JPH03251582A - Imidazo(1,2-a)pyridyl compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula I {B is (substituted) imidazo[1,2- a]pyridin-2-yl; Q is cyano or group of formula II [A is O, S or -NR<1>-(R<1> is H or lower alkyl); R is H, (substituted) hydrocarbon group or heterocyclic group; when A is -NR<1>-, R and R<1> are bonded with each other to form a heterocyclic group together with adjacent N and when A is O or -NR<1>-, R is group of formula III (R<2> and R<3> are lower alkyl, lower alkoxy, lower alkylthio, etc.)]}. EXAMPLE:2-(4-(3-Nitroimidazo[1,2-a]pyridin-2-yloxy)phenoxy)propionic acid ethyl ester. USE:A selective herbicide. PREPARATION:The objective compound can be produced by reacting a compound (salt) of formula B-Z (Z is eliminable group) with a compound of formula IV in the presence of a base.

Description

Detailed Description of the Invention (a) Industrial Application Field The present invention has an excellent herbicidal effect on paddy field weeds and upland weeds, and has no chemical damage to crops such as rice, wheat, barley, and soybeans. The present invention relates to novel imidazo El, 2-al pyrinol compounds that are useful as selective herbicides.

(b) Problems to be solved by conventional techniques and inventions Conventionally, many chemicals have been used as herbicides. However, it cannot be said that the herbicides are still sufficient in terms of these aspects, and there is a strong desire for the emergence of selective herbicides that are further improved in these respects.

(c) Means for solving the problem The present inventors have conducted repeated research aimed at developing a selective herbicide that has excellent herbicidal activity and does not cause chemical damage to crops, and has found the following general formula ( The compound represented by 1) has strong herbicidal activity in its salt (especially its optically active isomer, etc.), and has significantly reduced phytotoxicity on crops such as rice, wheat, barley, and soybeans. As a result of various studies based on these findings, we have completed the present invention. , B is optionally substituted imidazo[12-a
] pyridin-2-yl group, Q is a cyano group or the formula; 0% formula% (wherein A is an oxygen atom, a sulfur atom or a formula NR'
- (in the formula, R1 represents a hydrogen atom or a lower alkyl group), ・R represents a hydrogen atom or a hydrocarbon residue or a heterocyclic group which may have a substituent. or when A is -NR'-, R and R1 may be bonded to each other and form a heterocyclic group together with the adjacent nitrogen atom, and when A is an oxygen atom or -NR'-, R
is represented by the formula: (wherein R2 and R3 each represent a lower alkyl group, a lower alkoxy group, or a lower alkylthio group, or may form a 5- or 6-membered ring with adjacent carbon atoms.) (2) General formula (■): B-Z (I[) (wherein, Z
represents a leaving group, B has the meaning as described in item (1) above) or a salt thereof, and the general formula (■): (wherein, Q is as described in item (1) above). (3) A method for producing a compound according to the general formula (rV) (wherein B is A compound or a salt thereof (having the meaning as described in item (1) above) or a salt thereof (wherein W represents a leaving group, and Q has the meaning as described in item (1) above) A method for producing a compound according to (1) above, which is characterized by reacting the compound represented by the above in the presence of a base, and (4) a herbicidal method characterized by containing the compound according to (1) above. Regarding drugs.

In the above general formula (I), B represents an optionally substituted imidazo[1,2-a]pyridin-2-yl group,
The substituent on the pyridine ring (hereinafter referred to as Xn, where n represents 1 or 2) is (when n is 2, X
are the same or different and each independently) is a lower alkyl group which may be substituted with a halogen atom, a nitro group, a halogen atom, etc. The halokene atom represented by X means, for example, fluorine, chlorine, bromine, iodine, etc. The lower alkyl group in the lower alkyl group optionally substituted with a halogen atom represented by
Ethyl, n-propyl, isopropyl, n-butyl, t
-butyl, etc.) are used. As the halogen atom in the lower alkyl group which may be substituted with a halogen atom, fluorine, chlorine, bromine, etc. are used.

Preferred substituents represented by X include a halogen atom,
X is a lower alkyl group which may be substituted with a halogen atom, and more preferable examples of X include chlorine, bromine, methyl, trifluoromethyl and the like.

Examples of the substituent on the imidazole ring (hereinafter referred to as Y) include a halogen atom, an amino group, a cyano group, a nitro group, an acyl group, a lower alkoxycarbonyl group, and a carbamoyl group optionally substituted with a lower alkyl group. , calfoquinol group, lower alkylthio group, lower alkylsulfinyl group, lower alkylsulfonyl group, lower alkylamino group, di-lower alkylamino group, lower alkokene group, sulfamoyl group, lower alkylsulfamoyl group,
Lower alkyl which is a di-lower alkylsulfamoyl group or which may be substituted with 1 to 4 halogen atoms, hydroxyl group, amino group, lower alkylamino group, di-lower alkylamino group, lower alkoxy group or lower alkylthio group etc. are used.

The halogen atom represented by Y includes, for example, fluorine, chlorine,
It means bromine, iodine, etc.

The acyl group represented by Y refers to a C4-7 acyl group derived from aliphatic carboxylic acids such as formic acid, acetic acid, n-propionic acid, and n-butyric acid, and aromatic carboxylic acids such as benzoic acid, such as formyl. , acetyl, propionyl, butyryl, benzoyl, etc. are used.

The lower alkoxycarbonyl group represented by Y is an alkoxycarbonyl group having 2 to 6 carbon atoms, such as methoxycarbonyl, etquincarbonyl, propoquinecarbonyl, isobutoxycarbonyl, butoquinocarbonyl,
These include isobutoxycarbonyl, 5ec-butoquinocarbonyl, tert-butoquinocarbonyl, and the like.

The carbamoyl group optionally substituted with a lower alkyl group represented by Y is a mono- or di-lower alkyl-carbamoyl group optionally substituted with an alkyl group having 1 to 6 carbon atoms, such as carbamoyl, methylcarbamoyl. , dimethylcarbamoyl, methylethylcarbamoyl, etc.

The lower alkylthio group represented by Y is a linear or branched alkylthio group having 1 to 6 carbon atoms, such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, 5ec-butylthio, tert-butylthio, n-pentylthio, n-
Hexylthio etc.

The lower alkylsulfinyl group represented by Y has 1 carbon number.
to 6 straight-chain or branched alkylsulfinyl groups, such as methylsulfinyl, ethylsulfinyl,
n-propylsulfinyl, n-hequinlsulfinyl, etc. are used.

The lower alkylsulfonyl group represented by Y is a linear or branched alkylsulfonyl group having 1 to 6 carbon atoms,
For example, methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, etc. are used.

The lower alkylamino group represented by Y has 1 to 6 carbon atoms.
is a linear or branched alkylamino group, such as methylamino, ethylamino, n-propylamino, isopropylamino, etc.

The di-lower alkylamino group represented by Y is a di-lower alkylamino group in which the lower alkyl is a straight-chain or branched alkyl having 1 to 6 carbon atoms, such as dimethylamino, diethylamino, methylethylamino, etc. used.

The lower alkoxy group represented by Y is a straight chain or branched alkoxy group having 1 to 6 carbon atoms, such as methocino,
Etquine, n-propoquine, isopropoquine, etc. are used.

The lower alkylsulfamoyl group represented by Y is a linear or branched alkylsulfamoyl group having 1 to 6 carbon atoms, such as methylsulfamoyl, ethylsulfamoyl, n-propylsulfamoyl, etc. is used.

The di-lower alkylsulfamoyl group represented by Y is a di-lower alkylsulfamoyl group in which the lower alkyl is a linear or branched alkyl having 1 to 6 carbon atoms, such as dimethylsulfamoyl, diethylsulfamoyl, etc. famoile,
Methyl ethyl sulfamoyl and the like are used.

What is the lower alkyl group in the lower alkyl group optionally substituted with 1 to 4 halogen atoms, hydroxyl groups, amino groups, lower alkylamino groups, di-lower alkylamino groups, lower alkoxy groups, or lower alkylthio groups represented by Y? , a straight chain or branched alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and the like.

Examples of the halogen atom which may be substituted here include fluorine, chlorine, bromine, iodine, etc., and examples of the lower alkylamino group include a linear or branched alkylamino group having 1 to 6 carbon atoms (for example, methylamino , ethylamino, n
-propylamino, isopropylamino, etc.), and the di-lower alkylamino group is a di-lower alkylamino group in which the lower alkyl is a straight-chain or branched alkyl having 1 to 6 carbon atoms (for example, dimethylamino, diethylamino, methylethylamino, etc.), and the lower alkoxy group is a linear or branched alkoxy group having 1 to 6 carbon atoms (for example, methoxy, ethoxy, n-propoxy, isopropoxy, etc.), and the lower alkylthio group is teeth,
Straight chain or branched alkylthio groups having 1 to 6 carbon atoms (for example, methylthio, ethylthio, n-propylthio, isopropylthio, etc.) are used.

Preferred substituents for Y include a halogen atom,
These include a cyano group, a nitro group, a C1-4 anru group, a C1-4 alkoxycarbonyl group, a carbamoyl group, a C1-4 alkylsulfonyl group, and the like.

