the compound of formula ~ with the compound of Eormula t~ in a ~uitable organic i~.

' L 3 ,~ r~ ~ ~i 2 solvent in the presence of a base. This reaction is generally carried out under ice cooling or at a tempera-ture up to the refluxing temperature of the reaction mixture, preferably a~ room temperature to a temperature of about 80 C. The amount of the compound of formula lII~) used relative to the compound of formula (II) is no~ critical and can be varied widely. Generally, the suitable amount of the compound of formula (III) is 1 to 3 moles, preferably 1 to 2 moles~ per mole of the com-pound of formula (II~. Conveniently~ the base is used inan amount of usually 1 to 3 equivalents, preferably 1 to 2 equivalents, per mole of the co~pound of formula (II)~
Examples of the solvent used in the above reaction include alcohol~ such as methanol and ethanol, aromatic hydrocarbons such as benzene and toluene, acetone, acetonitrile9 dimethylformamide and dimethyl sulfoxide. Mixtures of these solvents with water may al~o be used.
Examples of the base used in ~he above reaction include ~er iary amines le.gO, pyrid~ne and triethyl-amine), sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate~ sodium ethylate and sodium hydride.
If diazome~hane i5 u~ed as the compound of formula tII), the use of the base may be omitted.
The reaction may be carried out in a two-layer sys~em. This reaction can be carried out by using a phase-transfer catalyst in an amount of~ for example~ 1 to 50 ~, preferably 5 to 30 % by weightJ ba~ed on the compound of formula ~II). Examples of the ph~se transfer catalyst are quaternary ammonium salts such as tetra-methyl ammonium bromide, tetrabutyl ammonium bromide and benzyl tributyl ammonium bromide and quaternary pho~-phonium salts sush as tetraphenyl phosphonium bromid~.
The compound of formula ~ used as a starting material in the above process ran be producedr for ~3~7~2 _ 9 _ example, by the following reaction in which the symbols are as deined above.

C X COH ll SO~12, etc. ~ C X C-N~OCHC-Z-R
3 ~ ~ 2 ) El NOCIICZR ~ 3 ~ ,~( n Y~}NO 2 2 1 2 Y~O~No2 R

(IV) (II) According to this method, 2-nitro-5-(substituted phenoxy)benzoic acid derivative (IV) is converted to an acid chloride with, for example~ thionyl chloride, and then reacted with an O-substituted hydroxylamine in ~he presence of a base in an organic solvent in a customary manner to give ~he hydroxamic acid derivative ~II).
In the reaction, the amount of thionyl chloride used may be varied properly, and is, for example, l ~o 10 equivalen~s per~equivalent o~ the Gompound of formula ~IV~. The reaction temperature can be properly ~elected, and may be, for example, room temperature to ~0 C~ In the reaction o the acid chloride with the O-~ubstitu~ed hydroxylamine, the amount of the O-substi~uted hydroxyl-amine may be properly varied~ and i~, for exampl~, 1 to 3 equivalen~s. The rea~ion temperature in this reaction may be, for example, under ice cooling to 100 C~
Examples of the organic solvent used include aromatic hydrocarbons ~uch as benzene and toluene; ethers such as tetrahydrofuran and dioxane; acetone; ace~o-nitrile; dimethylformamide; and dimethyl sulfoxideO A
mixture of the organic solvent with water may also be used. Examples of the base are pyridiner triethylaminel sodium carbonate, potassium carbonate and sodium hydrogen carbonate.
In the reaction scheme A above, the compound of formula ~I) may be isolated and purified by pouring the reaction ~ixture after the reaction into water and trea~-ing it by a conventional method, for example, extraction .
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13~7~'~2 with an organic solvent, recrystallization or column chromatography.
The following examples specifically illustrate the compound (I) of the invention and a startin~ material for it.

