JPS601156A - Substituted diphenyl ether compound, manufacture and herbicidal composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

The present invention relates to substituted diphenyl ether compounds useful as herbicides, methods for producing them, and herbicidal compositions and weeding methods using them. A number of substituted diphenyl ether compounds have been proposed for use as herbicides. An early example of the many publications containing such proposals is British Patent No. 974475.
No. 3,784, and a recent example is U.S. Pat.
No. 635, No. 3979437, No. 3928416
and European Patent Application Publication No. 20052, European Patent Application No. 231
Specifications include No. 00, No. 40898, No. 662.17, and No. 70990. According to the invention, a diphenyl ether compound represented by the following formula (11) is provided.
(α1, +61, (cl or (d+). (α) group Z R”, where Z is an oxygen atom or a sulfur atom, and 7 An aliphatic group having a fundamental sound is an alicyclic group (for example, an aliphatic group having 1 to 6 carbon atoms)
an aliphatic or alicyclic group); the substituent is a halogen atom dinitro group; a hydroxy group: cF; an alkoxy group (for example with 1 to 4 carbon atoms); an alkylthio group, an alkylsulfinyl group. groups or L alkylsulfonyl groups (e.g. each alkyl group has 1 to 4 carbon atoms);
Phenyl group; Heterocyclic group (e.g. carrying 5 or 6 ring atoms): Group -Nlt'R2 as defined below; Cyano group; Carboxy group or a salt thereof; Alkoxycarbonyl group (e.g. 2-5 ); group -CONR'
lt" (where -1sIR'R" is as defined below); formyl group; alkanoyl group (e.g. 2-
or a 1-virazolyl group optionally substituted with one or more nitrogen atoms, a methyl group, a methoxy group or a methylthio group, 1-
imidazolyl group, 1-(i.2.4-triazolyl) group or 2-(1,2゜3-triazolylne group. 1b1 group -NR'R2, where 11!1 is a hydrogen atom,
A substituted or unsubstituted aliphatic group or alicyclic group (for example, an aliphatic group having 1 to 6 carbon atoms or an alicyclic group having 3 to 6 carbon atoms) or a substituted or unsubstituted phenyl group, and R2 is a hydroxy group in addition to the group defined by R1;
Alkoxy group having 1 to 4 carbon atoms; Alkoxy group having 1 to 4 carbon atoms substituted with a phenyl group or substituted with a carboxyl group or a salt, ester or amide thereof; An amine group or a mono- or di- a dialkylamine group (here, the alkyl group represents, for example, an alkoxy group having 1 to 4 carbon atoms substituted with J having 1 to 4 carbon atoms, and the 1-carbon group -NR'R2 is substituted with a methyl group); Pyrrolidine, piperidine, which may be a morpholine ring; a succinimide group, or Q, a phthalimide group; or a group of the following formula). lcl group -A/S'S2, where 81 is a hydrogen atom, an alkyl group (e.g. C, -C, alkyl group), an agriculturally acceptable cation, or a chlorine, bromine or iodine atom, R2 is the group -coss, where R3
is a substituted or unsubstituted aliphatic or alicyclic group (e.g. having 1 to 6 carbon atoms), or a substituted or unsubstituted phenyl group, and BIB is independently a hydrogen atom,
CI'-C4 is an alkyl group or a phenyl group, n is 1.2 or 3, and R5 is a CN group or a group -
CON86S7, where 86 and S7 are each a hydrogen atom, a substituted or unsubstituted aliphatic group, 1 is an alicyclic group (e.g. having 1 to 6 carbon atoms), or a substituted or unsubstituted aliphatic group. is a phenyl group, and R5 is a group -<, o
s8, where 88 is a hydrogen atom, an agriculturally acceptable cation, a substituted or unsubstituted aliphatic or cycloaliphatic group (e.g. having 1 to 6 carbon atoms), or a substituted or unsubstituted It has a phenyl group. (dl Substituted 1 or unsubstituted phenoxy group or phenylthio group, 2-sulforadioxy group, or group -0N
= CR'R5, where R4 is an aqueous atom, a halogen atom, an alkyl group, a monocyclic aryl group, a Cl-06 alkoxy group, a C1-c6 alkylthio group, or a dialkylamino group, and 11 is substituted 1 or Unsubstituted alkyl group, trifluoromethyl group, cyano group, carboxy group, substituted or unsubstituted alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylthio group, aminocarbonyl group, monomial arylcarbonyl group, monocyclic aryloxy group, or a carboxy group or an agriculturally acceptable amide, ester, or salt of said carboxy group, where R'' and R2 are joined together to form a term containing 4 to 8 nuclear carbon atoms. In the above definition, the term halogen includes fluorine, chlorine, bromine and iodine atoms. The term aliphatic includes straight-chain or branched alkyl, alkenyl and alkynyl groups; It also includes an alkyl group with an alicyclic group as an it substituent, with one or more double or triple bonds.