The halogen atom used as a preferable substituent represented by Y is chlorine or bromine, the C+-a anru group is formyl or acetyl, and the Cl-4 alkoxycarbonyl group is methoxycarbonyl or ethoxycarbonyl. etc., and methylsulfonyl, ethylsulfonyl, etc. are used as the C1-4 alkylsulfonyl group.

More preferred substituents for Y include cyano and nitro.

1 Q represents a cyano group or a group represented by the formula: -C-AR, and A is an oxygen atom, an atom, or -NR'
- indicates. R1 represents a hydrogen atom or a lower alkyl group, and as such a lower alkyl group, the lower alkyl group described above for X is used.

The hydrocarbon residue represented by R includes an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, and the like. These may have 1 to 5 substituents. Such alkyl groups include not only lower alkyl groups as described above for X, but also carbon atoms of 7 to IO.
Also includes alkyl groups (e.g., heptyl group, octyl group, etc.), and substituents for such alkyl groups include, for example, halogen atom, hydroxyl group, amino group, mercapto group, nitro group, lower alkylamino group, di-lower alkyl group. An amino group, a lower alkylthio group, a lower alkylsulfinyl group, a lower alkylsulfonyl group, a lower alkoxy group, a tri-lower alkylsilyl group, a lower alkoxycarbonyl group, or the formula: (wherein R' and R' are hydrogen atoms or the above R *, R3
(which have the same or different meanings, respectively) are used.

The halogen atom as a substituent needle for the alkyl group is fluorine, chlorine, bromine, iodine, etc., and the lower alkylamino group is a linear or branched alkylamino group having 1 to 6 carbon atoms (for example, methylamino, ethylamino, n-propylamino, isopropylamino, etc.), and a di-lower alkylamino group is a di-lower alkylamino group in which the lower alkyl is a straight-chain or branched alkyl having 1 to 6 carbon atoms (e.g., dimethylamino). , diethylamino, methylethylamino, etc.), and a lower alkylthio group refers to a straight or branched alkylthio group having 1 to 6 carbon atoms (for example,
methylthio, ethylthio, n-propylthio, isopropylthio, etc.), and a lower alkylsulfinyl group refers to a straight or branched alkylsulfinyl group having 1 to 6 carbon atoms (e.g. methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, n-hexylsulfinyl, etc.), and lower alkylsulfonyl groups have 1 carbon number.
to 6 straight-chain or branched alkylsulfonyl groups (e.g., methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, etc.), and lower alkokino groups are straight-chain or branched alkylsulfonyl groups having 1 to 6 carbon atoms. Chained or branched alkokyne groups (e.g. metquine,
ethoxy, n-propoquine, isopropoxy, etc.), and a tri-lower alkylamino group means a tri-lower alkylsilyl group in which the lower alkyl group is a linear or branched tri-lower alkylsilyl group having 1 to 6 carbon atoms (trimethylsilyl, tert-butyldimethyl silyl, etc.), and the lower alkoxycarbonyl group is a straight-chain or branched alkoxycarbonyl group having 2 to 6 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl, etc.).

In the group represented by the above formula: %formula%), R', R3, R' and R5
The lower alkyl group represented by is a straight chain, branched or cyclic alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, ter
t-butyl, cyclohexane', etc.), and a lower alkoxy group is a linear or branched alkoxy group having 1 to 6 carbon atoms (e.g., methoxy, ethyne, n-propoquine, isopropoxy, etc.), and lower alkylthio The group is a linear or branched alkylthio group having 1 to 6 carbon atoms (for example, methylthio, ethylthio, n-propylthio, isopropylthio, etc.), and R'' and R3, or R4 and R5 are bonded together. It is also possible to form a 5- to 6-membered ring such as a 5- to 6-membered cycloalkane such as cyclopentane, cyclohexane).Also, R4 and R
5 can also represent a hydrogen atom.

In the optionally substituted aryl group, heterocyclic group, and aralkyl group represented by R, the aryl group refers to an aryl group having 6 to 14 carbon atoms (e.g., phenyl, naphthyl, biphenyl, etc.), and the heterocyclic group refers to a nitrogen group. atoms, oxygen atoms,
A 5- to 6-membered ring group containing 1 to 2 heteroatoms such as an atom or a fused ring group thereof (e.g., pyrrolyl, thienyl,
Furyl, pyrazolyl, imidazolyl, thiazolyl, oxacylyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, etc.), and the aralkyl group refers to an aralkyl group having 7 to 19 carbon atoms (for example, benzyl, phenethyl, phenylpropyl, biphenylylmethyl, trityl, etc.).

Examples of substituents for these aryl groups, heterocyclic groups, and aralkyl groups include lower alkyl groups, halogen atoms, nitro groups, cyano groups, lower alkoxy groups, and lower alkoxycarbonyl groups.

The lower alkyl group as a substituent for the above aryl group, heterocyclic group, aralkyl group, etc. refers to a straight chain or branched alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, etc.). A halogen atom is fluorine, chlorine, bromine, iodine, etc., and a lower alkoxy group is a linear or branched alkoxy group having 1 to 6 carbon atoms (
For example, methoxy, ethoxy, n-propoquine, isopropoxy, etc.), and a lower alkoxycarbonyl group refers to an alkoxycarbonyl group having 2 to 6 carbon atoms (e.g., methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, etc.). poxycarbonyl, etc.).

The alkenyl group represented by R has 2 to 6 carbon atoms.
Preferred are alkenyl groups such as allyl, isopropenyl, 1-butenyl, 2-pentenyl, 2-hexenyl and the like.

The alkynyl group represented by R is preferably an alkynyl group having 2 to 6 carbon atoms, such as propargyl, 2-butynyl, 3-butynyl, 3-pentynyl, 3-hexynyl, and the like.

Substituents for these alkenyl groups and alkynyl groups include:
Examples include the substituents for the alkyl groups mentioned above.

The heterocyclic group formed by R and R' together with the nitrogen atom to which they are bonded is, for example, a 5- to 6-membered nitrogen-containing heterocyclic group such as pyrrolidyl, piperidyl, morpholyl, isoxasilyl, etc. It will be done. When R is A, an oxygen atom, or =NR'-, R1 and R3 represent a lower alkyl group, a lower alkoxy group, a lower alkylthio group as described above, or a carbon atom to which they are bonded. Together they may form a 5- to 6-membered ring.

Preferred substituents represented by Q include 1 It is a group represented by the formula: -C-A-R.

I In the group represented by the formula C-A-R, A is -NR
When R1 is '-, a lower alkyl group is preferably a methyl group.

A preferable example of the alkyl group represented by R is, for example, a straight chain, branched or cyclic alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, cyclohexynol. etc. Such an alkyl group may have 1 to 3 substituents, and preferred substituents include the above-mentioned halogen atom, hydroxyl group, mercapto group, lower alkylamino group, di-lower alkylamino group, and lower These include an alkylthio group, a lower alkoxy group, a tri-lower alkylthio group, a lower alkoxycarbonyl group, and the like (R' and R5 have the same meanings as above). More preferable substituents for the alkyl group include a chlorine atom, trimethylsilyl group, and groups represented by R4' and R'' are preferably C1-
4 alkyl group, more preferably a methyl group.

Preferred examples of R and R include the above-mentioned lower alkyl groups, halogen atoms, nitro groups, cyano groups, lower alkoxy groups, and aryl groups optionally substituted with 1 to 5 lower alkoxycarbonyl groups. or a lower alkenyl group or a lower alkynyl group. More preferably, it is a phenyl group optionally substituted with 1 to 5 lower alkyl groups, a halogen atom, a nitro group, or a lower alkoxy group as described above, an allyl group, or a propargyl group.

Preferred examples of compound (1) or a salt thereof include a compound represented by the formula [wherein X'' represents a halogen atom and R' represents a C1-4 alkyl group or a C7-4 alkenyl group] or a salt thereof; A compound represented by the formula [the symbols in the formula have the same meanings as above] or a salt thereof, or a compound represented by the formula [wherein Xa has the same meaning as above and Rb represents a C3-4 alkenyl group] Or its salt etc.

In formulas (I'), (Ib), (, I'), X''+iC1
, Br.

Indicates a halogen atom such as F. Examples of the C1-4 alkyl group represented by R' include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, and butyl, and in particular, alkyl groups having 2 or 4 carbon atoms. The groups ethyl, n-propyl, i-propyl, n-butyl and the like are preferred. Examples of the C2-4 alkenyl group represented by R'' and Rb include vinyl, allyl, isopropenyl, l-butenyl, and allyl is preferred.

Compounds ([) [including ([”), (Ib), (1″)]
As the salt, acid addition salts such as inorganic acid addition salts and organic acid addition salts, and base salts such as inorganic base salts and organic base salts are used. Examples of inorganic acids that can generate inorganic acid addition salts include hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, and phosphoric acid; examples of organic acids that can generate organic acid addition salts include p-
) Luenesulfonic acid, methanesulfonic acid, formic acid, trifluoroacetic acid, etc. are used.