Synthesis of methoxycarbonylmethyl 5-(2,4-di-chloro-3-methylphenoxy)-2~nitrobenzohydraxamate (starting material):-34.2 g (0.10 mole) of 5-(2,4-dichloro-3-methyl-phenoxy)-2-nitrobenzoic acid was dissolved in 50 ml of thionyl chlorlde and the solution was heated under reflux for 1.5 hours. The excess of thionyl chloride was evaporated to give an acid chloride.
A solution of the acid chloride in 150 ml of a 1:1 mixture of ether and tetrahydrofuran was added dropwise to a solution of 10.5 g (0.1 mole) of methyl a~inoxyacetate and 10.1 g (0.1 mole) of triethylamine in 300 ml of dry ether under ice cooling with stirring over the course of about 20 mlnutes. Then, the mlxture was stirred for 30 minukes under ice cooling and for 1.5 hours at room temperature. The reaction mixture was poured into 300 ml of ice water and extracted with 200 ml of ethyl acetate three times. The extracts were wa~hed with a saturated aqueous solution of sodium chloride and dried over magnesium sulfate. The desiccan~ was separated by filtration, and ~he solYent was evaporated. The resulting solid was recrystalllzed from toluene to give 28.6 g (yield 66.5%) of methoxycarbonyl-methyl 5-(2,4-dichloro-3-methylphenoxy)-2-nitro-benzohydroxamate.

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- lOa - 67566-1103 Production of methyl O-methoxycarbonylmethyl-5-(2,4-dichloro-3-methylphenoxy)-2-nitrobenzo-hydroxlmate (compound No. 1):-A suspension in 15 ml of dimethylformamide of 2.15 g (5millimoles) of methoxycarbonylmethyl 5-(2,4-dichloro-3-methylphenoxy)2-nitrobenzohydroxamate and .

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1.10 g ~8 millimoles~ of anhydrous potassium carbonate was heated to 65 to 67 Cr and 1.1 g ~6 millimoles) of methyl p-toluenesulfonate was added dropwise over about 15 minutes. The mixture was then stirred at the same temperature for 1 hour. The reaction mixture was poured into about 150 ml of ice water~ and extracted with 30 ml of ethyl acetate twice~ The organic layers were washed with a saturated aqueous solution of sodium chloride and dried over magnesium sulfate. The desiccan~ was separated by filtration, and the solYent was evaporatedO The resulting oily substance wa~ purified by column chromato-graphy tsilica gei; n-he~aneJe~hyl acetate~3/1) to give 630 mg (yield 28.5 ~) of the desired compound No. 1. It had a melting point of 106.5 to 107~0 C.
Table 1 below shows diphenyl ether derivatives of the invention synthesized by a similar method as in Example 2.

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Table 1 ORl R2 H3C~_~X ,~C=NOCHC-Z-R
Y~O~-N02 No. X Y lRl R2 z R Physical property values Cl Cl Me H O Mem.p. 106.5~107.0~C (syn3 90.,5-93.0C tanti~
2 Cl Cl Me H O 3:t 3 Cl Cl Me H O i-Pr 4 Cl C:l Me H O n-Pr S Cl Cl Me H O n-Bu 6 Cl Cl Me H O t-Bu 7 Cl Cl Me H O H m.p~, 158 ~,0-160 .0C
8 Cl Cl Me H S Me mOp~5.5-128.0C
9 Cl Cl Me H S Et 10 Cl C:l Ne H S i-Pr 11 Cl Cl Me H S n-Pr 12 Cl Cl Me H S n-E~u 13 Cl Cl Me H S H
14 Cl Cl Me H O Na m~tp. 164 .0-166 .0 ~C

