CN101573035A

CN101573035A - Herbicide containing benzoylpyrazole compound

Info

Publication number: CN101573035A
Application number: CNA2007800486200A
Authority: CN
Inventors: 下原田洋; 冢本正满; 池口雅彦; 菊川弘司; 永山宗一郎; 佐野真喜子; 北原芳德; 大北达哉; 畑裕士
Original assignee: Ishihara Sangyo Kaisha Ltd
Current assignee: Ishihara Sangyo Kaisha Ltd
Priority date: 2006-12-27
Filing date: 2007-12-27
Publication date: 2009-11-04

Abstract

To provide a novel herbicide which has a wide range of applications to agricultural or non-agricultural fields and various methods for application such as soil treatment and foliage treatment and which exhibits excellent herbicidal effects. A herbicide containing a benzoylpyrazole compound represented by the formula (I) or its salt, as an active ingredient: wherein R 1 is alkyl or cycloalkyl, R 2 is a hydrogen atom or alkyl, R 3 is hydroxy, R 4 is alkyl, haloalkyl or the like, R 5 is halogen, cyano, cyanoalkyl or the like, and R 6 is haloalkyl, halogen or the like.

Description

The weed killer herbicide that contains benzoylpyrazole compound

Technical field

The present invention relates to contain the new herbicides of benzoylpyrazole compound as active ingredient.

Background technology

Patent documentation 1 discloses various benzoylpyrazole compounds.But, wherein openly do not contain the weed killer herbicide of the benzoylpyrazole compound shown in the following formula (I) as active ingredient.

Patent documentation 1: No. the 0352543rd, the open communique of european patent application

Summary of the invention

All the time, in order to realize with the management of weeds rapid operationization, improve the yielding ability of agriculture and garden that requirement has excellent herbicidal performance to weeds and raise crop had the weed killer herbicide of safety with crop.But, explore the weed killer herbicide that is suitable for such purpose and depend on repetition test.

The present application persons have carried out various researchs in order to find to solve the more excellent weed killer herbicide of aforesaid problem to benzoylpyrazole compound, and the result has finished the present invention.Promptly the present invention relates to contain the benzoylpyrazole compound shown in the formula (I) or its salt weed killer herbicide as active ingredient,

In the following formula, R ¹It is alkyl or cycloalkyl; R ²Be hydrogen atom or alkyl; R ³It is hydroxyl; R ⁴Be alkyl, alkylhalide group, alkoxyl, halogen, nitro, cyano group, alkylthio group, alkyl sulphinyl or alkyl sulphonyl; R ⁵Be halogen, cyano group, cyanoalkyl, halo alkoxy alkyl, can be selected from alkyl, cyano group, cyanoalkyl, (alkylthio group) carbonylic alkyl, alkyl (thiocarbonyl) alkyl ,-C (O) OR ⁷With-C (O) SR ⁷In amino (thiocarbonyl) alkyl that replaces of at least 1 substituting group, thiocyanate groups alkyl, halogen alkoxyl; the alkoxyl alkoxyl; by the alkoxyl that 2 above halogen alkoxyls replace, alkoxyl halogen alkoxyl, halogen alkoxyl halogen alkoxyl; by the alkoxyalkyl of 2 above alkoxyls replacements; by the alkylthio group of 2 above alkoxyls replacements, by the alkylthio group that 2 above halogen alkoxyls replace, alkoxyl alkyl halide sulfenyl; halogen alkoxyl alkyl halide sulfenyl; the alkylthio group alkylthio group, alkyl halide sulfenyl alkylthio group, alkylthio group alkyl halide sulfenyl; alkyl halide sulfenyl halides alkylthio group; the alkylthio group alkoxyl, alkyl sulphonyl, alkyl sulphonyl alkyl; alkoxy carbonyl alkyl; the alkoxy carbonyl alkoxyl, the heterocyclic radical alkyl is by the alkoxyl of 2 above heterocyclic radicals replacements; by the alkyl that 2 above heterocyclic radical alkoxyls replace ,-OC (O) SR ⁷Or can be selected from alkyl, cyano group, cyanoalkyl, (alkylthio group) carbonylic alkyl, alkyl (thiocarbonyl) alkyl ,-C (O) OR ⁷With-C (O) SR ⁷In the aminoalkyl that replaces of at least 1 substituting group; R ⁶Be alkylhalide group, halogen, nitro, cyano group, alkylthio group, alkyl sulphinyl or alkyl sulphonyl; R ⁷Be alkyl, alkylhalide group, alkoxyalkyl, thiazolinyl, haloalkenyl, alkynyl or can be by R ⁸The aryl alkyl that replaces; R ⁸Be halogen, alkyl or alkoxyl; Wherein, work as R ⁴When being halogen, R ⁵Not cyanoalkyl, by the alkyl of 1 halogen alkoxyl replacement or by the alkoxyl of 1 alkoxyl replacement.

The present invention relates to contain described benzoylpyrazole compound or its salt and agricultural Herbicidal composition in addition with adjuvant.The present invention relates to the herbicidally effective amount of described benzoylpyrazole compound or its salt is applied to the place of undesired plants or its growth in addition, thereby prevent and kill off undesired plants or suppress the method for its growth.

The weed killer herbicide that contains the compound shown in the above-mentioned formula (I) will be brought into play excellent herbicidal effect.

Embodiment

In the above-mentioned formula (I), alkyl or moieties can be any of straight or branched, as its concrete example, can enumerate C such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, neopentyl, tertiary pentyl, n-hexyl, isohesyl, n-heptyl, n-octyl, n-nonyl _1-9Alkyl.

In the above-mentioned formula (I),, for example can enumerate C such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl as cycloalkyl _3-6Cycloalkyl.

In the above-mentioned formula (I), thiazolinyl or alkenyl part can be any of straight or branched, as its concrete example, can enumerate C such as vinyl, 1-acrylic, 2-acrylic, isopropenyl, pi-allyl, 1-cyclobutenyl, 2-cyclobutenyl, 3-cyclobutenyl, 1,3-butadiene base, 2-pentenyl, 4-pentenyl, 2-hexenyl, 4-hexenyl, 2-heptenyl, 4-heptenyl, 2-octenyl, 6-octenyl, 2-nonene base _2-9Thiazolinyl.

In the above-mentioned formula (I), alkynyl can be any of straight or branched, as its concrete example, can enumerate C such as acetenyl, propargyl, 1-propinyl, 1-pentynyl, 3-pentynyl, 1-heptyne base, 1-n-heptylacetylene base _2-9Alkynyl.

In the above-mentioned formula (I), halogen or can enumerate fluorine, chlorine, each atom of bromine or iodine as substituent halogen.Can be as the replacement number of substituent halogen for more than 1 or 2, be that they can be the same or different under the situation more than 2.In addition, the position of substitution of halogen can be the optional position.

In the above-mentioned formula (I), as R ⁷In substituent aryl or aryl moiety can enumerate phenyl, naphthyl etc.The replacement number of aryl or aryl moiety can be for more than 1 or 2, are being that they can be the same or different under the situation more than 2.In addition, their the position of substitution can be the optional position.

In the above-mentioned formula (I), replace R ⁷The R of aryl alkyl ⁸The replacement number can be for more than 1 or 2, be that they can be the same or different under the situation more than 2.In addition, each substituent the position of substitution can be the optional position.

In the above-mentioned formula (I), R ⁵The alkoxyl that is replaced by 2 above halogen alkoxyls mean alkoxyl be combined with 2 identical or different above halogen alkoxyls.The position of substitution of halogen alkoxyl can be the optional position.

In the above-mentioned formula (I), R ⁵Alkoxyl halogen alkoxyl mean the halogen alkoxyl be combined with identical or different alkoxyl.The replacement number of alkoxyl can be for more than 1 or 2, and in addition, their the position of substitution can be the optional position.This also is identical for alkylthio group alkylthio group etc.

In the above-mentioned formula (I), as R ⁵In the heterocyclic radical part, for example, be to contain 1～4 to be selected from any among O, S or the N heteroatomic 5 yuan of rings or 6 yuan of rings more than a kind or 2 kinds, can be saturated also can be undersaturated, specifically, can enumerate oxa-cyclopenta, 1,3-dioxane amyl group, tetrahydrofuran base, tetrahydrochysene-2H-pyranose etc.In addition, the replacement number of heterocyclic radical part can be for more than 1 or 2, are being that they can be the same or different under the situation more than 2.The position of substitution of heterocyclic radical part can be the optional position.

Salt as the benzoylpyrazole compound shown in the above-mentioned formula (I), comprise all salt of allowing on the agricultural, for example can enumerate, alkali metal salt such as sodium salt, sylvite, alkali earth metal salt such as magnesium salts, calcium salt, amine salt such as dimethylamine salt, triethylamine salt, inorganic acid salts such as hydrochloride, perchlorate, sulphate, nitrate, organic acid salts such as acetate, mesylate etc.

Comprise the compound or its salt shown in the formula (I-a) of the benzoylpyrazole compound shown in the above-mentioned formula (I), can make according to the manufacture method of following reaction [A] and common salt.

In the following formula, R ¹, R ², R ³, R ⁴And R ⁶As mentioned above; R ^5-aBe hydrogen atom, alkyl, thiazolinyl, alkynyl, halogen, cyano group, cyanoalkyl, the cyano group thiazolinyl, alkylhalide group, alkoxyalkyl, halo alkoxy alkyl, can be selected from alkyl, cyano group, cyanoalkyl, (alkylthio group) carbonylic alkyl, alkyl (thiocarbonyl) alkyl ,-C (O) OR ⁷With-C (O) SR ⁷In amino (thiocarbonyl) alkyl that replaces of at least 1 substituting group, thiocyanate groups alkyl, alkoxyl; thiazolinyl oxygen base, alkynyloxy base, halogen alkoxyl; the alkoxyl alkoxyl, halogen alkoxyl alkoxyl, alkoxyl halogen alkoxyl; halogen alkoxyl halogen alkoxyl, alkoxy alkoxy alkyl, alkylthio group; the alkoxyl alkylthio group, halogen alkoxyl alkylthio group, alkoxyl alkyl halide sulfenyl; halogen alkoxyl alkyl halide sulfenyl, alkylthio group alkylthio group, alkyl halide sulfenyl alkylthio group; alkylthio group alkyl halide sulfenyl, alkyl halide sulfenyl halides alkylthio group, alkylthio group alkoxyl; alkyl sulphonyl, alkyl sulphonyl alkyl, alkoxy carbonyl alkyl; the alkoxy carbonyl alkoxyl; the heterocyclic radical alkyl, heterocyclyloxy base, heterocyclic radical alkoxyl; the heterocyclic radical alkoxyalkyl; heterocyclyloxy base alkyl, cycloalkyl oxy ,-OC (O) SR ⁷,-OC (O) OR ⁷,-C (O) OR ⁷,-C (O) SR ⁷,-C (S) OR ⁷,-C (S) SR ⁷, can be selected from alkyl, cyano group, cyanoalkyl, (alkylthio group) carbonylic alkyl, alkyl (thiocarbonyl) alkyl ,-C (O) OR ⁷With-C (O) SR ⁷In the aminoalkyl that replaces of at least 1 substituting group, or can be replaced 4 by alkyl, halogen or alkoxyl, 5-dihydro-isoxazole-3-base.

Above-mentioned reaction can be carried out in the presence of solvent as required.As solvent so long as any all can for the solvent of inertia to reaction, for example can enumerate, carrene, chloroform, dichloroethane, halogenated hydrocarbons such as trichloroethanes, benzene, toluene, dimethylbenzene, nitrobenzene, arenes such as chlorobenzene, methyl acetate, ethyl acetate, ester classes such as propyl acetate, acetonitrile, N, dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), dimethylacetylamide (DMA), HMPA (HMPA), non-proton property such as sulfolane polar solvent, ether, 1, the 4-dioxane, oxolane (THF), 1, ethers such as 2-dimethoxy-ethane etc.As solvent, can suitably select in them more than a kind or 2 kinds.

Above-mentioned reaction can be carried out in the presence of alkali as required.As alkali, can use any of organic base, inorganic base.As organic base, for example can enumerate triethylamine, N, tertiary amines such as N-diisopropylethylamine, pyridine, 4-(dimethylamino) pyridine, 2,6-lutidine etc.As inorganic base, for example can enumerate, alkali carbonates such as sodium carbonate, potash, cesium carbonate, alkali metal hydrogencarbonate such as sodium bicarbonate, saleratus, alkaline earth metals carbonate such as calcium carbonate, barium carbonate, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, alkaline-earth metal hydroxide such as slaked lime, barium hydroxide etc.As bases, can suitably select among them more than a kind or 2 kinds, and can mix use.

In above-mentioned reaction, can add catalyzer as required in addition.As catalyzer, can use the acetone cyanohydrin of 0.01～10 equivalent with respect to the compound of formula (II).

The reaction temperature of above-mentioned reaction is generally 0 ℃～150 ℃, and the reaction time can carry out 1 minute～48 hours usually.

Compound shown in the above-mentioned formula (II) can be made according to following reaction [B].

In the following formula, R ¹, R ², R ⁴, R ^5-aAnd R ⁶As mentioned above; Hal is a halogen atom.

As the salt of the compound shown in the formula (III), for example can enumerate hydrochloride, sulphate, nitrate etc.

Above-mentioned reaction can be carried out in the presence of solvent as required.As solvent so long as to reaction for the solvent of inertia any all can, can enumerate in the above-mentioned reaction [A] illustrated solvent etc.As solvent, can suitably select in them more than a kind or 2 kinds.

Above-mentioned reaction can be carried out in the presence of alkali as required.As alkali, can be any of inorganic base or organic base, can enumerate illustrated alkali etc. in the above-mentioned reaction [A].Bases can suitably select in them more than a kind or 2 kinds, and can mix use.

Compound shown in the above-mentioned formula (IV) can be made according to following reaction [C].

In the following formula, R ⁴, R ^5-a, R ⁶With Hal as mentioned above.

As the halogenating agent in the above-mentioned reaction, can enumerate for example thionyl chloride or oxalyl chloride etc.Halogenating agent can be with respect to the compound shown in the formula (V) with 1～100 equivalent reaction.

Above-mentioned reaction can be carried out in the presence of solvent as required.As solvent, any all can for the solvent of inertia so long as to reaction, for example can enumerate, halogenated hydrocarbons such as carrene, chloroform, dichloroethane, trichloroethanes, arenes such as benzene,toluene,xylene, nitrobenzene, chlorobenzene, ester classes such as methyl acetate, ethyl acetate, propyl acetate, ether, 1,4-dioxane, oxolane (THF), 1, ethers such as 2-dimethoxy-ethane etc.As solvent, can suitably select in them more than a kind or 2 kinds.

Above-mentioned reaction can used catalyzer as required.Can enumerate DMF etc. as catalyzer.

Except that said method, the compound shown in the formula (II) can be made according to following reaction [D].

In the following formula, R ¹, R ², R ⁴, R ^5-aAnd R ⁶As mentioned above.

As the dehydrating agent that in above-mentioned reaction, uses, for example can enumerate DCC (dicyclohexylcarbodiimide), 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride etc.

Above-mentioned reaction can be carried out in the presence of solvent as required.As solvent so long as to reaction for the solvent of inertia any all can, can be set forth in the above-mentioned reaction [A] illustrated solvent etc.As solvent, can suitably select in them more than a kind or 2 kinds.

Above-mentioned reaction can be carried out in the presence of alkali as required.As alkali, can enumerate triethylamine, N, tertiary amines such as N-diisopropylethylamine, pyridine, 4-(dimethylamino) pyridine, 2,6-lutidine etc.Bases can suitably select in them more than a kind or 2 kinds, and can mix use.

Compound shown in the above-mentioned formula (V) can be made according to following reaction [E].

In the following formula, R ⁴, R ^5-aAnd R ⁶As mentioned above; L is protecting groups such as alkyl.

Above-mentioned reaction can be carried out in the presence of water.

Above-mentioned reaction can be carried out in the presence of solvent as required.For example can enumerate, arenes such as benzene,toluene,xylene, nitrobenzene, chlorobenzene, non-proton property polar solvents such as acetonitrile, DMF, DMSO, DMA, HMPA, sulfolane, ether, 1,4-dioxane, THF, 1, ethers such as 2-dimethoxy-ethane, alcohols such as methyl alcohol, ethanol, propyl alcohol, water etc.As solvent, can suitably select in them more than a kind or 2 kinds.

Above-mentioned reaction can be carried out in the presence of alkali or acid as required.As alkali, can be any of inorganic base or organic base.As inorganic base, can enumerate alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, alkaline-earth metal such as slaked lime, barium hydroxide hydroxide, alkali carbonates such as sodium carbonate, potash, cesium carbonate, alkali metal hydrogencarbonate such as sodium bicarbonate, saleratus, alkaline earth metals carbonates such as calcium carbonate, barium carbonate etc.As organic base, for example can enumerate triethylamine, N, tertiary amines such as N-diisopropylethylamine etc.As acid, for example can enumerate hydrochloric acid, sulfuric acid, perchloric acid etc.Bases or acids can suitably select respectively in them more than a kind or 2 kinds, and can mix use.

In the compound shown in the above-mentioned formula (VI), R ^5-aBe R ^5-a-1Compound can make according to following reaction [F].

In the following formula, R ⁴, R ⁶With L as mentioned above; R ^5-a-1Be alkoxyl, halogen alkoxyl, alkoxyl alkoxyl, halogen alkoxyl alkoxyl, alkoxyl halogen alkoxyl, halogen alkoxyl halogen alkoxyl, heterocyclyloxy base, heterocyclic radical alkoxyl, cycloalkyl oxy ,-OC (O) SR ⁷,-OC (O) OR ⁷, alkylthio group alkoxyl, alkoxy carbonyl alkoxyl, thiazolinyl oxygen base or alkynyloxy base; R ^αBe alkyl, alkylhalide group, alkoxyalkyl, halo alkoxy alkyl, alkoxyl alkylhalide group, halogen alkoxyl alkylhalide group, heterocyclic radical, heterocyclic radical alkyl, cycloalkyl ,-C (O) SR ⁷,-C (O) OR ⁷, alkylthio alkyl, alkoxy carbonyl alkyl, alkenyl or alkynyl.

As the dehydrating agent that in above-mentioned reaction, uses, for example can enumerate DCC (dicyclohexylcarbodiimide), 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride etc.In addition, diethyl azodiformate can also be used with triphenylphosphine, tributylphosphine etc.

Above-mentioned reaction can be carried out in the presence of alkali as required.As alkali, for example can enumerate triethylamine, N, tertiary amines such as N-diisopropylethylamine, pyridine, 4-(dimethylamino) pyridine, 2,6-lutidine etc.Bases can suitably select in them more than a kind or 2 kinds, and can mix use.

Except that said method, the compound shown in the formula (VI-a-1) can also be made according to following reaction [G].

In the following formula, R ⁴, R ^5-a-1, R ⁶, R ^αWith L as mentioned above.X represents leaving groups such as halogen or mesyloxy.

As the alkali that in above-mentioned reaction, uses, can be any of inorganic base or organic base.As inorganic base, for example can enumerate, alkali carbonates such as sodium carbonate, potash, cesium carbonate, alkali metal hydrogencarbonate such as sodium bicarbonate, saleratus, alkaline earth metals carbonate such as calcium carbonate, barium carbonate, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, alkaline-earth metal hydroxide such as slaked lime, barium hydroxide, alkali metal hydrides such as sodium hydride, hydrofining etc.As organic base, for example can enumerate triethylamine, N, N-diisopropylethylamine, pyridine, 4-(dimethylamino) pyridine, 2,6-lutidine etc.Bases can suitably select in them more than a kind or 2 kinds, and can mix use.

Above-mentioned reaction can be carried out in the presence of catalyzer as required.As catalyzer, for example can enumerate potassium iodide, tetrabutylammonium iodide, cupric iodide, copper oxide etc.

The reaction temperature of above-mentioned reaction is generally 0 ℃～200 ℃, and the reaction time can carry out 1 minute～48 hours usually.

Above-mentioned reaction can be carried out under inert gas as required.As this inert gas, for example can enumerate nitrogen, argon gas etc.

Compound shown in the above-mentioned formula (VII) can be made according to following reaction [H].

In the following formula, R ⁴, R ⁶With L as mentioned above.

As the lewis acid that in above-mentioned reaction, uses, can enumerate Boron tribromide, ammonium chloride, ferric bromide etc.

Above-mentioned reaction can be carried out in the presence of solvent as required.As solvent, so long as to reaction for the solvent of inertia any all can, for example can enumerate, halogenated hydrocarbons such as carrene, chloroform, dichloroethane, trichloroethanes, arenes such as benzene,toluene,xylene, nitrobenzene, chlorobenzene, carbon disulphide, nitromethane etc.As solvent, can suitably select in them more than a kind or 2 kinds.

Compound shown in the above-mentioned formula (X) can be made according to following reaction [I].

In the following formula, R ⁴, R ⁶With L as mentioned above.

In above-mentioned reaction, formula L-OH can make the double as solvent by excessive.Above-mentioned in addition reaction can be carried out in the presence of other solvent as required.As solvent, any all can for the solvent of inertia so long as to reaction, for example, arenes such as benzene,toluene,xylene, nitrobenzene, chlorobenzene, ester classes such as methyl acetate, ethyl acetate, propyl acetate, halogenated hydrocarbons such as carrene, chloroform, dichloroethane, trichloroethanes, non-proton property such as acetonitrile, DMF, DMSO, DMA, HMPA, sulfolane polar solvent etc.As solvent, can suitably select in them more than a kind or 2 kinds.

Above-mentioned reaction can be carried out in the presence of acid as required.As the acid that can in above-mentioned reaction, use, can enumerate hydrochloric acid, sulfuric acid etc.

In the compound shown in the above-mentioned formula (VI), R ^5-aBe R ^5-a-2Compound can be made by following reaction [J].

In the following formula, R ⁴, R ⁶With L as mentioned above; R ^5-a-2The alkyl that is replaced by alkyl sulphonyl; R ^5-a-3It is alkylthio alkyl.

As the oxidant that in above-mentioned reaction, uses, for example can enumerate hydrogen peroxide, peracetic acid, metachloroperbenzoic acid etc.

As the solvent that in above-mentioned reaction, uses, any all can for the solvent of inertia so long as to reaction, for example can enumerate, halogenated hydrocarbons such as carrene, chloroform, dichloroethane, trichloroethanes, ketones such as acetone, MEK, ether, 1,4-dioxane, THF, 1, ethers such as 2-dimethoxy-ethane, arenes such as benzene,toluene,xylene, nitrobenzene, chlorobenzene, organic acids such as acetate, propionic acid.As solvent, can suitably select in them more than a kind or 2 kinds.

Above-mentioned reaction can be carried out in the presence of catalyzer as required.As the catalyzer that can in above-mentioned reaction, use, can enumerate for example sodium tungstate etc.

Compound shown in the above-mentioned formula (XII) can be made according to following reaction [K].

In the following formula, R ⁴, R ^5-a-3, R ⁶With L as mentioned above; R ^5-a-4It is the bromine alkyl.

As the slaine of alkyl hydrosulfide, for example can enumerate alkali metal salts such as sodium salt, sylvite etc.

As the solvent that in above-mentioned reaction, uses, any all can for the solvent of inertia so long as to reaction, for example can enumerate, halogenated hydrocarbons such as carrene, chloroform, dichloroethane, trichloroethanes, ketones such as acetone, MEK, ether, 1,4-dioxane, THF, 1, ethers such as 2-dimethoxy-ethane, water, non-proton property such as DMF, DMSO, DMA, HMPA, sulfolane polar solvent etc.As solvent, can suitably select in them more than a kind or 2 kinds.

In above-mentioned reaction, can in the presence of alkali, react as required.As alkali can be any of inorganic base or organic base.As inorganic base, can enumerate alkali carbonates such as sodium carbonate, potash, cesium carbonate, alkali metal hydrogencarbonate such as sodium bicarbonate, saleratus, alkaline earth metals carbonate such as calcium carbonate, magnesium carbonate, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, alkaline-earth metal such as slaked lime, barium hydroxide hydroxide, alkali metal hydrides such as sodium hydride, hydrofining etc.As organic base, for example can enumerate triethylamine, N, N-diisopropylethylamine, pyridine, 4-(dimethylamino) pyridine, 2,6-lutidine etc.As alkali can suitably select in them more than a kind or 2 kinds, and can mix use.

In the compound shown in the above-mentioned formula (VI), R ^5-aBe R ^5-a-5Compound can make according to following reaction [L].

In the following formula, R ⁴, R ^5-a-4, R ⁶With L as mentioned above; R ^5-a-5Be alkoxy alkoxy alkyl or heterocyclyloxy base alkyl.

That is, with the compound shown in formula (VI-a-5), alcohol that alcohol that can be by the moieties alkoxy is replaced, moieties are replaced by heterocyclic radical or their slaine and the compound shown in the formula (XIII) react to be made.

The slaine of the alcohol that alcohol that replaces as the moieties alkoxy that uses in above-mentioned reaction or moieties are replaced by heterocyclic radical for example can be enumerated alkali metal salts such as sodium salt, sylvite etc.