As the inorganic base salt of compound CI), salts with alkyl metals (e.g., sodium, potassium, etc.), alkaline earth metals (e.g., calcium, etc.), ammonia, etc. are used, and as the organic base salts of compound (I), for example, dimethylamine, triethylamine, piperazine, pyrrolidine,
Piperidine, salts with benzylamine, etc. are used.

Compound (1) of the present invention or a salt thereof has an asymmetric carbon atom and therefore can exist in two types of optical isomers. Compound (1) or a salt thereof of the present invention includes a single dextrorotatory or levorotatory isomer of each compound and a mixture of these isomers in any proportion.

Compound (1) or a salt thereof (including optically active isomers, the same shall apply hereinafter) can be used to control weeds found in paddy fields and fields (e.g., barnyard grass, Japanese aphrodisiac, cyperus japonica, azalea, Japanese horsetail, cyperus japonica, cyperus japonica, Japanese millet, cyperus japonica, Not only does it have an excellent herbicidal power against green foxtail, corn, Japanese millet, Japanese millet, Seiban sorghum, Japanese sorghum, Japanese grasshopper, Japanese black grub, firefly, water snail, etc.) at an extremely low dose, but also
It is highly safe, with no chemical damage to broad-leaved crops such as cotton, sugar beets, rapeseed, and sunflowers, as well as to legumes such as rice.

Compound (I) or a salt thereof exhibits an excellent selective herbicidal effect between crops and various weeds, has low toxicity to mammals and fish and shellfish, does not pollute the environment, and can be used in rice paddies, fields, It is extremely safe to use as a herbicide in orchards and non-agricultural lands.

When using compound (1) or a salt thereof as a herbicide, compound (1)
) or its salts (especially optically active isomers) are dissolved or dispersed in a suitable liquid carrier depending on the purpose of use, or mixed or adsorbed with a suitable solid carrier to form an emulsion, oil solution, or spray. agents, hydrating agents, powders, DL type powders,
Used in preparations such as granules, microgranules, microgranules F, and tablets. These preparations may contain emulsifiers, dispersants, spreading agents, penetrating agents, wetting agents, mucilage agents, stabilizers, etc., as required, and can be prepared by methods known per se.

Examples of liquid carriers (solvents) used include water, alcohols (e.g., methanol, ethanol, n-propatool, isopropatool, ethylene glycol, etc.), ketones (e.g., acetone, methyl ethyl ketone, etc.), ethers (e.g., acetone, methyl ethyl ketone, etc.), For example, dioxane.

Tetrahydrofuran Ethylene glycol, monomethyl ether, diethylene glycol monomethyl ether
propylene glycol monomethyl ether, etc.), aliphatic hydrocarbons (e.g., keronone kerosene; fuel oil, etc.),
Aromatic hydrocarbons (benzene, toluene, kiln, solvent naphtha, methylnaphthalene, etc.), halogenated hydrocarbons (e.g. dichloromethane, chloroform carbon tetrachloride, etc.), acid amides (e.g. dimethylformamide, dimethylacetamide) etc.), esters (e.g., ethyl acetate, butyl acetate, aliphatic glycerin ester, etc.), nitriles (e.g., acetonitrile, propionitrile, etc.), and one of these solvents is suitable.
Use one species or a mixture of two or more species in an appropriate ratio.

Solid carriers (diluents, bulking agents) include vegetable powders (e.g.
(soybean powder, tobacco powder, wheat flour, wood flour, etc.), mineral powders (e.g., clays such as kaolin, bentonite, acid clay, talcs such as talcum powder, waxite powder, silicas such as diatomaceous earth, mica powder, etc.) , alumina, sulfur powder, activated carbon, etc., and these may be used alone or in combination of two or more in an appropriate ratio.

Surfactants used as emulsifiers, spreaders, penetrants, dispersants, etc. may include soaps, polyoxine ethylene alkylaryl ethers [e.g., Neugen, E.N. 142 (E, A142' (manufactured by Kogyo Seiyaku Co., Ltd.)], polyoxyethylene aryl esters (Example: Nonal 0 (manufactured by Toho Chemical Co., Ltd.)), alkyl sulfates [e.g., Emar 10 @ Emar 40° (Kao Seiken ( Co., Ltd.)], alkyl sulfonates [eg, Neoken 0. Neogen T0 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): Neoperex @ (manufactured by Kao Sekiken Co., Ltd.)], polyethylene glycol ether lti [e.g., Noniball 85°, Noniball 100@, Nonipol 160 @ (Sanyo Kasei Co., Ltd.) )], polyhydric alcohol esters [e.g., Tween 20
Nonionic and anionic surfactants such as @Tween 80° (manufactured by Ken Hanamishiki Co., Ltd.) are used.

The content ratio of compound (r) or its salt in the herbicide is approximately 1 to 90% by weight for emulsions and wettable powders, and from 0.01 to 90% by weight for oils, powders, and DL type powders. Approximately IO weight % or so, fine granules F, 005 as granules
Approximately 10% by weight is appropriate, or these concentrations may be changed as appropriate depending on the purpose of use. Emulsions, wettable powders, etc., are suitably diluted and increased in volume (for example, 100 to 100,000 times) with water before use, and then sprayed.

When using compound (r) or its salt as a herbicide, does the amount used vary depending on the application location, application time, application method, target vehicle type, cultivated crops, etc.?
1) or its salt) is about 0.25 to 509, preferably about 1 to 109, per are of paddy field, and about 0.25 to 209, preferably about 1 to 1, per are of field.
It is about 09.

Compound (I) or a salt thereof can be applied to the soil before the emergence of undesirable grass species (pre-emergence application) or to the parts of the growing plant above the soil (post-emergence application). ).

The herbicide of the present invention may be used as necessary with other types of herbicides, plant growth regulators, fungicides (e.g., organochlorine fungicides, organic sulfur fungicides, azole fungicides, antibiotics, etc.), and insecticides (e.g. ,
pyrethroid insecticides, organophosphorus insecticides, carbamate insecticides, etc.), other acaricides, nematicides, synergists,
Attractants, repellents, pigments, fertilizers, etc. can be mixed and used together.

The compound (1) of the present invention or a salt thereof has the general formula (■): B
-Z (II) (wherein Z is a leaving group (e.g. halogen atom such as fluorine, chlorine, bromine, iodine, etc., Cl-10 aromatic hydrocarbon sulfonyloxy such as tri-toluenesulfonyloxy, methanesulfonyloxy etc.) 010. alkanesulfonyloxy, etc.), and B has the same meaning as in (1) above.) An appropriately substituted imidazo[1,2-a] having a leaving group at the 2-position It can be produced from bipyridines or their salts. There are five possible routes for converting imidazo[1,2-a]bipyridines II) having a leaving group at the 2-position or a salt thereof into the compound (1) of the present invention or a salt thereof. Below are routes A13 and C
, D support E.

Pathway A H5 H ([1) (I[[) (+) According to Pathway A, imidazo[1,
2-a] Bipyridines II) Mako's salt is 2(4-
The compound (T) of the present invention or a salt thereof is directly produced by reacting with the hydroxyphenoxy)propionic acid derivative (I) in the presence of a base. Derivative (III) is known per se and can be produced by conventional methods.

Examples of the base used in the reaction include inorganic bases (eg, alkali metal hydroxides or carbonates such as caustic soda, caustic potash, and sodium carbonate, and alkali metal hydrides such as sodium hydride).

The reaction is preferably carried out in a medium that is inert to the reaction. Examples of solvents include aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride, ethyl ether,
Ethers such as isopropyl ether, dioxane, and tetrahydrofuran (hereinafter abbreviated as THF), nitriles such as acetonitrile, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, dimethylformamide, dimethyl sulfoxide, etc. are used. It will be done.

The reaction temperature is usually 20 to 200°C, preferably 80 to 1
The temperature is 50°C. The reaction is completed in about 30 minutes to 20 hours, and its completion can be confirmed by thin layer chromatography or high performance liquid chromatography.

Route B: summarized in the reaction equation below.

(■) (■) (V) (1) In the route, Z has the same meaning as above, and W also represents a leaving group (for example, fluorine, chlorine, bromine).

halogen atoms such as iodine, C8-1° aromatic hydrocarbon sulfonyloxy groups such as p-toluenesulfonyloxy groups, C+-g alkanesulfonyloxy groups such as methanesulfonyloxy groups, etc.), and Z and W are the same. - or may be different. According to route B, imidazo[1,2-a]bipyridines II) having a leaving group at the 2-position or a salt thereof reacts with hydroquinone in the presence of a base to give compound (■) or a salt thereof.

As the base used in the reaction, for example, an inorganic base (eg, a hydroxide, carbonate or hydride of an alkali metal such as caustic soda, caustic potash, sodium carbonate, sodium hydride, etc.) is used. The reaction is preferably carried out in a reaction-inert solvent. Suitable solvents include, for example, benzene, aromatic hydrocarbons such as toluene, dichloromethane,
Halogenated hydrocarbons such as chloroform and carbon tetrachloride, ethers such as ethyl ether, isopropyl ether, dioxane, and THF, nitriles such as acetonitrile, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate and butyl acetate. , dimethylformamide, dimethyl sulfoxide, etc. are used. The reaction temperature is usually 20 to 200°C, preferably 80°C.
~150°C. The reaction is completed in about 30 minutes to 20 hours, and its completion can be confirmed by thin film chromatography or high performance liquid chromatography.