It also encapsulates groups consisting of alkenyl or alkynyl groups. The term cycloaliphatic group includes, for example, cycloalkyl groups such as cyclopropyl and cyclohexyl groups. R'
-5 or R2 is an aliphatic group or an alicyclic group,
Possible substituents thereof include, for example, a halogen atom: a hydroxy group; an alkoxy group (eg C1 to C+): a carboxy group or a salt thereof, an ester or an amide; a cyano group: a phenyl group; This includes 1 heterocyclic group. When R is a phenoxy group, or when R' or R2 is a phenyl group or a heterocyclic group, examples of possible substituents include when R1 or R2 is an aliphatic or alicyclic group: Substituents listed above and further alkyl groups (e.g. C1-C4), nitro a, CF
x groups, alkylthio groups, alkylsulfinyl groups and alkylsulfonyl groups (each alkyl MU having from 1 to 4 carbon atoms). When R3, R6, S7 or R8 is an aliphatic group,
It can be, for example, a straight-chain or branched alkyl, alkenyl or alkynyl group with 1 to 6 carbon atoms. When s R, s 6, S7 or S8 is an alicyclic group, it contains for example 3 to 6 carbon atoms and is a cyclohexyl group. S3, S", S"-! or S8 is an aliphatic group, examples of substituents that may be present on that group are halogen atoms (i.e. fluorine, chlorine, bromine or iodine atoms),
Hydroxy group, alkoxy group (e.g. Ct” to 4
) and phenyl group. S3, S6, S7 or S
When 8 is a phenyl group, examples of substituents that may be present on that group are a nitro group, a cyano group, a methyl group, a CF3 group, an alkoxy group (for example, numbers C1 to C), a hydroxy group and a halogen atom. Where the above definition refers to a salt, ester or amide of a carboxy group, the salt may contain agriculturally acceptable cations such as alkali metal cations, alkaline earth metal cations, ammonium cations or substituted ammonium cations (e.g. sodium, potassium Substituted ammonium cations composed of , lithium, calcium or magnesium thio/one are for example substituted ammonium cations in which 1, 2, 3 or 4 hydrogen atoms of the ammonium cation are substituted, for example by one or more hydroxy or phenyl groups. The esters of the above carboxy groups include esters formed from aliphatic and alicyclic alcohols.Amides include ammonia or monoalkyl Reeds include those formed from dialkylamines, each alkyl group having from 1 to 6 carbon atoms. Compounds falling within the scope of this invention are illustrated in Table 1 below. Table 1 In cases where compounds falling within the scope of formula (11) above may exist in optically isomeric forms, the present invention provides for the separation of the D and L forms of the compound, as well as all forms of the D and L forms. When normally produced by chemical synthesis, such optically isomerized adducts would usually be obtained as an iso-compound (i.e., a racemic mixture) of the L and L forms. The compounds of the present invention can be prepared by a conventional method, such as the method shown in Scheme A of F. Scheme A In scheme AVc, I and X have the meanings defined above. The carboxylic acid [(Ill) is a known adduct. The other reactant RH is also generally a known compound, or if itself new, can be prepared using known methods for preparing similar known compounds. In the scheme AI/CL, the carboxylic acid (2)) reacts with thionyl chloride to give the platelet tllll+. The reaction usually involves heating the carboxylic acid (2) with excess thionyl chloride under reflux. The reaction is carried out by removing the excess thionyl chloride under reduced pressure once the reaction is complete. wherein one reacts with compound R11, preferably in the presence of an acid acceptor.The reaction mixture contains selected specific reactants 11 II
It varies depending on the situation, but in order to accelerate the reaction, for example, 30
It may be heated to a temperature in the range of ~130°C or more than 1111°C. In some cases, the reaction mixture is initially mixed to suppress the violent reaction. Solvents or diluents that may be desirable to eliminate can be, for example, liquid hydrocarbons, ethers such as diethyl ether or tetrahydrofuran, or ketones such as methyl ethyl ketone. Other solvents and diluents are known to those skilled in the art, and the choice of solvent or diluent is not limiting. The acid acceptor is preferably present in at least equimolar amounts with respect to the reactants. Examples of acid acceptors include pyridyl
Tertiary amines such as dimethylaniline or triethylamine, and inorganic bases such as sodium or potassium carbonate are included. The product is isolated from the reaction mixture in conventional manner. Another method for preparing compounds of the invention is shown in the scheme BVr- below. Scheme B (1y) (V) (Vl) According to Scheme B, the carboxylic acid (IV) is converted to the corresponding acid chloride (V) as described in Scheme A. The acid chloride is then reacted with a suitable intermediate RH, also as described in Scheme A. The product thus obtained (Vl
) is converted to the given compound (11) by nitration or chlorination. Therefore, when blend)
will be processed. When X is a chlorine atom, the diphenyl ether (Vl) is treated with a chlorinating agent, for example by dissolving the diphenyl ether in a solvent (eg ice vtl: acid) and treating it with chlorine gas. In either case, the compound of interest is isolated from the reaction mixture in conventional manner. Various methods for the compound of the present invention in which R is -NS'S'' are shown in the following scheme 〇. Scheme 〇 (■) According to scheme 〇, the acid chloride (2) can be combined with such an amine, The reaction is preferably carried out in a solvent or diluent that is inert to the reactants and preferably in the presence of an acid acceptor. The reaction mixture will vary depending on the particular reactants selected for use. However, to accelerate the reaction, for example, 3
It may be heated to a temperature range of 0-130°C or higher. In some cases, it may be desirable to initially cool the reaction mixture to suppress strongly exothermic reactions. The solvent or diluent can be, for example, liquid hydrocarbons, ethers such as diethyl ether or tetrahydrofuran, or ketones such as methyl ethyl ketone. Other solvents and diluents are at the discretion of the operator and the choice of solvent or diluent is not critical. The acid acceptor is preferably present in at least ζI moles relative to the reactants. Examples of such acid acceptors include pyridine, tertiary amines such as dimethylaniline or triethylamine, and inorganic bases such as sodium or potassium carbonate. The product is isolated from the reaction mixture in conventional manner. The compound of the present invention in which Sl is an agriculturally acceptable kanone is a compound of formula (■) in which an equimolar amount of alkali gold scrap or alkaline earth metal hydroxide or carbonate, or ammonium hydroxide or substituted hydroxide is used. It can be produced from a compound of the formula (■) by treatment with ammonium. The compound of the present invention in which Sl is a chlorine atom, a bromine atom, or an iodine atom can be prepared by treating the compound of the formula (■) with an alkali of hypochlorogenic acid. It can be prepared by reaction with a metal salt (e.g. sodium hypohalite, such as sodium hypochlorite). The reaction is generally carried out in aqueous solvents such as alcohols or ketones (e.g. methanol, ethanol, acetone, methyl ethyl ketone or methyl imbutyl ketone) in an aqueous or aqueous-organic solution or suspension.The reaction is generally carried out at a temperature of -10 to +60°C, preferably at 1
It is carried out at temperatures between 0 and 40°C. The concentration of starting material in the reaction medium is between 0.5 and 30% by weight, preferably between 2 and 10% by weight. The amount of hypohalite used is generally 1 stoichiometric
~3 times as much. The compound of the present invention in which Sl is a hydrogen atom and S2 is a group -cos'' can be produced, for example, by the method shown in the diagram. The substituted benzamide derivative (■) is a compound or can be prepared by standard methods from the corresponding known carboxylic acid. In step (α) of the diagram, the substituted benzamide (■)
reacts with oxalyl chloride, preferably in a solvent enclosure or diluent inert to the reactants, to give the acid chloride (IK). This reaction is advantageously accelerated by heating to a temperature in the range, for example, from 50 to 120°C. After removing the solvent, the acid chloride derivative then reacts with alcohol or phenol 53011 to give the carbamate derivative (a). This is acid chloride (1) ()
11% alcohol or face shield, e.g. 50%
This is conveniently carried out by heating to a temperature in the range ˜100° C. or higher, with excess reactant 53011 serving as a solvent. As mentioned above, the compound ■ is an alkali or alkaline earth metal hydroxide or carbonate.
λ, or an ammonium cation/or a substituted ammonium cation and is converted into a salt. N-chloro, bromo, or iodo derivatives are also prepared as described above. In the scheme above, the substituent X is shown as being present throughout the reaction, but alternatively the X-substituent may be added to the
・Introduced by chlorination or chlorination. The compounds of this invention are useful as herbicides. Therefore, from another point of view, the present invention provides for the removal of unwanted plants or their growing places.