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, ~317~72 Since the compounds of this invention represented by formula (I~ have very high herbicidal activity, they show a very high herbicidal efficacy in low dosage. They also have good selectivity for cultivated crops~ and are agriculturally useful.
The compounds of this invention can control various weeds occurring in paddies and upland f arms in the preemergence period to the growth period after emergence. For example, they can control narrow-leaved and broad-leaved weeds in paddies such as barnyardgrass ~Echinochloa crus-galli, umbrella plant (Cyperus _ difformis)~ monochoria ~Monochoria aginalis), false pimpernel (Lindernia pyxidaria), waterwort (Elatine triandra), "kikashigusa~ (~otala indica), bulrush (Scirpus juncoides), and spikerush (Eleocharis acicularis), and narrow-leaved and broad-leaved weeds in upland farms such as crabgrass (~igitaria an~uinalis), giant foxtail ~Setaria faberi~, goosegrass ~~leusine in ~ ricegrass paspalum (PasPal-um orbiculare), water 2~ foxtail ~Alopscurus aequalis), common chickwe~d ~Stellaria media), various species of Polygonum, various species of Amaranthus, velve leaf ~Abutilon theophrasti), lambs~uarters SCheno~ium album), prickly sida ~Sida spinosa), cocklebur (Xanthium trumarium~, ragweed Ambrosia artemisiifolia~ purse (Capsella bursa-pastoris), flexuous bittercress (Cardamine flexuosa), common blackjack ~Bidens pilosa), cleavers ~Galium aparine) and wild buckwheat (Polygonum .. . .
convolvulus~ The compounds of ~his inven~ion may be used in orchards, mulberry fields and non-agricultural lands.
The compounds of this invention show particularly strong herbicidal activity against broad-leaved weeds growin~ in upland farmsO For example, by foliar treatment in upland farms, they show an excellent herbicidal efficacy agains~ such weeds as green 7 ~ 7 ~

amaranth ~Amaranthus viridi~, common purslane ~Portulaca oleracea), cocklebur, common blackjack, ragweed, .
burcucumber tSicyos an~ulatus), fig-leaved goosefoot (Chenopodium ficifolium)~ lambsquarters, smartweed (Polygonum lapathifolium), common chickweed, shepherd's purse, mouseear chickweed (Cerastium vulgatum), jimsonweed ~Datura stramonium), hemp sesbania ~Sesbania exaltata), sicklepod (Cassia tora), tall morningglory (Ipomoea purpurea)~ black nightshade ~Solanum nl ~, bullnettle (Solanum carolinense~, henbit (Lamium amplexicaule), plaintain (Plantago major~, velvetleaf, prickly sida, creeping woodsorrel (Oxalis corn_culata), cleavers, wild buckwheat, speadwell (Veronica persica) and poppy tPaPaver rhoeas). The compounds of this invention furthermore have selectivity ~or cul~ivated plants, and do not substantially cause significant phy~otoxicity to gramineous crops such as rice, corn, wheat, barley, sorghum and sugarcane, and broad-leaved crops such as soybean, rapeseed and sunflowerO
For use as herbicldes, the compounds of this invention may be mixed with agriculturally and horti-culturally acceptable carriers or diluents, addi~ives and adjuvants by know~ techniques and formulated into various forms normally used as agricultural chemicals, for ex-ample, a dust~ granules, a wettable powder, an emulsifi-able concentrate, a soluble powder, a sol, etc. They may be used in admixture or combination with other agricul-tural chemicals, such as ungicides, insecticides, miticides, other herbicides, plant growth regulating agents, fertilizers, and soil conditioners.
The combined use with another berbicide enables the dosage o~ the herbicide of this invention to be decreased and permits labor saving. Moreover, the cooperative action of the ~wo chemicals broadens the herbicidal spectrum and the synergistic action of bo~h can be expe~ted to give a higher efficacy.