The thus obtained 2-(4-hydroxyphenoxy)imidazo[1,2-a]pyridine derivative (IV) or a salt thereof is reacted with an alkanoic acid derivative (V) having a leaving group W in the presence of a base. In this way, the desired compound (r) or a salt thereof can be obtained. In addition, in this case, the optically active compound (
I) Mako can get the salt.

As the base used in the reaction, for example, an inorganic base (eg, a hydroxide, carbonate or hydride of an alkali metal such as caustic soda, caustic potash, sodium carbonate, sodium hydroxide, etc.) is used. The reaction is preferably carried out in a reaction-inert solvent. Suitable solvents include, for example, benzene,
Aromatic hydrocarbons such as toluene, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride,
Ethyl ether, isopropyl ether, dioxane,
Ethers such as THF, nitriles such as acetonitrile, ketones such as acetone, methyl ethyl ketone,
Esters such as ethyl acetate and butyl acetate, dimethylformamide, and dimethyl sulfoxide are used.

The reaction temperature is usually 20-200°C, preferably 80-15°C.
It is 0°C. The reaction is completed within 30 minutes to 50 hours, preferably 30 minutes to 20 hours, and its completion can be confirmed by thin layer chromatography or high performance liquid chromatography.

Compound (V) used as a raw material in this reaction is, for example, published in Journal of Pesticide Science 1
It can be synthesized by the method described in Vol. 0, p. 69 (1985) or a similar method.

Route C: summarized in the reaction equation below.

(ff) (V[) (IV) (V) In route C, imidazo[1,
2-a] Bipyridines [[) or a salt thereof is reacted with p-methoquinophenol in the presence of a base.

2-(4-methquinphenoquine)imidazo[l,2-
a] Pyridine derivative (■) Give the child its salt. The base and solvent used in the reaction are the same as those used in Route A and Route B, and no further explanation is necessary. The same applies to the reaction temperature and reaction time.

The 2-(4-methquinphenoquine)imidazo[1,2-a]bivirin derivative (VI) or its salt obtained is heated with pyridine hydrochloride or with hydrogen bromide, for example in acetic acid. or tetrahedron
Letters [Tetrahedron Letters] 132
7 (1970) or a method similar thereto to obtain the corresponding 2-(4-hydroxyphenoquine)imidazo[1,2-&]pyridine derivative (
IV).

The third step (■)+(V)-(1) of route C is the same as the second step of route B and does not require further explanation.

Route D = summarized in the following reaction equation.

B-Z + C> CHr Obe'times:'-OH→B-0so:'
OCHJ〉(If) (■) (IV) (V) In the route, imidazo[1,
2-a] Bipyridines n) or its salt reacts with p-benzyloxyphenol in the presence of a base to form 2-(4-
A benzyloxyphenoxy)imidazo[1,2-a]pyridine derivative (■) or a salt thereof is provided.

The base and solvent used in the reaction are the same as those used in Route A and Route B, and no further explanation is necessary. Further, the reaction temperature and reaction time are also the same. The thus obtained 2-(4-benzyloxyphenoxy)imidazo[1
, 2-a] Pyridine derivative (■): Other salts can be prepared, for example, in a suitable solvent (e.g., alcohols such as methanol, ethanol, n-propanol, ethers such as THF, dioxane, dimethine ethane, or their like). 2-(4 -hydroxyphenoxy)imidazo[1,2-a]pyridine derivative (IV) or a salt thereof.

The third step of route B is the same as the second step of route B and does not require further explanation.

(Space below) Route E THP H (B) (■) (IV) (In the formula, THP represents a tetrahydrobilan-2-yl group, hereinafter abbreviated as THP.) By route E, a leaving group is added to the 2-position. imidazo [1,
2-2L] Pyridine (II) or its salt reacts with p(tetrahydrobilan-2-yloxy)phenol in the presence of a base to form 2-[4-(tetrahydrobilan-2-yloxy)phenoxycoimidazo[ 1,2-a
] Gives a pyridine derivative (■') or its salt. The base and solvent used in the reaction are route A and route B.
This is the same as Ni et al., and there is no need for further explanation. The same applies to the reaction temperature and reaction time.

The thus obtained 2-[4-(tetrahydrobilan-2-yloxy)phenoxy]imidazo[1,2-a
] The pyridine derivative (■') or its salt can be prepared by, for example, p-toluenesulfonic acid, concentrated sulfuric acid,
T removal is achieved by adding an acid catalyst such as concentrated hydrochloric acid and stirring.
HP conversion is performed to give the corresponding 2-(4-hydroxyphenoxy)imidazo[1,2-a]pyrinone derivative ([V) or a salt thereof.

The third step of route E is the same as the second step of route B and does not require further explanation.

Compound (■) (in the formula, Q excludes a cyano group) or a salt thereof can be synthesized using formula (II) as a raw material. For example, the compound (■') or a salt thereof and the general formula (■): R-AH (■) (wherein R and A have the same meanings as above) are combined in the presence of a suitable dehydration condensation agent. Alternatively, after converting compound (bi) or a salt thereof into an acid halide such as acid fluoride, acid chloride, acid bromide, acid iodite, etc., reacting with compound (■) in the presence of a suitable base. You can get it.

Suitable dehydration condensation agents described here include, for example, dicyclohexylcarbodiimide (hereinafter abbreviated as DCC), N, N
2-halopyridinium salts such as '-carbonyldiimidazole and 1-methyl-2-chloropyridinium iodite are used.

This reaction using these is based on Newer Methods of Preparative Organic Chemistry [Ne
Were Methods of Preparation
e Organic Chemistry (Acadm
ic Press4ew York)] 5thL61~1
08 pages, Journal of American Chemical Society (J Am Chem 5oc) No. 80@6
204 pages (1958), Chemistry Letters (Ch.
It can be carried out according to the method described in J. Emlett, ) p. 1045 (1975).

In addition, methods for converting compound (bi) or its salt into acid halides are described in the New Experimental Chemistry Course (edited by the Chemical Society of Japan).
Volume 14, “Synthesis and Reactions of Organic Compounds (I[)J110
It can be carried out according to the method described on pages 4 to 1120.

The obtained acid halide is reacted with a compound of formula (■) in the presence of a tertiary amine such as triethylamine or pyridine or an inorganic base such as caustic soda or sodium carbonate to give compound (I).

The reaction is carried out in a solvent inert to the reaction.

Suitable solvents include, for example, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride, ethers such as ethyl ether, isopropyl ether, dioxane, and THF, and acetonitrile. Nitriles such as acetone, ketones such as methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, dimethylformamide, dimethylformhokind, and the like are used.

The reaction temperature is usually -10 to 100°C, preferably 20 to 100°C.
The temperature is 80°C. The reaction is completed in about 30 minutes to 20 hours, and its completion can be confirmed by thin layer chromatography or high performance liquid chromatography.

Compound (1) or a salt thereof can also be produced by converting the substituent represented by Y into another type of substituent, as shown in the reaction formula below.

(Margin below) CH, -Hal CH, SO, R CO, Me (!ta! 1okle, 0THP) Indicates the same meaning.

(■' ) (■) (IX) (XI) (■' ) (X[) (In the formula, R' and R' are hydrogen atoms, and f2 is a straight chain or A branched lower alkyl group, Me represents a methyl group.
e, 0 THP- is OMe, instead of OCH, C) in the formula.
Indicates that 0THP is used. ) The target compound (I) or a salt thereof thus obtained can be processed by known means such as concentration, liquid conversion, distillation, solvent extraction,
It can be isolated and purified by salting out, crystallization, recrystallization, chromatography, etc. Moreover, when compound (T) is obtained as an educt or a salt, it can also be converted into the salt or educt according to a conventional method.

Compound (I[), which can be used as a raw material compound for compound (1) or a salt thereof, is produced from the compound of formula (H') according to the reaction formula shown below.

(Left below) Me (■') (XV) (xl) (XI) (4) ll0 (II') 01) (Xff) (XX) (6) Uniform methyl esterification (1') (XXI ”) (Xx[) (XXV') (XV) (xl) (XW) The reactions included in (1) above are reactions that are known per se. In the nitration reaction, examples of the nitration agent include fuming nitric acid, concentrated Nitric acid, etc. is used. This reaction is carried out in a solvent such as concentrated sulfuric acid or acetic anhydride, and the reaction temperature is usually -20 to 1
It is 00℃. The reduction reaction is carried out under the usual nitro group reduction conditions.
For example, it is carried out by a method such as catalytic hydrogenation. (I
X) is reacted under usual azotization conditions, for example, with sodium nitrate in hydrochloric acid to form a diazonium salt (X), and then reacted with cuprous chloride to obtain compound (X[).

The above (2) and (3) are compounds (■) in which imidazole ring hydrogen is replaced with lithium and then reacted with an electrophile such as ethyl chlorocarbonate or dimethyl disulfide.