[Provided is a method for inhibiting the growth of the above-mentioned plants, which comprises spraying a compound of formula (1). The nature of the compounds used in this method will vary depending on the particular compound selected and the nature of the plant species whose growth is to be inhibited. However, generally u: 0.1 to 10 per hectare
An amount of 74 g per hectare would be suitable for many JDR combinations (125 to 1. The iFA method could easily determine its appropriate usage. The compound of the present invention has many a! ri f, Q unnecessary (TIT
'It's 2j effective for controlling things. The compound is either applied to the above-ground parts of the unwanted 4'fi (post-emergence application) or inhibits the growth of plants from seeds in the soil.
Sprayed on the soil for 1jlJ (pre-emergence application). For example, the compounds are used for selective weed control in soybean crops. The compounds used in the process of the invention are preferably used in the form of the same composition, in which the active ingredient is present in solid form or i.
consisting of a diluent of the t-form] is mixed with the υ-form (bulking agent). Therefore, in another aspect, the present invention provides herbicidal compositions comprising a compound of formula (1) as defined above as active ingredient in admixture with a solid or liquid diluent. Preferably, the composition further contains a surfactant. The solid compositions of the invention can be in the form of powders or granules for dispersion, for example. Suitable solid diluents include, for example, kaolin, bentonite, diatomaceous earth, dolomite, calcium carbonate, tar, powdered Madanesia 8, and Fuller's earth. Solid compositions may also contain, in addition to the active ingredient, a wetting agent.
The f7-c may be in the form of particles, which enhances the dispersion of the powder or particles within the facepiece. Such powders or particles may be provided with fillers, turbidity flJ, and the like. Liquids (including aqueous solutions, dispersions and emulsions containing the active ingredient preferably in the presence of 14'ii or more surfactants) include solutions, dispersions or emulsions of the active ingredient. Water or organic liquids can be used to prepare the liquid composite acids of the invention 1.j:t1 1
Corrosion inhibitors (e.g. lauryl quinolinium bromide) may also be included. The surfactant may be of the cationic, ionic or nonionic type. Suitable cationic surfactants are, for example, quaternary ammonium compounds such as cetyltrimethylammonium bromide. Suitable anionic surfactants are, for example, soaps, salts of aliphatic mono-esters of sulfuric acid (e.g. sodium lauryl sulfate), and salts of sulfonated aromatic compounds (e.g. dodecyl-benzenesulfonate,
The sodium, calcium and ammonium salts of lignosulfonic acid, butylnaphthalene sulfonate, a mixture of sodium diisopropyl-naphthalene sulfonate and sodium triisopropyl-naphthalene sulfone 11Σ). Suitable nonionic surfactants are, for example, condensation products of ethylene oxide with fatty alcohols (such as oleyl alcohol and cetyl alcohol) or alkylphenols (such as octylphenol, nonylphenol and octylcresol). Other nonionic surfactants are partial esters derived from long chain fatty acids and hexitol anhydride (eg sorbitol monolaurate), condensation products of the aforementioned partial esters with ethylene oxide, and lecithin. Compositions used in the form of aqueous solutions, dispersions or emulsions are generally supplied in the form of concentrates containing a high concentration of active ingredient, which concentrates are diluted with water before use. These concentrates can withstand long-term storage and after such storage can be diluted with water to form an aqueous preparation that remains homogeneous for a sufficient period of time to be able to be applied with conventional spray equipment. There is a need to. In addition to the carrier 76 They include, for example, buffer salts to keep the pH of the composition within a predetermined range, antifreeze agents (e.g. urea or propylene glycol), adjuvants (e.g. oils or humectants) and when diluting the composition with hard water. Sequestering agents (e.g. citric acid and ethylenediaminetetraacetic acid) may be included which serve to prevent the formation of insoluble precipitates. The aqueous fraction may also carry anti-settling and anti-caking agents. The acid may generally contain dyes or pigments to impart a distinctive color.Thickeners may be added to reduce the formation of wispy droplets, thereby reducing dispersion during dispersion. Other additives useful for particular purposes will be known to those skilled in the formulation art.Generally the concentrates will contain between 10 and 85 liters, preferably between 25 and 60 liters.
% active ingredient by weight. Although dilute preparations prepared at the time of use can contain variable amounts of active ingredient depending on the purpose for which they are used, dilute preparations suitable for many uses contain 0.
．． Contains 0.1-1% by weight of active ingredients. The compounds of the invention can be used together with other herbicides (eg in the form of mixtures). Examples of such herbicides include: Benzo-2,1,8-thiadiazin-4-one-2
, 2-dioxide: e.g. 8-inpropylbenzo-2
, 1,8-thiadiazin-4-one-2,2-dioxide (pentacine, bentazon); B, photo herbicide, '49 phenoxyalkanoic acid: for example, 4-chloro-2-methylphenoxyacetic acid C
MCPA), 2-(2,4-dichlorophenoxy)propion r+! ! 2 (dichlorprop, dichlorp
rop, ), 2,4,5-) dichlorophenoxyacetic acid (2,4,5-T), 4-(4-chloro-2-methylphenoxy) butyric acid (MCPE), 2,4-dichlorophenoxyacetic acid (2 , 4-D), 4-(2,4-dichlorophenoxy)butyric acid (2°4-DB), 2-(4-chloro-2-methylphenoxy)propion e<mecoprop,
rnecoprop), and their derivatives (e.g. salts, esters and amides): C18-C4-<4-halophenoxy) phenyl2
．． 1-Dialkylurea: e.g. s-[4-(4-chlorophenoxy)phenyl)-1,1-dimethylurea (Chloroη); D, dinitrophenol and their derivatives (e.g. acetate): e.g. 2 -Methyl-4゜6-dinitrophenol (
DNOC), 2-butyl-4,6-dinitrophenol (dinoterb), 2-5ec
-butyl-4,6-dinitrophenol (dinosep, d
inoseb) and its esters dinoceb acetate; E, dinitroaniline herbicides: e.g. #', #'-diethyl-2,6-sinitro-4-trifluoromethyl-
-Phenylenediamine (dinitramine, dinitr
amine), 2,6-dinitro-N. N-dipropyl-4-trifluoromethylaniline (trifluoromethylaniline)
, trifLuralin) and 4-methylsulfonyl-2,6-sinitro N,N-dipropylaniline to tralin, nltraLin) r F, phenylurea herbicides: e.g. #'(3,4-dichlorophenyl)-N,N- Dimethylurea (diuron, d
iwron8NlN-hemethy'-#'-(3-()lifluoromethyl)phenyl]urea (flumeturon, fl
ume ttbron), N. N-dimethyl-N'-C4-inpropylphenyl]urea (isoproturon, 1soproturon), and N,N-dimethyl-N'-C4-chloro-3-methylphenyl)urea-X (chlortoluron)
lwron): G, phenylcar/cumoyloxyphenylcarbamate: for example 3-[methoxycarbonylaminocophenyl (3-methylphenylancarbamate (phenmedipharn) and 3-[ethoxycarbonylaminocophenylphenyl Carbamate (desmgdipham); H,2-phenylpyridazin-3-one: e.g. 5-amino-4-chloro-2-phenylpyridazin-3-one (pyrazon); 1, uracil thread herbicide: e.g. 3 -Cyclohexyl-5,6-)rimethyleneuracil (Renacil, 1enaci)
