JPH06199810A - Biphenyl derivative and herbicide containing the derivative as active component - Google Patents

Abstract

PURPOSE:To provide a new biphenyl derivative having excellent herbicidal effect against various harmful weeds by soil treatment and foliar treatment in plowed land or submerged application in paddy field. Some of the derivatives exhibit excellent selectivity between main crops and weeds. CONSTITUTION:The compound of formula I {R<1> is H or group of formula II [R<4> and R<5> are H, 1-6C alkyl, 3-8C cycloalkyl, (substituted) phenyl, (substituted) benzyl (the substituent is 1-6C alkyl, 1-6C alkoxy or halogen) or bonded to each other at the terminals to form 4-6C alkylene, 4-6C alkylene containing hetero atom (each alkylene may be substituted with 1-6C alkyl)]; R<2> and R<3> are 1-6C alkyl, 1-6C (halo)alkoxy or 1-6C alkylthio; Y is O or S; X<1> to X<3> are H, OH, 1-6C (halo)alkyl, 1-6C alkoxy, NO2, CN or halogen} or its agrichemically permissible salt, e.g. 2-(2,6-dimethoxypyrimidin-4-yloxy)-6-phenylbenzoic acid.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a biphenyl derivative or a pesticidally acceptable salt thereof, and a herbicide containing the same as an active ingredient.

[0002]

2. Description of the Related Art Up to now, it has been described that certain phenyl derivatives are effective as herbicides in JP-A-3-31268 and JP-A-2-117661.

[0003]

However, these compounds have not always been satisfactory as herbicides.

[0004]

Means for Solving the Problems In view of such circumstances, the present inventors have made various studies and found that the biphenyl derivative represented by the following general formula 3 is an excellent herbicide. That is, the present invention provides a compound represented by the general formula

[Chemical 3] [Wherein R ¹ is a hydrogen atom or a compound represented by the general formula 4

[Chemical 4] (Here, R ⁴ and R ⁵ are the same or different and represent a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₃ -C ₈ cycloalkyl group, or a C ₁ -C ₆ alkyl group, C _1- C ₆
An alkoxy group or a phenyl group which may be substituted with a halogen atom, or a C ₁ -C ₆ alkyl group,
It represents a C ₁ -C ₆ alkoxy group or a benzyl group which may be substituted with a halogen atom, or R ⁴ and R ⁵ may be bonded at the terminal and substituted with a C ₁ -C ₆ alkyl group. Represents a C ₄ -C ₆ alkylene group, or represents a C ₄ -C ₆ alkylene group containing a hetero atom which may be substituted with a C ₁ -C ₆ alkyl group by connecting R ⁴ and R ⁵ at the terminal . ) Represents a group represented by. R ³ and R ² are
Identical or different, C ₁ -C ₆ alkyl group, C ₁ -C
₆ alkoxy group, C ₁ -C ₆ haloalkoxy group, C _1-
Represents a C ₆ alkylthio group or a halogen atom, Y represents an oxygen atom or a sulfur atom, X ¹ , X ² and X ³ are the same or different and each represents a hydrogen atom, a hydroxyl group, C ₁ -C ₆
It represents an alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₆ alkoxy group, a nitro group, a cyano group or a halogen atom. ] The biphenyl derivative shown by these or its agrochemically acceptable salt (henceforth compound of this invention), and the herbicide which makes it an active ingredient are provided. In the general formula 3, R ⁴ and R ⁵ are the same or different,
A C ₁ -C ₃ alkyl group is preferable, and more preferably,
R ⁴ and R ⁵ both represent a methyl group. R ² and R ³ are the same or different and are preferably C ₁ -C ₆ alkoxy groups, more preferably both R ² and R ³ represent methoxy groups. Y is preferably an oxygen atom.

In the general formula 3, the alkyl group is
For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, n-
A hexyl group and the like can be mentioned. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. Examples of the alkoxy moiety of the alkoxy group and the haloalkoxy group include a methoxy group, an ethoxy group, an n-butoxy group, a hexyloxy group and the like. Examples of the halogen atom and the halogen moiety of the haloalkoxy group include a fluorine atom, a chlorine atom and a bromine atom. Examples of the haloalkoxy group include a monofluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a 1,1,2,2-tetrafluorohexyloxy group, a 1,1-dichloroethoxy group, and a 1-chloro-group.
A 2-bromobutoxy group etc. are mentioned. Examples of the alkylthio group include a methylthio group, an ethylthio group and n-
Examples thereof include a propylthio group, an i-propylthio group, an n-butylthio group, a sec-butylthio group, a tert-butylthio group, and an n-hexylthio group. Examples of the alkylene group which may be substituted with an alkyl group include, for example, tetramethylene group, pentamethylene group, hexamethylene group, 1,4-dimethyltetramethylene group, 1,5-dimethylpentamethylene and 1-methylpentamethylene. Group, 2-methylpentamethylene group, 2-ethylpentamethylene group, 2-butylpentamethylene group, 2-hexyltetramethylene group and the like. The hetero atom-containing alkylene group optionally substituted with an alkyl group, an oxygen atom, a sulfur atom,
Examples thereof include alkylene groups containing one or more heteroatoms selected from nitrogen atoms.