(XV) and convert these into other substituents. As the lithiation agent used in these routes, alkyllithium such as methyllithium, n-butyllithium, and thi-butyllithium, lithium amide, lithium diisopropylamide, etc. are used. Compound (■) is hydrolyzed by a conventional method, and then halogenated with a halogenating agent such as thionyl chloride, phosphorus oxychloride, etc., to be converted to compound (XXI).

Compound (XI) is reacted with a suitable primary or secondary amine in the presence of a base (eg, pyridine, triethylamine, etc.) to give compound (Xff). Compound (XV) is oxidized with a suitable oxidizing agent such as hydrogen peroxide, potassium permanganate, m-chloroperbenzoic acid, etc. to form compound (XV).
W) is further oxidized to give compound (XW).

The reactions included in (4) above are reactions known per se. The formylation reaction is carried out, for example, by Pourtin de la Société de France (Bulletin de la
5ociete Cheique de France
) 1989-1999 (1962), Journal
of American Chemical Society (J
Am Chem 5oc) Volume 75.

989 (1953), etc., or according to the method described therein.

Compound (XW) is reacted with hydroxyamine to give compound (Xff). This reaction is preferably carried out in a solvent inert to the reaction, such as dimethylformamide or acetonitrile.

Compound (XI) is reacted with a suitable dehydrating agent such as phosphorus oxychloride, thionyl chloride, or acetic anhydride to give compound (XX).

The reactions included in (5) above are reactions known per se.

Examples of oxidizing agents used in the oxidation reaction include potassium permanganate, manganese dioxide, and silver oxide.

This reaction is carried out in a solvent such as water or ethyl alcohol, and the reaction temperature is usually 0 to 100°C.

The methyl esterification reaction can be carried out under conventional esterification conditions, such as using an acid catalyst such as concentrated sulfuric acid in methanol, hydrochloric acid, tri-toluenesulfonic acid, and the like.

The oxidative methyl esterification reaction of compound (XVI) was described in the Journal of Organic Chemistry [Jou
RNA of Organic Chemistry
It can be carried out by the method described in Ko, Vol. 54, p. 1213 (1989), or in accordance therewith.

The reactions included in (6) above are reactions known per se. In the sulfonation reaction, sulfonating agents such as sulfuric acid, fuming sulfuric acid, and chlorosulfonic acid are used. In the chlorination reaction, a chlorinating agent such as thionyl chloride, phosphorus oxychloride, etc. is used. The reduction reaction can be carried out using, for example, OrganicSynthesis Collective Volume CO11ect.
ive Volume] Volume 1, page 504, Canadian Journal of Chemistry [Canada
n Journal or Chemistry] No. 4
It can be carried out by the method described in Vol. 1, p. 1646 (1963), or in accordance therewith. In the methylation reaction, methyl iodide, dimethyl sulfate, etc. are used as the methylating agent.

Compounds (■') and their salts, which are the starting materials for the above reactions (L), (2), (3), (4), and (6), are available from The Chemistry of Heterocyclic Compounders [The Chemistry of Heteroc
yclic compounds (interscie
[Comprehensive Heterocyclic Chemistry] Volume 15, Part 1 and Part 2, Volume 30, Comprehensive Heterocyclic Chemistry
eterocyclic Chemistry (Perg.
amon Press)] Volume 4, Journal 1 year old Bu.
Heterocyclic chemistry (JHeteroc)
ycl, Chem), Vol. 2, p. 53 (1965), or according to the method described therein.

Compound (■') can also be produced by the reaction formula shown below.

(XI) (χri(XXI) X+ (XXI') (wherein, X and n have the same meanings as above)
er) Vol. 57, pp. H81 and 2091 (1924), or according to the method described therein. Compound (XXII) is halogenated with a halogenating agent such as phosphorus oxychloride or thionyl chloride to form compound (XXII).
XXff).

Compound (XXII) can also be prepared from compound (XX
V).

In the above reaction formula, compound (XXff) can also be directly obtained without going through compound (XXI) by reacting compound (XXII) with a halogenating agent such as phosphorus oxychloride.

(Left below) The substituent X on the pyrinone ring of the compound (Uo) can be converted to the substituent X according to the reaction formula shown below.

(XXVI) (XXl’ff) [1al (XXVIII) The reactions included above are reactions known per se.

Compound (XXVI) is converted to compound (XXVII) under conventional reducing conditions, such as catalytic hydrogenation.

The process from compound (XXHI) to compound (XXfX) is performed, for example, by Hemische Berichte (ChemBer).
It can be carried out by the method described in Vol. 60, p. 1189 (1927) or in accordance therewith. That is, the raw material for producing the compound of the present invention can be easily produced by a known method or a method analogous thereto.

Of the above raw materials or synthetic intermediates, the compound used in the form of a salt can be used in the form of a salt, such as the one described for compound (1).

(G) Effects of the Invention The compound (1) of the present invention or its salts, including its optical isomers, exhibits excellent herbicidal activity in fields, etc., as shown in the test examples below, and moreover, it exhibits excellent herbicidal activity against crops. There is little drug damage. Therefore, the present invention provides an excellent selective herbicide.

The present invention will be specifically explained below with reference examples, examples, and formulation examples, but the present invention is not limited thereto.

Symbols in Reference Examples and Examples have the following meanings.

S: singlet Me: methyl group d: doublet Et: ethyl group nitriblet Ph: phenyl group q quartet d, d: double tablet m: multibullet br or broad: wide J, coupling constant DMSO dimethyl sulfoxide (conducted) Example) Reference Example 1 2-chloroimidazo-[
1°2-a] pyridine (15.3 g) was dissolved under a stream of dry nitrogen, and the solution was cooled to -65°C. Then, 68.7xQ of n-butyllithium (16M hexane solution) was added to
The mixture was added dropwise over 40 minutes so as not to exceed 0°C.

Stir for 30 minutes below -60°C, then anhydrous THFlOI
11.99 of ethyl chlorocarbonate dissolved in 12 was added dropwise over 25 minutes. After stirring at −60°C or lower for 15 hours,
The reaction solution was slowly returned to room temperature, poured into about 0.5Q ice water, and extracted with dichloromethane. The dichloromethane layer was separated and dried over anhydrous sodium sulfate.

Dichloromethane was distilled off and the residue was purified by Norica gel column chromatography to obtain the title compound 1649. m, p61-62°C NMR (CDC13) δ: 1.45 (t, 3t()
, 4.48 (q, 2H).

6.92~7.38 (m, 1t(), 7.50
(dd, 21(), 9JO(dIH) Reference Example 2 2.6-dichloro-3-nitroimidazo E1.2-a]
2,6-dichloroimidazo-[l] in pyridine concentrated sulfuric acid 18zfj
2-a] Add 3.79 g of pyridine under water cooling, and add 2.7 g of concentrated nitric acid while stirring vigorously. SxQ was added dropwise over 15 minutes. The mixture was stirred for 30 minutes under water cooling and for 3 hours at room temperature, and the reaction solution was poured into 100×Q of ice water, and the precipitated crystals were collected by filtration and washed with water. The obtained crystals were dried to obtain the title compound 3.89. m
, p, 171-172°C NMR (CDCIz) δ: 7
．． 70 (s, 2H), 9.51 (s, IH) Reference Example 3 2.6-Dichloro-3-formylimidazo-121]pyridino Oquinochloride in anhydrous dimethylformamide 45zC at 5-10°C under a stream of dry nitrogen Phosphorus 6aQ was slowly added dropwise. Stir for 15 minutes below 5 °C, then 26 dichloroimidazo[
1,2-2L]pyridine 109 was added dropwise at 5-10°C,
Stirred at room temperature for 3 hours. The reaction solution was poured into about 0.5Q ice water, and the precipitated crystals were collected by filtration and washed with water. The obtained crystals were dried to obtain 1089 of the title compound. m, p,
9g-98, 5°CNMR (CDCl3) δ: 7,
60 (s, 2H), 8.54 (s, IH).

9.96 (s, IH) The aldedes obtained by the same method as Reference Example 3 were
Shown in the table.

(Left below) Table 1 Reference Example 4 General formula 267-trichloro-3-formylimidazo-1
, 2-a copyrinone.

Anhydrous dimethylformamide 50x (l) under a stream of dry nitrogen
Thereto, 5.39 g of phosphorus oxychloride was slowly added dropwise at 5 to 10°C. Stir for 20 minutes at 5-10℃, 2゜6.7-
Trichloroimidazo "l, 2-a] pyridine 5, L6
9 was added in crystal form and stirred at 35-40°C for 7 hours. −
The reaction solution was poured into ice water at a temperature of about 0.3 ρ, and the precipitated crystals were filtered and washed with water. When the obtained crystals were dried, the title compound 4.79 was obtained. m, p.

142-143.5°C NMR (CDC13) δ: 7.70 (d, LH), 9
．． 58 (d, 18), 10.05 (s, IB) Reference example 5 2,6-dichloro-3-cyanoimidazo[1,2-a]
10 g of 2,6-dichloro-3-formylimidazo[1,2-a]pyridine in pyridine dimethylformamide 60*Q
, add hydroxylamine hydrochloride 3.99 to 75-80
Stirred at ℃ for 35 hours. Thereafter, the mixture was cooled to 10° C. or lower, and Oquine Salt 1Hirin 881Q was slowly added dropwise thereto, and the mixture was stirred overnight at room temperature. The reaction solution was poured into approximately 0.5i7 ice water, and the precipitated crystals were collected by filtration and washed with water. The obtained crystals were dried and recrystallized from ethyl acetate to obtain the title compound 7.89 in the form of colorless needles. m, p, 155-159° CNM
R(CDCl2)δ: 7.50-7.70 (m, 28
), 8.30-8.48 (m, lH).