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The carrier or diluent may be any solid or liquid carriers or diluents generally used in the ~ield of agriculture. Solid carriers include talc or clays typified by kaolinite, montmorillonite and attapulgite;
inorganic materials such as mica, pyrophyllite, pumice, vermicullite, gypsum, calcium carbonate, dolomite, diatomaceous earth, magnesium lime, apa~ite, zeolite, silicic anhydride and synthetic c~lcium silicate; organic substances of the plant origin such as soybean meal, tobacco powder, walnut powder, wheat flour, wood powderv &tarch and crystalline cellulose; natural or synthetic polymeric compounds such as coumarone resins, pe~roleum resins~ alkyd resins, polyvinyl chloride, polyalkylene glycols, ketone resins, ester gum, copal gum and dammar ~S gum; waxes such as carnauba wax and beeswax; and urea~
Suitable liquid carriers or diluents include paraffinic or naphthenic hydrocarbons such as kerosenef mineral oils~ ~pindle oil and white oil; àromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene~ cumene and me~hylnaphthalene; chlorina~ed hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene, monochlorobenzene and o-chlorotoluene; ethers such as dioxane and ~etrahydrofuran7 ketones such a~ acetone, methyl ethyl ketone, diisobutyl ke one, cyclobexanone, acetophenone and isophorone; esters such as ethyl acetate, amyl acetate~ ethylene glycol acetate, diethylene glycol acetate9 di~utyl maleate and diethyl succinate; alcohols such as methanol, n-hexanol~ ethylene glycol, diethylene glycol, cyclo~exanol and benzyl alcohol ether alcohols such as ethylene glycol ethyl ether~ ethylene glycol phenyl ether, diethylene glycol ethyl ether and diethylene glycol butyl ether; polae solvents such as dimethyl formamide and dimethyl sulfoxide; and waterO
Surface-active a~ents and other adjuvants may be used to emulsify, disperse, wet, spread or bind the ~ ~ ~L 7 ~ r~ 2 compound of this invention, adjust its disintegrability~
stabilize the active ingredients of the herbicide, improve the flowability of the herbicide, prevent corrosion, or otherwise. The surface-active agents may be nonionic, anionic, cationic and amphotericO Usually, nonionic and anionic sur~ace-active agents are suitableO
Suitable nonionioc surface-ac~ive a~ents include, for example, polyaddition products of ethylene oxide with higher alcohols such as lauryl alcohol, stearyl alcohol and oleyl alcohol; polyaddition products of ethylene oxide with alkylphenols such as iso-octylphenol and nonylphenol; polyaddition products of ethylene oxides with alkylnaphthols such as butylnaphthol and octylnaphthol; polyaddition products of ethylene oxide with higher ~atty acids such as palmi~ic acid, stearic acid and oleic acid; polyaddition products o~ ethylene oxide with mono- or di-alkylphosphoric acids such as stearylphosphoric acid and dilaurylphosphoric acid~
polyaddition products of ethylene oxîde with ~mlne compounds such as dodecylamine and stearamide: higher fatty acid esters of polyhydric alcohols such as sorbitan, and polyaddition products of ethylene oxide with these esters; and a polyaddition product o~ ethylene oxide with propylene oxide. 5uitable anionic surface-active agents include, for example, alkylsulfuric ester salts such as sodium laurylsulfate and oleyl sulfate amine salt; alkylsulfonic acid salts such as sodium 2-ethylhexenesulfonate9 and arylsulfonic acid salts such as sodium isopropylnaphthale~e~ulfonate, 3~ sodium methylenebisnaphthalenesulfonate, sodium ligninesulfonate and sodium dodecylbenzenesulfonate, To improve the properties of the formulated herbicide and increase its herbicidal effioacy, the compound of the invention may also be used in combination with other adjuvants including such polymeric compounds as casein, gelatin, albumin~ glue, sodium alginater . ' ' carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose and polyvinyl alcohol.
The above carriers or diluents and various adjuvants may be used singly or in suitable combinations depending upon the form of the formulated herbicide, the place and time of application, etc.
The proportion of the compound of the invention as an active ingredien in the formulated herbicide may be varied with the form of the herbicide. For example~
it is usually from 0.1 to 99 ~ by weight, preferably from 1 to 80 % by weight.
The dust usually contains 1 to 25 ~ by weight of the active ingeedient and the remainder being a solid carrier.
The wettable powder usually contains 25 to 90 4 by weight of the active ingredient and the remainder being a solid carrier and a dispersing and wet~ing agent and optionally a protective colloid, a thixotropic agent, a defoamer~ etc.
The granules usually contain 1 ~o 35 % by weight of ~he active ingredient and the remainder being mostly a ~olid carrier. The active ingredient is uniformly mixed with the solid carrier, or uniformly fixed to, or adsorbed on, the surface of the solid carrier. The granules have a particle diameter of about 0.2 to 1~5 ~m~
The emulsifiable concentrate usually contains 1 to 30 % by weight of the active ingredient~ about 5 to 20 ~ by weight of an emulsifier and the remainder being a liquid carrier and optionally a corrosion inhibitor.
The compound of formula ~I) provided by this invention may be applied directly as a herbicide or in any desired form such as the formula~ions described above~
The herbicide of this invention can be applied to variou~ weeds occurring in paddies and upland farms in a preemergence period or in a growth period after ~3~7~