[0006]

[Chemical 5] And the like. Examples of the phenyl group or benzyl group which may be substituted with an alkyl group, a halogen atom or an alkoxy group include 3-methoxyphenyl, 3-ethoxyphenyl, 4-i-propoxyphenyl, 3-hexyloxyphenyl and 2-fluorophenyl. , 3-fluorophenyl, 2-chlorophenyl, 3-
Bromophenyl, 2,4-dichlorophenyl, 2,6-
Difluorophenyl, 2-methylphenyl, 3-ethylphenyl, 4-hexylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-chloro-4-methylphenyl, 2-fluoro-4-methoxy. Phenyl, 3-methoxybenzyl, 3-ethoxybenzyl, 4-i-propoxybenzyl, 3-hexyloxybenzyl, 2-fluorobenzyl, 3-fluorobenzyl, 2-methylbenzyl, 3-ethylbenzyl, 4-hexylbenzyl, 2,6-dimethylbenzyl, 2-chloro-4-methylbenzyl, 2-fluoro-4-methoxybenzyl and the like can be mentioned.

The pesticidally acceptable salts of the compounds of the present invention have the general formula 6

[Chemical 6] [In the formula, R ² , R ³ , X ¹ , X ² , X ³ and Y have the same meanings as described above. ], A is, for example, substituted with an alkali metal cation such as sodium, potassium, or lithium, an alkaline earth metal cation such as magnesium or calcium, or an alkyl group such as ammonium, isopropylammonium, or hexylammonium. There may be mentioned an ammonium group which may be present. Next, the manufacturing method will be described in detail. Among the compounds of the present invention, compounds in which R ¹ is a hydrogen atom (hereinafter, compound (I)
Called. ) Is the general formula

[0008]

[Chemical 7] [In the formula, X ¹ , X ² , X ³ and Y represent the same meaning as described above, and R ⁶ represents an alkyl group or a benzyl group. ]
And generalization 8

[Chemical 8] [Wherein R ² and R ³ have the same meanings as described above, and Z
Represents a halogen atom or an alkylsulfonyl group. ] The pyrimidine derivative represented by the following formula (reaction (a))

[0009]

[Chemical 9] [In the formula, X ¹ , X ² , X ³ , R ² , R ³ , R ⁶ and Y
Represents the same meaning as described above. ] The biphenyl derivative represented by the following is obtained, and the ester moiety is hydrolyzed in the presence of an acid or a base according to a conventional method (reaction (b)), or when R ⁶ is a benzyl group, It can also be produced by catalytically reducing the obtained biphenyl derivative.

The reaction (reaction (a)) for producing the biphenyl derivative represented by the general formula 9 is usually carried out without solvent or in the presence of a base. The reaction temperature range is usually
From room temperature to the boiling point of the solvent, the reaction time range is usually 10 minutes to 24 hours, and the amount of the reagent to be used in the reaction is usually represented by the formula 8 to 1 equivalent of the phenol derivative represented by the general formula. The pyrimidine derivative shown is 1-3 equivalents, the base is 1
~ 5 equivalents. Solvents that can be used include hexane, heptane, ligroin, petroleum ether and other aliphatic hydrocarbons, benzene, toluene, xylene and other aromatic hydrocarbons, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, dichlorobenzene and other halogens. Hydrocarbons, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethers such as diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone and other ketones, ethyl formate, ethyl acetate,
Butyl acetate, esters such as diethyl carbonate, nitro compounds such as nitroethane and nitrobenzene, nitriles such as acetonitrile and isobutyronitrile, pyridine, triethylamine, N, N-diethylaniline, tributylamine, N-methylmorpholine and the like. Examples thereof include acid amides such as primary amines, formamide, N, N-dimethylformamide and acetamide, sulfur compounds such as dimethyl sulfoxide and sulfolane, liquid ammonia, water and the like, or a mixture thereof. Examples of the base include organic bases such as pyridine, triethylamine and N, N-diethylaniline, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydride, sodium methoxide, sodium ethoxide and the like. Examples thereof include alkali metal alkoxides. After completion of the reaction, the reaction solution is added with water and subjected to usual post-treatments such as extraction with an organic solvent and concentration, and if necessary, chromatography, distillation,
The target biphenyl derivative represented by the general formula 9 can be obtained by purification by an operation such as recrystallization.