Above-mentioned reaction can be carried out in the presence of solvent as required.As solvent, any all can for the solvent of inertia so long as to reaction, for example can enumerate, alcohols such as methyl alcohol, ethanol, propyl alcohol, ester classes such as methyl acetate, ethyl acetate, propyl acetate, ether, 1,4-dioxane, THF, 1, ethers such as 2-dimethoxy-ethane, non-proton property such as acetonitrile, DMF, DMSO, DMA, HMPA, sulfolane polar solvent etc.As solvent, can suitably select in them more than a kind or 2 kinds.

Above-mentioned reaction can be carried out in the presence of alkali as required.As alkali, can enumerate alkali metal hydrides such as sodium hydride, hydrofining, sodium amide etc.

In the compound shown in the above-mentioned formula (VI), R ^5-aBe R ^5-a-6Compound can make according to following reaction [M].

In the following formula, R ⁴, R ⁶With L as mentioned above; R ^5-a-6Be alkylthio group, alkoxyl alkylthio group, halogen alkoxyl alkylthio group, alkoxyl alkyl halide sulfenyl, halogen alkoxyl alkyl halide sulfenyl, alkylthio group alkylthio group, alkyl halide sulfenyl alkylthio group, alkylthio group alkyl halide sulfenyl or alkyl halide sulfenyl halides alkylthio group; R ^5-a-7It is halogen.

As the slaine of the mercaptan that can in above-mentioned reaction, use, for example can enumerate alkali metal salts such as sodium salt, sylvite.

Above-mentioned reaction can be carried out in the presence of solvent as required.As solvent, any all can for the solvent of inertia so long as to reaction, for example can enumerate, alcohols such as methyl alcohol, ethanol, propyl alcohol, ether, 1,4-dioxane, THF, 1, ethers such as 2-dimethoxy-ethane, non-proton property polar solvents such as acetonitrile, DMF, DMSO, DMA, HMPA, sulfolane, water etc.As solvent, can suitably select in them more than a kind or 2 kinds.

Above-mentioned reaction can be carried out in the presence of alkali as required.As alkali, can enumerate alkali metal hydrides such as sodium hydride, hydrofining, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, alkaline-earth metal hydroxide such as slaked lime, barium hydroxide etc.As alkali can suitably select in them more than a kind or 2 kinds, and can mix use.

Above-mentioned reaction response temperature is generally 0 ℃～250 ℃, and the reaction time can carry out 1 minute～48 hours usually.

In the compound shown in the above-mentioned formula (I-a), R ^5-aBe R ^5-a-8Formula (I-a-8) shown in compound can make according to following reaction [N].

In the following formula, R ¹, R ², R ³, R ⁴, R ^5-a-4And R ⁶As mentioned above; R ^5-a-8It is the thiocyanate groups alkyl.

Above-mentioned reaction can be carried out in the presence of solvent as required.As solvent, any all can for the solvent of inertia so long as to reaction, for example can enumerate, halogenated hydrocarbons such as carrene, chloroform, dichloroethane, trichloroethanes, arenes such as benzene,toluene,xylene, nitrobenzene, chlorobenzene, ester classes such as methyl acetate, ethyl acetate, propyl acetate, non-proton property polar solvents such as acetonitrile, DMF, DMSO, DMA, HMPA, sulfolane, ether, 1,4-dioxane, THF, 1, ethers such as 2-dimethoxy-ethane, alcohols such as methyl alcohol, ethanol, propyl alcohol etc.As solvent, can suitably select in them more than a kind or 2 kinds.

In the compound shown in the above-mentioned formula (VI), R ^5-aBe R ^5-a-9Compound can make according to following reaction [O].

In the following formula, R ⁴, R ⁶With L as mentioned above; R ^5-a-9It is amino (thiocarbonyl) alkyl; R ^5-a-11It is cyanoalkyl.

As the solvent that in above-mentioned reaction, uses, so long as to reaction for the solvent of inertia any all can, can be set forth in illustrated solvent in the above-mentioned reaction [N].As solvent, can suitably select in them more than a kind or 2 kinds.

In the compound shown in the above-mentioned formula (VI), R ^5-aBe R ^5-a-10Compound can make according to following reaction [P].

In the following formula, R ⁴, R ⁶, R ^5-a-9, L and Hal as mentioned above; R ^5-a-10Be selected from alkyl, cyano group, cyanoalkyl, (alkylthio group) carbonylic alkyl, alkyl (thiocarbonyl) alkyl ,-C (O) OR ⁷With-C (O) SR ⁷In amino (thiocarbonyl) alkyl that replaces of at least 1 substituting group; Z be alkyl, cyano group, cyanoalkyl, (alkylthio group) carbonylic alkyl, alkyl (thiocarbonyl) alkyl ,-C (O) OR ⁷Or-C (O) SR ⁷R ⁷As mentioned above.

Above-mentioned reaction can be carried out in the presence of solvent as required.As the solvent that in above-mentioned reaction, uses, so long as to reaction for the solvent of inertia any all can, can enumerate illustrated solvent in the above-mentioned reaction [N].As solvent, can suitably select in them more than a kind or 2 kinds.

Above-mentioned reaction can be carried out in the presence of alkali as required.As alkali, can be any of inorganic base or organic base.As inorganic base, can enumerate alkali carbonates such as sodium carbonate, potash, cesium carbonate, alkali metal hydrogencarbonates such as sodium bicarbonate, saleratus, alkaline earth metals carbonates such as calcium carbonate, magnesium carbonate etc.As organic base, can enumerate triethylamine, N, N-dimethyl aminopyridine, diisopropylaminoethyl pyridine, DBU amines such as (1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene) etc.

Compound shown in the above-mentioned formula (VI-a-11) can be made according to following reaction [Q].

In the following formula, R ⁴, R ^5-a-11, R ⁶With L as mentioned above.

Above-mentioned reaction can be carried out in the presence of solvent as required.As solvent, any all can for the solvent of inertia so long as to reaction, for example can enumerate, halogenated hydrocarbons such as carrene, chloroform, dichloroethane, trichloroethanes, ketones such as acetone, MEK, ether, 1,4-dioxane, THF, 1, ethers such as 2-dimethoxy-ethane, arenes such as benzene,toluene,xylene, nitrobenzene, chlorobenzene, pyridine etc.As solvent, can suitably select in them more than a kind or 2 kinds.

Above-mentioned reaction can be carried out in the presence of alkali as required.As alkali, for example can enumerate triethylamine, N, N-dimethyl aminopyridine, diisopropylaminoethyl pyridine etc.As alkali can suitably select in them more than a kind or 2 kinds, and can mix use.

Compound shown in the above-mentioned formula (XVI) can be made according to following reaction [R].

In the following formula, R ⁴, R ⁶With L as mentioned above.

As the solvent that in above-mentioned reaction, uses, any all can for the solvent of inertia so long as to reaction, for example can enumerate, alcohols such as methyl alcohol, ethanol, propyl alcohol, halogenated hydrocarbons such as carrene, chloroform, dichloroethane, trichloroethanes, ketones such as acetone, MEK, ether, 1,4-dioxane, THF, 1, ethers such as 2-dimethoxy-ethane etc.As solvent, can suitably select in them more than a kind or 2 kinds.

Above-mentioned reaction can be carried out in the presence of acid or alkali as required.Can enumerate for example p-methyl benzenesulfonic acid etc. as acid.Can enumerate for example sodium acetate etc. as alkali.

Compound shown in the above-mentioned formula (XVII) can be made according to following reaction [S].

In the following formula, R ⁴, R ⁶With L as mentioned above; A is an alkyl.

As the acid of in above-mentioned reaction, using, can enumerate for example hydrochloric acid etc.

Above-mentioned reaction can be carried out in the presence of solvent as required.As solvent, so long as to reaction for the solvent of inertia any all can, for example can enumerate water, alcohols such as methyl alcohol, ethanol, propyl alcohol, ether, 1,4-dioxane, THF, 1, ethers such as 2-dimethoxy-ethane etc.As solvent, can suitably select in them more than a kind or 2 kinds.

Compound shown in the above-mentioned formula (XVIII) can be made according to following reaction [T].

In the following formula, R ⁴, R ⁶, L and A as mentioned above.

As the acid of in above-mentioned reaction, using, for example can enumerate hydrochloric acid, toluenesulfonic acid etc.

In above-mentioned reaction, formula A-OH can be by excessive use the double as solvent.Above-mentioned in addition reaction can be carried out in the presence of other solvent as required.As solvent, any all can for the solvent of inertia so long as to reaction, for example can enumerate, halogenated hydrocarbons such as carrene, chloroform, dichloroethane, trichloroethanes, arenes such as benzene,toluene,xylene, nitrobenzene, chlorobenzene, ester classes such as methyl acetate, ethyl acetate, propyl acetate, non-proton property polar solvents such as acetonitrile, DMF, DMSO, DMA, HMPA, sulfolane, ether, 1,4-dioxane, THF, 1, ethers such as 2-dimethoxy-ethane, ketones such as acetone, MEK etc.As solvent, can suitably select in them more than a kind or 2 kinds.

Compound shown in the above-mentioned formula (XIX) can be made according to following reaction [U].

In the following formula, R ⁴, R ⁶With L as mentioned above; T is a halogen.Ph represents phenyl, and Me represents methyl.

As the solvent that in above-mentioned reaction, uses, any all can for the solvent of inertia so long as to reaction, for example can enumerate, ether, 1,4-dioxane, THF, 1, ethers such as 2-dimethoxy-ethane, arenes such as benzene,toluene,xylene, nitrobenzene, chlorobenzene, non-proton property such as acetonitrile, DMF, DMSO, DMA, HMPA, sulfolane polar solvent etc.

Above-mentioned reaction can be carried out in the presence of alkali as required.As alkali, can enumerate sodium hydride (NaH), alkaline, lithium reagent such as n-BuLi, sodium amide (NaNH ₂) wait metal amide etc.

The reaction temperature of above-mentioned reaction is generally-80 ℃～150 ℃, and the reaction time can carry out 1 minute～48 hours usually.

Compound shown in the above-mentioned formula (XX) can be made according to following reaction [V].

In the following formula, R ⁴, R ^5-a-4, R ⁶With L as mentioned above.

As the oxidant that in above-mentioned reaction, uses, for example can enumerate organic oxidizing agents such as N-methylmorpholine oxide, inorganic oxidizer such as manganese dioxide etc.

As the solvent that in above-mentioned reaction, uses, any all can for the solvent of inertia so long as to reaction, for example can enumerate, non-proton property polar solvents such as acetonitrile, DMF, DMSO, DMA, HMPA, sulfolane, ether, 1,4-dioxane, THF, 1, ethers such as 2-dimethoxy-ethane etc.As solvent, can suitably select in them more than a kind or 2 kinds.

In the compound shown in the above-mentioned formula (VI), R ^5-aBe R ^5-a-12Compound can make according to following reaction [W].

In the following formula, R ⁴, R ^5-a-4, R ⁶With L as mentioned above; R ^5-a-12Be can be selected from alkyl, cyano group, cyanoalkyl, (alkylthio group) carbonylic alkyl, alkyl (thiocarbonyl) alkyl ,-C (O) OR ⁷With-C (O) SR ⁷In the aminoalkyl that replaces of at least 1 substituting group; Y ¹And Y ²Be respectively hydrogen atom, alkyl, cyano group, cyanoalkyl, (alkylthio group) carbonylic alkyl, alkyl (thiocarbonyl) alkyl ,-C (O) OR ⁷Or-C (O) SR ⁷R ⁷As mentioned above.

Above-mentioned reaction can be carried out in the presence of solvent as required.As solvent, so long as to reaction for the solvent of inertia any all can, can be set forth in the above-mentioned reaction [A] illustrated solvent etc.As solvent, can suitably select in them more than a kind or 2 kinds.

Above-mentioned reaction can be carried out in the presence of alkali as required.As alkali, can be any of inorganic base or organic base.As inorganic base, can enumerate alkali carbonates such as sodium carbonate, potash, cesium carbonate, alkali metal hydrogencarbonates such as sodium bicarbonate, saleratus, alkaline earth metals carbonate such as calcium carbonate, magnesium carbonate, sodium hydride (NaH), alkyl lithium reagents such as n-BuLi, sodium amide (NaNH ₂) wait metal amide etc.As organic base, can enumerate triethylamine, N, N-dimethyl aminopyridine, diisopropylaminoethyl pyridine, DBU amines such as (1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene) etc.

Above-mentioned reaction can be carried out in the presence of catalyzer as required.As catalyzer, for example can enumerate TBAI (tert-butyl group iodate ammonium) etc.

In the compound shown in the above-mentioned formula (VI), R ^5-aBe R ^5-a-13Compound can make according to following reaction [X].

In the following formula, R ⁴, R ⁶With L as mentioned above; R ^5-a-13By the aminoalkyl of alkyl or cyanoalkyl replacement; R ^5-a-16It is aminoalkyl.

Above-mentioned reaction can be carried out in the presence of solvent as required.As solvent, so long as to reaction for the solvent of inertia any all can, for example, can enumerate illustrated solvent in the above-mentioned reaction [N].As solvent, can suitably select in them more than a kind or 2 kinds.

In the compound shown in the above-mentioned formula (VI), R ^5-aBe R ^5-a-14Compound can make according to following reaction [Y].

In the following formula, R ⁴, R ⁶, L and Hal as mentioned above; R ^5-a-14It is the alkylthio group carbonyl.

As the slaine of the alkyl hydrosulfide that in above-mentioned reaction, uses, for example can enumerate alkali metal salts such as sodium salt, sylvite.

Above-mentioned reaction can be carried out in the presence of solvent as required.As solvent, any all can for the solvent of inertia so long as to reaction, for example can enumerate, ether, 1,4-dioxane, THF, 1, ethers such as 2-dimethoxy-ethane, arenes such as benzene,toluene,xylene, nitrobenzene, chlorobenzene, ester classes such as methyl acetate, ethyl acetate, propyl acetate, halogenated hydrocarbons such as carrene, chloroform, dichloroethane, trichloroethanes, non-proton property such as acetonitrile, DMF, DMSO, DMA, HMPA, sulfolane polar solvent etc.As solvent, can suitably select in them more than a kind or 2 kinds.

Above-mentioned reaction can be carried out in the presence of alkali as required.As alkali, can be any of inorganic base or organic base.As organic base, for example can enumerate triethylamine, N, N-diisopropylethylamine, pyridine, 4-(dimethylamino) pyridine, 2,6-lutidine etc.As inorganic base, for example can enumerate, alkali carbonates such as sodium carbonate, potash, cesium carbonate, alkali metal hydrogencarbonate such as sodium bicarbonate, saleratus, alkaline earth metals carbonate such as calcium carbonate, magnesium carbonate, alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, alkali metal hydrides such as sodium hydride, hydrofining etc.As alkali, can suitably select in them more than a kind or 2 kinds, and can mix use.

Compound shown in the above-mentioned formula (XXI) can be made according to following reaction [Z].

In the following formula, Hal, R ⁴, R ⁶With L as mentioned above.

This reaction can similarly be carried out with above-mentioned reaction [C].

Compound shown in the above-mentioned formula (XXII) can be made according to following reaction [AA].

In the following formula, R ⁴, R ⁶With L as mentioned above.

As the oxidant in the above-mentioned reaction, for example can enumerate potassium permanganate, chromium trioxide etc.

Above-mentioned reaction can be carried out in the presence of solvent as required.As solvent, so long as to reaction for the solvent of inertia any all can, for example can enumerate, ketone such as acetone, MEK, ester classes such as methyl acetate, ethyl acetate, propyl acetate, ether, 1,4-dioxane, THF, 1, ethers such as 2-Ethyl Methyl Ether etc.As solvent, can suitably select in them more than a kind or 2 kinds.

In the compound shown in the above-mentioned formula (VI), R ^5-aBe R ^5-a-15Compound can make according to following reaction [AB].

In the following formula, R ⁴, R ⁶With L as mentioned above; R ^5-a-15Be cyano group.

This reaction can similarly be carried out with above-mentioned reaction [Q].

Compound shown in the above-mentioned formula (XXIII) can be made according to following reaction [AC].

In the following formula, R ⁴, R ⁶With L as mentioned above.

This reaction can similarly be carried out with above-mentioned reaction [R].

In the compound shown in the above-mentioned formula (VI), R ^5-aBe R ^5-a-17, R ⁶Be R ^6-a-1Compound can make according to following reaction [AD].

In the following formula, R ⁴With L as mentioned above; R ^5-a-17Be alkoxyl, thiazolinyl oxygen base, alkynyloxy base, halogen alkoxyl, alkoxyl alkoxyl, halogen alkoxyl alkoxyl, alkoxyl halogen alkoxyl, halogen alkoxyl halogen alkoxyl, alkoxy carbonyl alkoxyl, heterocyclyloxy base, heterocyclic radical alkoxyl, cycloalkyl oxy or-OC (O) R ⁷R ^6-a-1Be alkyl sulphinyl or alkyl sulphonyl; R ^6-a-2It is alkylthio group.

This reaction can similarly be carried out with above-mentioned reaction [J].

Compound shown in the above-mentioned formula (VI-a-17-2) can be made according to following reaction [AE].

In the following formula, R ⁴, R ^5-a-17, R ^6-a-2With L as mentioned above.

As the alkali-metal mercaptides that in above-mentioned reaction, uses, for example can enumerate sodium methyl mercaptide, ethyl mercaptan sodium etc.

Above-mentioned reaction can be carried out in the presence of solvent as required.For example can enumerate non-proton property polar solvents such as acetonitrile, DMF, DMSO, DMA, HMPA, sulfolane, diox, dimethoxy-ethane etc.

Compound shown in the above-mentioned formula (VI-a-17-3) can be made according to following reaction [AF].

In the following formula, L, X, R ⁴And R ^5-a-17As mentioned above; R ^βBe alkyl, thiazolinyl, alkynyl, alkylhalide group, alkoxyalkyl, halo alkoxy alkyl, alkoxyl alkylhalide group, halogen alkoxyl alkylhalide group, alkoxy carbonyl alkyl, heterocyclic radical, heterocyclic radical alkyl, cycloalkyl or-C (O) R ⁷(R ⁷As mentioned above).

Above-mentioned reaction can be carried out in the presence of solvent as required.As solvent, can use illustrated solvent in the above-mentioned reaction [A].In addition, can suitably select in them more than a kind or 2 kinds.

As the alkali that in above-mentioned reaction, uses, can be any of inorganic base or organic base.As organic base, for example can enumerate triethylamine, N, N-diisopropylethylamine, pyridine, 4-(dimethylamino) pyridine, 2,6-lutidine etc.As inorganic base, for example can enumerate alkali carbonates such as sodium carbonate, potash, cesium carbonate, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, alkali metal hydrides such as sodium hydride, hydrofining etc.These bases are 0.5～100 equivalent with respect to the compound of formula (XXV), can suitably select in them more than a kind or 2 kinds, and can mix use.

Above-mentioned reaction can be carried out in the presence of catalyzer as required.As catalyzer, for example can enumerate potassium iodide, tetrabutylammonium iodide etc.

In the compound shown in the above-mentioned formula (V), R ^5-aBe R ^5-a-1Compound can make according to following reaction [AG].

In the following formula, R ⁴, R ^5-a-1, R ⁶, R ^αWith Hal as mentioned above.

As the alkali that can in above-mentioned reaction, use, can use and the identical alkali of above-mentioned reaction [G].

As the slaine of the compound shown in the formula of in above-mentioned reaction, using (VIII), for example can enumerate alkali metal salts such as sodium salt, sylvite.

Above-mentioned reaction can be carried out in the presence of catalyzer as required.As catalyzer, can use and the identical catalyzer of above-mentioned reaction [G].

In addition, as the solvent that can in reaction, use, the solvent of in above-mentioned reaction [A], enumerating, can also be by the alcohols shown in the excessive use formula (VIII), thus the double as solvent.

In the compound shown in the above-mentioned formula (I), R ⁵Be R ^5-a-1Compound can make according to following reaction [AH].

In the following formula, R ¹, R ², R ³, R ⁴, R ^5-a-1, R ⁶, R ^αWith Hal as mentioned above.

As the alkali that in above-mentioned reaction, uses, can use and the identical alkali of above-mentioned reaction [G].

In addition, as the solvent that can in reaction, use, the solvent of in above-mentioned reaction [A], enumerating, can also come the double as solvent by the alcohols shown in the excessive use formula (VIII).

In the compound shown in the above-mentioned formula (V-b), R ⁶Be R ^6-a-1Compound can make according to following reaction [AI].

In the following formula, Hal, R ⁴, R ^6-a-1And R ^6-a-2As mentioned above.

This reaction can similarly be carried out with above-mentioned reaction [J].

Compound shown in the above-mentioned formula (V-b-a-2) can be made according to following reaction [AJ].

In the following formula, R ⁴And R ^6-a-2As mentioned above; Hal and Hal-2 are halogens.Hal and Hal-2 can be the same or different each other.

As the solvent that in above-mentioned reaction, uses, so long as to reaction for the solvent of inertia any all can, for example can enumerate, ether, THF, 1,2-dimethoxy-ethane, 1, ethers such as 4-dioxane, arenes such as benzene,toluene,xylene, nitrobenzene, chlorobenzene etc.As solvent, can suitably select in them a kind or more than 2 kinds.As the CO that in above-mentioned reaction, uses ₂, can enumerate for example CO ₂Gas, dry ice etc.

The reaction temperature of above-mentioned reaction is generally-20 ℃～150 ℃, and the reaction time can carry out 1 minute～48 hours usually.

Compound shown in the above-mentioned formula (XXVI) can be made according to following reaction [AK].

In the following formula, R ⁴, R ^6-a-2, Hal and Hal-2 as mentioned above.

The solvent that in above-mentioned reaction, uses, so long as to reaction for the solvent of inertia any all can, for example can enumerate ether, THF, 1,2-dimethoxy-ethane, 1, ethers such as 4-dioxane etc.As solvent can suitably select in them more than a kind or 2 kinds.

The magnesium metal that uses in above-mentioned reaction can use in the scope of 1～5 equivalent with respect to the compound shown in the formula (XXVII).As the Grignard reagent of in above-mentioned reaction, using, can enumerate isopropylmagnesium chloride etc., can in the scope of 1 equivalent～10 equivalents, use as required with respect to the compound shown in the formula (XXVII).

Above-mentioned reaction can be carried out in the presence of catalyzer as required.As catalyzer, can enumerate for example alkyl halide such as iodine or iodomethane or isopropyl bromide.

The reaction temperature of above-mentioned reaction is generally 0 ℃～150 ℃, and the reaction time can carry out 10 minutes～48 hours usually.

Above-mentioned reaction can be carried out under inert gas as required.As inert gas, for example can enumerate nitrogen, argon gas etc.

Compound shown in the above-mentioned formula (XXVII) can be made according to following reaction [AL].

In the following formula, R ⁴, R ^6-a-2, Hal and Hal-2 as mentioned above; Y ^-Be Cl ^-, Br ^-, I ^-, BF ₄ ^-, HSO ₃ ^-, NO ₃ ^-, ClO ₄ ^-Or OH ^-

As the halogenating agent that in above-mentioned reaction, uses, for example can enumerate, copper halides such as copper chloride, copper bromide, cupric iodide, hydrogen halides or its aqueous solution such as hydrogen chloride, hydrogen bromide, hydrogen iodide, alkali metal salts such as sodium iodide, potassium iodide, potassium bromide, halogen monomers such as chlorine, bromine, iodine, polyhalides such as bromofom etc.

Above-mentioned reaction as required can be by making phosphine classes such as above-mentioned halogenating agent and triphenylphosphine, trialkyl phosphine, or methyl sulfide sulfides class coexistence or carry out with phosphine class or sulfide-based reacting in system.

Above-mentioned reaction can be carried out in the presence of solvent as required.As solvent so long as to reaction for the solvent of inertia any all can, for example can enumerate alcohol such as methyl alcohol, ethanol, halogenated hydrocarbons such as chloroform, bromofom, acetonitrile, water, DMSO isopolarity solvent.As solvent can suitably select in them more than a kind or 2 kinds.

The reaction temperature of above-mentioned reaction is generally-10 ℃～150 ℃, reaction time and can carries out usually 1 minute～48 hours.

Compound shown in the above-mentioned formula (XXVIII) can be made according to following reaction [AM].

In the following formula, R ⁴, R ^6-a-2, Y ^-With Hal as mentioned above.

As the diazotization agent that in above-mentioned reaction, uses, can enumerate alkali metal nitrites salts such as natrium nitrosum, potassium nitrite, alkaline-earth metal such as calcium nitrite, barium nitrite nitrite, nitrites such as methyl nitrite, nitrous ether (ethyl nitrite), Isopropyl Nitrite, butyl nitrite.

Above-mentioned reaction can be carried out in the presence of acid as required.As acid, can enumerate hydrogen halides class or its aqueous solution such as hydrogen chloride, hydrogen bromide, hydrogen iodide, acids or its aqueous solution such as sulfuric acid, nitric acid, perchloric acid.