l), 5-bromo-3-sec-'j-thyl-6-methyluracil (brorruxcil) and 3-1-butyl-5-chloro-6-methyluracil (terbacil); J,) lyazine herbicides : For example, 2-chloro-4-ethylamino-6-(impropylamino)-1,3,,5
-triazine (atrazine), 2-chloro-4,6-di(ethylamino)-1,3,5-)riazine (simazine) and 2-azido-4-(isopropylamino)-6-methylthio 1.3.5-]・Riazine (aziprotrin* aziprotr-yne)
: A, l-alkoxy-1-alkyl-3-phenylurea herbicide: e.g. 3-(3,4-dichlorophenyl)
-1-Methoxy-1-methylurea (Linuron + 1in
uron), 3- (4-chlorophenylene/l/)-1-
Methoxy-1-methylurea (monolinuron + monol
inuron) and 3-(4-bromo-4-chlorophenyl)-1-methoxy-l-methylurea (chlorobromuron); L, thiol carbamate herbicides: e.g. Baart, ve
#-1,2,4-) riazin-5-one herbicides: e.g. 4-amino-4,5-dihydro-3-methyl-6-phenyl-1,2,4-) riazin-5 -one (methamidrone + tnetamitron) and 4-amino-6-t-butyl-4,5-dihydro-3-methylthio-1,3,4-triazin-5-one (methy
, metribuzin); N, benzoic acid herbicides: e.g. 2, 3, 6-) IJ dichlorobenzoic acid 2.3.6-TEA), 3゜6-dichloro-2-methoxybenzoic acid (dicamba, dicamba) b and 3-amino-2,5-dichlorobenzoic acid (chloramben): 0, anilide herbicide:
For example, N-butoxymethyl-N-chloroacetyl 2 /
, s /-diethylacet h72+)do(lp C1
-/l/l butachlor), corresponding N-
Methoxy compound (alachlor, αtachlor), corresponding N-isopropyl compound (propachlor)
and 3,4-dichloro-propionanilide (propanil/l/, propanil) #P, dihalobenzonitrile herbicides: e.g. 2,5-Schiff/o o
/<Nzonitrile (d, 1chlobenil), 3r 5-dibromo-4-hydroxybenzonitrile (bromoxynil) and 3,5-short-
4=Hydroxybenzonitrile (io:cynil): Q, hao Alkanoic acid herbicides: e.g. 2,2-dichloropropionic acid (DaLapon), trichloroacetic acid (7″CA) and their salts 2R , diphenyl ether herbicides: e.g. 4-nitrophenyl 2-
Nitro-4-) IJ fluoromethylphenyl ether (fluorodifen), methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate (bifenoz, x, bifenoz), 2- = draw 5-(2-70 rho 4-trifluoromethylphenoxy)benzoic acid and 2-chloro-4-trifluoromethylphenyl 3-ethoxy-4-nitrophenyl ether S, other herbicides 1 such as N,N-dimethyl- Diphenylacetamide (siphenamide), N-(1-naphthyltophthalamic acid (naptalan, alphaptalan) and 3
-amino-1,2,4-triazole; 7"-bipyridium thread herbicides: for example those whose activated character type is i, i'-dimethyl-4,4'-dipyridylium ion (paraquat, paraquat); those whose activated character is 1,1'-ethylene-2,2'-dipyridylium ion (diquat, diqu-αt); U, aryloxyphenoxypropionic acids and their derivatives (e.g. their salts, esters and Amide):
For example, 2-44-(3-chloro-5-trifluoromethylpyridyl-2-oxy)phenoxyiopropionic acid, 244-(5-trifluoromethylpyridyl-2-oxy)phenoxy,]propionic acid, 244-(4 −)
Lifluoromethylphenoxy)phenoxy]propionic acid, 2-[4-(2,4-dichlorophenoxy)phenoxy]propionic acid, 2-L4- (5--Etarfi, 6-"OObe7zooxazolyl-2- oxy)phenoxy]propionic acid,
and 4-methyl-4-(4-)lifluoromethylphenoxy]phenoxy-2-butenoic acid. The acid chloride (■1) required as an intermediate for preparing the 6-terminal compound by the method of scheme A is prepared in the known carboxylic acid (II)' (i = excess thionyl chloride) as described above. It can be prepared by heating under reflux and removing the excess thionyl chloride once the reaction is complete.
) reacts with excess ammonia to form a white solid, 5-(
2-chloro-6-fluoro-4-trifluoromethylphenoxy)-2-nitrobenzamide (melting point 176-1
77°C). The invention is illustrated by the following examples, in which all parts are by weight and all temperatures are expressed in degrees Celsius (U) unless otherwise specified. Example 1 This example uses 5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-2-nitrobenzoin 42
i-methyl-1-ethoxycarbonyl-methyl (1st
The production of compound number 27) in the table is shown. 5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy) -2-= ) o -benzoic 21,
oag was dissolved in 15 ml of dimethyl sulfoxide and 1 g of dry potassium carbonate was added. This mixture was thoroughly stirred, and 0.49.9.9 g of ethyl 2-bromopropionate dissolved in 5 ml of dimethyl sulfoxide was added dropwise. The reaction mixture was stirred at room temperature for 8 hours and then stored overnight. Dilute hydrochloric acid and water were added and the product was extracted with ethyl acetate. The extract was washed, smoked dry and evaporated to give an oil. The product was purified by preparative thin layer chromatography and its structure (compound number 27 in Table 1) was confirmed by elemental analysis, infrared spectrum and NMR spectrum. Example 2 This example shows that 5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-2-=trobenzoic acid 2
- shows the production of chloroethyl (compound number 1 in Table 1). 5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-2-ditorobenzoic acid was treated with thionyl chloride and heated and stirred under reflux for 2 hours. The reaction mixture was evaporated under partial vacuum at 50° C. to give a yellow oil. 20 ml of toluene were then added and evaporated under partial vacuum to remove the last traces of thionyl dihydride from the acid chloride formed. The acid chloride was dissolved in toluene (Jmi), 9.4 m of triethylamine was added dropwise, followed by 0.25.9 m of 2-chloroethanol, and the cloudy mixture was stirred until the reaction was complete. Heated under reflux (for 8 hours). The toluene was evaporated under partial vacuum, the residue was finely triturated with ether and the solid residue (triethylamine hydrochloride) was removed by i″i filtration, and the r liquid was evaporated under partial vacuum. Six preparative thin layer chromatography plates (silica) were coated with ether:hexane:acetic acid (6
The sample was developed with a mixed solvent of 0:40:5), and the main band, which had migrated more rapidly, was scraped off. The product was extracted with ethyl acetate and evaporated under partial vacuum to give 0.9 g of a yellow oil. The structure of the product (number 1 in Table 1) was confirmed by elemental analysis, infrared spectrum and N II (R spectrum). Example 3 This example shows that 5-(2-chloro-6-fluoro-4-tri Fluoromethylphenoxy)-2-nitrobenzoic acid 2
-9Ni of nitrophenyl (compound number ai in Table 1)
It shows the structure. 5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-2-nitro-benzoic acid 1.08,
! 20 ml of thionyl chloride as described in Example 2
The acid chloride was obtained by treatment with Its acid chloride Kettle F 2
0mlK'fa, 2-nitrophenol o, a s
Then 0.4 m of triethylamine was added. The mixture was heated and stirred under reflux until the reaction was complete (8 hours). The reaction mixture was evaporated under partial vacuum and dilute hydrochloric acid was added followed by water. The product was extracted with ethyl acetate and the JrJ1 output was washed with sodium hydroxide solution, prine and water and finally dried over magnesium sulfate. The dried extract was evaporated under partial vacuum to a% shrinkage to give an oily residue which solidified on standing. The product was recrystallized from methanol to give 0.89 g of an off-white solid (melting point 105-106°C).