The reaction for hydrolyzing the obtained biphenyl derivative represented by the general formula 9 (reaction (b)) is usually carried out in a solvent under acidic or basic conditions, and the reaction temperature is usually within a range. The range of room temperature to the boiling point of the solvent and the reaction time is usually 10 minutes to 48 hours. The amount of the reagent used in the reaction is 0.01 to 100 equivalents of the acid or base with respect to 1 equivalent of the compound represented by the general formula 9. As an acid,
Examples thereof include hydrochloric acid and sulfuric acid. Examples of the base include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. When a solvent is used, examples of the solvent that can be used include aliphatic hydrocarbons such as hexane, heptane, ligroin, and petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, and halogenated hydrocarbons such as chlorobenzene and dichlorobenzene. , Diethyl ether,
Ethers such as diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, methanol, ethanol, isopropanol,
Examples thereof include alcohols such as tert-butanol, octanol, cyclohexanol, diethylene glycol and glycerin, pyridine, triethylamine, tertiary amines such as N, N-diethylaniline, tributylamine and N-methylmorpholine, water, or a mixture thereof. . After completion of the reaction, the reaction solution is added with water to adjust the liquidity of the reaction solution and subjected to usual post-treatments such as extraction with an organic solvent and concentration, and if necessary, operations such as chromatography, distillation and recrystallization. The desired compound (I) can be obtained by purification with. Further, the catalytic reduction reaction of the biphenyl derivative represented by the general formula 9 is usually carried out without solvent or in the presence of a catalyst, and the reaction temperature range is
Usually, the temperature is from room temperature to 200 ° C, and the reaction time is usually 10
Minutes to 48 hours. Further, the reaction may be performed under pressure. When using a solvent, as a solvent that can be used, hexane, heptane, ligroin, aliphatic hydrocarbons such as petroleum ether, benzene, toluene, aromatic hydrocarbons such as xylene, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, Halogenated hydrocarbons such as dichlorobenzene, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethers such as diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone and other ketones, ethyl formate, ethyl acetate, acetic acid Butyl, esters such as diethyl carbonate, acetonitrile, nitriles such as isobutyronitrile, methanol, ethanol, isopropanol, t-butanol, octanol, silane. Rohekisanoru, 2-methyl-ethoxyethanol, diethylene glycol, alcohols such as glycerin, pyridine, triethylamine,
Examples thereof include tertiary amines such as N, N-diethylaniline, tributylamine and N-methylmorpholine, water and the like, or a mixture thereof. As the catalyst, palladium-
Examples thereof include carbon, platinum oxide, Raney nickel and the like. After completion of the reaction, the reaction solution is filtered to remove the catalyst, subjected to usual post-treatments such as concentration, and if necessary, purified by operations such as chromatography, distillation, recrystallization and the like to give the desired compound (I ) Can be obtained.

The compound (I) thus obtained can be reacted with a base to produce a pesticidally acceptable salt thereof. This reaction is usually carried out without solvent or in a solvent, and the reaction temperature range is usually from room temperature to the boiling point of the solvent,
The reaction time is usually 10 minutes to 24 hours, and the amount of the reagent used in the reaction is 1 equivalent to a large excess amount of the base with respect to 1 equivalent of the compound (I). When a solvent is used, usable solvents include hexane, heptane, ligroin,
Aliphatic hydrocarbons such as petroleum ether, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene and dichlorobenzene, diethyl ether, diisopropyl ether, dioxane. , Ethers such as tetrahydrofuran and diethylene glycol dimethyl ether, ketones such as methyl ethyl ketone, methyl isobutyl ketone and isophorone, nitro compounds such as nitroethane and nitrobenzene, nitriles such as acetonitrile and isobutyronitrile, formamide, N, N-dimethylformamide, Examples thereof include acid amides such as acetamide, sulfur compounds such as dimethyl sulfoxide and sulfolane, liquid ammonia, water and the like, or a mixture thereof. As the base, carbonates, hydrides, hydroxides and the like of alkali metals, alkaline earth metals and the like, or amines which may be substituted with an alkyl group, and the like, specifically lithium hydroxide, sodium hydroxide, water Potassium oxide, sodium carbonate, potassium carbonate, lithium hydride, sodium hydride, potassium hydride, calcium hydride, lithium methoxide, sodium methoxide, sodium ethoxide, ammonia, methylamine, ethylamine, propylamine, isopropylamine, Butylamine, pentylamine, hexylamine and the like can be mentioned. After completion of the reaction, the reaction solution is subjected to usual post-treatment such as concentration, and if necessary, purified by an operation such as recrystallization to obtain an agrochemically acceptable salt of the target compound (I). be able to.

Of the compounds of the present invention, R ¹ is referred to as a compound represented by the general formula 4 (hereinafter referred to as compound II). ) Is the general formula 10

[Chemical 10] [In the formula, R ⁴ , R ⁵ , Y, X ¹ , X ² and X ³ have the same meanings as described above. ] A phenol derivative represented by
It can be produced by reacting with a pyrimidine derivative represented by the general formula: This reaction and the post-treatment after the reaction are performed according to the above reaction (a). In addition, the compound (II) is obtained by reacting the compound (I) with an acid halogenating agent or an active esterifying agent (reaction (i)), and subsequently reacting the reaction product with a compound represented by the general formula:
1

[0014]

[Chemical 11] [In the formula, R ⁴ and R ⁵ have the same meanings as described above. ] It can manufacture also by making it react with the hydroxylamine derivative shown by (reaction (ii)). In the above reaction (i), the acid halogenating agent includes thionyl chloride, thionyl bromide, phosphorus trichloride, phosphorus tribromide, phosphorus pentoxide, phosphorus oxychloride, phosgene, oxalic acid dichloride and the like. Further, as the active esterifying agent,
N, N'-dicyclohexylcarbodiimide, N, N '
-Diisopropylcarbodiimide, 1-ethyl-3-
N, N′-disubstituted carbodiimides such as (3-dimethylaminopropyl) carbodiimide hydrochloride, 2,4,6 chloride
-Arylsulfonyl chloride such as trimethylbenzenesulfonyl, 2,4,6-triisopropylbenzenesulfonyl chloride, N, N'-carbonyldiimidazole, diphenylphosphoryl azide, N-ethoxycarbonyl-2
-Ethoxy-1,2-dihydroquinoline, N-ethyl-
Examples thereof include 2'-hydroxybenzisoxazolium tetrafluoroborate and N-ethyl-5-phenylisoxazolium-3'-sulfonate. By such a reaction, the compound represented by the general formula:

[0015]

[Chemical 12] [In the formula, R ² , R ³ , Y, X ¹ , X ² and X ³ represent the same meaning as described above. In the above, the substituent W represents a halogen atom when an acid halogenating agent is used, and N, N ′ when an N, N′-disubstituted carbodiimide is used as an active esterifying agent. Represents a -disubstituted-2-isoureido group, and when an arylsulfonyl chloride is used, represents an arylsulfonyloxy group, N,
When N'-carbonyldiimidazole is used, it represents an imidazolyl group, and when diphenylphosphoryl azide is used, it represents an azido group, and N-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline is used. When it is present, it represents an ethoxycarbonyloxy group, and N-
When ethyl-2'-hydroxybenzisoxazolium tetrafluoroborate is used, it represents a 3- (N-ethylaminocarbonyl) -2-hydroxyphenoxy group, and N-ethyl-5-phenylisoxa Zolium-
When the 3'-sulfonate is used,

[0016]

[Chemical 13] Represents a group represented by. In addition, in the reaction system,
W is the formula 14

[0017]

[Chemical 14] ^{(Wherein, R 2, R 3, X} 1, X 2, X 3 and Y represent. As defined above) may also take the form of acid anhydride represented by. ] Pyrimidine derivative is produced. The amount of the acid halogenating agent or active esterifying agent used is usually 1 to 10 equivalents relative to 1 equivalent of the compound (I). Also,
The amount of the hydroxylamine derivative represented by the general formula 11 is usually 1 to 5 equivalents relative to 1 equivalent of the compound (I). The reactions (i) and (ii) can be carried out in the presence of a base, if necessary. Such bases include 1-methylimidazole, 3-nitro-1H-1,2,4-triazole, 1H-tetrazole, 1H-1,2,4-
Examples thereof include organic bases such as triazole, imidazole, pyridine and triethylamine, and inorganic bases such as potassium carbonate, and the amount thereof is 1 to 20 with respect to 1 equivalent of the compound (I).
It is equivalent.

The reactions (i) and (ii) are usually carried out in the presence of an inert solvent, and examples of such a solvent include hexane, heptane, ligroin, petroleum ether and other aliphatic hydrocarbons, benzene, Toluene, aromatic hydrocarbons such as xylene, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, halogenated hydrocarbons such as dichlorobenzene, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethers such as diethylene glycol dimethyl ether, acetone, Methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone and other ketones, ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate and other esters, nitroethane, nitrobenzene and other nitro compounds, acetonitrile, isobutane Nitriles such as ronitrile, tertiary amines such as pyridine, triethylamine, N, N-diethylaniline, tributylamine and N-methylmorpholine, acid amides such as N, N-dimethylformamide, sulfur compounds such as dimethyl sulfoxide and sulfolane. Etc., or a mixture thereof. In addition, the reaction temperature is generally 0 ° C. to the boiling point of the solvent, and the reaction temperature is usually 1 to 24 hours, through the reactions (i) and (ii). After completion of the reaction, water may be added to carry out usual post-treatments such as extraction with an organic solvent and concentration, and if necessary, purification by operations such as chromatography, distillation, recrystallization and the like may give the desired compound of the present invention. it can. The phenol derivative represented by the general formula 10 as a raw material compound is

[0019]

[Chemical 15] After reacting the compound represented by with an acid halogenating agent or an active esterifying agent (reaction (iii)), the reaction product and the hydroxyamine derivative represented by the general formula 11 are subsequently reacted (reaction (iv)) can be manufactured by Reaction (iii) and reaction (iv) are performed according to reaction (i) and reaction (ii), respectively. After completion of the reaction, the target compound can be obtained by performing the same post-treatment as described above. In addition, the phenol derivatives represented by the general formulas 7 and 15 which are the starting compounds are SYNTHESIS, 1
980, 814, CHEMISTRY LETTERS, 1990, 143, CHEMISTRY
LETTERS, 1990, 807, SYNTHESIS, 1992, 413, JP-A-2-
108674, JP 3-31268, JP 4-112876
It can be manufactured according to the method described in Japanese Patent Publication No. W091 13065, etc. Some of the compounds of the present invention have an optically active substance, but all optical isomers having herbicidal activity are also included in the present invention. The compounds of the present invention have excellent herbicidal efficacy, and some exhibit excellent selectivity between crops and weeds. That is, the compound of the present invention has herbicidal activity against various weeds which cause the following problems in the foliage treatment and soil treatment of upland fields (including ridges and fallow land).