Above-mentioned reaction can be carried out in the presence of solvent as required.The solvent that in above-mentioned reaction, uses, so long as to reaction for the solvent of inertia any all can, can enumerate in the above-mentioned reaction [AL] illustrated solvent etc.As solvent can suitably select in them more than a kind or 2 kinds.

Compound shown in the above-mentioned formula (XXIX) can be made according to following reaction [AN].

In the following formula, R ⁴, R ^6-a-2With Hal as mentioned above.

Above-mentioned reaction can be carried out in the presence of solvent as required.As solvent, so long as to reaction for the solvent of inertia any all can, can enumerate in water or the above-mentioned reaction [A] illustrated solvent etc.As solvent, can suitably select in them more than a kind or 2 kinds.

As the alkylating agent that in above-mentioned reaction, uses, alkyl halides such as iodomethane, iodoethane, isopropyl iodide, n-propyl iodide, Celfume, bromoethane, isopropyl bromide, positive propyl bromo, dimethyl suflfate etc.

As the alkali that can in above-mentioned reaction, use, can use akali sulphide slaines such as vulcanized sodium, potassium sulfide or its hydrate or with the identical alkali of above-mentioned reaction [G].

Above-mentioned reaction can be carried out in the presence of catalyzer as required.Can use illustrative catalyzer etc. in above-mentioned reaction [AF] as catalyzer.

The reaction temperature of above-mentioned reaction is generally-10 ℃～200 ℃, and the reaction time can carry out 1 minute～48 hours usually.

Compound shown in the above-mentioned formula (XXX) can come synthetic according to following reaction [AO].

In the following formula, R ⁴With Hal as mentioned above.

Above-mentioned reaction can be carried out in the presence of water.

Above-mentioned reaction can be carried out in the presence of solvent as required.As solvent, so long as to reaction for the solvent of inertia any all can, can enumerate in the above-mentioned reaction [E] illustrated solvent etc.As solvent, can suitably select in them more than a kind or 2 kinds.

Above-mentioned reaction can be carried out in the presence of alkali as required.As alkali, can be any of inorganic base or organic base.As organic base, for example can enumerate triethylamine, N, N-diisobutyl ethamine, pyridine, 4-(dimethylamino) pyridine, 2,6-lutidine etc.As inorganic base, for example can enumerate alkali carbonates such as sodium carbonate, potash, cesium carbonate, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, alkali metal sulphides such as vulcanized sodium, potassium sulfide, their hydrate etc.These alkali are 0.1～100 equivalent with respect to the compound of formula (XXXI), can suitably select in them more than a kind or 2 kinds, and can mix use.

In the compound shown in the above-mentioned formula (V), R ⁶Be R ^6-a-3Formula (V-a-1-3) shown in compound can make according to following reaction [AP].

In the following formula, R ⁴, R ^5-a-1With Hal as mentioned above; R ^6-a-3It is alkyl sulphonyl.

That is, the compound shown in the formula (V-a-1-3) can make compound shown in the formula (XXXII) and carbon monoxide or its equivalents and H by in the presence of catalyzer and alkali ₂O reacts and makes.

As the alkali that in above-mentioned reaction, uses, can be any of inorganic base or organic base.As organic base, for example can enumerate triethylamine, tri-butylamine, N, N-diisobutyl ethamine, pyridine, 4-(dimethylamino) pyridine, 2,6-lutidine etc.As inorganic base, for example can enumerate alkali carbonates such as sodium carbonate, potash, cesium carbonate, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, alkaline-earth metal such as slaked lime, barium hydroxide hydroxide, alkali metal acetates such as sodium acetate, potassium acetate.These alkali are 0.1～100 equivalent with respect to the compound shown in the formula (XXXII), can suitably select in them more than a kind or 2 kinds, and can mix use.

As the catalyzer that in above-mentioned reaction, uses, for example can enumerate, palladium catalysts such as palladium bichloride, acid chloride, tetrakis triphenylphosphine palladium, dichloro two (triphenylphosphine) palladium, trans-two (μ-acetate) two [adjacent (di-o-tolyl phosphino-) benzyl] two palladiums, palladium carbon, ruthenium catalysts such as ten dicarbapentaborane, three rutheniums, two (cyclo-octene) radium chloride metal series catalysts such as rhodium catalyst such as (I).These catalyzer are 10 with respect to the compound shown in the formula (XXXII) ^-10～1 equivalent, can suitably select in them more than a kind or 2 kinds, and can mix use.

As the equivalents of the carbon monoxide that can in above-mentioned reaction, use, for example can enumerate hexacarbonylmolybdenum, formic acid, chloroform etc.Carbon monoxide or its equivalents are 1～1000 equivalent with respect to the compound shown in the formula (XXXII), can react adding to depress as required.Pressure can suitably be selected in the scope of 1～100MPa.

Above-mentioned reaction can be carried out in the presence of solvent as required.As solvent, so long as to reaction for the solvent of inertia any all can, can enumerate water or illustrated solvent etc. in above-mentioned reaction [A].As solvent, can suitably select in them more than a kind or 2 kinds.

Above-mentioned reaction can be carried out in the presence of part as required.As part, can enumerate tri-butyl phosphine, tricyclohexyl phosphine, triphenylphosphine, three (o-tolyl) phosphine, 4-two (diphenylphosphino) butane, 1,3-two (diphenylphosphino) pentane, 1,1 '-two (diphenylphosphino) ferrocene etc.These parts are 10 with respect to the compound shown in the formula (XXXII) ^-10～1 equivalent, can suitably select in them more than a kind or 2 kinds, and can mix use.

Above-mentioned reaction can be carried out in the presence of co-catalyst as required.As co-catalyst, can enumerate alkali halides such as sodium chloride, potassium chloride, sodium bromide, potassium bromide, quaternary ammonium salts such as four (normal-butyl) ammonium bromide.These co-catalysts are 0.001～1 equivalent with respect to the compound shown in the formula (XXXII), can suitably select in them more than a kind or 2 kinds, and can mix use.

The reaction temperature of above-mentioned reaction is generally 0 ℃～300 ℃, and the reaction time can carry out 1 minute～72 hours usually.

Compound shown in the above-mentioned formula (XXXII) can be made according to following reaction [AQ].

In the following formula, R ^α, R ⁴, R ^5-a-1, R ^6-a-3, Hal-1 and Hal as mentioned above.

Above-mentioned reaction can be carried out in the presence of alkali as required.As alkali, can enumerate alkali carbonates such as sodium carbonate, potash, cesium carbonate, alkaline earth metals carbonate such as calcium carbonate, barium carbonate, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide or potassium hydroxide, alkaline-earth metal such as slaked lime, barium hydroxide hydroxide, alkali metal hydrides such as lithium hydride, sodium hydride or hydrofining, alkaline, lithium reagent such as n-BuLi, sodium amide (NaNH ₂), Grignard reagent such as methyl-magnesium-bromide, isopropylmagnesium chloride.

As the slaine of the compound shown in the formula (VIII) that can in above-mentioned reaction, use, can use and the same slaine of above-mentioned reaction [AH].

Above-mentioned reaction can be carried out in the presence of solvent as required.As solvent so long as any all can for the solvent of inertia to reaction, can enumerate for example alcohols such as methyl alcohol, ethanol, methyl cellosolve, ether, oxolane, 1,4-dioxane, 1, ethers such as 2-dimethoxy-ethane, cyclohexyl methyl ether, non-proton property polar solvents such as DMF, DMSO, DMA, sulfolane, non-polar solvens such as benzene, toluene etc.In addition, the compound shown in the formula (VIII) can also double as reaction reagent and solvent.As solvent, can suitably select in them more than a kind or 2 kinds.

Compound shown in the above-mentioned formula (XXXIII) can be made according to following reaction [AR].

In the following formula, R ⁴, R ^6-a-3, Hal-1 and Hal as mentioned above, Hal-3 is a halogen, can be the same or different each other.

As the acid of in above-mentioned reaction, using, can enumerate lewis acids such as zinc chloride, zinc bromide, ammonium chloride, ammonium bromide, iron chloride, bismuth chloride, inidum chloride, antimony chloride, Boron tribromide, ferric bromide, methanesulfonic acid, sulfuric acid, trifluoromethanesulfonic acid etc. can be used in the scope of 0.01 equivalent～10 equivalents with respect to the compound shown in the formula (XXXIV).As acid, can suitably select more than a kind or 2 kinds as required.

As alkyl sulfonyl halogenation the thing [(R that in above-mentioned reaction, uses ^6-a-3) (Hal-3)] or alkyl sulfonic acid acid anhydride [(R ^6-a-3) ₂O], can in the scope of 1 equivalent～10 equivalents, use with respect to the compound shown in the formula (XXXIV).Halogen in the alkyl sulphonyl halide can be enumerated fluorine, chlorine, bromine, iodine etc.

Above-mentioned reaction can be carried out in the presence of solvent as required.As solvent so long as to reaction for the solvent of inertia any all can, can enumerate halogenated hydrocarbons such as carrene, chloroform, dichloroethane, trichloroethanes, carbon disulphide, nitromethane etc.As solvent, can suitably select in them more than a kind or 2 kinds.

The reaction temperature of above-mentioned reaction is generally 0 ℃～250 ℃, and the reaction time can carry out 1 minute～48 hours usually.

In the compound shown in the above-mentioned formula (I-a), R ⁶Be R ^6-a-3Formula (I-a-3) shown in compound can make according to following reaction [AS].

In the following formula, R ¹, R ², R ³, R ⁴, R ^5-a-1, R ^6-a-3With Hal as mentioned above.

That is, the compound shown in the formula (I-a-3) can react the compound or its salt shown in compound shown in the formula (XXXII) and carbon monoxide or its equivalents and the formula (III) and make by in the presence of catalyzer and alkali.

In the following formula, R ¹And R ²As mentioned above.

As the salt of the compound shown in the formula (III), can enumerate illustrated salt etc. in the above-mentioned reaction [B].

As the alkali that in above-mentioned reaction, uses, can be any of inorganic base or organic base, can enumerate illustrated alkali etc. in the above-mentioned reaction [AP].These alkali are 0.1～100 equivalent with respect to the compound shown in the formula (XXXII), can suitably select in them more than a kind or 2 kinds, and can mix use.

As the catalyzer that in above-mentioned reaction, uses, can enumerate illustrated catalyzer etc. in the above-mentioned reaction [AP].These catalyzer are 10 with respect to the compound shown in the formula (XXXII) ^-10～1 equivalent, can suitably select in them more than a kind or 2 kinds, and can mix use.

As the carbon monoxide equivalents that can in above-mentioned reaction, use, for example can enumerate hexacarbonylmolybdenum, formic acid, chloroform etc.Carbon monoxide or its equivalents are 1～1000 equivalent with respect to the compound shown in the formula (XXXII), can react adding to depress as required.Pressure can suitably be selected in the scope of 1～100MPa.

Above-mentioned reaction can be carried out in the presence of part as required.As part, can enumerate illustrated part etc. in the above-mentioned reaction [AP].These parts are 10 with respect to the compound shown in the formula (XXXII) ^-10～1 equivalent, can suitably select in them more than a kind or 2 kinds, and can mix use.

Above-mentioned reaction can be carried out in the presence of co-catalyst as required.As co-catalyst, can enumerate illustrated co-catalyst etc. in the above-mentioned reaction [AP].These co-catalysts are 0.001～1 equivalent with respect to the compound shown in the formula (XXXII), can suitably select in them more than a kind or 2 kinds, and can mix use.

In the compound shown in the above-mentioned formula (I-a-Hal), R ⁶Be R ^6-a-3Formula (I-a-Hal-3) shown in compound can make according to following reaction [AT].

In the following formula, R ¹, R ², R ³, R ⁴, R ^6-a-3, Hal-1 and Hal as mentioned above.

That is, the compound shown in the formula (I-a-Hal-3) can react the compound or its salt shown in compound shown in the formula (XXXIII) and carbon monoxide or its equivalents and the formula (III) and make by in the presence of catalyzer and alkali,

In the following formula, R ¹And R ²As mentioned above.

This reaction can similarly be carried out with above-mentioned reaction [AS].

Weed killer herbicide of the present invention shows excellent herbicidal effect.Its range of application spreads all over crop lands such as paddy field, dry land, fruit tree garden, mulberry field, and non-agricultural cultivated lands such as mountain forest, road, farmland, place, factory place etc. are multiple, and application method also can suitably be selected soil treatment, cauline leaf processing, submerging treatment etc.

Weed killer herbicide of the present invention can be prevented and kill off various injurious weeds, barnyard grass grass for example, the water barnyard grass, rise lady's-grass, green foxtail, faber bristlegrass herb, eleusine indica, wild oat, false Chinese sorghum, quackgrass, Herba Brachiariae Villoae, big broomcorn millet, Ba Lacao, moleplant seed, nit grass, annual bluegrass, amur foxtail, grassy weeds such as light fringe roegneria kamoji, cyperus iria, the rhizome of nutgrass flatsedge, earth almona, thin stalk firefly Lin, Herba Cyperi Glomerati, difformed galingale herb, needle spikesedge herb, sedge weeds such as wild water chestnut, short arrowhead, angustifolia arrowhead herb, Alismataceae weeds such as alisma canaliculatum, Monochoria vaginalis, Pontederiaceae weeds such as Monochoria korsakowii, Procumbent Falsepimpernel, Scrophulariaceae weeds such as horsefly eye, India's water pig breast milk, spend more Lythraceae weeds such as water amaranth, Elatinaceae weeds such as waterwort, piemarker, sting Malvaceae weeds such as golden Portulaca grandiflora, Siberian cocklebur, artemisiifolia, composite family weeds such as field thistle, black nightshade, Solanaceae weeds such as datura metel, wrinkle fruit amaranth, Amaranthaceae weeds such as Amaranthus retroflexus, pale persicaria, knotweeds such as lady's thumb, the knuckle-tooth Hairy Bittercress, cruciferous weeds such as shepherd's purse, Pharbitis purpurea, field bindweed, Convolvulaceae weeds such as pharbitis nilChoisy, Chenopodiaceae weeds such as lamb's-quarters, Portulacaceae weeds such as kitchen garden, pulse family weeds such as blunt leaf Cassia tora, Caryophyllaceae weeds such as chickweed, Labiatae weeds such as benbie, Rubiaceae weeds such as psilate catchweed bedstraw herb, Euphorbiaceae weeds such as acalypha copperleaf, Commelianaceae weeds such as dayflower etc.Therefore, can in cultivations such as useful crop, for example corn, soybean, cotton, wheat, rice, barley, oat, Chinese sorghum, rape, sunflower, beet, sugarcane, lawn, peanut, flax, tobacco, coffee, optionally prevent and kill off the situation of injurious weed or non-selectively prevent and kill off under the situation of injurious weed and use effectively.Weed killer herbicide particularly of the present invention can be in cultivations such as corn, soybean, cotton, wheat, rice, rape, sunflower, beet, sugarcane, lawn, peanut, flax, tobacco, coffees, especially optionally prevents and kill off in the cultivations such as corn, wheat, rice, lawn under the situation of injurious weed and uses effectively.

Weed killer herbicide of the present invention, the compound of above-mentioned formula (I) can be mixed with adjuvant on the common various agriculturals, the modulation preparation becomes forms such as pulvis, granula, particle hydrating agents, hydrating agents, tablet, pill, capsule (comprising the form of packing with water-solubility membrane), aqueous suspension agent, oiliness suspending agent, microemulsion formulation, outstanding emulsion formulation, aqueous solvent, emulsion, liquor, paste, thereby use, but as long as purpose according to the invention can be made employed all preparation forms in this field usually.

As the adjuvant that uses in the preparation, can enumerate diatomite, calcium hydroxide, calcium carbonate, talcum, white carbon, kaolin, bentonite, kaolinite, sericite, clay, sodium carbonate, sodium bicarbonate, saltcake, zeolite, solid carriers such as starch, water, toluene, dimethylbenzene, solvent naphtha diox, acetone, isophorone, methyl iso-butyl ketone (MIBK), chlorobenzene, cyclohexane, dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide, the N-N-methyl-2-2-pyrrolidone N-, the alcohol equal solvent, soap, benzoate, alkyl sulfo succinate, dialkyl sulfosuccinates, polycarboxylate, alkyl sodium sulfate ester salt, alkyl sulfate, alkyl aryl sulfate, alkyl biphenyl sulphate, sulfuric acid alcohol ester salt, alkylsulfonate, alkylaryl sulfonates, arylsulphonate, lignosulfonates, alkyl diphenyl base ether disulfonate, poly styrene sulfonate, alkylphosphonate salt, alkylaryl phosphate, the styryl aryl orthophosphate, the polyoxyethylene alkyl ether sulfuric acid, polyoxyethylene alkylaryl ether sulphate, the polyoxyethylene alkylaryl ether sulfuric acid, polyoxyethylene alkyl ether phosphate, polyxyethylated aryl phosphate ester salt, polyoxyethylene aryl ether phosphate ester salt, naphthalenesulfonate formaldehyde condensation compound, anion such as alkylnaphthalene sulfonate formaldehyde condensation products are surfactant, spreader-sticker, sorbitan fatty ester, fatty glyceride, fatty acid polyglycerol ester, the alcohol fatty acid ester polyglycol ether, acetylenic glycols, alkynol, oxygen base alkylidene block polymer, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene styryl aryl ether, polyoxyethylene glycol alkyl ether, polyethylene glycol, polyoxyethylene fatty acid ester, the polyoxyethylene sorbitan fatty acid ester, the polyoxyethylene fatty acid glyceride, polyoxyethylene hardened castor oil, nonionics such as polyoxypropylene fatty acid ester are surfactant, spreader-sticker, olive oil, kopok oil, castor oil, palm oil, camellia oil, cocoa butter, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, tung oil, vegetable oil such as atoleine, the mineral wet goods.These adjuvants only otherwise break away from purpose of the present invention, just can suitably select to use more than a kind or 2 kinds, in addition, for example can also use normally used various adjuvants such as incremental agent, tackifier, antiprecipitant, antifreezing agent, dispersion stabilizer, poisoning palliative, mould inhibitor, blowing agent, disintegrant, bond.The compound of above-mentioned formula (I) is 0.1: 99.9～95: 5 with the ratio that cooperates of various adjuvants, is preferably 0.2: 99.8～85: 15.

Herbicidal composition of the present invention shows excellent herbicidal effect.Its range of application relates to crop lands such as paddy field, dry land, fruit tree garden, mulberry field, and non-agricultural cultivated lands such as mountain forest, road, farmland, place, factory place etc. are multiple, and application method also can suitably be selected soil treatment, cauline leaf processing, submerging treatment etc.

The amount of application of weed killer herbicide of the present invention is different and different according to the kinds of meteorological condition, soil condition, preparation form, object weeds, time of application etc., can not stipulate entirely, but the compound of general above-mentioned formula (I) is generally 0.1～10,000 gram/hectare, be preferably 1～2,000 gram/hectare, more preferably 1～1,000 gram/hectare is used like that.The present invention also comprises by using such weed killer herbicide and prevents and kill off the method for injurious weed.

In addition, weed killer herbicide of the present invention can use with other agricultural chemicals, fertilizer, poisoning palliative etc. or and usefulness, show more excellent effect, functionality in this case sometimes.As other agricultural chemicals, can enumerate weed killer herbicide, bactericide, antibiotic, plant hormone, agrochemical.Particularly, use with or and used the compound of above-mentioned formula (I) and the Herbicidal mixture composition of the active ingredient compound of other weed killer herbicide more than a kind or 2 kinds, may will use the time, activity of weeding etc. of scope, the chemicals treatment of grass seeds to preferred direction improvement.In addition, both can with the active ingredient compound of the compound of above-mentioned formula (I) and other weed killer herbicide respectively preparation when scattering, mix then and use, also can with both together preparation use.The present invention also comprises above-mentioned Herbicidal mixture composition.

As the active ingredient compound of other weed killer herbicide among the present invention, can enumerate for example following compound (common name: comprise compound or pilot code in the part ISO application), can suitably select in them more than a kind or 2 kinds.In addition, even under the situation that does not have special instruction,, also comprise wherein certainly if having salt, Arrcostab, hydrate, different crystal habits, various constitutional isomers etc. in these compounds.

(1) quilt is pointed out to show by the hormonal action of upsetting plant the compound of herbicide action, as 2,4-drips (2,4-D), 2,4-drips-2-butoxy ethyl ester (2,4-D-butotyl), 2,4-d butyl ester (2,4-D-butyl), 2,4-drips Dimethyl Ammonium (2,4-D-dimethylammonimum), 2,4-drips diethanol amine (2,4-D-diolamine), 2,4-drips ethyl ester (2,4-D-ethyl), 2,4-drips-2-Octyl Nitrite (2,4-D-2-ethylhexyl), 2,4-drips isobutyl ester (2,4-D-isobutyl), 2,4-drips different monooctyl ester (2,4-D-isoctyl), 2,4-drips isopropyl ester (2,4-D-isopropyl), 2,4-drips isopropyl ammonium (2,4-D-isopropylammonium), 2,4-drips sodium (2,4-D-sodium), 2,4-drips isopropyl alcohol ammonium (2,4-D-isopropanolammonium), 2,4-drips triethanolamine (2,4-D-trolamine), 2,4-Embutox (2,4-DB), 2,4-Embutox butyl ester (2,4-DB-butyl), 2,4-Embutox Dimethyl Ammonium (2,4-DB-dimethylammonium), 2, the different monooctyl ester (2 of 4-Embutox, 4-DB-isoctyl), 2,4-Embutox potassium (2,4-DB-potassium), 2,4-Embutox sodium (2,4-DB-sodium), 2,4-drips propionic acid (dichorprop), 2,4-drips propionic acid-2-butoxy ethyl ester (dichorprop-butotyl), 2,4-drips propionic acid Dimethyl Ammonium (dichorprop-dimethylammonium), 2,4-drips the different monooctyl ester of propionic acid (dichorprop-isoctyl), 2,4-drips potassium propionate (dichorprop-potassium), high by 2,4-drips propionic acid (dichlorprop-P), high by 2,4-drips propionic acid Dimethyl Ammonium (dichlorprop-P-dimethylammonium), high by 2,4-drips potassium propionate (dichlorprop-P-potassium), high by 2,4-drips sodium propionate (dichlorprop-P-sodium), 2 first, 4 chlorine (MCPA), 2 first, 4 chloro-2-butoxy ethyl esters (MCPA-butotyl), 2 first, 4 Chlorodimethyl ammoniums (MCPA-dimethylammonium), 2 first, 4 chloro-2-Octyl Nitrites (MCPA-2-ethylhexyl), 2 first, 4 chlorine potassium (MCPA-potassium), 2 first, 4 chlorine sodium (MCPA-sodium), 2 first, 4 chlorine sulfo-ethyl esters (MCPA-thioethyl), Thistrol (MCPB), Thistrol ethyl ester (MCPB-ethyl), Thistrol sodium (MCPB-sodium), Vi par (mecoprop), Vi par-2-butoxy ethyl ester (mecoprop-butotyl), Vi par sodium (mecoprop-sodium), mecopropP (mecoprop-P), mecopropP-2-butoxy ethyl ester (mecoprop-P-butotyl), mecopropP Dimethyl Ammonium (mecoprop-P-dimethylammonium), mecopropP-2-Octyl Nitrite (mecoprop-P-2-ethylhexyl), mecopropP potassium (mecoprop-P-potassium), naproanilide (naproanilide), clomeprop phenoxy groups such as (clomeprop) system, trysben (2,3,6-TBA), dicamba (dicamba), dicamba-2-butoxy ethyl ester (dicamba-butotyl), dicamba diglycolamine (dicamba-diglycolamine), dicamba Dimethyl Ammonium (dicamba-dimethylammonium), dicamba diethanol amine (dicamba-diolamine), dicamba isopropyl ammonium (dicamba-isopropylammonium), dicamba potassium (dicamba-potassium), dicamba sodium (dicamba-sodium), dichlobenil (dichlobenil), picloram (picloram), picloram Dimethyl Ammonium (picloram-dimethylammonium), the different monooctyl ester of picloram (picloram-isoctyl), picloram potassium (picloram-potassium), picloram three isopropyl alcohol ammoniums (picloram-triisopropanolammonium), picloram triisopropyl ammonium (picloram-triisopropylammonium), picloram triethanolamine (picloram-trolamine), Triclopyr (triclopyr), Triclopyr-2-butoxy ethyl ester (triclopyr-butotyl), Triclopyr triethyl ammonium (triclopyr-triethylammonium), clopyralid (clopyralid), clopyralid monoethanolamine (clopyralid-olamine), clopyralid potassium (clopyralid-potassium), clopyralid three isopropyl alcohol ammoniums (clopyralid-triisopropanolammonium), chloro amido pyridine acid aromatic carboxylic acids such as (aminopyralid) system, and quinclorac (naptalam), quinclorac sodium (naptalam-sodium), herbicide (benazolin), herbicide ethyl ester (benazolin-ethyl), dichloro quinolinic acid (quinclorac), quinmerac (quinmerac), the dichloro pyrrole swells (diflufenzopyr), the dichloro pyrrole swells sodium (diflufenzopyr-sodium), fluroxypyr (fluroxypyr), fluroxypyr-2-butoxy-1-methyl ethyl ester (fluroxypyr-2-butoxy-1-methylethyl), fluroxypyr-1-meptyl ester (fluroxypyr-meptyl), chlorflurenol (chlorflurenol), chlorflurenol methyl esters (chlorflurenol-methyl) etc.