I got it. Its structure (compound number 81 in Table 881) was confirmed by elemental analysis, infrared spectrum, NMR spectrum and mass spectrometry. Example 4 This example shows (1)-(5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-2-nitrobenzoyltuoximino-1-methylethylidene (
The production of compound number 37) in Table 1 is shown. -5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-2-nitrobenzoic acid 1.03.
9 was treated with 15 ml of thionyl chloride as described in Example 2 to give the acid chloride. The acid chloride is toluene 20
0.2 I of acetoxime was added followed by 0.5 d of triethylamine. The mixture was heated and stirred under reflux until the reaction was complete (8 hours). The reaction mixture was evaporated under partial vacuum;
Dilute hydrochloric acid was added followed by water. The product was extracted with ethyl acid and the extracts were washed, dried and reduced with IlI+5 to give a brown semi-solid residue. The residue was recrystallized from methanol to form a grayish-white solid 89I (melting point 105-106°C).
I got it. The homologue was purified by preparative thin layer chromatography (developing solvent: ether:hexane:acetic acid 6o:4o:2), and the yellow residue after concentrating the extract was triturated with Betrol to form an off-white solid. o, e 2 g
(melting point 128-129°C) was obtained. Its structure (compound number 87 in Table 1) was confirmed by elemental analysis, infrared spectrum and NMR spectrum. This example demonstrates the preparation of tetrahydrofurfuryl 5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-2-nitrobenzoate (Compound No. 5B in Table 1). 5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-2-nitro-benzoic acid 1.08.9
was treated with thionyl chloride as described in Example 2 to give the acid chloride. The acid chloride was dissolved in 20 g of toluene, 0.8 g of tetrahydrofurfuryl alcohol dissolved in about 5 ml of toluene was added, and then 9 g of triethylamine was added.
．． 5 tnl was added and the mixture was heated and stirred under reflux until the reaction was complete (2 hours). The reaction mixture was evaporated under partial vacuum and dilute hydrochloric acid was added followed by water. The product was extracted with ethyl acetate and the extracts were washed, dried and concentrated to yield overnight. The oil was purified by preparative thin layer chromatography (developing solvent: ether:hexane:acetic acid 60:40:2) to give a tan viscous oil 0.58%. Its structure (compound number 58 in Table 1) was confirmed by elemental analysis, infrared spectrum and NMR spectrum. Examples include 5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-2-nitrobenzoic acid 1
- Shows the production of methylene bisizole (compound number 5 in pAt coating). 5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-2-nitro-benzoic acid 1.1. Treatment of V with thionyl chloride as described in Example 2 provided the acid chloride. The r3A chloride was dissolved in toluene at 20 meK, and 0.5 yl of triethylamine and 0.5 g of 1-(hydroxymethyl)pyrazole were added thereto. The mixture was heated and stirred under reflux until the reaction was complete (4 hours). After cooling, the reaction mixture was filtered once to remove the white solid (triethylamine hydrochloride), and the liquid was evaporated to give a yellow oil. : Acetic acid 60:40:
The main band was extracted with ethyl acetate. After spontaneous evolution, the resulting yellow oil was transferred to a vial with ether and evaporated to give 0.8 g of a white solid (melting point 88-8
9°C). Its structure (compound number 5 in Table 1) was confirmed by elemental analysis, infrared spectrum and NMR spectrum. Example 7 This example demonstrates the preparation of N-methyl-5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-2-nitrobenzamide (Compound No. 39 of Table 1). 5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-2-nitro-benzoic acid 1.03 g
was treated with thionyl chloride as described in Example 2 to give the acid chloride. The acid chloride was dissolved in toluene and the reaction mixture was stirred vigorously while methylamine gas was bubbled through the solution. Concentration gave an oily residue, which was partitioned between water and ethyl acetate. The ethyl acetate extracts were washed with prine, dried over magnesium sulfate, and concentrated to give a sticky yellow residue. The residue was purified by thin layer chromatography (opening solvent: chloroform:acetone:acetic acid 90:10:5). The ethyl acetate extract of the major band was concentrated to give a solid residue, which was finely triturated with ether/petroleum to give a white solid 0.789°C (mp 152-158°C). Its structure (compound number 89 in Table 1) was determined by elemental analysis and NM
Confirmed by n spectrum. Example 8 This example shows N-ethoxycarbonylmethyl-5-(2
-Chloro-6-fluoro-4-trifluoromethylphenoxy)-2-nitrobenzamide (compound number 55 in Table 1) is shown. 5-(2-chloro-6-
Fluoro-4-1-lifluoromethylpheno*cy)-2
- a solution of 1"2.84 I of nitropenzoylchloride,
Sodium hydroxide aqueous solution 10#/(10g/100
#1. / containing sodium hydroxide) glycine 0.4
8 g of solution was added followed by 8 drops of Triton B (Triton B is the trade name for benzyltrimethylammonium hydroxide solution). The mixture was stirred at room temperature for 4 hours and then left overnight. Ice was then added at ~1 and the mixture was acidified to Congo Red by adding concentrated hydrochloric acid. The aqueous layer was separated and extracted with 8×75 ml of ethyl acetate. The extract was washed with water 2X100#I/, dried and Cyh
SOa) evaporated under reduced pressure to a pale yellow solid 2.81.9
obtained, which is N-carboxymethyl-5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)
It was confirmed to be -2-nitrobenzamide. Add this to 150 Inl of ethanol! and hydrogen chloride gas was passed through the solution for 1 hour. The mixture was heated under reflux for 8.5 hours, left overnight, reheated under reflux for a further 1.5 hours, then left for 2 days. The mixture was then evaporated under reduced pressure to yield a yellow solid. Add this to 10 ethyl acetate
01 nl and the solution was washed with 3 x 70 ml of saturated sodium bicarbonate solution and t o o mt of water,
Dry Na, 804) and evaporate to 1.4g white solid.