emergence, preferably to weeds in a growth period~
Application ~o upland farms is especially suitable.
In controlling weeds by usin~ the compounds of this invention, a herbicidally effective amount of the compound of this invention may be applied to the soil in the locus where weeds before emergence are desired to be controlled, or directly ~o weeds after emergence.
The rate of applica~ion can be low because the compounds of this invention have very high herbicidal activity~ It may be properly varied with the type of weeds to be controlled, the stage of growth, the place of application, the time of application, weather~ etc.
Generally, the rate of application is about 0.01 to 10,000 g, preferably about Ool to 5,000 9, per hectare as 1~ the amount of the compound o~ general formula (I) ~the amount of the acti~e ingredient). ~lore preferably, it i~
about 50 to 2,000 g/ha before emergence (soil t~eatment), and about 1 to 100 g/ha after em~:rgenc~ (foliar treatment).
~ he following Formulation Example~ show some example~ of formulating the compound o~ this inv~ntion.
All part~ herein are by weightO
FORMU~ATION EXAMPLE 1 Granules:
~n~redient Part~
Compound of formula (I~ ~e.g., 5 compound No. 1~
Bentonite 50 T~lc 4 o Sodium dodecylbenzenesulfonate 2 Sodium ligninsulfona~e 2 Polyoxyethylene alkyl aryl ether The above ingredien~s were ~horoughly mixed, and a suitable amount of wa~er was then added. The mixture was kneaded and granulated by a granulator to give 100 parts of granulesO

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-- 19 -- , We~table powder:-Ingredient Parts Compound of formula ~I~ 20 ~e.g., compound No. 1) Clay 70 White carbon 5 Sodium ligninsulfonate 3 Sodium dodecylbenæenesulfonate2 The above ingredients were mixed and kneaded and pulveri~ed uniformly by a kneader to give 100 parts of a wettable powder~

Emulsifiable concentrate:-Ingredient Parts Compound of formula II) 20 (e~gO, compound No. 1~
Cyclohexanone 70 Calcium dodecylbenzenesulfonate 5 Polyoxyethylene alkyl aryl ether 5 The above ingredients were uniformly ~ixed and.
dissol~ed to form 100 parts of an emulsifiable concentrate.

Plowable composition:-In~edient Parts Compound No~ 1 20 Polyoxyethylene alkylaryl e~her 2 Cal~ium dodecylbenzenesulfonate 3 3o Silicone-type defoamer 0.2 prQpylene glycol 8 2% Aqueous solution of guar gum 12 Water (remainder) 5408 `~ The above ingredient~ were mixed and pulverized uniformly.for several h by a wet-type pulverizer to give 100 parts of a flowable composition.

-~3~72 Other forms of the formulation of the compound of this invention could be prepared substantially in accordance with the above ~ormulation Examples.
The following Test Examples demonstrate the excell~nt herbicidal activity of the compounds of formula SI) provided by this inventionO

Foliar treatment:-Upland farm soil was filled in square pots ~30 x 30 x ~ cm). Seeds of various crops and weeds indicatedin Table 2 were sown each in fixed amounts, and grown in a greenhouse until the plants grew to the 1.5- to 3-leaf stage ~18th day after sowing~.
Each of the test compounds was dis~olved in a lS mixture of acetone and water ~1:1) containing 0.2 ~ of Tween 20 and applied uniformly ~o ~he foliage of the plants at each of th~ rates o~ application shown in Table 2.
Twenty-one days after the application, the herbicidal efficacy on the weeds and the degree of phytotoxicity to the crops were evaluated on the follow~
ing standards~ and the results are shown in Table 2.
Ra~ing S~andards ~11 rates~
.
Herbicidal efficacy ~hytotoxicity to Sherbi~idal rate, %, crops tphytotoxicity based on a non- rateO %~ based on a Rating treated area) non-treated area) ~ . .
0 0 Same as left 1 over 0 to 10 2 over 10 to 20 3 over 20 to 30 4 over 30 to 40 over 40 to 50 6 over S0 to 60 7 over 60 to 70 8 over 70 to 80 9 over 80 to 90 over 90 to 100 ~withered) - :.- ' . , . , ' , ~, ' :