(2) pointed out by suppressing the compound that photosynthesis of plants shows herbicide action, as chlortoluron (chlorotoluron), diuron (diuron), fluometuron (fluometuron), lorox (linuron), isoproturon (isoproturon), metobenzuron (metobenzuron), grand (dimefuron) Yi Evil of Metribuzin (tebuthiuron) oxazole grand (isouron), karbutilate (karbutilate), methabenz thiazuron (methabenzthiazuron), metoxuron (metoxuron), afesin (monolinuron), neburea (neburon), also careless grand (siduron), Te Dingtong (terbumeton), trietazine ureas such as (trietazine) system, Simanex (simazine), atrazine (atrazine), atraton (atratone), symetryne (simetryn), prometryn (prometryn), penta grass clean (dimethametryn), Hexazinone (hexazinone), metribuzin (metribuzin), Garagard (terbuthylazine), bladex (cyanazine), ametryn (ametryn), uncle's 2-fourth amino-4-cyclopropylamino-6-methyl mercapto-1,3,5-triazine (cybutryne), triaziflam (triaziflam), terbutryn (terbutryn), propazine (propazine), metamitron (metamitron), prometryn triazines such as (prometon) system, bromacil (bromacil), bromo acyl lithium (bromacyl-lithium), lenacil (lenacil), terbacil uracils such as (terbacil) system, Stam F-34 (propanil), encircle careless amine anilides such as (cypromid), swep (swep), different phenmedipham (desmedipham), phenmedipham carbamates such as (phenmedipham) system, Brominal (bromoxynil), bromoxynil octanoate (bromoxynil-octanoate), bromoxynil enanthate (bromoxynil-heptanoate), ioxynil (ioxynil), Octanoate (ioxynil-octanoate), ioxynil potassium (ioxynil-potassium), ioxynil sodium 4-hydroxy-benzonitriles such as (ioxynil-sodium) system, and pyridate (pyridate), bentazone (bentazone), bentazone sodium (bentazone-sodium), amicarbazone (amicarbazone), methazole (methazole), pentanochlor (pentanochlor) etc.

(3) by being pointed out that itself is converted into free radical in plant corpus, generate active oxygen, thereby show herbicidal effect fast as paraquat (paraquat), diquat (diquat) quaternary ammonium salt of etc.ing be.

(4) pointed out by suppressing the biosynthesis of plant chlorophyll, thereby photosensitive peroxide is accumulated in plant corpus unusually and shown the compound of herbicidal effect, as nitrofen (nitrofen), chlomethoxyfen (chlomethoxyfen), bifenox (bifenox), acifluorfen (acifluorfen), acifluorfen sodium (acifluorfen-sodium), Fomesafen (fomesafen), Fomesafen sodium (fomesafen-sodium), Oxyfluorfen (oxyfluorfen), lactofen (lactofen), aclonifen (aclonfen), ethoxyfenethyl ethyl ester (ethoxyfen-ethyl, HC-252), fluoroglycofen-ethyl ethyl (fluoroglycofen-ethyl), fluoroglycofen-ethyl diphenyl ethers such as (fluoroglycofen) system, chlorine phthalimide (chlorphthalim), flumioxazin (flumioxazin), Flumiclorac pentyl (flumiclorac), Flumiclorac pentyl pentyl ester (flumiclorac-pentyl), cinidon-ethyl (cinidon-ethyl), fluthiacetmethyl cyclic imides such as (fluthiacet-methyl) system, and Bing Que oxazole grass (oxadiargyl) Evil grass spirit (oxadiazon), sulfentrazone (sulfentrazone), carfentrazoneethyl (carfentrazone-ethyl), thiadiazoles grass amine (thidiazimin) Wu oxazole grass (pentoxazone), azoles pyridine alkynes grass (azafenidin), fluazolate (isopropazole), fluorine carfentrazone (pyraflufen-ethyl), benzfendizone (benzfendizone), the fluorine third phonetic humulone (butafenacil), saflufenacll, flupoxam (flupoxam), fluazolate (fluazolate), profluazol (profluazol), pyraclonil (pyraclonil), flufenpyrethyl (flufenpyr-ethyl), bencarbazone (a kind of triazolineone weed killer herbicide) etc.

(5) pointed out to suppress the plant pigment biosynthesis of carotenoid etc., thereby show with the whitening action to be the compound of the herbicidal effect of feature, as monometflurazone (norflurazon), Pynamin (chloridazon), diformazan reaches grass volt pyridazinones such as (metflurazon) system, pyrazolate (pyrazolate), pyrazoxyfen (pyrazoxyfen), benzofenap (benzofenap), BAS-670H (topramezone), pyrazoles such as pyrasulfotole system, and Amrol (amitrol), fluridone (fluridone), flurtamone (flurtamone), Diflufenican (diflufenican), Kayaphenone (methoxyphenone) clomazone (clomazone), sulphur humulone (sulcotrione), Mesotrione (mesotrione), tembotrione, AVH-301 (tefuryltrione) isoxazole humulone (isoxaflutole), difenzoquat (difenzoquat), difenzoquat Methylsulfate (difenzoquat-metilsulfate) Yi Evil chlorine humulone (isoxachlortole), benzobicylon (benzobicyclon), fluorine pyrrole acyl grass amine (picolinafen), beflubutamid (beflubutamid) etc.

(6) be found the compound that gramineous plants is shown strong specificity herbicidal effect, as diclofop-methyl (diclofop-methyl), 2-[4-(2, the 4-dichlorophenoxy) phenoxy group] propionic acid (diclofop), pyrifenox sodium (pyriphenop-sodium), fluazifop (fluazifop-butyl), the free acid of fluazifop (fluazifop), the free acid of efficient fluazifop (fluazifop-P), efficient fluazifop (fluazifop-P-butyl), haloxyfop-P-methyl (haloxyfop-methyl), pyrrole fluorine chlorine standing grain spirit (haloxyfop), pyrrole fluorine chlorine standing grain spirit ethoxy ethyl ester (haloxyfop-etotyl), haloxyfop-P-methyl (haloxyfop-P), haloxyfop-methyl (haloxyfop-P-methyl), quizalofop-ethyl (quizalofop-ethyl), the free acid of Quizalotop-ethyl (quizalofop-P), Quizalotop-ethyl (quizalofop-P-ethyl), sugar careless ester (quizalofop-P-tefuryl), the free acid of cyhalofop-butyl (cyhalofop-butyl) oxazole diclofop-methyl (fenoxaprop-ethyl) fenoxaprop (fenoxaprop-P) fenoxaprop (fenoxaprop-P-ethyl) oxazole acyl grass amine propyl ester (metamifop-propyl) oxazole acyl grass amine (metamifop), alkynes oxalic acid (clodinafop-propargyl), alkynes oxalic acid (clodinafop) Evil oxalic acid aryloxy phenoxy propionic acids such as (propaquizafop) system, alloxydimsodium (alloxydim-sodium), withered reach extremely (alloxydim), clethodim (clethodim), sethoxydim (sethoxydim), tralkoxydim (tralkoxydim), fourth oxygen cyclic ketones (butroxydim), tepraloxydim (tepraloxydim), clefoxidim (profoxydim), cycloxydim cyclohexanediones such as (cycloxydim) system, and efficient flampropmethyl (flamprop-M-methyl), efficient wheat straw fluorine (flamprop-M), efficient flampropisopropyl (flamprop-M-isopropyl) etc.

(7) pointed out by suppressing the compound that the plant amino acid biosynthesis shows herbicidal effect; as chlorimuronethyl (chlorimuron-ethyl); the free acid of chlorimuronethyl (chlorimuron); sulfometuronmethyl (sulfometuron-methyl); the free acid of sulfometuronmethyl (sulfometuron); primisulfuronmethyl (primisulfuron-methyl); the free acid of primisulfuronmethyl (primisulfuron); bensulfuron-methyl (bensulfuron-methyl); the free acid of bensulfuron-methyl (bensulfuron); chlorine sulphur swells (chlorsulfuron); metsulfuron-methyl (metsulfuron-methyl); the free acid of metsulfuron-methyl (metsulfuron); cinosulfuron (cinosulfuron); pyrazosulfuron (pyrazosulfuron-ethyl); the free acid of pyrazosulfuron (pyrazosulfuron); azimsulfuron (azimsulfuron); flazasulfuron (flazasulfuron); rimsulfuron (rimsulfuron); nicosulfuron (nicosulfuron); imazosulfuron (imazosulfuron); AC322140 (cyclosulfamuron); prosulfuron (prosulfuron); flupyrsulfuron-methyl-sodium sodium (flupyrsulfuron-methyl-sodium); the free acid of flupyrsulfuron-methyl-sodium (flupyrsulfuron); triflusulfuronmethyl (triflusulfuron-methyl); the free acid of triflusulfuronmethyl (triflusulfuron); halosulfuronmethyl (halosulfuron-methyl); the free acid of halosulfuronmethyl (halosulfuron); thifensulfuron methyl (thifensulfuron-methyl); the free acid of thifensulfuron methyl (thifensulfuron); ethoxysulfuron (ethoxysulfuron); oxasulfuron (oxasulfuron); ethametsulfuron (ethametsulfuron); ethametsulfuron formic acid esters (ethametsulfuron-methyl); iodine sulphur swells (iodosulfuron); methyl iodide sulphur swells sodium (iodosulfuron-methyl-sodium); Sulfosulfuron (sulfosulfuron); triasulfuron (triasulfuron); tribenuron-methyl (tribenuron-methyl); the free acid of tribenuron-methyl (tribenuron); tritosulfuron (tritosulfuron); foramsulfuron (foramsulfuron); trifloxysulfuron (trifloxysulfuron); trifloxysulfuron sodium (trifloxysulfuron-sodium); mesosulfuronmethyl (mesosulfuron-methyl); methyl two sulphurs swell (mesosulfuron); phonetic aniline sulphur swells (orthosulfamuron); fluorine pyrrole sulphur swells (flucetosulfuron); amidosulfuron (amidosulfuron); TH-547; sulfonylureas such as the compound system that international open communique WO2005092104 is put down in writing; Flumetsulam (flumetsulam); metosulam (metosulam); diclosulam (diclosulam); cloransulammethyl (cloransulam-methyl); florasulam (florasulam) penoxsuam triazolopyrimidine sulfonamides such as (penoxsulam) system; weed eradication cigarette (imazapyr); isopropyl weed eradication cigarette ammonium (imazapyr-isopropylammonium); Imazethapyr (imazethapyr); Imazethapyr ammonium (imazethapyr-ammonium); weed eradication quinoline (imazaquin); weed eradication quinoline ammonium (imazaquin-ammonium); imazamox (imazamox); imazamox ammonium (imazamox-ammonium); miaow grass ester (imazamethabenz); miaow oxalic acid (imazamethabenz-methyl); AC 263222 imidazolones such as (imazapic) system; pyrithiobac-sodium (pyrithiobac-sodium); two KIH 6127 (bispyribac-sodium); KIH 6127 (pyriminobac-methyl); pyribenzoxim (pyribenzoxim); pyriftalid (pyriftalid); KUH-021 pyrimidine radicals salcylic acids such as (pyrimisulfan) system; flucarbazonesodium (flucarbazone); flucarbazonesodium sodium (flucarbazone-sodium); procarbazone sodium (propoxycarbazone-sodium); procarbazone sulfonyl amino carbonyl Triazolinones such as (propoxycarbazone) system, and glyphosate (glyphosate); glyphosate sodium (glyphosate-sodium); glyphosate potassium (glyphosate-potassium); ammonium glyphosate (glyphosate-ammonium); glyphosate two ammoniums (glyphosate-diammonium); isopropyl ammonium glyphosate (glyphosate-isopropylammonium); sulphosate (glyphosate-trimesium); glyphosate sesquisodium (glyphosate-sesquisodium); grass fourth phosphine (glufosinate); grass ammonium phosphine (glufosinate-ammonium); bilanafos (bilanafos); bilanafos sodium (bilanafos-sodium); cinmethylin (cinmethylin) etc.

(8) pointed out by suppressing the compound that plant cell mitosis shows herbicidal effect, as trefanocide (trifluralin), ammonia sulphur spirit (oryzalin), nitralin (nitralin), Pendimethalin (pendimethalin), fourth fluchloralin (ethalfluralin), benfluralin (benfluralin), amino trefanocide (prodiamine), butralin (butralin), dinitramine dinitroanilines such as (dinitramine) system, bensulide (bensulide), proproanmide (napropamide), pentyne grass amine (propyzamide), pronamide acid amides such as (pronamide) system, amiprophos-methyl (amiprofos-methyl), butamifos (butamifos), anilofos (anilofos), piperophos organic phosphors such as (piperophos) system, propham (propham), chlorpropham (chlorpropham), oatax (barban), block careless amine carbanilates such as (carbetamide) system, daimuron (daimuron), cumyluron (cumyluron), bromobutide (bromobutide), methyldymron cumyl amine such as (methyldymron) system, and sulphur grass spirit (asulam), sulphur grass clever sodium (asulam-sodium), dithiopyr (dithiopyr), thiophene grass fixed (thiazopyr), chlorine dimethyl phthalate (chlorthal-dimethyl), chlorine phthalandione (chlorthal), diphenamide (diphenamid) etc.

(9) pointed out by protein biosynthesis that suppresses plant or the compound that the lipid biosynthesis shows herbicidal effect, as alachlor (alachlor), metazachlor (metazachlor), butachlor (butachlor), the third careless amine (pretilachlor), isopropyl methoxalamine (metolachlor), smart isopropyl methoxalamine (S-metolachlor), P DimethenamidP (thenylchlor), pethoxamid (pethoxamid), Acetochlor (acetochlor), propachlor (propachlor), P DimethenamidP (dimethenamid), smart P DimethenamidP (dimethenamid-P), propisochlor (propisochlor), dimethachlor chloroacetamides such as (dimethachlor) system, molinate (molinate), dimepiperate (dimepiperate), pyributicarb (pyributicarb), EPTC (EPTC), fourth grass special (butylate), vernolate (vernolate), tillam (pebulate), ring grass special (cycloate), prosulfocarb (prosulfocarb), esprocarb (esprocarb), benthiocarb (thiobencarb), Avadex (diallate), triallate (tri-allate), orbencarb thiocarbamates such as (orbencarb) system, and ethobenzanid (etobenzanid), mefenacet (mefenacet), flufenacet (flufenacet), tridiphane (tridiphane), benzophenone azoles (cafenstrole), fentrazamide (fentrazamide) oxazine humulone (oxaziclomefone), indanofan (indanofan), benfuresate (benfuresate), KIH-485 (pyroxasulfone), dalapon (dalapon), dalapon sodium (dalapon-sodium), sodium trichloroacetate (TCA-sodium), trichloroacetic acid (trichloroaceticacid) etc.

(10) monosodium methanearsonate (MSMA), disodioum methanearsonate (DSMA), arsenic acid trimethyl (CMA), mattress kills (endothall) more, mattress kills dipotassium (endothall-dipotassium) more, mattress kills sodium (endothall-sodium) more, mattress kills single (N more, N-dimethyl alkylammonium) (endothall-mono (N, N-dimethylalkylammonium)), ethofumesate (ethofumesate), sodium chlorate (sodiumchlorate), n-nonanoic acid (pelargonic acid), n-nonanoic acid (nonanoic acid)), kill wooden phosphorus (fosamine), kill wooden phosphorus ammonium (fosamine-ammonium), azoles quinoline grass ester (pinoxaden), N-(2,4-difluorophenyl-1,5-dihydro-N-isopropyl-5-oxo-1-[(tetrahydrochysene-2H-pyrans-1-yl) methyl]-4H-1,2,4-triazole-4-formamide (HOK-201), acrolein (aclolein), Amcide Ammate (ammonium sulfamate), borax (borax), monoxone (chloroacetic acid), sodium chloroacetate (sodium chloroacete), cyanamide (cyanamide), methanearsonic acid (methylarsonic acid), cacodylic acid (dimethylarsinic acid), sodium dimethyl arsine (sodium dimethylarsinate), dinoterb (dinoterb), dinoterb ammonium (dinoterb-ammonium), dinoterb diethanol amine (dinoterb-diolamine), dinoterb acetate (dinoterb-acetate), Chemox PE (DNOC), ferrous sulfate (ferrous sulfate), fluorine propionic acid (flupropanate), fluorine sodium propionate (flupropanate-sodium) Yi Evil acyl grass amine (isoxaben), mefluidide (mefluidide), mefluidide diethanol amine (mefluidide-diolamine), metham-sodium (metam), metham-sodium ammonium (metam-ammonium), metham-sodium potassium (metam-potassium), metham-sodium sodium (metam-sodium), methyl-isorhodanate (methyl isothiocyanate), pentachlorophenol (pentachlorophenol), sodium pentachlorophenol (sodiumpentachlorophenoxide), lauric acid pentachlorobenzene phenolic ester (pentachlorophenol laurate), quinoclamine (quinoclamine), sulfuric acid (sulfuric acid), ureasulfuric acid (urea sulfate) etc.

(11) by point out by colonize in shows on the plant herbicidal effect as sarson Xanthomonas campestris (Xanthomonas campestris), Epicoccosirus nematosorus, Epicoccosirusnematosperus, prominent navel spore bacterium (Exserohilum monoseras), the interior navel of the barnyard grass spore bacterium (Drechsrela monoceras) etc. that wriggles that wriggles.

The cooperation ratio of the compound shown in the formula of the present invention (I) and the active ingredient compound of above-mentioned other weed killer herbicide is different and different according to the kinds of meteorological condition, soil condition, preparation form, object weeds, time of application etc., can not stipulate entirely, be generally 1: 1000～1000: 1, be preferably 1: 800～100: 1, used like that in more preferably 1: 600～20: 1.

Put down in writing an example of optimal way of the present invention below, but the invention is not restricted to this.

(1) a kind of weed killer herbicide contains benzoylpyrazole compound or its salt as active ingredient, and described benzoylpyrazole compound is in above-mentioned formula (I), R ⁴It is alkyl; R ⁵Be cyano group, cyanoalkyl, halo alkoxy alkyl, can be selected from alkyl, cyano group, cyanoalkyl, (alkylthio group) carbonylic alkyl, alkyl (thiocarbonyl) alkyl ,-C (O) OR ⁷With-C (O) SR ⁷In amino (thiocarbonyl) alkyl that replaces of at least 1 substituting group; the thiocyanate groups alkyl; the halogen alkoxyl; the alkoxyl alkoxyl, alkyl sulphonyl, alkyl sulphonyl alkyl; alkoxy carbonyl alkyl; the alkoxy carbonyl alkoxyl, the heterocyclic radical alkyl, can be selected from alkyl, cyano group, cyanoalkyl, (alkylthio group) carbonylic alkyl, alkyl (thiocarbonyl) alkyl ,-C (O) OR ⁷With-C (O) SR ⁷In the compound of the aminoalkyl that replaces of at least 1 substituting group.

(2) according to above-mentioned (1) contain benzoylpyrazole compound or its salt weed killer herbicide as active ingredient, in the described formula (I), R ¹It is alkyl; R ²It is hydrogen atom; R ³It is hydroxyl; R ⁴It is alkyl; R ⁵It is the alkoxyl alkoxyl; R ⁶It is alkyl sulphonyl.

(3) according to above-mentioned (2) contain benzoylpyrazole compound or its salt weed killer herbicide as active ingredient, in the described formula (I), R ¹Be methyl, ethyl or isopropyl; R ²It is hydrogen atom; R ³It is hydroxyl; R ⁴It is methyl; R ⁵It is the 2-methoxy ethoxy; R ⁶It is mesyl.

(4) according to above-mentioned (3) contain benzoylpyrazole compound or its salt weed killer herbicide as active ingredient, in the described formula (I), R ¹It is methyl.

(5) according to above-mentioned (3) contain benzoylpyrazole compound or its salt weed killer herbicide as active ingredient, in the described formula (I), R ¹It is ethyl.

(6) according to above-mentioned (3) contain benzoylpyrazole compound or its salt weed killer herbicide as active ingredient, in the described formula (I), R ¹It is isopropyl.

(7) contain the benzoylpyrazole compound of described formula (I) or the Herbicidal composition of its salt and agricultural usefulness adjuvant.

(8) benzoylpyrazole compound of described formula (I) or the herbicidally effective amount of its salt are applied to the place of undesired plants or its growth, thereby prevent and kill off undesired plants or suppress the method for its growth.

(9) according to the method for above-mentioned (8), prevent and kill off undesired plants or suppress its growth in corn plantation field.

(10) according to the method for above-mentioned (9), corn is the corn through transforming.

(11) according to the method for above-mentioned (8), prevent and kill off undesired plants or suppress its growth in wheat class plantation field.

(12) according to the method for above-mentioned (8), prevent and kill off undesired plants or suppress its growth in rice plantation field.

(13) according to the method for above-mentioned (8), prevent and kill off undesired plants or suppress its growth at non-agricultural cultivated land.

(14) use the benzoylpyrazole compound of described formula (I) or its salt is planted the selective herbicide of field as corn active ingredient.

(15) manufacture method of the compound shown in the included formula (I-a) of the compound shown in the described formula (I), be to make compound and the alkali reaction shown in compound shown in the formula (I-b) and the formula (VIII), perhaps make the reacting metal salt of the compound shown in compound shown in the described formula (I-b) and the described formula (VIII), thereby make the compound shown in the formula (I-a) included in the compound shown in the described formula (I)

In the following formula, R ¹It is alkyl or cycloalkyl; R ²Be hydrogen atom or alkyl; R ³It is hydroxyl; R ⁴Be alkyl, alkylhalide group, alkoxyl, halogen, nitro, cyano group, alkylthio group, alkyl sulphinyl or alkyl sulphonyl; R ^5-a-1Be alkoxyl, halogen alkoxyl, alkoxyl alkoxyl, halogen alkoxyl alkoxyl, alkoxyl halogen alkoxyl, halogen alkoxyl halogen alkoxyl, heterocyclyloxy base, heterocyclic radical alkoxyl, cycloalkyl oxy ,-OC (O) SR ⁷,-OC (O) OR ⁷, alkylthio group alkoxyl, alkoxy carbonyl alkoxyl, thiazolinyl oxygen base or alkynyloxy base; R ⁶Be alkylhalide group, halogen, nitro, cyano group, alkylthio group, alkyl sulphinyl or alkyl sulphonyl;

In the following formula, R ¹, R ², R ³, R ⁴And R ⁶As mentioned above; Hal is a halogen;

HO-R ^α(VIII)

In the following formula, R ^αBe alkyl, alkylhalide group, alkoxyalkyl, halo alkoxy alkyl, alkoxyl alkylhalide group, halogen alkoxyl alkylhalide group, heterocyclic radical, heterocyclic radical alkyl, cycloalkyl ,-C (O) SR ⁷,-C (O) OR ⁷, alkylthio alkyl, alkoxy carbonyl alkyl, alkenyl or alkynyl; R ⁷Be alkyl, alkylhalide group, alkoxyalkyl, thiazolinyl, haloalkenyl, alkynyl or can be by R ⁸The aryl alkyl that replaces; R ⁸Be halogen, alkyl or alkoxyl.

(16) according to the method for above-mentioned (15), R ¹It is alkyl; R ²It is hydrogen atom; R ⁴It is alkyl; R ^5-a-1It is the alkoxyl alkoxyl; R ^αIt is alkoxyalkyl.

(17) according to the method for above-mentioned (15), R ¹The Ga alkyl; R ²It is hydrogen atom; R ⁴It is alkyl; R ^5-a-1It is alkoxyl; R ^αIt is alkyl.

(18) manufacture method of the compound shown in the formula (I-a-Hal-3), be that compound or its salt shown in compound shown in the formula (XXXIII) and the formula (III) and carbon monoxide or its equivalents are reacted in the presence of catalyzer and alkali, thereby the method for the compound shown in the manufacturing formula (I-a-Hal-3)

In the following formula, R ¹It is alkyl or cycloalkyl; R ²Be hydrogen atom or alkyl; R ³It is hydroxyl; R ⁴Be alkyl, alkylhalide group, alkoxyl, halogen, nitro, cyano group, alkylthio group, alkyl sulphinyl or alkyl sulphonyl; R ^6-a-3It is alkyl sulphonyl; Hal-1 is a halogen;

In the following formula, R ^6-a-3As mentioned above; Hal-1 and Hal are halogens, can be the same or different each other;

In the following formula, R ¹And R ²As mentioned above.

(19) according to the method for above-mentioned (18), R ¹It is alkyl; R ²It is hydrogen atom; R ⁴It is alkyl.