Nitriles obtained by the same method as Reference Example 5 were
Shown in the table.

(Margin below) Table 2 Reference Example 6 2-(4-Benzoloxyphenoxy)toquincarbonylimidazo[1 2-aco3 epiridine 60% oily sodium hydride 079 was suspended in anhydrous dimethylformamide 50RQ. After slowly adding 3.59 g of hydroquinone monohenzyl ether in crystal form to this solution, the mixture was stirred at room temperature for 30 minutes and then at 100° C. for 10 minutes. Next, 3.79 g of 2-chloro-3-ethquincarbonylimidazo[1,2-a]pyridine was added in crystal form and stirred at 105-110°C for 8 hours.

The reaction solution was poured into a 0.3μ Hyomotosuri bottle and extracted with chloroform. The chloroform layer was separated and dried over anhydrous sodium sulfate. When chloroform was distilled off and the residue was purified by silica gel column chromatography, the title compound 2.8 was obtained.
9 was obtained. ,, p, 119-120°C Reference Example 7 The liquid was concentrated, ethanol was distilled off, Honsuri 501 was added to the residue, and the mixture was neutralized with concentrated hydrochloric acid. The precipitated crystals were collected by filtration and dried, and the resulting colorless crystals were heated in a round bottom flask at 140~
Heating to 150°C for 20 minutes resulted in vigorous foaming and formation of an oil. After cooling to room temperature, the oil was dissolved in chloroform and washed with water, and the chloroform layer was separated and dried over anhydrous sodium sulfate. When the solvent was distilled off and the residue was purified by silica gel column chromatography, the title compound 10 was obtained.
59 was obtained as brown needles. m, p, 124.5-1
25.5°C NMR (CDCIJδ: 5.05 (s, 2
H), 6.75 (t, 2H), 6.90-7.09
(+11.3I(), 7.10~7.29(m, 3H)
, 7.40 (s, 5H) 7.99 (d, IH) Reference Example 8 1.59 of 2-(4-benzyloxyphenoquine)-3-ethoxycarbonylimidazo[1,2-a]pyridine was added to ethanol 15a + I2 Add 10% sodium hydroxide aqueous solution 10xQ to this and stir at room temperature for 40 minutes.
The mixture was stirred for 10 minutes while heating under reflux. Reaction 2-(4-benzyloxyphenoxy)imidazo-[1,2-a]pyridine (19 g) was added to 25 mQ of tetrahydrofuran and 2 ethanol (25 mQ) of ethanol.
Dissolved in a mixed solvent of 5x & 10% palladium-
02 g of carbon catalyst was added and catalytic hydrogenation was carried out at normal pressure for 12 hours. The reaction solution was filtered to remove the catalyst, and the filtrate was condensed. The residue obtained was purified by silica gel column chromatography to obtain the title compound 039 as colorless crystals. m, p
, 163-164°C NMR (d,-DMSO) δ: 6.70-7.516
(m, 7H), 8.41 (d, IH), 9.30 (
s, IH).

Reference Example 9 The title compound was obtained in the form of colorless crystals from 2-(4-benzyloxyphenoxy)-3-ethoxycarbonylimidazo[1,2-a]pyridine in the same manner as described in Reference Example 8. m, p, 186-187°C Reference Example 10 3.29 g of 2,6-fuchloro-3-formylimidazo[1,2-a3 birinone is suspended in 10 glIc of anhydrous methanol, and N-iodoscunonimidazo is suspended in this solution. 101
g and 529 g of potassium carbonate were added thereto, and the mixture was stirred at room temperature in the dark for 24 hours. After the reaction, add 709 parts of sodium thiosulfate to 15 parts of water.
A solution dissolved in 0+v+2 was added to the reaction solution and stirred vigorously for about 20 minutes. The resulting solution was extracted with chloroform. The chloroform layer was separated and dried over anhydrous sodium sulfate. Chloroform was distilled off, and the residue was diluted with ethanol 6
Girard reagents 1, 39 and concentrated hydrochloric acid 2-3a were added to the mixture dissolved in 0111, and the mixture was heated under reflux for 15 minutes. The precipitated crystals were removed by filtration, and the filtrate was concentrated under reduced pressure to obtain 1.5 g of the title compound as colorless crystals. m, p, : 1
33-134°C NMR (CDCl3) δ: 4.0
(s, 31(), 7.41 (dd, lH).

7.59 (d, IH), 9.42 (d, IH)
.

Reference Example 11 Reference Example [2] 60% oily sodium hydride 0849 was suspended in 601 anhydrous dimethylformamide, and 2.69 g of p-methoxyphenol in crystal form was added thereto. After stirring at room temperature for 20 minutes and further stirring at about 60°C for 10 minutes, 4.99% of 2,6-dichloro-3-methoxycarbonylimidazo[1,2-a]pyridine in crystal form was added, and the mixture was stirred at 135-140°C. The mixture was stirred for 5 hours. The reaction solution was poured into 0.3Q ice water, made weakly acidic with concentrated hydrochloric acid, and extracted with dichloromethane. The dichloromethane layer was separated and dried over anhydrous sodium sulfate.

Dichloromethane was distilled off, and the residue was purified by silica gel column chromatography to obtain 1.99 of the title compound as colorless crystals. m, p, : 162-165℃
NMR (CDCl3) δ: 3.80 (s, 3H)
, 3.98(s, 3H) 6.91(d, 21(),
7.21 (d, 2H), 7.32-7.49 (m,
2H).

9.43(s, 18) 2-(4-methoxyphenoxy)-6-chloro-3methoxycarbonylimidazo[1,2-a]pyridine2.
39 was dissolved in ethanol 35xQ, 5% aqueous sodium hydroxide solution 20xQ was added thereto, and the mixture was heated under reflux for 1 hour. Add 50jIQ of water to the residue obtained by distilling off the solvent,
It was neutralized with concentrated hydrochloric acid, and the crystals were collected by filtration and washed with water.

The resulting crystals were placed in a 100xp round bottom flask and heated for 18
It was heated at 0 to 190°C until the generation of carbon dioxide gas stopped. Approximately 60 g of chloroform was added to the resulting residue to dissolve the contents, and insoluble matter was removed by filtration. The residue obtained by concentrating the chloroform-soluble material was purified by silica gel column chromatography to obtain the title compound I59 as colorless crystals.

m, l): 122-124°C 1tMR (CDCl3) δ: 3. H(s, 3H)
, 6.89 (d, 2H) 6.98 (s, LH),
7.0-7.30(m, 3t(), 7.41(d
, 1H) 8.05 (s, LH).

Reference Example 13 Honsuri 50, MO, was added to the distillate, neutralized with concentrated hydrochloric acid, and then extracted with ethyl acetate. The ethyl acetate solution was dried over anhydrous sodium sulfate. The residue obtained by distilling off ethyl acetate was purified by silica gel column chromatography to obtain 0.59% of the title compound as pale yellow crystals. n, p,
: 140-143°C NMR (d, -DMSO) δ:
6.80 (d, 2H), 6.96-7,23 (
m, 4H), 7.38 (d, IH), 8.29 (s,
18), 9.01 (s, IH).

Reference Example 14 Under a stream of dry nitrogen, 0.369% of 60% oily sodium hydride was suspended in 1OxQ of anhydrous dimethylformamide, and 0.579 of ethyl mercaptan dissolved in 1OJIQ of dimethylformamide was added dropwise to this solution at room temperature.

After stirring for 5 minutes at room temperature, 1.09 of 2-(4-methquinphenoxy)-6-chloroimidazo[1,2-a]pyridine dissolved in 1 Optl of dimethylformamide was added.

The solution thus obtained was heated under reflux and stirred for 3 hours, cooled to room temperature, filtered, and the filtrate was a-condensed. 60% oily sodium hydride in 60 ml of residual anhydrous dimethylformamide 0
．． 669 was suspended, and dimethylformamide 101 was added to this.
29 g of tetrahydropyranyl-2-yloxyphenol dissolved in 26-dichloro-3-
Cyanoimidazo[1,2-a copyridine 219 was added in crystal form and stirred at 130-135°C for 15 hours.