I got it. This was then transferred onto a glass plate coated with a thin Jfa (2 m) of silica gel, with toluene as the developing solvent:
Chromatographed using a mixture of ethyl acetate 8:1 (by volume). The fastest moving hand is 5-(
It was confirmed to be ethyl 2-chloro-6-fluoro-4-trifluoromethylphenoxy)-2-nitrobenzoate. This was followed by a pale blue fluorescent band, followed by the desired product. This is a white solid with a melting point of 140-141 °C. obtained as. Example 9 This example shows N-methoxy-[5-(2-chloro-6-
Fluoro-4-trifluoromethylphenoxy)-2-
nitrobenzamide) (compound number 57 in Table 1). 5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-2-nitro-benzoic acid 1.08. ?
was treated with thionyl chloride as described in Example 2 to give the acid chloride. The acid chloride was dissolved in toluene and the solution was mixed with 0.22% of methyloxyamine hydrochloride in 20IR1 of toluene. ? and ToIJ x thylamine 0.5m
1 of the stirred solution. The reaction mixture was stirred at room temperature for 2 hours and then left at room temperature overnight. Concentration gave an oily residue, which was partitioned between water and ethyl acetate. The ethyl acetate extract was washed, dried, and concentrated to give an oil, which was purified with preparative thin layer Chromadog 2F (chloroform:acetone:acetic acid 90:10:5 developing solvent). The ethyl acetate extract of the main band was condensed with θ′ to obtain a residue,
This is finely ground with ether/petroleum to produce a white solid with 0
．． 21.9 (melting point 162-168°C) was obtained. Its structure (compound number 57 in Table 1) was confirmed by elemental analysis and NMn spectrum. Example i. This example shows 0-(5-(2-chloro-6-fluoro-
4-) IJ 5-(2-chloro-6- Fluoro-4-)! J Fluoromethylphenoxy)-2-nitrobenzoic acid 1.0B& was treated with thionyl chloride as described in Example 2 to give the acid chloride. The acid chloride was dissolved in 715 m of toluene, and 0.4 g of ethyl oxime acetoacetate was added.
After 5 hours, 0.5 ml of triethylamine was added. This mixture was heated and stirred at 110 to 120°C under reflux for 3 hours.
Then I let it go overnight. The reaction mixture was concentrated and partitioned between water and ethyl acetate. The ethyl acetate extract was washed, dried, and concentrated to an oil (
It was. The oil was subjected to preparative thin layer chromatography (developing solvent of vinegar 1゛αethyl:hexane:acetic acid 60:40:2).
The product was finely ground with ether/vetrol to give a grayish-white solid Todohan 48I (melting point 106-108
°C) was obtained. Its (1;9 structure (compound number 59 in Table 1)
) was slightly observed in elemental analysis, NMR spectrum and quality R1 spectrum. . This example describes the preparation of 1-methyl-1-ethoxycarbonyl-methyl 2-chloro-5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-ambuzoate (Compound No. 28 in Table 1). Indicates manufacture. 5-(2-chloro-6-fluoro-4-
2-chloro-5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)benzoic acid 1. instead of trifluoromethylphenoxy)-2-nitrobenzoic acid.
11,! The method of Example 10 was repeated using Example 9. The product was an oil. The f1°■1 structure (compound number 28 in Table 1) was confirmed by elemental analysis, infrared spectrum and NM-R spectrum. This example is 〇-[2-chloro-5-(2-chloro-
6-fluoro-4-) 1. ) Fluoromethylphenoxy)benzoyltuoxiimino-1-methylethylidene (Compound No. 38 in Table 1). 5-(2-chloro-6-fluoro0-4-
17fluoromethylphenoxy)-2-nitrobenzoic acid, 2-chloro-5-(2-chloro6-fluoro-4-trifluoromethylphenoxy)-benzoic acid 1
．． The method of Example 4 was repeated using 11 g. The product was a yellow viscous oil that crystallized on standing (melting point 72-75°C λ). Its structure (compound number 38 in Table 1) was determined by elemental analysis, infrared spectroscopy and NMR analysis.
Confirmed by spectrum. Example ia This example demonstrates the preparation of 2-chloro-5-(2-chloro-6-fluoro-4-trifluoromethylphenokidine tetrahydrofurfuryl benzoate (Compound No. 54 in Table 1). Starting Materials as 5-(2-chloro-6-fluoro-4-
2-chloro-5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)benzoic acid instead of trifluoromethylphenoxy)-2-nitrobenzoic acid! 1.
119t - The method of Example 5 was used to turn the gold rim. The product was an oil. Its structure (compound number 54 in Table 1) was confirmed by elemental analysis, infrared spectrum and NMR spectrum. This example shows 2-chloro-5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)benzoic acid l
- Shows the production of methylene pyrazole (addition number 6 in Table 1). 5-(2-chloro-6-fluoro-4-
2-chloro-5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)benzoic acid instead of trifluoromethylphenoxy)-2-nitrobenzoic acid!