(20) according to the method for above-mentioned (18), catalyzer is the metal series catalysts.

(21) according to the method for above-mentioned (20), the metal series catalysts is a palladium catalyst.

(22) manufacture method of the compound shown in the formula (XXXIII) is to make compound shown in the formula (XXXIV) and formula (R ^6-a-3) (Hal-3) or (R ^6-a-3) ₂Thereby the compound shown in the O reacts the method for the compound shown in the manufacturing formula (XXXIII) in the presence of acid,

In the following formula, R ⁴Be alkyl, alkylhalide group, alkoxyl, halogen, nitro, cyano group, alkylthio group, alkyl sulphinyl or alkyl sulphonyl; R ^6-a-3It is alkyl sulphonyl; Hal-1 and Hal are halogens; Hal-1 and Hal can be the same or different each other;

In the following formula, R ⁴, Hal-1 and Hal as mentioned above;

Formula (R ^6-a-3) (Hal-3) or (R ^6-a-3) ₂Among the O, R ^6-a-3As mentioned above; Hal-3 is a halogen; Hal-1, Hal and Hal-3 can be the same or different each other.

(23) according to the method for above-mentioned (22), R ⁴It is alkyl.

(24) manufacture method of the compound shown in the formula (V-a-1-3) is to make the compound shown in the formula (XXXII) and carbon monoxide or its equivalents and H ₂O reacts in the presence of catalyzer and alkali, thus the method for the compound shown in the manufacturing formula (V-a-1-3),

In the following formula, R ⁴Be alkyl, alkylhalide group, alkoxyl, halogen, nitro, cyano group, alkylthio group, alkyl sulphinyl, or alkyl sulphonyl; R ^5-a-1Be alkoxyl, halogen alkoxyl, alkoxyl alkoxyl, halogen alkoxyl alkoxyl, alkoxyl halogen alkoxyl, halogen alkoxyl halogen alkoxyl, heterocyclyloxy base, heterocyclic radical alkoxyl, cycloalkyl oxy ,-OC (O) SR ⁷,-OC (O) OR ⁷, alkylthio group alkoxyl, alkoxy carbonyl alkoxyl, thiazolinyl oxygen base or alkynyloxy base; R ^6-a-3It is alkyl sulphonyl; R ⁷Be alkyl, alkylhalide group, alkoxyalkyl, thiazolinyl, haloalkenyl, alkynyl or can be by R ⁸The aryl alkyl that replaces; R ⁸Be halogen alkyl or alkoxyl;

In the following formula, R ⁴, R ^5-a-1, R ^6-a-3As mentioned above; Hal is a halogen.

(25) according to the method for above-mentioned (24), R ⁴It is alkyl; R ^5-a-1It is the alkoxyl alkoxyl.

(26) according to the method for above-mentioned (24), catalyzer is the metal series catalysts.

(27) according to the method for above-mentioned (26), the metal series catalysts is a palladium catalyst.

(28) manufacture method of the compound shown in the formula (XXXII), be make the compound shown in the formula (XXXIII), with formula (VIII) shown in compound in the presence of alkali, react, perhaps make the reacting metal salt of the compound shown in compound shown in the described formula (XXXIII) and the described formula (VIII), thereby the method for the compound shown in the manufacturing formula (XXXII)

In the following formula, R ⁴Be alkyl, alkylhalide group, alkoxyl, halogen, nitro, cyano group, alkylthio group, alkyl sulphinyl or alkyl sulphonyl; R ^5-a-1Be alkoxyl, halogen alkoxyl, alkoxyl alkoxyl, halogen alkoxyl alkoxyl, alkoxyl halogen alkoxyl, halogen alkoxyl halogen alkoxyl, heterocyclyloxy base, heterocyclic radical alkoxyl, cycloalkyl oxy ,-OC (O) SR ⁷,-OC (O) OR ⁷, alkylthio group alkoxyl, alkoxy carbonyl alkoxyl, thiazolinyl oxygen base or alkynyloxy base; R ^6-a-3It is alkyl sulphonyl; Hal is a halogen;

In the following formula, R ⁴And R ^6-a-3As mentioned above; Hal-1 and Hal are halogens; Hal-1 and Hal can be the same or different each other;

HO-R ^α(VIII)

(29) according to the method for above-mentioned (28), R ⁴It is alkyl; R ^5-a-1It is the alkoxyl alkoxyl; R ^αIt is alkoxyalkyl.

(30) according to the method for above-mentioned (28), R ⁴It is alkyl; R ^5-a-1It is alkoxyl; R ^αIt is alkyl.

(31) compound shown in the formula (XXXII-a),

In the following formula, R ^4-aIt is alkyl; R ^5-a-1Be alkoxyl, halogen alkoxyl, alkoxyl alkoxyl, halogen alkoxyl alkoxyl, alkoxyl halogen alkoxyl, halogen alkoxyl halogen alkoxyl, heterocyclyloxy base, heterocyclic radical alkoxyl, cycloalkyl oxy ,-OC (O) SR ⁷,-OC (O) OR ⁷, alkylthio group alkoxyl, alkoxy carbonyl alkoxyl, thiazolinyl oxygen base or alkynyloxy base; R ^6-a-3It is alkyl sulphonyl; Hal is a halogen.

(32) according to the compound of above-mentioned (31), R ^5-a-1It is the alkoxyl alkoxyl.

(33) manufacture method of described formula (XXVI) is to make the compound shown in the formula (XXVII), react in the presence of solvent with magnesium metal or Grignard reagent, thus the method for the compound of manufacturing formula (XXVI),

In the following formula, R ⁴Be alkyl, alkylhalide group, alkoxyl, halogen, nitro, cyano group, alkylthio group, alkyl sulphinyl or alkyl sulphonyl; R ^6-a-2It is alkylthio group; Hal and Hal-2 are halogens, and Hal and Hal-2 can be the same or different each other;

In the following formula, R ⁴, R ^6-a-2, Hal and Hal-2 as mentioned above.

(34) according to the method for above-mentioned (33), R ⁴It is alkyl.

(35) manufacture method of the compound shown in the described formula (XXVII), be by make the compound shown in the formula (XXVIII), with halogenating agent reaction, thereby the method for the compound shown in the manufacturing formula (XXVII),

In the following formula, R ⁴, R ^6-a-2, Hal as mentioned above; Y ^-Be Cl ^-, Br ^-, I ^-, BF ₄ ^-, HSO ₃ ^-, NO ₃ ^-, ClO ₄ ^-Or OH ^-

(36) according to the method for above-mentioned (35), R ⁴It is alkyl.

(37) manufacture method of the compound shown in the described formula (XXVIII), be make the compound shown in the formula (XXIX), with diazotization agent reaction, thereby the method for the compound shown in the manufacturing formula (XXVIII),

In the following formula, R ⁴Be alkyl, alkylhalide group, alkoxyl, halogen, nitro, cyano group, alkylthio group, alkyl sulphinyl or alkyl sulphonyl; R ^6-a-2It is alkylthio group; Hal is a halogen; Y is Cl ^-, Br ^-, I ^-, BF ₄ ^-, HSO ₃ ^-, NO ₃ ^-, ClO ₄ ^-Or OH ^-

In the following formula, R ⁴, R ^6-a-2, Hal as mentioned above.

(38) according to the method for above-mentioned (37), R ⁴It is alkyl.

(39) manufacture method of the compound shown in the described formula (XXIX) is by making the compound shown in the formula (XXX), react in the presence of alkali with alkylating agent, thereby makes the method for the compound shown in the described formula (XXIX),

In the following formula, R ⁴Be alkyl, alkylhalide group, alkoxyl, halogen, nitro, cyano group, alkylthio group, alkyl sulphinyl or alkyl sulphonyl; R ^6-a-2It is alkylthio group; Hal is a halogen;

In the following formula, R ⁴As mentioned above.

(40) according to the method for above-mentioned (39), R ⁴It is alkyl.

(41) compound shown in described (XXVII),

In the following formula, R ⁴Be alkyl, alkylhalide group, alkoxyl, halogen, nitro, cyano group, alkylthio group, alkyl sulphinyl or alkyl sulphonyl; R ^6-a-2It is alkylthio group; Hal and Hal-2 are halogens, and Hal and Hal-2 can be the same or different each other.

(42) according to the compound of above-mentioned (41), R ⁴It is alkyl.

(43) compound shown in the described formula (XXIX),

In the following formula, R ⁴Be alkyl, alkylhalide group, alkoxyl, halogen, nitro, cyano group, alkylthio group, alkyl sulphinyl or alkyl sulphonyl; R ^6-a-2It is alkylthio group; Hal is a halogen.

(44) according to the compound of above-mentioned (43), R ⁴It is alkyl.

Embodiment

Following notebook inventive embodiment, but the invention is not restricted to this.Below, put down in writing the synthesis example of the compound of above-mentioned formula (I).

Synthesis example 1

Synthetic (following compound N o.1) of [5-hydroxyl-1-methyl-pyrazol-4-yl] [3-(2,2-dimethoxy ethyoxyl)-2-methyl-4-(mesyl) phenyl] ketone

(1) 3-hydroxy-2-methyl-4-(mesyl) benzoic acid (300mg) is dissolved in N, in the dinethylformamide (10mL), at room temperature adds potash (360mg) and bromoacetaldehyde dimethylacetal (660mg).Reactant mixture is heated to 80 ℃, stirred 32 hours.Reactant mixture is cooled to room temperature, adds the water of 100mL and the sodium hydrate aqueous solution (10mL) of 0.5N.Then, extract with ethyl acetate (200mL), with the organic layer anhydrous sodium sulfate drying.Distillation under reduced pressure removes desolvates, thereby obtains 3-(2,2-dimethoxy ethyoxyl)-2-methyl-4-(mesyl) benzoic acid-2 of oily, 2-dimethoxy ethyl ester.

¹H-NMR 400MHz(CDCl ₃δppm)：2.54(s，3H)，3.31(s，1H)，3.39(s，6H)，3.44(s，6H)，4.06(d，2H，J＝5.4Hz)，4.31(d，2H，J＝5.4Hz)，4.73(t，1H，J＝5.4Hz)，4.87(t，1H，J＝5.4Hz)，7.76(d，1H，J＝8.4Hz)，7.82(d，1H，J＝8.4Hz).

(2) with the 3-(2 of above-mentioned operation (1) gained; 2-dimethoxy ethyoxyl)-2-methyl-4-(mesyl) benzoic acid-2; 2-dimethoxy ethyl ester is dissolved in the methyl alcohol (20mL), at room temperature adds the sodium hydrate aqueous solution that concentration is 20 weight % (2mL).After stirring 30 minutes, in reaction solution, add the hydrochloric acid 100mL of 1 equivalent, extract with ethyl acetate (200mL).Organic layer with saturated common salt water washing 2 times, is used anhydrous sodium sulfate drying then.Distillation under reduced pressure removes desolvates, thereby obtains 3-(2,2-dimethoxy ethyoxyl)-2-methyl-4-(mesyl) benzoic acid (390mg) as white solid.

¹H-NMR 400MHz(acetone-d ₆δppm)：2.56(s，3H)，3.31(s，3H)，3.44(s，6H)，4.06(d，2H，J＝5.2Hz)，4.88(t，1H，J＝5.2Hz)，7.82(br s，2H).

(3) 3-(2,2-dimethoxy ethyoxyl)-2-methyl-4-(mesyl) benzoic acid (390mg) is dissolved in the chloroform (15mL), adds the DMF of oxalyl chloride (0.5mL) and catalytic amount.Reactant mixture was at room temperature stirred 30 minutes, and distillation under reduced pressure removes desolvates.Residue is dissolved among the anhydrous THF (20mL), adds 5-hydroxyl-1-methylpyrazole (132mg), triethylamine (250mg) and N, N-dimethyl aminopyridine (300mg) added hot reflux 1 hour.Reactant mixture is cooled to room temperature, adds ethyl acetate (200mL), use the saturated common salt water washing then 2 times.With the organic layer anhydrous sodium sulfate drying, distillation under reduced pressure removes and desolvates then.Residue is dissolved in the anhydrous acetonitrile (10mL), adds the acetone cyanohydrin of triethylamine (250mg) and catalytic amount, at room temperature stirred 12 hours.Distillation under reduced pressure removes desolvates, thereby obtains thick [5-hydroxyl-1-methyl-pyrazol-4-yl] [3-(2,2-dimethoxy ethyoxyl)-2-methyl-4-(mesyl) phenyl] ketone.

¹H-NMR(400MHz CDCl ₃δppm)：2.38(s，3H)，3.29(s，3H)，3.47(s，6H)，3.70(s，3H)，4.09(d，2H，J＝5.2Hz)，4.1(br s，1H)，4.83(t，1H，J＝5.2Hz)，7.32(s，1H)，7.35(d，1H，J＝8.4Hz)，7.91(d，1H，J＝8.4Hz).

(4) [3-(2 with thick [the 5-hydroxyl-1-methyl-pyrazol-4-yl] of above-mentioned operation (3) gained; 2-dimethoxy ethyoxyl)-and 2-methyl-4-(mesyl) phenyl] ketone is dissolved among the anhydrous THF (10mL); add triethylamine (250mg) and purity 96% chlorine thiol formic acid S-ethyl ester (200mg), at room temperature stirred 1 hour.In the reactant mixture that obtains, add ethyl acetate (200mL), with saturated common salt water washing 2 times.Organic layer is under reduced pressure distilled except that desolvating then with anhydrous sodium sulfate drying.With residue with silica gel column chromatography (n-hexane: purifying ethyl acetate=1: 1), thereby obtain [5-(ethylmercapto group) ketonic oxygen base-1-methyl-pyrazol-4-yl] [3-(2,2-dimethoxy ethyoxyl)-2-methyl-4-(mesyl) phenyl] ketone (150mg).

(5) [5-(ethylmercapto group) ketonic oxygen base-1-methyl-pyrazol-4-yl] [3-(2,2-dimethoxy ethyoxyl)-2-methyl-4-(mesyl) phenyl] ketone (91mg) with above-mentioned operation (4) gained is dissolved in the sodium hydrate aqueous solution (3ml) that also at room temperature adds 0.5N in the methyl alcohol (10ml).Reaction solution was at room temperature stirred 1 hour, add ethyl acetate (200ml) then, with saturated common salt water washing 1 time.With the organic layer anhydrous sodium sulfate drying, distillation under reduced pressure removes and desolvates then, thereby obtains object (80mg).

Synthesis example 2

[5-hydroxyl-1-methyl-pyrazol-4-yl] [3-(2-methoxy ethoxy)-2-methyl-4-(mesyl) phenyl] ketone synthesizes (following compound N o.151)

(1) 3-hydroxy-2-methyl-4-nitrobenzoic acid methyl esters (63.3g) is dissolved among the DMF (400mL), adds potash (41.4g) and potassium iodide (3g) and stir.In this mixed liquor, add chloroethyl methyl ether (56.7g), stirred 20 hours being heated under 90 ℃ the condition.Reaction mixture is added in the saline solution, extract with ethyl acetate-n-hexane mixed solvent.With organic layer saturated common salt water washing, then with the organic layer anhydrous sodium sulfate drying.Distillation under reduced pressure removes desolvates, thereby obtains 3-(2-methoxy ethoxy)-2-methyl-4-nitrobenzoic acid methyl esters (80.0g).

¹H-NMR(400MHz，CDCl ₃，δppm)2.54(3H，s)，3.39(3H，s)，3.70(2H，m)，3.91(3H，m)，4.11(2H，m)，7.59(1H，d，J＝8.0Hz)，7.64(1H，d，J＝8.0Hz).

(2) 3-(2-methoxy ethoxy)-2-methyl-4-nitrobenzoic acid methyl esters (50g) is dissolved in DMF (320mL), under the water-cooled condition, add sodium methyl mercaptide (95 weight % product, 14.4g).After stirring 30 minutes, in reactant liquor, add ethyl acetate-n-hexane mixed solvent (300mL/100mL) successively, 1N hydrochloric acid (300mL) stirs.Organic layer is washed with saline solution, use anhydrous sodium sulfate drying then, decompression distillation removes and desolvates, thereby obtains 3-(2-methoxy ethoxy)-2-methyl-4-(methyl mercapto) methyl benzoate (47.7g) as solid.

¹H-NMR(400MHz，CDCl ₃，δppm)；2.24(3H，s)，2.53(3H，s)，3.48(3H，s)，3.78(2H，m)，3.86(3H，s)，4.01(2H，m)，6.96(1H，d，J＝8.4Hz)，7.68(1H，d，J＝8.4Hz).

(3) 3-(2-methoxy ethoxy)-2-methyl-4-(methyl mercapto) methyl benzoate (47.7g) is dissolved in acetate (350mL), at room temperature slowly drips wolframic acid (IV) sodium 2 hydrates (4.6g), 30% aquae hydrogenii dioxidi (60.0g) successively.After stirring 1 hour, heat and stirred 40 minutes at 60 ℃.In reaction mixture, add saline solution, extract with ethyl acetate-n-hexane mixed solvent (1: 1).With organic layer saturated common salt water washing, use anhydrous sodium sulfate drying then.Distillation under reduced pressure removes desolvates, and by recrystallizing methanol, thereby obtains 3-(2-methoxy ethoxy)-2-methyl-4-(mesyl) methyl benzoate (46.8g).

¹H-NMR(400MHz，CDCl ₃，δppm)；2.54(3H，s)，3.26(3H，s)，3.46(3H，s)，3.79(2H，m)，3.91(3H，s)，4.19(2H，m)，7.71(1H，d，J＝8.4Hz)，7.84(1H，d，J＝8.4Hz).

(4) 3-(2-methoxy ethoxy)-2-methyl-4-(mesyl) methyl benzoate (46.79g) is dissolved in methyl alcohol-DMSO mixed solvent (280mL/100mL), at room temperature adds 20 weight % sodium hydrate aqueous solutions (77.5g).After stirring is spent the night, in reaction solution, add saline solution, wash with ether then with wet chemical furnishing alkalescence.Water layer is used ethyl acetate extraction then with watery hydrochloric acid furnishing acidity.With organic layer saturated common salt water washing, use anhydrous sodium sulfate drying then.Distillation under reduced pressure removes desolvates, thereby obtains 3-(2-methoxy ethoxy)-2-methyl-4-(mesyl) benzoic acid (30.4g).

¹H-NMR(400MHz，CDCl ₃，δppm)；2.63(3H，s)，3.31(3H，s)，3.49(3H，s)，3.83(2H，m)，4.23(2H，m)，7.91(2H，s).

(5) 3-(2-methoxy ethoxy)-2-methyl-4-(mesyl) benzoic acid (16.98g) is dissolved in the chloroform (200mL), adds the DMF of oxalyl chloride (15g) and catalytic amount then.Reactant mixture was at room temperature stirred 1 hour, and distillation under reduced pressure removes and desolvates then.Residue is dissolved in the anhydrous tetrahydro furan (150mL), adds 5-hydroxyl-1-methylpyrazole (6.35g), triethylamine (8.92g) and 4-(N, N-dimethylamino) pyridine (10.8g), at room temperature stirred 17 hours.Reactant mixture is dropped in the water, use hcl acidifying, use the ethyl acetate extraction product then.Ethyl acetate solution is washed for 2 times with the saturated common salt water washing.With the organic layer anhydrous sodium sulfate drying, distillation under reduced pressure removes and desolvates then.Residue is dissolved in the anhydrous acetonitrile (200mL), adds the acetone cyanohydrin of triethylamine (8.1g) and catalytic amount (0.75g), at room temperature stir stirring in 3 hours.Decompression distillation removes and desolvates, and drops into then in the water, uses the ethyl acetate extraction product then with the watery hydrochloric acid acidifying, uses anhydrous sodium sulfate drying, and decompression distillation removes and desolvates then, thereby obtains fusing point 112-114 ℃ object (16.8g).

¹H-NMR(400MHz，CDCl ₃，δppm)；2.41(3H，s)，3.31(3H，s)，3.48(3H，s)，3.73(3H，s)，3.82(2H，m)，4.26(2H，m)，7.34(1H，s)，7.36(1H，d，J＝8.4Hz)，7.94(1H，d，J＝8.4Hz).

Synthesis example 3

Synthesizing of [5-hydroxyl-1-methyl-pyrazol-4-yl] [3-(2-methoxy ethoxy)-2-methyl-4-(mesyl) phenyl] ketone

(1) thionyl chloride (120g) and methanesulfonic acid (240g) are at room temperature mixed, when stirring, refluxed 1 hour at 120 ℃.Confirm that gas generates end, is cooled to 50 ℃ with reactant mixture.Add 1 therein, 3-two chloro-2-methylbenzene (81g) and trifluoromethanesulfonic acid (5g) refluxed 5 hours at 120 ℃.Reactant mixture is cooled to 50 ℃, drops in the frozen water of 1L.The coarse crystallization of precipitation is dissolved in the chloroform (1L), and the sodium hydrate aqueous solution of water and 2M respectively washs 1 time.With the organic layer anhydrous sodium sulfate drying, distillation under reduced pressure removes and desolvates then.Make the coarse crystallization recrystallization that obtains with ethanol, thereby obtain 1 as white crystal, 3-two chloro-2-methyl-4-(mesyl) benzene (88g).

¹H-NMR 400MHz(CDCl ₃δppm)：2.58(s，3H)，3.28(s，3H)，7.50(d，1H，J＝8.2Hz)，7.97(d，1H，J＝8.2Hz).

(2) with 1; 3-two chloro-2-methyl-4-(mesyl) benzene (31g), sodium bicarbonate (33g), acid chloride (0.875g) and 1; pack into the stainless steel autoclave of capacity 500mL of 4-two (diphenylphosphino) butane (3.25g); mixed solvent after adding is handled with the nitrogen degassing (tert-butyl alcohol: water=10: 1,250mL).With seal of vessel, inside is replaced 2 times with carbon monoxide, the pressure with carbon monoxide is set at 2MPa then, stirs at 125 ℃ and stirs in 8 hours, is cooled to room temperature then.Similarly stirred 8 hours in second day, and be cooled to room temperature then, similarly stirred 4 hours in second day afterwards at 125 ℃ at 125 ℃.After the reaction vessel cooling, add 2M sodium hydroxide solution (200mL).After stirring 15 minutes, use the diatomite filtration insoluble matter, with 2M sodium hydroxide solution (200mL) washing residue.Filtrate with toluene (200mL) washing 3 times, is added concentrated hydrochloric acid then to pH1 in water layer.Leach the precipitation of separating out, dry then, thus obtain 3-chloro-2-methyl-4-(mesyl) benzoic acid (30g) as white solid.

¹H-NMR 400MHz(CDCl ₃δppm)：2.72(s，3H)，3.30(s，3H)，7.97(d，1H，J＝8.4Hz)，8.11(d，1H，J＝8.4Hz).

(3) under nitrogen atmosphere, sodium hydroxide (0.8g) is at room temperature added in the 2-methyl cellosolve (30mL), stir at 120 ℃ and dissolved fully to solid in 15 minutes.Reactant mixture is cooled to room temperature, and the solvent of about 15mL is removed in distillation under reduced pressure.Add 3-chloro-2-methyl-4-(mesyl) benzoic acid (1g) therein, stirred 12 hours at 120 ℃.Then reaction solution is cooled to room temperature, adds concentrated hydrochloric acid to pH1.Extract 2 times with ethyl acetate (100mL), organic layer is merged the back anhydrous sodium sulfate drying, distillation under reduced pressure removes and desolvates then.Residue is dissolved in the ethyl acetate (20mL), adds hexane (5mL) then.This solution was left standstill 12 hours in refrigerator (about 5 ℃), thereby obtain 3-(2-methoxy ethoxy)-2-methyl-4-(mesyl) benzoic acid (0.92g) as filbert solid.

¹H-NMR 400MHz(CDCl ₃，δppm)：2.63(3H，s)，3.31(3H，s)，3.49(3H，s)，3.83(2H，m)，4.23(2H，m)，7.91(2H，s).

(4) use 3-(2-methoxy ethoxy)-2-methyl-4-(mesyl) benzoic acid, similarly operate with described synthesis example 2 (5), thereby obtain object.

Synthesis example 4

(1) 3-chloro-2-methyl-4-(mesyl) benzoic acid (40g) and chloroform (400mL) are at room temperature mixed, add oxalyl chloride (28.1mL) and DMF (3) again.Stir about stirred 30 minutes at 40 ℃ until gas generation end in 4 hours then.Distillation under reduced pressure removes desolvates and excessive reagent, adds chloroform (400mL), 5-hydroxyl-1-methyl isophthalic acid H-pyrazoles (16.6g) and triethylamine (17.9g) and at room temperature stirred then 5 hours in residue.Reaction solution with watery hydrochloric acid (100mL) washing, is extracted water layer with chloroform (100mL).Merge organic layer, use anhydrous sodium sulfate drying, distillation under reduced pressure removes and desolvates then.Residue is dissolved in the anhydrous acetonitrile (400mL), adds 5-hydroxyl-1-methyl isophthalic acid H-pyrazoles (1.58g), acetone cyanohydrin (1.37g) and triethylamine (16.3g) then, stirred 12 hours at 40 ℃.Reaction solution is under reduced pressure concentrated, add toluene (200mL) and use 1N sodium hydrate aqueous solution (200mL) to extract.In water layer, add concentrated hydrochloric acid to pH1, leach the solid of generation.The solid that leaches is dry then with toluene and ethyl acetate washing, thus [5-hydroxyl-1-methyl-pyrazol-4-yl] [3-chloro-2-methyl-4-(mesyl) phenyl] ketone (42g) obtained as faint yellow solid.