The reaction solution was concentrated under reduced pressure, chloroform was added to the resulting residue, and insoluble materials were filtered off. Chloroform was distilled off, and the residue was purified by silica gel column chromatography to obtain 1.9 g of the title compound in the form of colorless crystals.

m, p, +172-175℃ NMR (CDCl5
) δ: 1.33 to 2.12 (br, m, 6H), 3
J8-3.71 (br, m, 18), 3.75-4.
10 (br9m, IH), 5.31-5.44 (
m, LH), 6.93-7.31 (m, 4H), 7
．． 35-7.60 (m, 2H), 8.25 (s, L
H) Reference Example 15 = 3-cyanoimidazo[1,2-a]pyridine 2-(4-(tetrahydrobilan-2-yluoquine)phenoquino)-6-chloro3-cyanoimidazo[1,2- 179% of a3 pyridine was suspended, 0.099% of p-toluenesulfonic acid was added thereto, and the mixture was stirred at room temperature for 2 hours. The reaction solution was filtered and the resulting crystals were washed with chloroform to obtain the title compound 119 as colorless crystals.

m, p,: 280-283°C (decomposition) NMR (DM
SO-do) δ・6.82 (d, 2H), 7.
13 (d, 2H) 7.62 (s, 2H), 8.73 (s
jH), 9.42 (br, s, IH) Example 1 Ethyl 2-(4-hydroxyphenoxy)propionate 4,39 was dissolved in 60zf2 of acetonitrile, and 2.89% of potassium carbonate was added to this solution and heated. 3 under reflux
Stirred for 0 minutes. Next, 2-chloro-3-nitroimidazo[1,2-a]copyridine, 09 was added and the mixture was heated under reflux for 4.5 hours. The reaction solution was filtered, the filtrate was condensed, and the residue was dissolved in dichloromethane and washed with water.

The chloromethane layer was separated and dried over anhydrous sodium sulfate. Dichloromethane was distilled off, and the residue was recrystallized from ethanol to obtain the title compound 7.09 as yellow crystals. ff1. I), 125-f27℃ NMR (CD
C13) δ: 1.25 (t, 3H), 1.60 (d
, 3H).

4.23 (Q, 2H), 4.75 (Q, LH), 6
．． 71-7.10 (m, 2H) 7.10-7.42 (m
, 3H), 7.50-7.90 (m, 2H), 9.
49 (d.

IH).

Example 2 The title compound was obtained in the form of colorless crystals from 2,6-dichloro-3-nitroimidazo[1,2-a copyridine in a similar manner to that described in Example 1. H, p, 121-12
2.5°C NMR (CDC1,) 61.24 (t, 3H), 1.6
5 (d, 3H) 4.23 (Q, 2H) , 4.75 (
Q, 1l(), 6.94(d, 2H), 7.28(
d.

21(), 7.57(s, 2H), 9.55(s,
LH).

Example 3 Compound No. 3) 2-(4-hydroxyphenoxy)imidazo[12-a
] Pyridine 0279 was suspended in acetonitrile 1011ρ. Add potassium carbonate 0179 and heat to reflux for 1
After stirring for an hour, ethyl α-bromopropionate 0.22
9 was added and the mixture was further refluxed for 7 hours. The reaction solution was filtered, the filtrate was concentrated, and the resulting residue was purified by silica gel column chromatography to obtain 0.379 of the title compound as a yellow oil.

NMR (CDC1a) δ: 1.18 (t, 3H),
1.60 (d, 3H).

4.21 (q, 2H), 4.70 (q, 1) 1),
6.60-7.65 (m, 8) 1) 8.0 (d, LH)
.

(Left below) Example 4 The title compound was obtained as colorless crystals from 2-(4-hydroxyphenoquine)-3-ethquinecarbonylimidazo[1,2-a]pyridine in the same manner as described in Example 3. Obtained. m, p, 98-99° CNMR (CDCl3
) δ・1.22 (t, 3B), 1.35 (t, 3H)
.

1.60 (d, 3H), 4.21 (q, 2H), 4
．． 41 (Q, 2) ri, 4.70 (q.

18), 6.80-7.59 (m, 7H), 9.3
5 (d, IFI).

Example 5 Heat to 150°C and stir for 4 hours. The reaction solution was poured into 0.2C ice water, made weakly acidic with hydrochloric acid, and then extracted with ethyl ether. The ether layer was separated, washed several times with water, and then dried over anhydrous sodium sulfate. The residue obtained by distilling off the ether was purified by silica gel column chromatography to obtain the title compound as colorless crystals. m
, p, 144-146℃N! IIR(CDCl5)δ:
1.25 (t, 3H), 1.64 (d, 3H)4.
25 (q, 2H), 4.77 (Q, LH), 6.8
5-7.10 (m, 3H).

7.12-7.38 (m, 2H), 7.51 (t, 2
H), 8.25 (d, IH) Example 6 1.29 ethyl α-(4-hydroxyphenoxy)propionate was dissolved in 30 x fl of dimethyl sulfoxide, 089 potassium carbonate was added thereto, and the mixture was stirred at 80°C for 30 minutes. did. Next, 2-chloro-3-cyanoimidazo[1,
Add 2-a3 pyridine 109 to 140-2-(4-(
4.69 ethyl 3-cyanoimidazo[1,2-a]pyridin-2-yloxy)phenoxy)propionate was suspended in ethanol 50xQ, and a 10% aqueous sodium hydroxide solution low (!) was added thereto at room temperature. The reaction mixture was stirred under reflux for 1 hour.The reaction solution was filtered, and the resulting crystals were dissolved in water and neutralized with concentrated hydrochloric acid.The precipitated crystals were filtered to obtain the title compound 3.09. Ta.

IR(nujol)am-': 3500. 3
250. 3167, obtained by subtracting 11 from 1700 harm. m,! ], 208-209°C! IMR
(CDCl3) δ 1.65 (d, 3tD, 4.7
5 (q, 1H) 6.10 (br, s, 2H), 6.
80-7.80 (m, 12H), 9.62 (d, L
H) Example 8 2-(4-(3-carbamoylimidazo[1,2-a
1.39 of pyridin-2-yloxy)phenoquine)propionic acid and 1.039 of 1-methyl-2-chloropyridinium iodite were suspended in 15z12 of dichloromethane. To this solution, 0.379 g of aniline dissolved in 5×Q dichloromethane and 0.41 g of triethylamine dissolved in 5×Q dichloromethane were simultaneously added dropwise at room temperature over 10 minutes. After stirring at room temperature for 4.5 hours, 10h+Q of chloroform was added to the reaction mixture, and the mixture was washed with water five times.

The chloroform layer was separated and dried over anhydrous sodium sulfate. The residue obtained by distilling off chloroform was purified by silica gel column chromatography to obtain the title compound 059.
is 6 in colorless crystals and 20 mQ of anhydrous dimethylformamide.
Suspend 0.49% oily sodium hydride and add 10%
2.19 ethyl 2-(4-hydroquinophenoxy)propionate dissolved in 1Q of methylformamide was added dropwise at room temperature. Stir for 20 minutes to give 2,6-dichloro-3
2.19 -cyanoimidazo[1,2-a]pyridine was added in crystal form, heated to 120°C and stirred for 4 hours. The reaction solution was poured into ice-cold water and extracted with chloroform.

The chloroform layer was washed with water four times, separated, and dried over anhydrous sodium sulfate. The residue obtained by distilling off chloroform was purified by silica gel column chromatography to obtain 1.8 g of the title compound as colorless crystals. m, l), 1
11-112°CNMR (CDCl, )61.25(
t, 31 (), 1.61 (d, 3H) 4.22 (q
, 2H), 4.75 (q, IH), 6.91 (d, 2
H), 7.20 (d2H), 7.32-7.51
(m, 2H), 8.29 (s, LH) Example 9 2-(4-(3-cyano-6-
2.4 g of ethyl chloroimidazo[1,2-a]-pyridin-2-yloxy)phenoxy)propionate was suspended. To this solution was added 0.369 ml of sodium hydroxide dissolved in 5xQ of water, and the mixture was stirred at room temperature overnight.

After neutralization with concentrated hydrochloric acid, the precipitated crystals were collected by filtration and dried.

1.6 g of the title compound was obtained as colorless crystals. m, p, 1
73-177°C (decomposition) NMR (DMSOd-) δ: 1.53 (d, 3H),
4.82 (q, LH) 6.95 (d 2H), 7.
29 (d, 2H), 7.68 (s, 2H), 8.8
0(s.

LH), 12.85 (br, s, IH).

(The following is a blank space) Example 10 0.69 of 2-(4-(3-cyano6-chloroimidazo[1,2-a]-pyridin-2-yloxy)phenoquine)propionic acid was suspended in 5IlQ of dichloromethane. 0.49% of N,N'-carbonyldiimidazole was added to this solution and stirred at room temperature for 1 hour. Then, 0.2xQ of methanol was added to the reaction mixture, and the mixture was stirred at room temperature for 2 hours. Add dichloromethane 30xρ to the reaction solution, dilute hydrochloric acid,
The dichloromethane was separated by washing with water and dried over anhydrous sodium sulfate. The residue obtained by distilling off dichloromethane was purified by silica gel column chromatography to obtain 0.429 of the title compound as colorless crystals. m, p, 1
51-152°C NIIIR (CDC1,) δ: 1.6
2 (dJH), 3.79 (s, 3H) 4.78 (q
, LH), 6.95 (d, 2H), 7.25 (d,
2H), 7.40-7.61 (m, 2H), 8.3
0(s, LH) Example 11 8.35(s, IH) Example 12 2-(4-(3-cyano6-chloroimidazo[1,2-aipyridin-2-yloxy)phenoquine) in nochloromethane LOxQ ) suspending 0.69 propionic acid;
N,N'-carbonyldiimidazole 059 was added to this, and the mixture was stirred at room temperature for 1 hour. Next, N-methylaniline 0
．． 189 was added thereto, the mixture was stirred at room temperature for 2 hours, heated under reflux for 3 hours, and left at room temperature for 2 weeks. Add 5 dichloromethane to the reaction solution.
After adding 0xQ and washing with water, the nochloromethane layer was separated and dried over anhydrous sodium sulfate. The residue obtained by distilling off dichloromethane was purified by silica gel column chromatography to obtain 0.49 of the title compound as colorless crystals.

m, p, 174-175°C NMR (CDCl3) δ2 1.51 (d, 3
H), 3.32 (s, 3H) 4.79 (q, lH)
, 6.81 (d, 2H), 7.10-7.68 (m
, 9H) From 2-(4-hydroxyphenoquine)-6-chloroimidazo[1,2-a]pyridine, the title compound was obtained as a pale yellow oil in analogy to the method described in Example 3.