Repeat Example 60 method using 0.759, 1-
The amount of hydroxymethylpyrazole was 0.21 g7, the product was a white solid with a melting point of 97-99°C. Its structure (compound number 6 in Table 1) was confirmed by Element Corporation NMR spectrum and mass spectrum. -This example shows N-methyl-2-chloro-5-(2-chloro-6-
The preparation of fluoro-4-trifluoromethylphenoxyph-benzamide (compound number 40 in Table 1) is shown. 5-(2-chloro6-fluoro4-
2-chloro-5-(2-chloro-6-fluoro-4-)IJfluoromethylphenoxy)benzoic acid instead of trifluoromethylphenoxy)-2-nitrobenzoic acid
The method of Example 7 was repeated using 1,'-11 g. The product was a solid with a melting point of 132-133.5°C. Its structure (compound number 40 in Table 1) was determined by elemental analysis, N
Confirmed by AiR spectrum and mass spectrum. Example IG This example demonstrates the preparation of N-ethoxycarbonylmethyl-2-chloro-5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)benzamide (first coat Compound No. 56). 1.5 g of 2-chloro-5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)benzoic acid was heated under reflux in excess thionyl chloride. Excess thionyl chloride was removed under reduced pressure. The resulting oil was dissolved in dry ether and this solution was slowly added to a freshly prepared solution of glycine ethyl ester at room temperature with vigorous stirring. (This situation was prepared by treating 0.569 glycine ethyl ester hydrochloride with an equal amount of triethylamine in dichloromethane. The dichloromethane was removed under reduced pressure and the residue was stirred with ether and filtered. (triethylamine hydrochloride was removed.) This mixture was
After stirring for a minute, the ether was removed under reduced pressure. The resulting oil was partitioned between ethyl acetate and water. The ethyl acetate layer was separated, washed twice with water, dried over Mg S 04 ) and evaporated under reduced pressure. The oil was dissolved in boiling ether and hexane was added to cool the solution. The separated solid was recrystallized from a mixed solvent of chloroform and hexane to yield 0.47 g of N-ethoxycarbonylmethyl-2-chloro-5-(2-io-6-fluoro-4-trifluoromethylphenoxy)benzamide. (melting point 94°C) was obtained. Example 17 This example shows O-[2-chloro-5-(2-chloro-6
-fluoro-4-) IJ fluoromethylphenoxy)
The preparation of benzoyl]-oxyimino-1-ethoxycarponyletheridene (compound number 60 in Table 1) is shown. 5-(2-chloro-6-fur 1:l-
4-)! jfluoromethylphenoxy)-2-nitrobenzoic acid, 2-chloro-5-(2-chloro-6-
Fluoro-4-trifluoromethylphenokidine benzoic acid 1. J, 1. The method of Example 1O was repeated using i: The product was a solid with a melting point of 80-82°C. Its structure (compound 8 in Table 1? II No. 60) was determined by elemental analysis, N
Confirmed by MR spectrum and mass spectrum. Implementation -1,! ll l& This example shows #-'(1-methyl-1-ethoxycarbonyl-methyl)-2-chloro-5-(2-chloro-6-
The preparation of fluoro-4-trifluoromethylphenoxyphenzamide (compound number 62 in Table 1) is shown. 1.03 g of 2-chloro-5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)benzoic acid was treated with thionyl chloride 15- as previously described to give the acid chloride. The acid chloride was dissolved in 5 toluene and this solution was added dropwise to a stirred mixture of 15 g of toluene, 0.35 g of L-alanine ether ester, and 0.5 g of triethylamine. The mixture was stirred at room temperature for 2 hours and then stored overnight. The reaction mixture f:fa was condensed and partitioned between water and ethyl acetate. The organic extracts were washed, dried and concentrated to give an oil. The oil was purified by preparative thin layer chromatography (ether nihexane:'#acid 60:4
A very viscous oil was obtained. Its structure (compound number 62 in Table 1) was determined by elemental analysis.
Confirmed by NMR spectrum and gas chromatography/mass spectrum. Example 1a This example shows N-methoxycarbonyl-5-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-2-nitrobenzamide (Compound No. 63 in Table 1).
) is shown. The known compound 3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)benzoic acid was heated under reflux in excess thionyl chloride for 3 hours. The thionyl chloride of PerIP11 was removed under reduced pressure. The remaining oil (3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)benzoyl chloride) was treated with excess aqueous ammonia to give 3-(2-chloro-6-fluoro-4-)Q
Fluoromethylphenoxy)benzamide was obtained. A 1.67 fl sample of this material was heated to reflux with 4 ml of oxalyl chloride in 1,2- and the oxalyl chloride was removed under reduced pressure. Add 100 grams of methanol to the remaining brown oil,
The solution was heated under reflux for 1 hour and then left at room temperature overnight. Excess methanol was removed under reduced pressure and the remaining solid was dissolved in dichloromethane and petroleum ether (
It was recrystallized from a mixture with a boiling point of 40-60°. N-methoxycarbonyl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy) thus obtained
1.65 g of benzamide has a melting point of 128-129
It was ℃. 1.18 g of the above substituted benzamide derivative was mixed with 10 m/l of 1,2-dichloroethane and concentrated sulfuric acid I under vigorous stirring at 0°C.
Added portionwise to the mixture with Qml. Thereafter, 0.33 g of potassium nitrate was added in small portions over 15 minutes while maintaining the temperature at 0°C. The mixture was stirred for an additional 30 minutes at θ°C and then warmed to room temperature. The mixture was poured into ice and water (50g) and extracted with ether. The extract was washed with saturated prine, dried and filtered. Petroleum ether (boiling point 40-60
°C) and the product separated as a colorless powder. Collection f
J: 0.8g, melting point 144-146°C. Analytical and spectral data for the compound indicate that the compound is N-methoxycarbonyl-5-(2-chloro-6-fluoro-
It was consistent with that it was 4-trifluoromethylphenoxy)-2-nitrobenzamide. Example 2-29 These examples demonstrate the herbicidal properties of each of the compounds of Examples 1-10. Each compound was subjected to herbicide testing as described below. Each compound was added in its appropriate amount to 21.81/II Span 80 and 78.2 g/73 Tween 20 k in methylcyclohexanone.
It was formulated for testing by mixing with milk liquid 5- prepared by fiQ by diluting Solu 7 Kai 160++14 with water to 500 mg. SPA/80 is the official name for the surfactant surfactant Nrubitan Monolaurate Color. Tween zO is the designation for a surfactant consisting of a condensate of sorbitan monolaurate and 20 mole fractions of ethylene oxide. The mixture of adduct and emulsion was then shaken using glass beads and diluted with water to 40πeK. The injectable fat composition thus prepared dI4 was applied to young potted plants (post-emergence test 11a) at 7° C., using the above-mentioned coating, in pieces equal to 1 oooz per hectare. Damage to plants ranged from 0 to 1 on day 1 after application of the composition compared to untreated plants.