¹H-NMR 400MHz(DMSO-d ₆δppm)：2.32(s，3H)，3.40(s，3H)，3.53(s，3H)，7.35(s，1H)，7.51(d，1H，J＝8.0Hz)，7.97(d，1H，J＝8.0Hz).

(2) under nitrogen atmosphere, sodium hydroxide (0.6g) is added 2-methyl cellosolve (30mL), stir at 100 ℃ and dissolved fully until solid in 15 minutes.Reaction solution is cooled to room temperature, and the solvent of about 15mL is removed in distillation under reduced pressure then.Add [5-hydroxyl-1-methyl-pyrazol-4-yl] [3-chloro-2-methyl-4-(mesyl) phenyl] ketone (1g) therein, stirred 2 hours at 85 ℃, and then stirred 3 hours at 120 ℃.The sodium hydrate aqueous solution (150mL) that adds 1M is used ether (150mL) washing then.In water layer, add concentrated hydrochloric acid to pH1, use ethyl acetate (100mL) to extract then 2 times.To use anhydrous sodium sulfate drying after the organic layer merging, distillation under reduced pressure removes and desolvates then, thereby obtains the crude product of oily.This crude product is dissolved in the ethyl acetate (20mL), at room temperature adds hexane (5mL) then and left standstill 12 hours, thereby obtain object (0.84g) as filbert crystal.

Synthesis example 5

(1), at room temperature, stirred then 2 hours to wherein dripping the mixture that in ethanol (250mL), is suspended with 3-chloro-2-methyl-4-isothiocyanic acid ester aniline (13g) with vulcanized sodium nonahydrate (18g) water-soluble (50mL).Reactor is placed under the ice bath, slowly add iodomethane (13g) and stirred 10 minutes, further at room temperature stirred 3 hours then.Distillation under reduced pressure removes desolvates, and adds saturated aqueous common salt (150mL) then and uses chloroform (100mL) to extract 2 times.To use anhydrous sodium sulfate drying after the organic layer merging, distillation under reduced pressure removes and desolvates then, obtains 3-chloro-2-methyl-4-(methyl mercapto) aniline (13g).

¹H-NMR 400MHz(CDCl ₃δppm)：2.25(s，3H)，2.40(s，3H)，6.60(d，1H，J＝8.4Hz)，7.01(d，1H，J＝8.4Hz).

(2) 3-chloro-2-methyl-4-(methyl mercapto) aniline (0.94g) and natrium nitrosum (0.69g) are dissolved in DMSO (25mL) and are heated to 35 ℃, drip the mixture of 47 weight % bromination hydracids (2.35mL) and DMSO (25mL) then.Under uniform temp, stirred 20 hours, drop into then and dissolved in the frozen water solution (100mL) of potash (5g), extract 2 times with ether (50mL).To wash with water after the organic layer merging, then anhydrous sodium sulfate drying.The reactant mixture that will concentrate and get separates with silica gel column chromatography, thereby obtains (4-bromo-2-chloro-3-aminomethyl phenyl) (methyl) sulphur (0.61g).

¹H-NMR 400MHz(CDCl ₃δppm)：2.45(s，3H)，2.53(s，3H)，6.85(d，1H，J＝8.4Hz)，7.43(d，1H，J＝8.4Hz).

(3) in reflux condensing tube being installed and placing container under the nitrogen atmosphere, add magnesium metal (0.58g) and anhydrous THF (10mL), slowly drip isopropyl bromide (0.70mL) and make excessively rising of temperature.At room temperature stirred then 25 minutes, and, and then at room temperature stirred again 3 hours through the anhydrous THF solution (15mL) of 20 minutes dropping (4-bromo-2-chloro-3-aminomethyl phenyl) (methyl) sulphur (3.7g).When reaction vessel being put into ice bath and being blown into carbonic acid gas, stirred 1 hour, after getting back to room temperature, add 20 weight % hydrochloric acid (12mL) then, and then stirred 30 minutes.In reactant mixture, add chloroform (40mL) and carry out 3 extraction operations.With washing with water after the organic layer merging, carry out alkaline extraction with 20 weight % sodium hydrate aqueous solutions (50mL), be adjusted to pH1 with 35 weight % hydrochloric acid and use ethyl acetate (50mL) to extract then 3 times.Organic layer is merged water and saturated common salt water washing afterwards, use anhydrous sodium sulfate drying, distillation under reduced pressure removes and desolvates then, thereby obtains 3-chloro-2-methyl-4-(methyl mercapto) benzoic acid (2.1g).

¹H-NMR 400MHz(CDCl ₃δppm)：2.51(s，3H)，2.72(s，3H)，7.03(d，1H，J＝8.4Hz)，7.93(d，1H，J＝8.4Hz).

(4) use 3-chloro-2-methyl-4-(methyl mercapto) benzoic acid, similarly operate with above-mentioned reaction [AI], thereby obtain 3-chloro-2-methyl-4-(mesyl) benzoic acid.

(5) use 3-chloro-2-methyl-4-(mesyl) benzoic acid, similarly operate with (1) and (2) of above-mentioned synthesis example 4, thereby obtain object.

Synthesis example 6

(1) in the flask of 1L, add 2,6-dichlorotoleune (100g), mesyl chloride (71g) and anhydrous ammonium chloride (83g) stirred 12 hours when being heated to 120 ℃ with oil bath.With the ice bath cooling, slowly add 2N hydrochloric acid (400mL) simultaneously.Stirred 1 hour under the room temperature, add hexane (300mL) then, at room temperature continue to stir 2 hours.The white crystals that obtains is filtered water (100mL) and hexane (100mL) washing then, drying.Thereby obtain 1 as white crystal (fusing point: 125-127 ℃), 3-two chloro-2-methyl-4-(mesyl) benzene (90g).

¹H-NMR 400MHz(CDCl ₃，δppm)：2.55(3H，s)，3.25(3H，s)，7.47(1H，d，J＝8.4Hz)，7.94(1H，d，d＝8.4Hz).

(2) in anhydrous THF (50mL), add 60 weight % sodium hydrides-paraffin and disperse thing (550mg), in the suspension that obtains, at room temperature slowly add 2-methyl cellosolve (1.15g).After stirring 30 minutes, add 1,3-two chloro-2-methyl-4-(mesyl) benzene (3g) stirred 2 hours down at 50 ℃.Reactant mixture is cooled to room temperature, adds ethyl acetate (250mL), move to separatory funnel then.With saturated common salt water washing 2 times, then with the organic layer anhydrous sodium sulfate drying, distillation under reduced pressure removes desolvates.Thereby obtain 1-chloro-3-(2-methoxy ethoxy)-2-methyl-4-(mesyl) benzene (3.4g) as white solid (fusing point: 83-85 ℃).

¹H-NMR 400MHz(CDCl ₃，δppm)：2.39(3H，s)，3.23(3H，s)，3.46(3H，s)，3.77(2H，m)，4.18(2H，m)，7.30(1H，d，J＝8.8Hz)，7.73(1H，d，J＝8.8Hz).

(3) with 1-chloro-3-(2-methoxy ethoxy)-2-methyl-4-(mesyl) benzene (2g), 5 weight % palladium carbon (20mg), 1; 4-two (diphenylphosphino) butane (16mg) and sodium carbonate (1.1g) autoclave of packing into adds isopropyl alcohol (8.5mL), water (1.5mL).Inside is replaced with carbon monoxide, under 190 ℃, the pressure of 2MPa, stirred 18 hours then.Remove excessive gas, in reactant mixture, add 1N-sodium hydrate aqueous solution (10mL) and t-butyl methyl ether (10mL).Vigorous stirring 5 minutes is removed insoluble matter with diatomite filtration then.Filtrate is moved to separatory funnel, add t-butyl methyl ether (200-mL), extract with 1N-sodium hydrate aqueous solution (100mL * 2).With 2N hydrochloric acid (150mL) furnishing acidity, use ethyl acetate (150mL * 2) to extract then water layer.With the organic layer anhydrous sodium sulfate drying, distillation under reduced pressure removes desolvates.Thereby obtain 3-(2-methoxy ethoxy)-2-methyl-4-(mesyl) benzoic acid (1.93g) as white crystals (fusing point: 104-106 ℃).

(4) use 3-(2-methoxy ethoxy)-2-methyl-4-(mesyl) benzoic acid, similarly operate with above-mentioned synthesis example 2 (5), thereby obtain object.

Synthesis example 7

(1) 1; dissolving 1 in the 4-dioxane (20mL); 3-two chloro-2-methyl-4-(mesyl) benzene (1g), 5-hydroxyl-1-methyl-pyrazoles (820mg); add acid chloride (50mg), triethylamine (630mg), potash (1.15g) and 1,1 '-two (diphenylphosphino) ferrocene (230mg) therein.With this mixture autoclave of packing into, inside is replaced with carbon monoxide, under 130 ℃, the pressure of 2MPa, stirred 12 hours.Be cooled to after the room temperature, remove excessive gas, in reaction solution, add 1N-sodium hydrate aqueous solution (10mL) and ether (10mL).Vigorous stirring 5 minutes is used the diatomite filtration insoluble matter then, and filtrate is moved to separatory funnel.Add ether (200mL), use 1N-sodium hydrate aqueous solution (100mL * 2) to extract then.Water layer is merged afterwards with 2N hydrochloric acid (150mL) furnishing acidity, with ethyl acetate (150mL * 2) extraction.With the organic layer anhydrous sodium sulfate drying, distillation under reduced pressure removes desolvates, thereby obtains (3-chloro-2-methyl-4-(mesyl) phenyl) (5-hydroxyl-1-methyl isophthalic acid H-pyrazoles-4-yl) ketone (620mg).

(2) use (3-chloro-2-methyl-4-(mesyl) phenyl) (5-hydroxyl-1-methyl isophthalic acid H-pyrazoles-4-yl) ketone, similarly operate with above-mentioned synthesis example 4 (2), thereby obtain object.

Synthesis example 8

(1) in the autoclave of internal volume 50mL, add anhydrous THF (18mL) and disperse thing (316mg) with 60 weight % sodium hydrides-paraffin, under nitrogen atmosphere and ice-cold stirring condition, add 5-hydroxyl-1-methylpyrazole (739mg) bit by bit.Stirred 1 hour in cold putting; add 1-chloro-3-(2-methoxy ethoxy)-2-methyl-4-(mesyl) benzene (2.0g), 1 then; the moisture product of 53 weight % (100mg) of 4-two (diphenylphosphino) butane (100mg) and 10 weight % palladium carbon; be forced into 2MPa with carbon monoxide; heat then to 190 ℃, stirred 20 hours.Reaction is cooled to room temperature after finishing, and stirs in the mixture of input water (200mL) and organic solvent (ether 30mL, ethyl acetate 70mL).Water layer is acidified to about pH3 with watery hydrochloric acid and use the ethyl acetate extraction product, use dried over sodium sulfate, decompression distillation is except that desolvating then, thereby obtains object (1.6g).

Then, enumerate the typical example and the compound on every side thereof of the compound of above-mentioned formula (I) at table 1, table 2 is enumerated theirs ¹The H-NMR spectroscopic data.These compounds can synthesize based on above-mentioned synthesis example or above-mentioned various manufacture method.In addition, in 1～2 table, No. represents compound number.In addition, in the table 1, Me represents methyl, and Et represents ethyl, n-Pr basis representation n-pro-pyl, and i-Pr represents isopropyl, t-Bu represents the tert-butyl group.

[table 1]

No.	R ¹	R ²	R ³	R ⁴	R ⁵	R ⁶
No.	R ¹	R ²	R ³	R ⁴	R ⁵	R ⁶	1	Me	H	OH	Me	OCH ₂CH(OCH ₃) ₂	SO ₂Me
2	Me	H	OH	Me	CH ₂SCN	SO ₂Me	1	Me	H	OH	Me	OCH ₂CH(OCH ₃) ₂	SO ₂Me
2	Me	H	OH	Me	CH ₂SCN	SO ₂Me	3	Me	H	OH	Me	CH ₂C(S)NH ₂	SO ₂Me
4	Me	H	OH	Me	OCH ₂CH ₂SMe	SO ₂Me	3	Me	H	OH	Me	CH ₂C(S)NH ₂	SO ₂Me
4	Me	H	OH	Me	OCH ₂CH ₂SMe	SO ₂Me	5	Me	H	OH	Me	OC(O)SMe	SO ₂Me
6	Me	H	OH	Me	OC(O)SEt	SO ₂Me	5	Me	H	OH	Me	OC(O)SMe	SO ₂Me
6	Me	H	OH	Me	OC(O)SEt	SO ₂Me	7	Me	H	OH	Cl	OCH ₂CHFOCF ₃	SO ₂Me
8	Et	H	OH	Cl	OCH ₂CHFOCF ₃	SO ₂Me	7	Me	H	OH	Cl	OCH ₂CHFOCF ₃	SO ₂Me
8	Et	H	OH	Cl	OCH ₂CHFOCF ₃	SO ₂Me	9	Me	H	OH	Me	OCH ₂CHFOCF ₃	SO ₂Me
10	Me	H	OH	Cl	OCH ₂CHFOMe	SO ₂Me	9	Me	H	OH	Me	OCH ₂CHFOCF ₃	SO ₂Me
10	Me	H	OH	Cl	OCH ₂CHFOMe	SO ₂Me	11	Et	H	OH	Cl	OCH ₂CHFOMe	SO ₂Me
12	Me	H	OH	Me	OCH ₂CHFOMe	SO ₂Me	11	Et	H	OH	Cl	OCH ₂CHFOMe	SO ₂Me
12	Me	H	OH	Me	OCH ₂CHFOMe	SO ₂Me	13	Et	H	OH	Me	OCH ₂CHFOMe	SO ₂Me
14	Me	H	OH	CF ₃	OCH ₂CHFOMe	SO ₂Me	13	Et	H	OH	Me	OCH ₂CHFOMe	SO ₂Me
14	Me	H	OH	CF ₃	OCH ₂CHFOMe	SO ₂Me	15	Et	H	OH	CF ₃	OCH ₂CHFOMe	SO ₂Me
16	Me	H	OH	Br	OCH ₂CHFOMe	SO ₂Me	15	Et	H	OH	CF ₃	OCH ₂CHFOMe	SO ₂Me
16	Me	H	OH	Br	OCH ₂CHFOMe	SO ₂Me	17	Et	H	OH	Br	OCH ₂CHFOMe	SO ₂Me
18	Me	H	OH	SO ₂Me	OCH ₂CHFOMe	CF ₃	17	Et	H	OH	Br	OCH ₂CHFOMe	SO ₂Me
18	Me	H	OH	SO ₂Me	OCH ₂CHFOMe	CF ₃	19	Et	H	OH	SO ₂Me	OCH ₂CHFOMe	CF ₃
20	Me	H	OH	Cl	OCHFCH ₂OCF ₃	SO ₂Me	19	Et	H	OH	SO ₂Me	OCH ₂CHFOMe	CF ₃
20	Me	H	OH	Cl	OCHFCH ₂OCF ₃	SO ₂Me	21	Et	H	OH	Cl	OCHFCH ₂OCF ₃	SO ₂Me
22	Me	H	OH	Cl	SCH ₂CH ₂SCH ₃	SO ₂Me	21	Et	H	OH	Cl	OCHFCH ₂OCF ₃	SO ₂Me
22	Me	H	OH	Cl	SCH ₂CH ₂SCH ₃	SO ₂Me	23	Et	H	OH	Cl	SCH ₂CH ₂SCH ₃	SO ₂Me
24	Me	H	OH	Me	SCH ₂CH ₂SCH ₃	SO ₂Me	23	Et	H	OH	Cl	SCH ₂CH ₂SCH ₃	SO ₂Me
24	Me	H	OH	Me	SCH ₂CH ₂SCH ₃	SO ₂Me	25	Et	H	OH	Me	SCH ₂CH ₂SCH ₃	SO ₂Me

Table 1 is continuous

No.	R ¹	R ²	R ³	R ⁴	R ⁵	R ⁶
No.	R ¹	R ²	R ³	R ⁴	R ⁵	R ⁶	26	Me	H	OH	CF ₃	SCH ₂CH ₂SCH ₃	SO ₂Me
27	Et	H	OH	CF ₃	SCH ₂CH ₂SCH ₃	SO ₂Me	26	Me	H	OH	CF ₃	SCH ₂CH ₂SCH ₃	SO ₂Me
27	Et	H	OH	CF ₃	SCH ₂CH ₂SCH ₃	SO ₂Me	28	Me	H	OH	Br	SCH ₂CH ₂SCH ₃	SO ₂Me
29	Et	H	OH	Br	SCH ₂CH ₂SCH ₃	SO ₂Me	28	Me	H	OH	Br	SCH ₂CH ₂SCH ₃	SO ₂Me
29	Et	H	OH	Br	SCH ₂CH ₂SCH ₃	SO ₂Me	30	Me	H	OH	SO ₂Me	SCH ₂CH ₂SCH ₃	CF ₃
31	Et	H	OH	SO ₂Me	SCH ₂CH ₂SCH ₃	CF ₃	30	Me	H	OH	SO ₂Me	SCH ₂CH ₂SCH ₃	CF ₃
31	Et	H	OH	SO ₂Me	SCH ₂CH ₂SCH ₃	CF ₃	32	Me	H	OH	Cl	SCH ₂CH ₂SCF ₃	SO ₂Me
33	Et	H	OH	Cl	SCH ₂CH ₂SCF ₃	SO ₂Me	32	Me	H	OH	Cl	SCH ₂CH ₂SCF ₃	SO ₂Me
33	Et	H	OH	Cl	SCH ₂CH ₂SCF ₃	SO ₂Me	34	Me	H	OH	Me	SCH ₂CH ₂SCF ₃	SO ₂Me
35	Et	H	OH	Me	SCH ₂CH ₂SCF ₃	SO ₂Me	34	Me	H	OH	Me	SCH ₂CH ₂SCF ₃	SO ₂Me
35	Et	H	OH	Me	SCH ₂CH ₂SCF ₃	SO ₂Me	36	Me	H	OH	CF ₃	SCH ₂CH ₂SCF ₃	SO ₂Me
37	Et	H	OH	CF ₃	SCH ₂CH ₂SCF ₃	SO ₂Me	36	Me	H	OH	CF ₃	SCH ₂CH ₂SCF ₃	SO ₂Me
37	Et	H	OH	CF ₃	SCH ₂CH ₂SCF ₃	SO ₂Me	38	Me	H	OH	Br	SCH ₂CH ₂SCF ₃	SO ₂Me
39	Et	H	OH	Br	SCH ₂CH ₂SCF ₃	SO ₂Me	38	Me	H	OH	Br	SCH ₂CH ₂SCF ₃	SO ₂Me
39	Et	H	OH	Br	SCH ₂CH ₂SCF ₃	SO ₂Me	40	Me	H	OH	SO ₂Me	SCH ₂CH ₂SCF ₃	CF ₃
41	Et	H	OH	SO ₂Me	SCH ₂CH ₂SCF ₃	CF ₃	40	Me	H	OH	SO ₂Me	SCH ₂CH ₂SCF ₃	CF ₃
41	Et	H	OH	SO ₂Me	SCH ₂CH ₂SCF ₃	CF ₃	42	Me	H	OH	Cl	OCH ₂CF ₂OCH ₃	SO ₂Me
43	Et	H	OH	Cl	OCH ₂CF ₂OCH ₃	SO ₂Me	42	Me	H	OH	Cl	OCH ₂CF ₂OCH ₃	SO ₂Me
43	Et	H	OH	Cl	OCH ₂CF ₂OCH ₃	SO ₂Me	44	Me	H	OH	Me	OCH ₂CF ₂OCH ₃	SO ₂Me
45	Et	H	OH	Me	OCH ₂CF ₂OCH ₃	SO ₂Me	44	Me	H	OH	Me	OCH ₂CF ₂OCH ₃	SO ₂Me
45	Et	H	OH	Me	OCH ₂CF ₂OCH ₃	SO ₂Me	46	Me	H	OH	CF ₃	OCH ₂CF ₂OCH ₃	SO ₂Me
47	Et	H	OH	CF ₃	OCH ₂CF ₂OCH ₃	SO ₂Me	46	Me	H	OH	CF ₃	OCH ₂CF ₂OCH ₃	SO ₂Me
47	Et	H	OH	CF ₃	OCH ₂CF ₂OCH ₃	SO ₂Me	48	Me	H	OH	Br	OCH ₂CF ₂OCH ₃	SO ₂Me
49	Et	H	OH	Br	OCH ₂CF ₂OCH ₃	SO ₂Me	48	Me	H	OH	Br	OCH ₂CF ₂OCH ₃	SO ₂Me
49	Et	H	OH	Br	OCH ₂CF ₂OCH ₃	SO ₂Me	50	Me	H	OH	SO ₂Me	OCH ₂CF ₂OCH ₃	CF ₃
51	Et	H	OH	SO ₂Me	OCH ₂CF ₂OCH ₃	CF ₃	50	Me	H	OH	SO ₂Me	OCH ₂CF ₂OCH ₃	CF ₃
51	Et	H	OH	SO ₂Me	OCH ₂CF ₂OCH ₃	CF ₃	52	Me	H	OH	Me	OCH ₂CH(OMe)CH ₂OEt	SO ₂Me
53	Me	H	OH	Me	OCH ₂CH(CF ₃)OMe	SO ₂Me	52	Me	H	OH	Me	OCH ₂CH(OMe)CH ₂OEt	SO ₂Me
53	Me	H	OH	Me	OCH ₂CH(CF ₃)OMe	SO ₂Me	54	Et	H	OH	Me	OCH ₂CH(CF ₃)OMe	SO ₂Me
55	t-Bu	H	OH	Me	OCH ₂CH(OMe) ₂	SO ₂Me	54	Et	H	OH	Me	OCH ₂CH(CF ₃)OMe	SO ₂Me
55	t-Bu	H	OH	Me	OCH ₂CH(OMe) ₂	SO ₂Me	56	Me	H	OH	Me	CH ₂N(CO ₂Me) ₂	SO ₂Me
57	Et	H	OH	Me	CH ₂N(CO ₂Me) ₂	SO ₂Me	56	Me	H	OH	Me	CH ₂N(CO ₂Me) ₂	SO ₂Me
57	Et	H	OH	Me	CH ₂N(CO ₂Me) ₂	SO ₂Me	58	Me	H	OH	Me	CH ₂N(CH ₂CN) ₂	SO ₂Me
59	Et	H	OH	Me	CH ₂N(CH ₂CN) ₂	SO ₂Me	58	Me	H	OH	Me	CH ₂N(CH ₂CN) ₂	SO ₂Me