Polygonum convolvulus, weed, Polygonum convolvulus
ygonum lapathifolium), American scepter (Polygon
um pensylvanicum), Hartade (Polygonum persicari)
a), Rumex crispus, Rumex crispus
(Rumex obtusifolius), Weeds of the purslane family Purslane (Portulaca oleracea) Weeds of the family Caryophyllaceae (Stellaria media) Weeds of the family Schizophyllum (Chenopodium album), Hochigi (Kochia scopar)
ia) Amaranthaceous weeds Amaranthus retroflexus, Aconanthus amaranthus hybridns Brassica weeds Wild radishes Raphanus raphanistrum, Brassica Kaber, Capsella bursa-pa
storis) Leguminous weed American hemlock (Sesbania exaltata), Ebisugusa (Cassia obtusifolia), Florida begger weed (Des
modium tortuosum), white clover (Trifolium repens) mallow weed Abutilon theophrasti, American stag deer (S
ida spinosa) Violet arvensis (Viola arvensis), wild pansies (Viola tricolor) Rubiaceae weeds (Galium aparine) bindweed weeds American morning glory (Ipomoea hederacea)
ea hederacea var.integriuscula), Yellow-faced morning glory (Ipo
moea lacunosa), bindweed (Convolvulus arven)
sis) Lamiaceae weeds

[Lamium purpureum], Lambium amplexicaure, Weeds of Solanaceae, Datura stramonium, Weeds of Solanum nigrum, Veronica persica, Veronica persica
eronica hederaefolia) Weeds Asteraceae (Xanthium pensylvanicum), Wild sunflower (Hel
ianthus annuus), dog chamomile (Matricaria inodor)
a), corn marigold (Chrysanthemum segetum),
Forsythia (Matricaria matricarioides), Ragweed
(Ambrosia artemisiifolia), Black ragweed (Ambrosia
trifida), Erioderma canadensis (Erigeron canadensis), weeds (Myosotis arvensis) Eno Kologsa (Set
aria viridis), Achinoe foxtail (Setaria faber)
i), Crabgrass (Digitaria sanquinalis), Crabgrass (Ele
usine indica), Bluegrass (Poa annua), Blackgrass (Alopecurus myosuroides), Oat (Ave)
na fatua), Seiban sorghum (Sorghum halepense),
Wheatgrass (Agropyron repens), Japanese horse chestnut (Bromus)
tectorum), Cynodon dactylon, Panicum dichotomiflorum, Texas Panicum
(Panicum texanum), Shatter cane (Sorghum vulgar
e)

Commelina communis Commelina communis Equisetum arvense Cyperus iria, Cyperus rot
undus), Cyperus esculentus, and some of the compounds of the present invention are corn (Z
ea mays), wheat (Triticum aestivum), barley (Hor)
deum vulgare), rice (Oryza sativa), soybean (Glycine
max), cotton (Gossypium spp.), sugar beet (Beta vulgar)
is), peanuts (Arachis hypogaea), sunflowers (Helia
nthus annuus), rapeseed (Brassica napus), and other horticultural crops such as flowers and vegetables. Further, the compound of the present invention can effectively weed out various weeds that are problematic in non-tillage cultivation of soybean, peanut, corn and the like. Moreover, some of the compounds of the present invention do not show any harmful phytotoxicity to these crops. In addition, the compound of the present invention has herbicidal activity against various weeds which cause the following problems in the flooding treatment of paddy fields. Weeds of grass family Echinochloa oryzicola Weeds of Sesameaceae Lindernia procumbens Weeds of the family Lythraceae (Rotala indica), Lathyrus serrata (Ammannia)
multiflora) Weed weed (Elatine triandra) Weed weed

Cyperus difformis, firefly (Scirpus juncoides), pine (Eleocharis acic)
ularis), Cyperus serotinus, Elmocharis kuroguwai, Weed Spodoptera, Monochoria vaginalis Weeds, Sagittaria pygmaea, Sadittaria
trifolia), Heraomodaka (Alisma canaliculatum), weeds (Potamogeton distinctus), weeds (Oenan the javanica). Not shown. Further, the compounds of the present invention can control a wide range of weeds that occur in orchards, meadows, lawns, forestry or waterways, canals or other non-agricultural lands.

When the compound of the present invention is used as an active ingredient of a herbicide, it is usually mixed with a solid carrier, a liquid carrier, a surfactant or other auxiliaries for formulation to prepare emulsions, wettable powders, suspensions, granules. Used as an active ingredient of a herbicide by formulating it into a herbicide or granule wettable powder. In these formulations, the compound of the present invention as an active ingredient is contained in a weight ratio of 0.002 to 90%, preferably 0.003 to 8%.
Contains 0%. As solid carriers, kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, mineral fine powder such as calcite, organic fine powder such as walnut shell powder, water-soluble organic fine powder such as urea. Powders, fine powders of inorganic salts such as ammonium sulfate and fine powders of synthetic hydrous silicon oxide and the like can be mentioned, and liquid carriers include methylnaphthalene, phenylxylylethane, aromatic hydrocarbons such as alkylbenzenes such as xylene, isopropanol, and the like. Ethylene glycol, alcohols such as 2-ethoxyethanol, esters such as dialkyl phthalate, ketones such as acetone, cyclohexanone and isophorone, mineral oil such as machine oil, soybean oil, vegetable oil such as cottonseed oil, dimethyl sulfoxide , N, N-dimethylformamide, acetonitril , N- methylpyrrolidone, water and the like. Surfactants used for emulsification, dispersion, wet extension, etc. include alkyl sulfate ester salts, alkyl sulfonates, alkylaryl sulfonates, dialkylsulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, etc. Nonionic surfactants such as anionic surfactants, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and the like. . Other auxiliaries for formulation include lignin sulfonate, alginate, polyvinyl alcohol,
Examples include gum arabic, CMC (carboxymethyl cellulose), PAP (isopropyl acid phosphate) and the like. The compound of the present invention is usually formulated and subjected to soil treatment, foliage treatment or flooding treatment before or after emergence of weeds. The soil treatment includes a soil surface treatment, a soil admixture treatment, and the like, and the foliage treatment includes a treatment from above the plant body and a local treatment such that only the weeds are treated so as not to adhere to the crop.
Further, when used in combination with other herbicides, the herbicidal effect may be enhanced. Furthermore, it can be used by mixing with insecticides, acaricides, nematicides, fungicides, plant growth regulators, fertilizers, soil conditioners and the like. When the compound of the present invention is used as an active ingredient of a herbicide, its treatment amount varies depending on weather conditions, formulation form, treatment time, method, place, target weed, target crop, etc., but usually 0.5 g to 10000 g per hectare. , Preferably from 1 g to 8000
The amount of emulsions, wettable powders, suspensions, hydrated granules, etc. is usually 10 liter to 100 per hectare.
It is diluted with 0 liters of water (if necessary, an auxiliary agent such as a spreading agent is added) and treated, and the granules and the like are generally treated without any dilution. As auxiliary agents, in addition to the above-mentioned surfactants, polyoxyethylene resin acid (ester), lignin sulfonate, abietic acid salt, dinaphthyl mewandisulfonate, crop oil concentrate, soybean oil , Corn oil, cottonseed oil, sunflower oil, and other vegetable oils.