- ' , - : , .

317~72 Note to Table 2 a in the column of ~Compound No.~ represents sodium 5-~2'-chloro-4'-trifluoromethylphenoxy~-2-nitro-ben~oate~
b in the column of "Ccmpound No.~ repre ents methyl 5-(2'ochloro-4'-tri~luoromethylphenoxy)-2~nitro-acetophensrleoxime-O-acetate.
The alphabets in the colum~s of ~Herbicidal efficacy" and ~Phy~otoxicity to crops~ represent the following weeds and crops.
A: crabgrass B: green amaranth C: velvetleaf D: jimsonweed E: ~all morningglory F: cocklebur G: corn ~: wheat I: rice--.
J: soybean K: rapeseed ~3~ 7~2 '~able 2 Amount Herbicidal Phytotoxicity Co~pourld of the efficacy to crop No~ active ingredient (g/ha) A B C D E F G H I J K
_ 1 90 6 1010 1~ 10 îO O 0 1 0 0 _ 7 90 6 1010 1~ 1~10 O ~ 1 Q O

14 90 8 1010 10 1010 ~ O 1 0 0 1010 10 lû 1~ O O O O O
. _ 8 101~ 10 1010 ~ 1 1 0 9 . .
8 1010 10 10 7 û O O O O
. . , _ . _ C~arison 300 8 1010 10 10 10 5 3 2 2 10 _ _ 6 1010 N 9 7 1 2 1 0 10 Comparison 90 8 10 ïO 10 10 10 3 6 6 8 10 b 30 S 1010 10 10 7 U 3 3 2 10 __ No~treated O O O O O O

.

~: :

Claims (11)

1. A compound of the formula:

(I) (in which each of X and Y represents a halogen atom, R represents a hydrogen atom, a lower alkyl group or an ion forming an agronomically acceptable soluble salt, R1 represents a lower alkyl group, R2 represents a hydrogen atom or a lower alkyl group, and Z
represents an oxygen or sulfur atom).

2. The compound of claim 1, in which both X and Y are a chlorine atom.

3. The compound of claim 1, in which R1 is a methyl group and R2 is a hydrogen atom.

4. The compound of claim 1, in which R is a methyl group.

5. The compound of claim 1, which is in a syn form.

6. Methyl O-methoxycarbonylmethyl-5-(2,4-dichloro-3-methylphenoxy)-2-nitrobenzohydroximate.

7. A process for producing the compound of formula (I) set forth in claim 1, which comprises reacting a compound of the formula:

(II) (wherein X, Y, Z, R and R2 are defined as in claim 1), with (i) a compound of the formula:

(wherein X1 represents an acid residue, and R1 is as defined in claim 1), to form the compound of formula (I) or (ii) diazomethane, to form a compound of the formula (I) in which R1 is methyl.

8. The process of claim 7, wherein each reaction is conducted in a reaction-inert organic solvent in the presence of a base, except that the base may be omitted when diazomethane is employed.

9. A herbicidal composition comprising a herbicidally effective amount of the compound as defined in claim 1, 2, 3, 4, 5 or 6, and an agriculturally and horticulturally acceptable carrier or diluent.

10. A method of controlling weeds which comprises applying a herbicidally effective amount of the compound as defined in claim 1, 2, 3, 4, 5 or 6, to the locus where the weeds are to be controlled, or to the weeds to be controlled.

11. Use of the compound as defined in claim 1, 2, 3, 4, 5, or 6, as a herbicide.