Table 1 is continuous

No.	R ¹	R ²	R ³	R ⁴	R ⁵	R ⁶
No.	R ¹	R ²	R ³	R ⁴	R ⁵	R ⁶	60	Me	H	OH	Me	OCH ₂CH(CF ₃)OCF ₃	SO ₂Me
61	Et	H	OH	Me	OCH ₂CH(CF ₃)OCF ₃	SO ₂Me	60	Me	H	OH	Me	OCH ₂CH(CF ₃)OCF ₃	SO ₂Me
61	Et	H	OH	Me	OCH ₂CH(CF ₃)OCF ₃	SO ₂Me	62	Me	H	OH	Me	CH ₂OCH ₂CH(OMe) ₂	SO ₂Me
63	Et	H	OH	Me	CH ₂OCH ₂CH(OMe) ₂	SO ₂Me	62	Me	H	OH	Me	CH ₂OCH ₂CH(OMe) ₂	SO ₂Me
63	Et	H	OH	Me	CH ₂OCH ₂CH(OMe) ₂	SO ₂Me	64	Me	Me	OH	Me	OCH ₂CH(OCH ₃) ₂	SO ₂Me
65	Me	Me	OH	Me	OCH ₂CH(OMe)CH ₂OEt	SO ₂Me	64	Me	Me	OH	Me	OCH ₂CH(OCH ₃) ₂	SO ₂Me
65	Me	Me	OH	Me	OCH ₂CH(OMe)CH ₂OEt	SO ₂Me	66	Me	Me	OH	Me	CH ₂SCN	SO ₂Me
67	Me	Me	OH	Me	CH ₂C(S)NH ₂	SO ₂Me	66	Me	Me	OH	Me	CH ₂SCN	SO ₂Me
67	Me	Me	OH	Me	CH ₂C(S)NH ₂	SO ₂Me	68	Me	Me	OH	Me	OC(O)SMe	SO ₂Me
69	Me	Me	OH	Me	OC(O)SEt	SO ₂Me	68	Me	Me	OH	Me	OC(O)SMe	SO ₂Me
69	Me	Me	OH	Me	OC(O)SEt	SO ₂Me	70	Me	Me	OH	Cl	OCH ₂CHFOCF ₃	SO ₂Me
71	Et	Me	OH	Cl	OCH ₂CHFOCF ₃	SO ₂Me	70	Me	Me	OH	Cl	OCH ₂CHFOCF ₃	SO ₂Me
71	Et	Me	OH	Cl	OCH ₂CHFOCF ₃	SO ₂Me	72	Me	Me	OH	Me	OCH ₂CHFOCF ₃	SO ₂Me
73	Me	Me	OH	Cl	OCH ₂CHFOMe	SO ₂Me	72	Me	Me	OH	Me	OCH ₂CHFOCF ₃	SO ₂Me
73	Me	Me	OH	Cl	OCH ₂CHFOMe	SO ₂Me	74	Et	Me	OH	Cl	OCH ₂CHFOMe	SO ₂Me
75	Me	Me	OH	Me	OCH ₂CHFOMe	SO ₂Me	74	Et	Me	OH	Cl	OCH ₂CHFOMe	SO ₂Me
75	Me	Me	OH	Me	OCH ₂CHFOMe	SO ₂Me	76	Et	Me	OH	Me	OCH ₂CHFOMe	SO ₂Me
77	Me	Me	OH	CF ₃	OCH ₂CHFOMe	SO ₂Me	76	Et	Me	OH	Me	OCH ₂CHFOMe	SO ₂Me
77	Me	Me	OH	CF ₃	OCH ₂CHFOMe	SO ₂Me	78	Et	Me	OH	CF ₃	OCH ₂CHFOMe	SO ₂Me
79	Me	Me	OH	Br	OCH ₂CHFOMe	SO ₂Me	78	Et	Me	OH	CF ₃	OCH ₂CHFOMe	SO ₂Me
79	Me	Me	OH	Br	OCH ₂CHFOMe	SO ₂Me	80	Et	Me	OH	Br	OCH ₂CHFOMe	SO ₂Me
81	Me	Me	OH	SO ₂Me	OCH ₂CHFOMe	CF ₃	80	Et	Me	OH	Br	OCH ₂CHFOMe	SO ₂Me
81	Me	Me	OH	SO ₂Me	OCH ₂CHFOMe	CF ₃	82	Et	Me	OH	SO ₂Me	OCH ₂CHFOMe	CF ₃
83	Me	Me	OH	Cl	OCHFCH ₂OCF ₃	SO ₂Me	82	Et	Me	OH	SO ₂Me	OCH ₂CHFOMe	CF ₃
83	Me	Me	OH	Cl	OCHFCH ₂OCF ₃	SO ₂Me	84	Et	Me	OH	Cl	OCHFCH ₂OCF ₃	SO ₂Me
85	Me	Me	OH	Cl	SCH ₂CH ₂SCH ₃	SO ₂Me	84	Et	Me	OH	Cl	OCHFCH ₂OCF ₃	SO ₂Me
85	Me	Me	OH	Cl	SCH ₂CH ₂SCH ₃	SO ₂Me	86	Et	Me	OH	Cl	SCH ₂CH ₂SCH ₃	SO ₂Me
87	Me	Me	OH	Me	SCH ₂CH ₂SCH ₃	SO ₂Me	86	Et	Me	OH	Cl	SCH ₂CH ₂SCH ₃	SO ₂Me
87	Me	Me	OH	Me	SCH ₂CH ₂SCH ₃	SO ₂Me	88	Et	Me	OH	Me	SCH ₂CH ₂SCH ₃	SO ₂Me
89	Me	Me	OH	CF ₃	SCH ₂CH ₂SCH ₃	SO ₂Me	88	Et	Me	OH	Me	SCH ₂CH ₂SCH ₃	SO ₂Me
89	Me	Me	OH	CF ₃	SCH ₂CH ₂SCH ₃	SO ₂Me	90	Et	Me	OH	CF ₃	SCH ₂CH ₂SCH ₃	SO ₂Me
91	Me	Me	OH	Br	SCH ₂CH ₂SCH ₃	SO ₂Me	90	Et	Me	OH	CF ₃	SCH ₂CH ₂SCH ₃	SO ₂Me
91	Me	Me	OH	Br	SCH ₂CH ₂SCH ₃	SO ₂Me	92	Et	Me	OH	Br	SCH ₂CH ₂SCH ₃	SO ₂Me

Table 1 is continuous

No.	R ¹	R ²	R ³	R ⁴	R ⁵	R ⁶
No.	R ¹	R ²	R ³	R ⁴	R ⁵	R ⁶	93	Me	Me	OH	SO ₂Me	SCH ₂CH ₂SCH ₃	CF ₃
94	Et	Me	OH	SO ₂Me	SCH ₂CH ₂SCH ₃	CF ₃	93	Me	Me	OH	SO ₂Me	SCH ₂CH ₂SCH ₃	CF ₃
94	Et	Me	OH	SO ₂Me	SCH ₂CH ₂SCH ₃	CF ₃	95	Me	Me	OH	Cl	SCH ₂CH ₂SCF ₃	SO ₂Me
96	Et	Me	OH	Cl	SCH ₂CH ₂SCF ₃	SO ₂Me	95	Me	Me	OH	Cl	SCH ₂CH ₂SCF ₃	SO ₂Me
96	Et	Me	OH	Cl	SCH ₂CH ₂SCF ₃	SO ₂Me	97	Me	Me	OH	Me	SCH ₂CH ₂SCF ₃	SO ₂Me
98	Et	Me	OH	Me	SCH ₂CH ₂SCF ₃	SO ₂Me	97	Me	Me	OH	Me	SCH ₂CH ₂SCF ₃	SO ₂Me
98	Et	Me	OH	Me	SCH ₂CH ₂SCF ₃	SO ₂Me	99	Me	Me	OH	CF ₃	SCH ₂CH ₂SCF ₃	SO ₂Me
100	Et	Me	OH	CF ₃	SCH ₂CH ₂SCF ₃	SO ₂Me	99	Me	Me	OH	CF ₃	SCH ₂CH ₂SCF ₃	SO ₂Me
100	Et	Me	OH	CF ₃	SCH ₂CH ₂SCF ₃	SO ₂Me	101	Me	Me	OH	Br	SCH ₂CH ₂SCF ₃	SO ₂Me
102	Et	Me	OH	Br	SCH ₂CH ₂SCF ₃	SO ₂Me	101	Me	Me	OH	Br	SCH ₂CH ₂SCF ₃	SO ₂Me
102	Et	Me	OH	Br	SCH ₂CH ₂SCF ₃	SO ₂Me	103	Me	Me	OH	SO ₂Me	SCH ₂CH ₂SCF ₃	CF ₃
104	Et	Me	OH	SO ₂Me	SCH ₂CH ₂SCF ₃	CF ₃	103	Me	Me	OH	SO ₂Me	SCH ₂CH ₂SCF ₃	CF ₃
104	Et	Me	OH	SO ₂Me	SCH ₂CH ₂SCF ₃	CF ₃	105	Me	Me	OH	Cl	OCH ₂CF ₂OCH ₃	SO ₂Me
106	Et	Me	OH	Cl	OCH ₂CF ₂OCH ₃	SO ₂Me	105	Me	Me	OH	Cl	OCH ₂CF ₂OCH ₃	SO ₂Me
106	Et	Me	OH	Cl	OCH ₂CF ₂OCH ₃	SO ₂Me	107	Me	Me	OH	Me	OCH ₂CF ₂OCH ₃	SO ₂Me
108	Et	Me	OH	Me	OCH ₂CF ₂OCH ₃	SO ₂Me	107	Me	Me	OH	Me	OCH ₂CF ₂OCH ₃	SO ₂Me
108	Et	Me	OH	Me	OCH ₂CF ₂OCH ₃	SO ₂Me	109	Me	Me	OH	CF ₃	OCH ₂CF ₂OCH ₃	SO ₂Me
110	Et	Me	OH	CF ₃	OCH ₂CF ₂OCH ₃	SO ₂Me	109	Me	Me	OH	CF ₃	OCH ₂CF ₂OCH ₃	SO ₂Me
110	Et	Me	OH	CF ₃	OCH ₂CF ₂OCH ₃	SO ₂Me	111	Me	Me	OH	Br	OCH ₂CF ₂OCH ₃	SO ₂Me
112	Et	Me	OH	Br	OCH ₂CF ₂OCH ₃	SO ₂Me	111	Me	Me	OH	Br	OCH ₂CF ₂OCH ₃	SO ₂Me
112	Et	Me	OH	Br	OCH ₂CF ₂OCH ₃	SO ₂Me	113	Me	Me	OH	SO ₂Me	OCH ₂CF ₂OCH ₃	CF ₃
114	Et	Me	OH	SO ₂Me	OCH ₂CF ₂OCH ₃	CF ₃	113	Me	Me	OH	SO ₂Me	OCH ₂CF ₂OCH ₃	CF ₃
114	Et	Me	OH	SO ₂Me	OCH ₂CF ₂OCH ₃	CF ₃	115	Me	Me	OH	Me	OCH ₂CH(CF ₃)OMe	SO ₂Me
116	Et	Me	OH	Me	OCH ₂CH(CF ₃)OMe	SO ₂Me	115	Me	Me	OH	Me	OCH ₂CH(CF ₃)OMe	SO ₂Me
116	Et	Me	OH	Me	OCH ₂CH(CF ₃)OMe	SO ₂Me	117	t-Bu	Me	OH	Me	OCH ₂CH(OMe) ₂	SO ₂Me
118	Me	Me	OH	Me	CH ₂N(CO ₂Me) ₂	SO ₂Me	117	t-Bu	Me	OH	Me	OCH ₂CH(OMe) ₂	SO ₂Me
118	Me	Me	OH	Me	CH ₂N(CO ₂Me) ₂	SO ₂Me	119	Et	Me	OH	Me	CH ₂N(CO ₂Me) ₂	SO ₂Me
120	Me	Me	OH	Me	CH ₂N(CH ₂CN) ₂	SO ₂Me	119	Et	Me	OH	Me	CH ₂N(CO ₂Me) ₂	SO ₂Me
120	Me	Me	OH	Me	CH ₂N(CH ₂CN) ₂	SO ₂Me	121	Et	Me	OH	Me	CH ₂N(CH ₂CN) ₂	SO ₂Me
122	Me	Me	OH	Me	OCH ₂CH(CF ₃)OCF ₃	SO ₂Me	121	Et	Me	OH	Me	CH ₂N(CH ₂CN) ₂	SO ₂Me
122	Me	Me	OH	Me	OCH ₂CH(CF ₃)OCF ₃	SO ₂Me	123	Et	Me	OH	Me	OCH ₂CH(CF ₃)OCF ₃	SO ₂Me
124	Me	Me	OH	Me	CH ₂OCH ₂CH(OMe) ₂	SO ₂Me	123	Et	Me	OH	Me	OCH ₂CH(CF ₃)OCF ₃	SO ₂Me
124	Me	Me	OH	Me	CH ₂OCH ₂CH(OMe) ₂	SO ₂Me	125	Et	Me	OH	Me	CH ₂OCH ₂CH(OMe) ₂	SO ₂Me

Table 1 is continuous

No.	R ¹	R ²	R ³	R ⁴	R ⁵	R ⁶
No.	R ¹	R ²	R ³	R ⁴	R ⁵	R ⁶	126	Me	H	OH	Me	CO ₂Me	SO ₂Me
127	Et	H	OH	Me	CO ₂Me	SO ₂Me	126	Me	H	OH	Me	CO ₂Me	SO ₂Me
127	Et	H	OH	Me	CO ₂Me	SO ₂Me	128	Et	H	OH	Me	CO ₂(i-Pr)	SO ₂Me
129	Me	H	OH	Cl	CO ₂Et	SO ₂Me	128	Et	H	OH	Me	CO ₂(i-Pr)	SO ₂Me
129	Me	H	OH	Cl	CO ₂Et	SO ₂Me	130	Et	H	OH	Me	CO ₂Me	CF ₃
131	Et	H	OH	Me	OCH ₂CH ₂OMe	SO ₂Me	130	Et	H	OH	Me	CO ₂Me	CF ₃
131	Et	H	OH	Me	OCH ₂CH ₂OMe	SO ₂Me	132	Et	H	OH	SO ₂Me	CO ₂Me	CN
133	Me	H	OH	Me	C(O)SMe	SO ₂Me	132	Et	H	OH	SO ₂Me	CO ₂Me	CN
133	Me	H	OH	Me	C(O)SMe	SO ₂Me	134	Me	H	OH	Me	C(O)SEt	SO ₂Me
135	Me	H	OH	Me	2-(2-oxa-cyclopenta) ethyoxyl	SO ₂Me	134	Me	H	OH	Me	C(O)SEt	SO ₂Me
135	Me	H	OH	Me	2-(2-oxa-cyclopenta) ethyoxyl	SO ₂Me	136	Me	H	OH	Me	2-(2-(1,3-dioxane amyl group)) ethyoxyl	SO ₂Me
137	Et	H	OH	Me	CH ₂OMe	SO ₂Me	136	Me	H	OH	Me	2-(2-(1,3-dioxane amyl group)) ethyoxyl	SO ₂Me
137	Et	H	OH	Me	CH ₂OMe	SO ₂Me	138	Et	H	OH	Me	2-oxa-cyclopenta methoxy	SO ₂Me
139	Me	H	OH	Cl	CO ₂Me	SO ₂Me	138	Et	H	OH	Me	2-oxa-cyclopenta methoxy	SO ₂Me
139	Me	H	OH	Cl	CO ₂Me	SO ₂Me	140	Et	H	OH	Cl	CO ₂Me	SO ₂Et
141	Me	H	OH	Cl	C(O)SMe	SO ₂Me	140	Et	H	OH	Cl	CO ₂Me	SO ₂Et
141	Me	H	OH	Cl	C(O)SMe	SO ₂Me	142	Me	H	OH	Cl	C(O)SEt	SO ₂Me
143	Me	H	OH	Me	OMe	SO ₂Me	142	Me	H	OH	Cl	C(O)SEt	SO ₂Me
143	Me	H	OH	Me	OMe	SO ₂Me	144	Me	H	OH	Me	OEt	SO ₂Me
145	Me	H	OH	Me	O(i-Pr)	SO ₂Me	144	Me	H	OH	Me	OEt	SO ₂Me
145	Me	H	OH	Me	O(i-Pr)	SO ₂Me	146	Me	H	OH	Me	OCHF ₂	SO ₂Me
147	Me	H	OH	Me	4,5-dihydro-isoxazole-3-base	SO ₂Me	146	Me	H	OH	Me	OCHF ₂	SO ₂Me
147	Me	H	OH	Me	4,5-dihydro-isoxazole-3-base	SO ₂Me	148	Me	H	OH	Me	O(n-Pr)	SO ₂Et
149	Me	H	OH	Cl	CH ₂OMe	SO ₂Me	148	Me	H	OH	Me	O(n-Pr)	SO ₂Et
149	Me	H	OH	Cl	CH ₂OMe	SO ₂Me	150	Me	H	OH	Me	OCO ₂Me	SO ₂Me

Table 1 is continuous

No.	R ¹	R ²	R ³	R ⁴	R ⁵	R ⁶
No.	R ¹	R ²	R ³	R ⁴	R ⁵	R ⁶	151	Me	H	OH	Me	OCH ₂CH ₂OMe	SO ₂Me
152	Et	H	OH	Me	OEt	SO ₂Me	151	Me	H	OH	Me	OCH ₂CH ₂OMe	SO ₂Me
152	Et	H	OH	Me	OEt	SO ₂Me	153	Et	H	OH	Cl	CO ₂Et	SO ₂Me
154	Et	H	OH	Cl	CO ₂(n-Pr)	SO ₂Me	153	Et	H	OH	Cl	CO ₂Et	SO ₂Me
154	Et	H	OH	Cl	CO ₂(n-Pr)	SO ₂Me	155	Et	H	OH	Me	CO ₂Et	SO ₂Me
156	Me	H	OH	Me	CH ₂CO ₂Me	SO ₂Me	155	Et	H	OH	Me	CO ₂Et	SO ₂Me
156	Me	H	OH	Me	CH ₂CO ₂Me	SO ₂Me	157	Me	H	OH	Me	OCH ₂CO ₂Et	SO ₂Me
158	Me	H	OH	Me	O(n-Pr)	SO ₂Me	157	Me	H	OH	Me	OCH ₂CO ₂Et	SO ₂Me
158	Me	H	OH	Me	O(n-Pr)	SO ₂Me	159	Et	H	OH	SO ₂Me	H	CF ₃
160	Me	H	OH	Me	CH ₂OCH ₂CF ₃	SO ₂Me	159	Et	H	OH	SO ₂Me	H	CF ₃
160	Me	H	OH	Me	CH ₂OCH ₂CF ₃	SO ₂Me	161	Me	H	OH	Cl	CH ₂OCH ₂CF ₃	SO ₂Me
162	Et	H	OH	Me	Cl	SO ₂Me	161	Me	H	OH	Cl	CH ₂OCH ₂CF ₃	SO ₂Me
162	Et	H	OH	Me	Cl	SO ₂Me	163	Me	H	OH	Me	CH ₂SO ₂Me	SO ₂Me
164	Me	H	OH	Me	CH ₂OEt	SO ₂Me	163	Me	H	OH	Me	CH ₂SO ₂Me	SO ₂Me
164	Me	H	OH	Me	CH ₂OEt	SO ₂Me	165	Me	H	OH	Me	CH ₂CH ₂OMe	SO ₂Me
166	Me	H	OH	Me	CH ₂OCH ₂CH ₂OMe	SO ₂Me	165	Me	H	OH	Me	CH ₂CH ₂OMe	SO ₂Me
166	Me	H	OH	Me	CH ₂OCH ₂CH ₂OMe	SO ₂Me	167	Me	H	OH	Me	OCH ₂CH ₂OEt	SO ₂Me
168	Me	H	OH	Me	OCH ₂CH ₂Cl	SO ₂Me	167	Me	H	OH	Me	OCH ₂CH ₂OEt	SO ₂Me
168	Me	H	OH	Me	OCH ₂CH ₂Cl	SO ₂Me	169	Me	H	OH	Me	OCH ₂CF ₃	SO ₂Me
170	Me	H	OH	Me	CH ₂OCH ₂OMe	SO ₂Me	169	Me	H	OH	Me	OCH ₂CF ₃	SO ₂Me
170	Me	H	OH	Me	CH ₂OCH ₂OMe	SO ₂Me	171	Me	H	OH	Me	CN	SO ₂Me
172	Me	H	OH	Me	CH ₂CN	SO ₂Me	171	Me	H	OH	Me	CN	SO ₂Me
172	Me	H	OH	Me	CH ₂CN	SO ₂Me	173	Me	H	OH	Br	CO ₂Me	SO ₂Me
174	Et	H	OH	Cl	CO ₂Me	SO ₂Me	173	Me	H	OH	Br	CO ₂Me	SO ₂Me
174	Et	H	OH	Cl	CO ₂Me	SO ₂Me	175	Me	H	OH	Cl	OCH ₂CH ₂OCF ₃	SO ₂Me
176	Et	H	OH	Cl	OCH ₂CH ₂OCF ₃	SO ₂Me	175	Me	H	OH	Cl	OCH ₂CH ₂OCF ₃	SO ₂Me
176	Et	H	OH	Cl	OCH ₂CH ₂OCF ₃	SO ₂Me	177	Me	H	OH	Me	OCH ₂CH ₂OCF ₃	SO ₂Me
178	Et	H	OH	Me	OCH ₂CH ₂OCF ₃	SO ₂Me	177	Me	H	OH	Me	OCH ₂CH ₂OCF ₃	SO ₂Me
178	Et	H	OH	Me	OCH ₂CH ₂OCF ₃	SO ₂Me	179	Me	H	OH	CF ₃	OCH ₂CH ₂OCF ₃	SO ₂Me
180	Et	H	OH	CF ₃	OCH ₂CH ₂OCF ₃	SO ₂Me	179	Me	H	OH	CF ₃	OCH ₂CH ₂OCF ₃	SO ₂Me
180	Et	H	OH	CF ₃	OCH ₂CH ₂OCF ₃	SO ₂Me	181	Me	H	OH	Br	OCH ₂CH ₂OCF ₃	SO ₂Me
182	Et	H	OH	Br	OCH ₂CH ₂OCF ₃	SO ₂Me	181	Me	H	OH	Br	OCH ₂CH ₂OCF ₃	SO ₂Me
182	Et	H	OH	Br	OCH ₂CH ₂OCF ₃	SO ₂Me	183	Me	H	OH	SO ₂Me	OCH ₂CH ₂OCF ₃	CF ₃
184	Et	H	OH	SO ₂Me	OCH ₂CH ₂OCF ₃	CF ₃	183	Me	H	OH	SO ₂Me	OCH ₂CH ₂OCF ₃	CF ₃

Table 1 is continuous

No.	R ¹	R ²	R ³	R ⁴	R ⁵	R ⁶
No.	R ¹	R ²	R ³	R ⁴	R ⁵	R ⁶	185	Me	H	OH	Cl	OCH ₂CH ₂OCHClF	SO ₂Me
186	Et	H	OH	Cl	OCH ₂CH ₂OCHClF	SO ₂Me	185	Me	H	OH	Cl	OCH ₂CH ₂OCHClF	SO ₂Me
186	Et	H	OH	Cl	OCH ₂CH ₂OCHClF	SO ₂Me	187	Me	H	OH	Me	OCH ₂CH ₂OCHClF	SO ₂Me
188	Et	H	OH	Me	OCH ₂CH ₂OCHClF	SO ₂Me	187	Me	H	OH	Me	OCH ₂CH ₂OCHClF	SO ₂Me
188	Et	H	OH	Me	OCH ₂CH ₂OCHClF	SO ₂Me	189	Me	H	OH	CF ₃	OCH ₂CH ₂OCHClF	SO ₂Me
190	Et	H	OH	CF ₃	OCH ₂CH ₂OCHClF	SO ₂Me	189	Me	H	OH	CF ₃	OCH ₂CH ₂OCHClF	SO ₂Me
190	Et	H	OH	CF ₃	OCH ₂CH ₂OCHClF	SO ₂Me	191	Me	H	OH	Br	OCH ₂CH ₂OCHClF	SO ₂Me
192	Et	H	OH	Br	OCH ₂CH ₂OCHClF	SO ₂Me	191	Me	H	OH	Br	OCH ₂CH ₂OCHClF	SO ₂Me
192	Et	H	OH	Br	OCH ₂CH ₂OCHClF	SO ₂Me	193	Me	H	OH	SO ₂Me	OCH ₂CH ₂OCHClF	CF ₃
194	Et	H	OH	SO ₂Me	OCH ₂CH ₂OCHClF	CF ₃	193	Me	H	OH	SO ₂Me	OCH ₂CH ₂OCHClF	CF ₃
194	Et	H	OH	SO ₂Me	OCH ₂CH ₂OCHClF	CF ₃	195	Me	H	OH	Cl	OCH ₂CH ₂OCF ₂Cl	SO ₂Me
196	Et	H	OH	Cl	OCH ₂CH ₂OCF ₂Cl	SO ₂Me	195	Me	H	OH	Cl	OCH ₂CH ₂OCF ₂Cl	SO ₂Me
196	Et	H	OH	Cl	OCH ₂CH ₂OCF ₂Cl	SO ₂Me	197	Me	H	OH	Me	OCH ₂CH ₂OCF ₂Cl	SO ₂Me
198	Et	H	OH	Me	OCH ₂CH ₂OCF ₂Cl	SO ₂Me	197	Me	H	OH	Me	OCH ₂CH ₂OCF ₂Cl	SO ₂Me
198	Et	H	OH	Me	OCH ₂CH ₂OCF ₂Cl	SO ₂Me	199	Me	H	OH	CF ₃	OCH ₂CH ₂OCF ₂Cl	SO ₂Me
200	Et	H	OH	CF ₃	OCH ₂CH ₂OCF ₂Cl	SO ₂Me	199	Me	H	OH	CF ₃	OCH ₂CH ₂OCF ₂Cl	SO ₂Me
200	Et	H	OH	CF ₃	OCH ₂CH ₂OCF ₂Cl	SO ₂Me	201	Me	H	OH	Br	OCH ₂CH ₂OCF ₂Cl	SO ₂Me
202	Et	H	OH	Br	OCH ₂CH ₂OCF ₂Cl	SO ₂Me	201	Me	H	OH	Br	OCH ₂CH ₂OCF ₂Cl	SO ₂Me
202	Et	H	OH	Br	OCH ₂CH ₂OCF ₂Cl	SO ₂Me	203	Me	H	OH	SO ₂Me	OCH ₂CH ₂OCF ₂Cl	CF ₃
204	Et	H	OH	SO ₂Me	OCH ₂CH ₂OCF ₂Cl	CF ₃	203	Me	H	OH	SO ₂Me	OCH ₂CH ₂OCF ₂Cl	CF ₃
204	Et	H	OH	SO ₂Me	OCH ₂CH ₂OCF ₂Cl	CF ₃	205	Me	H	OH	Cl	SCH ₂CH ₂OCH ₃	SO ₂Me
206	Et	H	OH	Cl	SCH ₂CH ₂OCH ₃	SO ₂Me	205	Me	H	OH	Cl	SCH ₂CH ₂OCH ₃	SO ₂Me
206	Et	H	OH	Cl	SCH ₂CH ₂OCH ₃	SO ₂Me	207	Me	H	OH	Me	SCH ₂CH ₂OCH ₃	SO ₂Me
208	Et	H	OH	Me	SCH ₂CH ₂OCH ₃	SO ₂Me	207	Me	H	OH	Me	SCH ₂CH ₂OCH ₃	SO ₂Me
208	Et	H	OH	Me	SCH ₂CH ₂OCH ₃	SO ₂Me	209	Me	H	OH	CF ₃	SCH ₂CH ₂OCH ₃	SO ₂Me
210	Et	H	OH	CF ₃	SCH ₂CH ₂OCH ₃	SO ₂Me	209	Me	H	OH	CF ₃	SCH ₂CH ₂OCH ₃	SO ₂Me
210	Et	H	OH	CF ₃	SCH ₂CH ₂OCH ₃	SO ₂Me	211	Me	H	OH	Br	SCH ₂CH ₂OCH ₃	SO ₂Me
212	Et	H	OH	Br	SCH ₂CH ₂OCH ₃	SO ₂Me	211	Me	H	OH	Br	SCH ₂CH ₂OCH ₃	SO ₂Me
212	Et	H	OH	Br	SCH ₂CH ₂OCH ₃	SO ₂Me	213	Me	H	OH	SO ₂Me	SCH ₂CH ₂OCH ₂	CF ₃
214	Et	H	OH	SO ₂Me	SCH ₂CH ₂OCH ₃	CF ₃	213	Me	H	OH	SO ₂Me	SCH ₂CH ₂OCH ₂	CF ₃
214	Et	H	OH	SO ₂Me	SCH ₂CH ₂OCH ₃	CF ₃	215	Me	H	OH	Cl	SCH ₂CH ₂OCF ₃	SO ₂Me