[0025]

INDUSTRIAL APPLICABILITY The compound of the present invention has an excellent herbicidal activity against various weeds which are problematic in soil treatment and foliage treatment in upland fields, and in flooding treatment in paddy fields. Since it exhibits excellent selectivity, it can be used for various purposes as an active ingredient of a herbicide.

[0026]

The present invention will be described in more detail below with reference to production examples, formulation examples and test examples, but the present invention is not limited to these examples. First, production examples of the compound of the present invention will be shown. Production Example 1 2- (2,6-dimethoxypyrimidin-4-yloxy) -6-phenylbenzoic acid benzyl ester 10.3 g
Was dissolved in 100 ml of ethyl acetate, 0.5 g of 10% palladium-carbon (containing 50% water) was added, and catalytic reduction was carried out at room temperature under normal pressure (hydrogen pressure) for 3 hours. Palladium-carbon was filtered off, the obtained filtrate was concentrated under reduced pressure, and 2- (2,6-dimethoxypyrimidin-4-yloxy) -6-phenylbenzoic acid (the compound of the present invention (1 )) Got. ¹ H-NMR (CDCl ₃ / acetone-dδ): δ 3.87 (s, 3H) 3.96 (s, 3H) 5.84 (s, 1H) 7.15 to 7.62 (m, 8H)

Production Example 2 0.072 g of 60% oily sodium hydride was washed with hexane, and 5 ml of tetrahydrofuran was added. To this, 2-
(2,6-dimethoxypyrimidin-4-yloxy)-
0.63 g of 6-phenylbenzoic acid was added to 5 ml of tetrahydrofuran.
The solution dissolved in was added dropwise. After stirring at room temperature for 1 hour, the solvent was evaporated under reduced pressure to give 2- (2,6-dimethoxypyrimidin-4-yloxy) -6-phenylbenzoic acid sodium salt (the present compound (2)). It was

Production Example 3 In Production Example 1, 2- (2,6-dimethoxypyrimidine-4) was used as the starting material instead of 2- (2,6-dimethoxypyrimidin-4-yloxy) -6-phenylbenzoic acid benzyl ester. By using -ylthio) -6-phenylbenzoic acid benzyl ester, 2- (2,2
6-Dimethoxypyrimidin-4-ylthio) -6-phenylbenzoic acid is obtained.

Production Example 4 1.06 g of 2- (2,4-dimethoxypyrimidin-6-yloxy) -6-phenylbenzoic acid was dissolved in 20 ml of N, N-dimethylformamide, and 2,4,6 chloride was added to the solution.
-1.36 g of triisopropylbenzenesulfonyl was added. After stirring at room temperature for 10 minutes, 0.82 g of 1-methylimidazole was added. After stirring at room temperature for 30 minutes, N,
A solution of 0.40 g of N-diethylhydroxylamine in 1 ml of N, N-dimethylformamide was added. After stirring at room temperature for 1 hour, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was subjected to thin layer chromatography (silica gel, ethyl acetate / hexane (1: 1 (v / v)) to give 1.05 g of 2,6-dimethoxy-4. - {2- (N, N- diethylamino-butyloxycarbonyl) -3-phenyl} to give phenoxy pyrimidine (the present compound (236)) the _{^{1 H-NMR (CDCl 3)}} δ:. 0.81 (t, 6H, J
= 7.0 Hz) 2.65 (q, 4H, J = 7.0 Hz) 3.84 (s, 3H) 3.91 (s, 3H) 5.81 (s, 1H) 7.10 to 7.62 (M, 8H)

Production Example 5 In accordance with Production Example 4, 2- (2,4-
By using 2- (2,4-dimethoxypyrimidin-6-ylthio) -6-phenylbenzoic acid instead of dimethoxypyrimidin-6-yloxy) -6-phenylbenzoic acid, 4- {2- (N, N-diethylaminooxycarbonyl) -3-phenylphenylthio} -2,
6-dimethoxypyrimidine is obtained. Next, the compounds of the present invention produced according to the above production method are summarized in Table 1-
43. The compounds in Table 1-18 can be produced according to Production Example 1-3, and the compounds in Table 19-44 can be produced according to Production Examples 4 and 5.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Table 3]