5 schools (0 indicates damage from 0 to 2096, and 5 indicates Kozensatsukai, (go taste). In the table showing 7 milled rice, a dash symbol (-) indicates that no test was conducted. Trial!i:'! was carried out to determine the herbicidal activity of the pre-emergent herbicidal activity. Seeds of the test plants were placed on the soil surface in fiber trays and the composition was applied at a rate of 100 OJ per hectare. Spread. After 7, the seeds were covered with soil. After 3
After a week, the germination status of the sprayed fiber trays was compared with the germination status of the unsprayed 7'c control trays, and damage in this case was similarly evaluated on a scale of 0 to 5. The test results are shown in Table 2 below. Names of test plants in Table 2 sb 1 sugar beet p Rapeseed Ct Cotton sy Soybean Mz ) Corn Wto Winter wheat Ec Rice Sn Wildflower lp Common morning glory A Rin Blue-bellied daisy Pi Mitchasagi Cα Pigweed Gα Yaemugura A7! Sparrow gnome St Red foxtail Ec Golden grass sh Seiban sorghum Ag Shiba wheat Cn Yellowtail patent applicant Imperial Chemical (4 others 2 Continued from page 1 ■ Int, C1,' Identification code Office serial number A 0
1 N 43156 7215-4H43/647 7
215-4 H 43/653 72152 4H 43/80 102 7215-4H 10372'15-4H AOIN 47102 7144-4H47/1271
44-4H 47/42 7144-4 H CO7C79/18 7118-4H 79/46 7118-4H 79/48 7118-4H 83/10 7118-4 H 1031007375-4H 103/76 7375-4 H 103/84 73 75- 4 H 121/43' 7451-4H 1531077144-4H C07D 231/12 6779-4C231/16
6779-4 C 233/60 103 7133-4C2491047
132-4C 2491087132-4C 2751007330-4C 307/46 6640-4 C 333/48 8214-4 C Priority claim @ April 11, 1983 ■ United Kingdom (GB
) ■ 8309773 ■) Inventor: David Cartwright Research Station, Blatsknell Zierots Hill, Berkshire, United Kingdom (no street address) Research Station (no street address)

Claims (1)

[Claims] A diphenyl ether compound represented by the formula 111. In the formula, a sulfur atom, R3 is an aliphatic or alicyclic group having one or more substituent groups of 61 carbon atoms, said substituent being a halogen atom; a nitro group; a hydroxy group; cF; Group: C2-C4 alkoxy group: 01-C4 alkylthio group: C□-C4 alkylsulfinyl group: C
1-C4 Alkylsulfonyl group: Phenyl group; Heterocyclic group having 5-6 ring atoms; Group defined below -NRIR21 Cyano group: Carboxy group or its salt 202-C, alkoxycarbonyl group; Group -CONR 'R2(-NR'
R2 is as defined below); formyl group; C2~
C, alkanoyl group: or 1-pyrazolyl group, l-imidazolyl group, which may be substituted with one or more norogen atoms, methyl group, methoxy group or methylthio group,
It is a 1-(1,2,4-triazolyl) group or a 2-(1°2.3-triazolyl) group. (bl group -NR"R", where R1 is a hydrogen atom, a substituted or unsubstituted aliphatic group having 1 to 6 carbon atoms, a substituted or unsubstituted alicyclic group having 3 to 6 carbon atoms, or a substituted or an unsubstituted phenyl group, and R2 is a C I'' which is further substituted with a hydroxy group; a C8-C4 alkoxy group; a phenyl group or a hacarboxy group, or a salt, ester or amide thereof in addition to the group defined in R1. (?4 represents a C8-C4 alkoxy group substituted with di- or amino group or mono- or di-dialkylamino group (alkyl group has 1 to 4 carbon atoms), and also represents a group -NR'R2 is a morpholine ring spanning pyrrolidine or piperidine which may be substituted with a methyl group; a succinimide group or a phthalimide group or a group of the following formula 20: tCr group -NS'S'', where 81 is a hydrogen atom , an alkyl group (for example, a C1-C4 alkyl group), an agriculturally acceptable cation, or a chlorine atom, a bromine atom, an alicyclic group (
For example, the number of carbon atoms is 1 to 6), or a substituted or unsubstituted phenyl group, and S2 independently is a water A atom, ct
~C4 alkyl group or phenyl group, n is 1.2
or 3, and 81 is a CM group, a group -CONS"
In S', R6 and S7 are each a hydrogen atom, a substituted or unsubstituted aliphatic group, or an alicyclic group (for example, a carbon atom number of 1
to 6), or a substituted or unsubstituted phenyl group, a group group or an alicyclic group (for example, having 1 to 6 carbon atoms), or a substituted or unsubstituted phenyl group. (d+ Substituted or unsubstituted phenoxy group or phenylthio group, 2-sulfolaneoxy group, moji group -0N
=CR')7s, where It' is a hydrogen atom, a halogen atom, an alkyl group, a monocyclic aryl group, C1-C6
an alkoxy group, a 01-C6 alkylthio group, or a dialkylamino group, and R5 is a substituted or unsubstituted alkyl group, trifluoromethyl group, cyano group, carboxy group, substituted or unsubstituted alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylthio group, aminocarbonyl group, monomial arylcarbonyl group, monocyclic aryloxy group, or carboxy group or an agriculturally acceptable salt thereof, ester 19 is an amide, and R' and R2 are Bonded together to form the nuclear carbon atoms, tl[4
Forms ~8 rings. (21 In formula (II, -sulfolaneoxy group or group -0N
= C(C11s)t, Claim 1
Compounds described in Section. (3) In the formula, X is a nitro group or a chlorine atom, and IC is a group -NS'S'', Claim 1
Compounds described in Section. (41R is the group ztt'', where Z is an oxygen atom and a force) 3 is one or more of the following substituents: a halogen atom; a nitro group; a carboxyl group, a salt thereof or a C1-C6 thereof alkyl esters; or l-imidazolyl groups, 1-(1,2,4-triazolyl) groups, or 1-(1,2,4-triazolyl) groups optionally substituted with chloro, methyl or methoxy;
-pyrazolyl group: The compound according to claim 1, which is an alkyl group having 1 to 6 carbon atoms and +Ut+. (5) The compound according to claim 1, wherein R is a group ZR'C containing a phenoxy group or a phenylthio group which may be substituted with a nitro group. (61R is a group -NR'lt", where 81 is a hydrogen atom or a C1-C6 alkyl group, and R2 is a hydrogen atom, a C1-C6 alkoxy group or a carboxy group, a salt thereof or a C1-C, alkyl group thereof, A C1-C6 alkoxy group substituted with an ester, and a group -Nll'E
2. The compound according to claim 1, wherein 2 is a pyrrolidine, piperidine or morpholine group optionally substituted with a methyl group; a succinimide group or a phthalimide group; or a group of the following formula: 0. (7; R is the group -NS'S", where s"Fi, one hydrogen atom -ch-ir, R2 is the group -CIiS"5s(
C, S" is a water-based atom or a CI-C4 alkyl group, S is a hydrogen atom, a cation, or a C7-C, alkyl group. A compound described on the third apex. (8) R is a group -0N= with No4<5, where No4 is a C0-C4 alkyl group and R5 may be substituted with an alkoxy (C+-C,) carbonyl group. A compound according to claim 1, which is a C8-C4 alkyl group. (9111 is a method for inhibiting the growth of plants, which comprises spraying a phytotoxic amount of the chemical compound according to any one of claims 1 to 8 on unnecessary plants or their growing locations. 0(1) (2) 1 according to claim 1, which comprises reacting a compound represented by the following formula with a compound of formula: ltH in the presence of an acid acceptor to recover a compound of formula (II). - of the formula (1) according to claim 1, which consists of reacting a compound of the following formula with a nitrating agent or a nitrating agent to recover a compound of formula (Il). A method for producing a compound. Parabolic.