NMR(CDCl5)δ: 1.22(t, 3[()
, 1.60 (d, 3H) 4.21 (q, 2H), 4
．． 69 (q, IH), 6.90 (d, 2H), 6.
99 (sIH), 7.14 (d, 2H), 7.23
(d, IH), 7.42 (d, LH).

8.05 (s, IH) Example 13 Ethyl 2-(4-(6-chloroimidazo[1,2-&]pyridin-2-yloquino)phenoxy)propionate 069 was dissolved in chloroform LSxQ and in this solution Add 022 g of N-chlorosphnonimide at room temperature and stir for 2 hours. The reaction solution was concentrated, and the resulting residue was purified by column chromatography to obtain 0.549 of the title compound as a pale yellow oil.

NMR (CDCl3) δ: 1.25 (t, 3H),
1.60 (d, 3H).

4.20 (Q, 21 (), 4.70 (q, 1) 1),
6.89 (d, 2H), 7.15 (d.

2H), 7.23 (dd, LH), 7.41 (d,
IH), 8.05(d, 11()) and dried over magnesium sulfate.The residue obtained by distilling off the ether was purified by Norica gel column chromatography to obtain the title compound 09.
9 was obtained as colorless crystals with Lo[α]. ”=+23.6° (CHCL3.c=
2.0%) IR(Nujol)am-'; 221
0,174011MR(CDCl3)δ: 1.25
(t, 3H, J=6.3), 1.63 (d.

31 (, J=6.3), 4.22 (Q, 2)1. J＝
6.3), 4.84 (Q, LH, J・6.3) 6.92
(d, 2H, J = 9.0), 7.22 (d, 2H, J
=9.0), 7.40-7.61 (m, 2H), 8
．． The optical purity of the 29(d, IH1J=1.5) sample was ≧71%ee by 'HNMR analysis in the presence of E u (hfc)s.

1.0 g of 2-(4-hydroxyphenoxy)-6-chloro-3-cyanoimidazo[1,2-a]pyridine, 0.4 potassium carbonate in 1OzQ of anhydrous dimethyl sulfoxide.
89 and O-methanesulfonyl-(S)-(-)lactate ethyl ester 0.79 were added, and the mixture was stirred at room temperature for 48 hours. The reaction solution was filtered, ether 20011!12 was added to the filtrate, the mixture was washed twice with water, and the ether layer was separated. Table 3 shows the compounds obtained in the same manner as in Anhydrous Examples 1-13.

(Leaving space below) Table 3 General formulas Table 3 (continued) Table 3 (continued) Table 3 (continued) Table 3 (continued) Table 3 (continued) Table 3 (continued) Table 3 (continued) ) Table 3 (continued) Table 3 (continued) Table 3 (continued) Table 3 (continued) Table 3 (continued) Table 3 (continued) Formulation example ■ Emulsion compound No. 8 Quinlendodenlebenzene Emulsion containing sodium sulfonate (DBS-50X@) polyethylene glycol ether (Nonipol 85@) (used after diluting with water appropriately) 3% by weight 20% by weight 74 double star 3% by weight 11% No.2 Wettable powder compound No, 41 40'1li
96 Sodium ligninsulfonate 5% by weight Polyethylene glycol 5% by weight Ether (Noniball 85°) Clay Wettable powder made by mixing and pulverizing 50% by weight (used after appropriately diluting with water) Formulation example 3 Granule compound No. 47 2.5% by weight Sodium ligninsulfonate 5% by weight CMC (Celogen 7A@) 3% by weight Clay
Test example 1 of granules made by adding water to an 89.5% by weight mixture and kneading to granulate. Weeding effect test by field post-emergence treatment Diameter 10
Fill clay loam into C+++ Shifiebot 0, sow crabgrass, hackberry, corn, and dive.
After covering with 5 cm of soil, cultivate in a greenhouse for 2 to 3 weeks until the plants grow
When the plants reached the ~3-leaf stage, a diluted drug solution containing compound (1) was sprayed onto the foliage using a spray gun at a rate of 209°/109.59°/are. In addition, the drug dilution liquid is compound (1) 209.1OL5g and surfactant twin 20@
It was dissolved in acetone 5001 containing 2% (w/v) and diluted with water to a total volume of 5ν.

After the chemical treatment 2a, the herbicidal effects and phytotoxicity of each compound were evaluated using the following index.

Index Effect Suppression rate (weed killing rate) %0 None 0 ■ Slight 0.1-5002 Small 50.1-7503 Medium
751~87.54 large
87.6~9995 Maximum 10
0 Dive damage is expressed using the following index (the same applies to the following test examples).

Index drug damage 0 nothing ■Fine 2nd grade 3rd year 4 major 5 Maximum Damage rate% 0.1-12.5 12.6~25゜0 25.1-500 50.1-99.9 00 Table 4 The results are shown in Table 4.

Kihi and Saban sorghum were sown, covered with 5 cm of soil, and then cultivated in a greenhouse for 2 to 3 times. When the plants reached the 2 to 3 leaf stage, the diluted drug containing compound (1) and the control drug Allochinum were grown. A predetermined amount of was applied to the leaves using a spray gun.

Two weeks after the chemical treatment, herbicidal effects and chemical damage were evaluated using the same criteria as Test Example 1. The results are shown in Table 5.

Test Example 2 Comparison test with control drug by field post-emergence treatment Diameter foa
Paddy clay loam is filled in a Siphibot 0 of m, and paddy clay loam is filled in a 1/10,000-meter Aruwakner pot, which is filled with rice paddy clay loam, and is cultivated for a predetermined period of time in a 3 cm submerged water tank. On the other hand, fill a 1/10,000 Earl Wagnerbot with paddy soil, and after soaking and puddling, transplant two paddy rice seedlings at the 2-leaf stage, and make the water depth 3 cm. Seven days after transplanting paddy rice, when the Japanese millet reaches the one-leaf stage, a diluted drug solution containing a predetermined amount of compound (I) is applied to the pot.

The drug diluent was prepared by dissolving a predetermined amount of compound (D) in acetone 2Q containing surfactant Twin 2032% (w/v) and diluting it with water to give 5012.

Three weeks after the chemical treatment, the herbicidal effects on various weeds and the chemical damage to transplanted paddy rice were evaluated using the same index as in Test Example 1.

The results are shown in Table 6.

(Left below) 1) Sodium salt: Chemical name 3-(1-7lyl-t-x-1-minobutylidene)-6,6-dimethyl-2,4-dioxosifa to imasancarboxylic acid sodium salt test FAJ3
゜Selectivity test for rice Table 6 (blank below) Table 6 (continued) 2) n-Butyl 2-(4-(5-)lifluoromethyl-2-pyridyloxy)fehashi)bua pionate

Claims (1)

[Claims] 1. General formula: ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, B is optionally substituted imidazo[1,2-
a] Represents a pyridin-2-yl group, Q is a cyano group or formula: ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ {In the formula, A is an oxygen atom, a sulfur atom, or a formula: -NR^
1- (wherein R^1 represents a hydrogen atom or a lower alkyl group), R is a hydrogen atom or a hydrocarbon residue or a heterocyclic ring which may have a substituent group, or when A is -NR^1-, R and R^1 may be bonded to each other and form a heterocyclic group together with the adjacent nitrogen atom, and when A is an oxygen atom or -NR^1 −
When R is a formula: ▲A mathematical formula, a chemical formula, a table, etc.▼ (In the formula, R^2 and R^3 each represent a lower alkyl group, a lower alkoxy group, or a lower alkylthio group, or
It may form a 5- or 6-membered ring together with adjacent carbon atoms. ) or a salt thereof. 2. A compound represented by the general formula: B-Z (wherein Z represents a leaving group and B has the meaning as described in claim 1) or a salt thereof and the general formula: ▲ Numerical formula, chemical formula, ▼ A method for producing the compound according to claim 1, which comprises reacting the compound represented by the formula (wherein Q has the meaning as described in claim 1) in the presence of a base. 3. General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, B has the meaning as stated in claim 1)
The compound or its salt and general formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, W represents a leaving group, and Q has the meaning as stated in claim 1) 2. The method for producing the compound according to claim 1, which comprises reacting the compound with the compound in the presence of a base. 4. A herbicide containing the compound according to claim 1.