[0034]

[Table 4]

[0035]

[Table 5]

[0036]

[Table 6]

[0037]

[Table 7]

[0038]

[Table 8]

[0039]

[Table 9]

[0040]

[Table 10]

[0041]

[Table 11]

[0042]

[Table 12]

[0043]

[Table 13]

[0044]

[Table 14]

[0045]

[Table 15]

[0046]

[Table 16]

[0047]

[Table 17]

[0048]

[Table 18]

[0049]

[Table 19]

[0050]

[Table 20]

[0051]

[Table 21]

[0052]

[Table 22]

[0053]

[Table 23]

[0054]

[Table 24]

[0055]

[Table 25]

[0056]

[Table 26]

[0057]

[Table 27]

[0058]

[Table 28]

[0059]

[Table 29]

[0060]

[Table 30]

[0061]

[Table 31]

[0062]

[Table 32]

[0063]

[Table 33]

[0064]

[Table 34]

[0065]

[Table 35]

[0066]

[Table 36]

[0067]

[Table 37]

[0068]

[Table 38]

[0069]

[Table 39]

[0070]

[Table 40]

[0071]

[Table 41]

[0072]

[Table 42]

[0073]

[Table 43]

[0074]

[Table 44] Next, a production example of a pyrimidine derivative represented by the general formula 7 as a raw material compound will be shown as a reference example.

Reference Example 1 2.41 g of 60% oily sodium hydride was suspended in 100 ml of N, N-dimethylformamide, and 17.44 g of 6-phenylsalicylic acid benzyl ester was dissolved in 50 ml of N, N-dimethylformamide. Added gradually. 30 at room temperature
Stir for minutes. 4-chloro-2,6-dimethoxypyrimidine
A solution prepared by dissolving 10.01 g in 50 ml of N, N-dimethylformamide was added to the reaction system, and heated and stirred at 100-110 ° C for 3 hours. After cooling, the reaction solution was poured into 1N hydrochloric acid and extracted with ethyl acetate. The organic total was washed with saturated saline three times, and the organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was treated by column chromatography (silica gel, hexane / ethyl acetate (10: 1 to 3: 1, V / V), and 21.55 g of 2- (2, 6-Dimethoxypyrimidin-4-yloxy) -6-phenylbenzoic acid benzyl ester was obtained ¹ H-HMR (CDCl ₃ ): δ 3.77 (s, 3H) 3.87 (s, 3H) 4.89 (s, 2H) 5.65 (S, 1H) 6.76 ~ 7.43 (m, 13H)

Formulation examples are shown below. The compounds of the present invention are shown by the compound numbers in Table 1-44. Parts are parts by weight. Formulation Example 1 50 parts of the compound of the present invention, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide are well pulverized and mixed to obtain each wettable powder. Formulation Example 2 10 parts of the compound of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzene sulfonate, 35 parts of xylene and 35 parts of cyclohexanone are mixed well to obtain each emulsion. Formulation Example 3 2 parts of each of the compounds of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay are well pulverized and mixed, and water is well kneaded, and then granulated. Dry to obtain each granule. Formulation Example 4 25 parts of each of the compounds of the present invention, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC, and 69 parts of water are mixed and wet-ground until the particle size becomes 5 microns or less to obtain a suspension agent. Formulation Example 5 Compound of the present invention (2)-(11), (13)-(15), (25)-(28), (30)-(3
3), (35)-(38), (40)-(43), (45)-(48), (50)-(53), (55)-(5
8), (60)-(63), (65)-(68), (70)-(73), (75)-(78), (80)-(8
3), (85), (87)-(89), (91)-(94), (96)-(99), (101)-(104),
(106)-(109), (111)-(114), (116)-(119), (121)-(124), (1
26)-(129), (131)-(134), (136)-(139), (141)-(144), (14
6)-(149), (151)-(154), (156)-(159), (161)-(164), (166)
-(169), (171)-(174), (178), (179), (182)-(184), (185),
Mix 1 part each of (192), (193), (195)-(198), (200)-(203), (205)-(208), 1 part polyoxyethylene styryl phenyl ether, 98 parts water. To obtain each solution.

Next, it is shown in Test Examples that the compound of the present invention is useful as an active ingredient of herbicides. In addition, this invention compound is shown by the compound number of Table 1-44. The comparative compounds are shown by the compound symbols in Table 45.

[Table 45] For the evaluation of herbicidal efficacy and phytotoxicity, the test plants (weeds and crops) at the time of the survey were evaluated as "0" when they had no or almost no emergence and growth condition compared to those of the untreated plants. A plant whose plant is completely killed or whose budding or growth is completely suppressed is defined as "5", and it is 0 to 5
It is divided into 6 stages and is shown as 0,1,2,3,4,5.

Test Example 1 Field soil surface treatment test Field soil was packed in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm, and barnyard grass and Malaga morning glory were sown.
Covered with soil. Compounds (2), (3) and (9) are Preparation Example 5
Other compounds are made into liquid solutions or emulsions in accordance with Preparation Example 2, and the predetermined amount thereof is 10 per 1 hectare.
The soil surface was diluted with 00 liters of water and treated with a small sprayer. After the treatment, the plants were grown in a greenhouse for 19 days, and the herbicidal efficacy was investigated. The results are shown in Table 46.

[Table 46]

Test Example 2 Field foliage treatment test Field soil was filled in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm, and wild radish and Malaba morning glory were sown and grown in a greenhouse for 7 days. Then, the compounds (2), (3) and (9) were prepared in the same manner as in Formulation Example 5 and the other compounds were prepared into liquid solutions or emulsions according to Formulation Example 2,
The predetermined amount was diluted with water containing 1000 liters of spreading agent per hectare, and foliage treatment was carried out by a small sprayer according to the usual method for plant bodies. After the treatment, the plants were grown in a greenhouse for 19 days, and the herbicidal efficacy was investigated. The results are shown in Table 47.

[Table 47]

Test Example 3 Paddy Water Submersion Treatment Test Paddy soil was filled in a cylindrical plastic pot having a diameter of 8 cm and a depth of 12 cm, and firefly seeds were mixed to a depth of 1 to 2 cm. After flooding to make paddy fields, tubers of Urikawa were embedded at a depth of 1 to 2 cm, and rice at the two-leaf stage was further transplanted and grown in a greenhouse. 6 days later (early generation of each weed),
The test compound (9) was made into a liquid preparation according to Preparation Example 5, and the other compounds were made into emulsions according to Preparation Example 2, and a predetermined amount thereof was diluted with 5 ml of water and treated on the water surface. After treatment, the plants were grown in a greenhouse for 19 days, and herbicidal efficacy and phytotoxicity were investigated. The results are shown in Table 48.

[Table 48]

Test Example 4 Upland Soil Treatment Test A vat having an area of 33 × 23 cm ^{2 and a} depth of 11 cm was filled with upland soil, and wheat, barley, sunflower seed, yaemgra, and blackgrass were sown to cover the soil with a thickness of 1 to 2 cm. The test compound was made into an emulsion according to the formulation example, and a predetermined amount thereof was diluted with water equivalent to 1000 liters per hectare, and the soil surface was treated with a small sprayer. After the treatment, the plants were grown in a greenhouse for 25 days, and phytotoxicity and herbicidal efficacy were investigated. The results are shown in Table 49.

[Table 49]

Test Example 5 Field Stem / Leaf Treatment Test Field soil was filled in a vat having an area of 33 × 23 cm ² and a depth of 11 cm, and wheat, barley, chickweed, yamgrass, and black grass were sown and grown for 31 days. Then the compound
(2) (3) (9) is the formulation example 5 for other compounds, and the other test compound is made into a solution or emulsion according to the formulation example 2, and a predetermined amount of 10 liters of water per hectare containing a spreading agent is equivalent to water. And the whole foliage was treated uniformly from above the plant with an automatic sprayer. At this time, the growth conditions of weeds and crops differed depending on the grass species, but at the 1 to 4 leaf stage, the plant height was 2 to 12 cm. The phytotoxicity and herbicidal efficacy were investigated 25 days after the treatment. The results are shown in Table 50. This test was conducted in a greenhouse throughout the entire period.

[Table 50]

Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number for FI Technical indication C07D 239/52 8615-4C (72) Inventor Kazuo Saito 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Kagaku Kogyo Co., Ltd. (72) Hiroyuki Kogai Inventor Hiroyuki, Takarazuka-shi, Hyogo 4-2-1, Sumitomo Kagaku Kogyo Co., Ltd.

Claims (4)

[Claims] 1. A general formula: ## STR1 ## [Wherein R ¹ is a hydrogen atom or a compound represented by the general formula 2] (Here, R ⁴ and R ⁵ are the same or different and represent a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₃ -C ₈ cycloalkyl group, or a C ₁ -C ₆ alkyl group, C _1- C ₆
An alkoxy group or a phenyl group which may be substituted with a halogen atom, or a C ₁ -C ₆ alkyl group,
It represents a C ₁ -C ₆ alkoxy group or a benzyl group which may be substituted with a halogen atom, or R ⁴ and R ⁵ may be bonded at the terminal and substituted with a C ₁ -C ₆ alkyl group. Represents a C ₄ -C ₆ alkylene group, or represents a C ₄ -C ₆ alkylene group containing a hetero atom which may be substituted with a C ₁ -C ₆ alkyl group by connecting R ⁴ and R ⁵ at the terminal . ) Represents a group represented by. R ³ and R ² are
Identical or different, C ₁ -C ₆ alkyl group, C ₁ -C
₆ alkoxy group, C ₁ -C ₆ haloalkoxy group, C _1-
Represents a C ₆ alkylthio group or a halogen atom, Y represents an oxygen atom or a sulfur atom, X ¹ , X ² and X ³ are the same or different and each represents a hydrogen atom, a hydroxyl group, C ₁ -C ₆
It represents an alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₆ alkoxy group, a nitro group, a cyano group or a halogen atom. ] The biphenyl derivative shown by these, or its agrochemically acceptable salt. 2. The biphenyl derivative according to claim ¹ , wherein R ¹ is a hydrogen atom, or an agrochemically acceptable salt thereof. 3. The biphenyl derivative according to claim 1, wherein R ¹ is a group represented by the general formula 2. 4. A herbicide containing the biphenyl derivative according to claim 1 or a pesticidally acceptable salt thereof as an active ingredient.