Table 1 is continuous

No.	R ¹	R ²	R ³	R ⁴	R ⁵	R ⁶
No.	R ¹	R ²	R ³	R ⁴	R ⁵	R ⁶	216	Et	H	OH	Cl	SCH ₂CH ₂OCF ₃	SO ₂Me
217	Me	H	OH	Me	SCH ₂CH ₂OCF ₃	SO ₂Me	216	Et	H	OH	Cl	SCH ₂CH ₂OCF ₃	SO ₂Me
217	Me	H	OH	Me	SCH ₂CH ₂OCF ₃	SO ₂Me	218	Et	H	OH	Me	SCH ₂CH ₂OCF ₃	SO ₂Me
219	Me	H	OH	CF ₃	SCH ₂CH ₂OCF ₃	SO ₂Me	218	Et	H	OH	Me	SCH ₂CH ₂OCF ₃	SO ₂Me
219	Me	H	OH	CF ₃	SCH ₂CH ₂OCF ₃	SO ₂Me	220	Et	H	OH	CF ₃	SCH ₂CH ₂OCF ₃	SO ₂Me
221	Me	H	OH	Br	SCH ₂CH ₂OCF ₃	SO ₂Me	220	Et	H	OH	CF ₃	SCH ₂CH ₂OCF ₃	SO ₂Me
221	Me	H	OH	Br	SCH ₂CH ₂OCF ₃	SO ₂Me	222	Et	H	OH	Br	SCH ₂CH ₂OCF ₃	SO ₂Me
223	Me	H	OH	SO ₂Me	SCH ₂CH ₂OCF ₃	CF ₃	222	Et	H	OH	Br	SCH ₂CH ₂OCF ₃	SO ₂Me
223	Me	H	OH	SO ₂Me	SCH ₂CH ₂OCF ₃	CF ₃	224	Et	H	OH	SO ₂Me	SCH ₂CH ₂OCF ₃	CF ₃
225	Me	H	OH	Cl	OCH ₂CH(CH ₃)OCH ₃	SO ₂Me	224	Et	H	OH	SO ₂Me	SCH ₂CH ₂OCF ₃	CF ₃
225	Me	H	OH	Cl	OCH ₂CH(CH ₃)OCH ₃	SO ₂Me	226	Et	H	OH	Cl	OCH ₂CH(CH ₃)OCH ₃	SO ₂Me
227	Me	H	OH	Me	OCH ₂CH(CH ₃)OCH ₃	SO ₂Me	226	Et	H	OH	Cl	OCH ₂CH(CH ₃)OCH ₃	SO ₂Me
227	Me	H	OH	Me	OCH ₂CH(CH ₃)OCH ₃	SO ₂Me	228	Et	H	OH	Me	OCH ₂CH(CH ₃)OCH ₃	SO ₂Me
229	Me	H	OH	CF ₃	OCH ₂CH(CH ₃)OCH ₃	SO ₂Me	228	Et	H	OH	Me	OCH ₂CH(CH ₃)OCH ₃	SO ₂Me
229	Me	H	OH	CF ₃	OCH ₂CH(CH ₃)OCH ₃	SO ₂Me	230	Et	H	OH	CF ₃	OCH ₂CH(CH ₃)OCH ₃	SO ₂Me
231	Me	H	OH	Br	OCH ₂CH(CH ₃)OCH ₃	SO ₂Me	230	Et	H	OH	CF ₃	OCH ₂CH(CH ₃)OCH ₃	SO ₂Me
231	Me	H	OH	Br	OCH ₂CH(CH ₃)OCH ₃	SO ₂Me	232	Et	H	OH	Br	OCH ₂CH(CH ₃)OCH ₃	SO ₂Me
233	Me	H	OH	SO ₂Me	OCH ₂CH(CH ₃)OCH ₃	CF ₃	232	Et	H	OH	Br	OCH ₂CH(CH ₃)OCH ₃	SO ₂Me
233	Me	H	OH	SO ₂Me	OCH ₂CH(CH ₃)OCH ₃	CF ₃	234	Et	H	OH	SO ₂Me	OCH ₂CH(CH ₃)OCH ₃	CF ₃
235	Me	H	OH	Me	CH ₂N(Me)CH ₂CN	SO ₂Me	234	Et	H	OH	SO ₂Me	OCH ₂CH(CH ₃)OCH ₃	CF ₃
235	Me	H	OH	Me	CH ₂N(Me)CH ₂CN	SO ₂Me	236	Me	H	OH	Me	(oxolane-2-yl) methoxyl group	SO ₂Me
237	Me	H	OH	Cl	SMe	SO ₂Me	236	Me	H	OH	Me	(oxolane-2-yl) methoxyl group	SO ₂Me
237	Me	H	OH	Cl	SMe	SO ₂Me	238	Me	H	OH	Cl	Cl	SO ₂Me
239	Me	H	OH	Cl	OMe	SO ₂Me	238	Me	H	OH	Cl	Cl	SO ₂Me
239	Me	H	OH	Cl	OMe	SO ₂Me	240	Me	H	OH	Me	(tetrahydrochysene-2H-pyrans-2-yl) methoxyl group	SO ₂Me
241	Me	H	OH	Cl	OCH ₂CH ₂OMe	SO ₂Me	240	Me	H	OH	Me	(tetrahydrochysene-2H-pyrans-2-yl) methoxyl group	SO ₂Me

Table 1 is continuous

No.	R ¹	R ²	R ³	R ⁴	R ⁵	R ⁶
No.	R ¹	R ²	R ³	R ⁴	R ⁵	R ⁶	242	Me	H	OH	Me	Oxolane-3-base oxygen base	SO ₂Me
243	Me	H	OH	Me	OCH ₂CH ₂CH ₂OMe	SO ₂Me	242	Me	H	OH	Me	Oxolane-3-base oxygen base	SO ₂Me
243	Me	H	OH	Me	OCH ₂CH ₂CH ₂OMe	SO ₂Me	244	Et	H	OH	Cl	(1,3-diox-2-yl) ethyoxyl	SO ₂Me
245	Me	H	OH	Me	Propargyloxy	SO ₂Me	244	Et	H	OH	Cl	(1,3-diox-2-yl) ethyoxyl	SO ₂Me
245	Me	H	OH	Me	Propargyloxy	SO ₂Me	246	Me	H	OH	Me	(oxolane-3-base oxygen base) methyl	SO ₂Me
247	Me	H	OH	Cl	SO ₂Me	SO ₂Me	246	Me	H	OH	Me	(oxolane-3-base oxygen base) methyl	SO ₂Me
247	Me	H	OH	Cl	SO ₂Me	SO ₂Me	248	Me	H	OH	Me	(CH ₂) ₆Me	SO ₂Me
249	Me	H	OH	Me	CH ₂CH ₂CH ₂OMe	SO ₂Me	248	Me	H	OH	Me	(CH ₂) ₆Me	SO ₂Me
249	Me	H	OH	Me	CH ₂CH ₂CH ₂OMe	SO ₂Me	250	Et	H	OH	Cl	(1,3-diox-2-yl) methoxyl group	SO ₂Me
251	Me	H	OH	Me	CH ₂N[C(O)SEt]CH ₂CN	SO ₂Me	250	Et	H	OH	Cl	(1,3-diox-2-yl) methoxyl group	SO ₂Me
251	Me	H	OH	Me	CH ₂N[C(O)SEt]CH ₂CN	SO ₂Me	252	Me	H	OH	Me	CH＝CHCN	SO ₂Me
253	Me	H	OH	Me	CH ₂CH ₂CN	SO ₂Me	252	Me	H	OH	Me	CH＝CHCN	SO ₂Me
253	Me	H	OH	Me	CH ₂CH ₂CN	SO ₂Me	254	Me	H	OH	Me	OCH(CH ₃)CH ₂OMe	SO ₂Me
255	Me	H	OH	Me	OCH ₂CH(Et)OMe	SO ₂Me	254	Me	H	OH	Me	OCH(CH ₃)CH ₂OMe	SO ₂Me
255	Me	H	OH	Me	OCH ₂CH(Et)OMe	SO ₂Me	256	Me	H	OH	Me	(1,3-diox-2-yl) methyl	SO ₂Me
257	Me	H	OH	Me	CH ₂O(i-Pr)	SO ₂Me	256	Me	H	OH	Me	(1,3-diox-2-yl) methyl	SO ₂Me
257	Me	H	OH	Me	CH ₂O(i-Pr)	SO ₂Me	258	i-Pr	H	OH	Me	OCH ₂CH ₂OMe	SO ₂Me
259	Me	Me	OH	Me	OCH ₂CH ₂OMe	SO ₂Me	258	i-Pr	H	OH	Me	OCH ₂CH ₂OMe	SO ₂Me
259	Me	Me	OH	Me	OCH ₂CH ₂OMe	SO ₂Me	260	i-Pr	Me	OH	Me	OCH ₂CH ₂OMe	SO ₂Me
261	Me	Et	OH	Me	OCH ₂CH ₂OMe	SO ₂Me	260	i-Pr	Me	OH	Me	OCH ₂CH ₂OMe	SO ₂Me

[table 2]

No.	¹H-NMR δ ppm (solvent: under situation about not specifying, be CDCl ₃, determining instrument: JEOL-GSX (400MHz) or VARIAN MERCURY plus (300MHz)/following identical)
No.		1	2.38(s，3H)，3.29(s，3H)，3.47(s，6H)，3.70(s，3H)，4.09(d，2 H，J＝5.2Hz)，4.1(br s，1H)，4.83(t，1H，J＝5.2Hz)，7.32(s，1H) ，7.35(d，1H，J＝8.4Hz)，7.91(d，1H，J＝8.4Hz).
2	2.58(s，3H)，2.80-3.20(br s，1H)，3.25(s，3H)，3.73(s，3H)，4 .89(s，2H)，7.33(s，1H)，7.58(d，1H，J＝8.1Hz)，8.07(d，1H，J＝ 8.1Hz).	1
2		3	2.50(s，3H)，3.20(s，3H)，3.72(s，3H)，4.66(s，2H)，7.32(s，1 H)，7.40-7.50(br s，1H)，7.52(d，1H，J＝8.1Hz)，8.11(d，1H，J＝ 8.1Hz).
126	2.32(s，3H)，3.13(s，3H)，3.61(s，3H)，3.93(s，3H)，7.28(s， 1H)，7.56(d，1H，J＝7.8Hz)，7.93(d，1H，J＝7.8Hz)，8.44(br.s，1 H).	3
126		127	1.46(t，3H)，2.38(s，3H)，3.18(s，3H)，3.98(s，3H)，4.07( q，2H)，7.32(d，1H，J＝7.8Hz)，7.61(s，1H)，7.98(d，1H，J＝7 .8Hz).
131	1.40(t，3H，J＝7.0Hz)，2.39(s，3H)，3.25(s，3H)，3.42(s，3H)， 3.76(m，2H)，4.02(q，2H，J＝7.0Hz)，4.20(m，2H)，7.28(s，1H)， 7.31(d，1H，J＝7.6Hz).7.87(d，1H，J＝7.6Hz).	127
131		143	2.31(s，3H)，3.20(s，3H)，3.66(s，3H)，3.92(s，3H)，7.1(br s ，1H)，7.29(d，1H，J＝7.6Hz)，7.30(s，1H)，7.85(d，1H，J＝7.6Hz ).
144	1.48(t，3H，J＝7.2Hz)，2.36(s，3H)，3.34(s，3H)，3.71(s，3H)， 4.10(q，2H，J＝7.2Hz)，6.98(br s，1H)，7.37(m，2H)，7.90(d，1H ，J＝7.2Hz).	143
144		145	1.34(d，6H，J＝6.4Hz)，2.33(s，3H)，3.22(s，3H)，3.70(s，3H)， 4.82(qq.1H，J＝6.4，6.4Hz)，6.90(br s，1H)，7.29(d，1H，J＝7.6 Hz)，7.33(s，1H)，7.94(d，1H，J＝7.6Hz).
146	2.43(s，3H)，2.23(s，3H)，3.71(s，3H)，5.30(br s，1H)，6.75(t ，1H，J＝74.8Hz)，7.33(s，1H)，7.50(d，1H，J＝8.0Hz)，8.00(d，1 H，J＝8.0Hz).	145

Table 2 is continuous

No.	¹H-NMR δppm
No.	¹H-NMR δppm	151	2.39(s，3H)，3.29(s，3H)，3.46(s，3H)，3.71(s，3H)，3.81(m，2 H)，4.24(m，2H)，7.34(s，1H)，7.35(d，1H，J＝7.6Hz)，7.92(d，1 H，J＝7.6Hz).
152	1.44(t，3H，J＝7.2Hz)，1.48(t，3H，J＝7.2Hz)，2.36(s，3H)，3.27 (s，3H)，4.06(q，2H，J＝7.2Hz)，4.13(q，2H，J＝7.2Hz)，5.2(br s ，1H)，7.33(d，1H，J＝8.0Hz)，7.34(s，1H)，7.90(d，1H，J＝8.0Hz ).	151
152		153	(Acetone-d ₆)1.30(br s，3H)，1.37(t，3H，J＝7.0Hz)，3.25(s，3H )，3.95(br s，2H)，4.43(q，2H，J＝7.0Hz)，7.27(br s，1H)，7.75 (br s，1H)，8.07(br s，1H).
154	(Acetone-d ₆)1.18(t，3H，J＝7.4Hz)，1.34(br s，3H)，1.80(m，2H )，3.25(s，3H)，3.98(br s，2H)，4.33(t，2H，J＝5.6Hz)，7.32(br s，1H)，7.81(br s，1H)，8.08(br s，1H).	153
154		156	2.33(s，3H)，3.16(s，3H)，3.73(s，2H)，3.76(s，3H)，4.42(s，2 H)，7.20-7.60(br s，1H)，7.34(s，1H)，7.52(d，1H，J＝8.1Hz)， 8.10(d，1H，J＝8.1Hz).
157	1.27(t，3H，J＝7.6Hz)，2.32(s，3H)，3.32(s，3H)，3.66(s，3H)， 4.25(q，2H，J＝7.6Hz)，4.61(s，2H)，7.30(s，1H)，7.35(d，1H，J ＝8.0Hz)，7.88(d，1H，J＝8.0Hz).	156
157		160	2.48(s，3H)，3.16(s，3H)，3.71(s，3H)，3.98-4.04(m，2H)，5.23 (s，2H)，7.30(s，1H)，7.55(d，1H，J＝8.0Hz)，8.04(br s，1H)，8 .09(d，1H，J＝8.0Hz)
163	(Acetone-d ₆)2.51(s，3H)，3.12(s，3H)，3.23(s，3H)，3.29(s，3 H)，5.4(br s，2H)，6.8(br s，1H)，7.42(d，1H，J＝8.0Hz)，8.00( d，1H，J＝8.0Hz).	160
163		171	2.72(s，3H)，3.34(s，3H)，3.74(s，3H)，5.10-5.60(br s，1H)，7 .32(s，1H)，7.81(d，1H，J＝8.1Hz)，8.16(d，1H，J＝8.1Hz).
172	2.53(s，3H)，3.24(s，3H)，3.74(s，3H)，4.47(s，2H)，6.70-7.20 (br s，1H)，7.33(s，1H)，7.60(d，1H，J＝8.1Hz)，8.14(d，1H，J＝ 8.1Hz).	171
172		174	1.42(t，3H，J＝7.3Hz)，3.20(s，3H)，4.04(s，3H)，4.09(q，2 H，J＝7.3Hz)，7.34(s，1H)，7.64(d，1H，J＝7.8Hz)，8.07(d，1H， J＝7.8Hz).
227	1.23(d，3H，J＝6.4Hz)，2.34(s，3H)，3.24(s，3H)，3.41(s，3H)， 3.65(s，3H)，3.77(m，2H)，3.99(dd，1H，J＝9.2，4.0Hz)，4.05(dd ，1H，J＝9.2，6.4Hz)，7.28(s，1H)，7.29(d，1H，J＝8.4Hz)，7.86( d，1H，J＝8.4Hz).	174

Table 2 is continuous

No.	¹H-NMR δppm
No.	¹H-NMR δppm	235	2.41(s，3H)，2.48(s，3H)，3.27(s，3H)，3.63(s，2H)，3.72(s，3 H)，4.23(s，2H)，7.29(s，1H)，7.51(d，1H，J＝8.1Hz)，8.12(d，1 H，J＝8.1Hz).
238	2.55(s，3H)，3.45(s，3H)，7.29-7.33(m，2H)，7.35(d，1H，J＝8.4 Hz).	235
238	2.55(s，3H)，3.45(s，3H)，7.29-7.33(m，2H)，7.35(d，1H，J＝8.4 Hz).	244	1.43(t，3H，J＝7.3Hz)，2.28(m，2H)，3.29(s，3H)，3.86(m，2 H)，3.96(m，2H)，4.08(m，2H)，4.39(m，2H)，5.13(t，1H，J＝ 5.5Hz)，7.32(s，1H)，7.33(d，1H，J＝7.8Hz)，7.96(d，1H，J＝7. 8Hz).
247	2.49(s，3H)，3.54(s，3H)，3.57(s，3H)，7.40(s，1H)，7.63(d，1 H，J＝7.6Hz)，8.06(d，1H，J＝7.6Hz).	244
247		250	1.42(t，3H，J＝7.3Hz)，3.35(s，3H)，3.95(m，2H)，4.04-4.12 (m，4H)，4.29(m，2H)，5.46(t，1H，J＝5.5Hz)，7.32(s，1H)，7 .36(d，1H，J＝7.8Hz)，7.98(d，1H，J＝7.8Hz).
254	1.25(t，3H，J＝7.3Hz)，2.35(s，3H)，3.25(s，3H)，3.34(s，3 H)，3.53(m，1H)，3.70(s，3H)，3.74(m，1H)，4.88(m，1H)，7 .24(s，1H)，7.31(d，1H，J＝7.8Hz)，7.85(d，1H，J＝7.8Hz).	250
254		256	2.41(s，3H)，3.14(s，3H)，3.61(d，2H，J＝5.2Hz)，3.65(s，3H)， 3.77-3.82(m，2H)，3.88-3.96(m，2H)，5.12(t，1H，J＝4.8Hz)，5.4 5(br s，1H)，7.24(s，1H)，7.37(d，1H，J＝8.0Hz)，8.01(d，1H，J ＝8.0Hz).
257	1.25(d，6H，J＝6.4Hz)，1.44(t，3H，J＝7.4Hz)，2.47(s，3H)，3.25 (s，3H)，3.83(m，1H)，4.06(q，2H，J＝7.4Hz)，4.7(br s，1H)，5. 00(s，2H)，7.31(s，1H)，7.50(d，1H，J＝8.4Hz)，8.07(d，1H，J＝8 .4Hz).	256
257		258	1.48(d，6H，J＝6.8Hz)，2.40(s，3H)，3.30(s，3H)，3.46(s，3H)， 3.80(t，2H J＝8.4Hz)4.24(t，2H，J＝8.4Hz)5.89(m，1H)7.35(d， 1H，J＝8.0Hz)7.37(s，1H)7.91(d，1H，J＝8.0Hz).
259	1.62(s，3H)，2.26(s，3H)，3.25(s，3H)，3.42(s，3H)，3.58(s，3 H)，3.76(t，2H，J＝4.4Hz)，4.19(t，2H，J＝4.4Hz)，7.11(d，1H，J ＝8.0Hz)，7.87(d，1H，J＝8.0Hz).	258
259		260	1.46(d，6H，J＝6.8Hz)，1.67(s，3H)，2.32(s，3H)，3.27(s，3H)， 3.56(s，3H)，3.80(t，2H J＝8.4Hz)4.23(t，2H，J＝8.4Hz)4.55(m， 1H)7.15(d，1H，J＝8.0Hz)，7.91(d，1H，J＝8.0Hz).
261	0.85(t，3H，J＝7.2Hz)，2.00(q，2H，J＝7.2Hz)，2.30(s，3H)，3.28 (s，3H)，3.45(s，3H)，3.62(s，3H)，3.79(t，2H，J＝4.4Hz)，4.22 (t，2H，J＝4.4Hz)，7.16(d，1H，J＝8.0Hz)，7.89(d，1H，J＝8.0Hz).	260

Test example 1

The dry crop soil of packing in 1/170,000 hectare of basin is sowed the seed of each plant species.Then, reach certain leaf age ((1) barnyard grass grass: 1.0～3.0 leaf phases plant, (2) rise lady's-grass: 1.0～3.0 leaf phases, (3) green foxtail: 1.0～3.0 leaf phases, (4) Amaranthus retroflexus: cotyledon～2.0 leaf phases, (5) sting golden Portulaca grandiflora: cotyledon～1.0 leaf phases, (6) piemarker: 0.1～1.5 leaf phase, (7) rice: 1.0～3.0 leaf phases, (8) wheat: 1.7～3.4 leaf phases, (9) corn: 2.0～3.5 leaf phases, (10) soybean: in the time of primary leaf～0.4 leaf phase), to modulate hydrating agents or the emulsion that the compound of above-mentioned formula (I) forms according to the formulation method of routine and weigh regulation active ingredient amount, be diluted to the water that is equivalent to per 1 hectare 500 liters and (, contain the Network サリノ one of 0.1 capacity %: Nihon Nihyaku Co., Ltd's system) as the agricultural spreader-sticker.The spreading liquid of modulation is carried out the cauline leaf processing with miniaturised nebuliser.

The growth conditions of the 17th～25 day each plant species of perusal after chemicals treatment is estimated herbicidal effect with the growth inhibition ratio (%) of 0 (being equal to the non-processor district)～100 (withered fully killing), thereby is obtained the result of table 3.

[table 3]

Test example 2

The dry crop soil of packing in 1/170,000 hectare of basin is sowed the seed (barnyard grass grass, rise lady's-grass, green foxtail, Amaranthus retroflexus, thorn gold Portulaca grandiflora, piemarker, rice, wheat, corn and soybean) of each plant species.At after planting second day, to modulate hydrating agents or the emulsion that the compound of above-mentioned formula (I) forms according to the formulation method of routine and weigh regulation active ingredient amount, be diluted to and be equivalent to per 1 hectare 500 liters water, the spreading liquid of modulation is carried out cauline leaf with miniaturised nebuliser handle.

The growth conditions of the 19th～28 day each plant species of perusal after chemicals treatment is estimated herbicidal effect with the growth inhibition ratio (%) of 0 (being equal to the non-processor district)～100 (withered fully killing), thereby is obtained the result of table 4.

[table 4]

Test example 3

1/1,000, the dry crop soil of packing in 000 hectare of basin is sowed the seed of each plant species.Then, when plant reaches certain leaf age ((1) green foxtail: 4.0～4.5 leaf phases, (2) big broomcorn millet: 3.5～4.3 leaf phases, (3) corn: 4.0～4.3 leaf phases)), to modulate hydrating agents or the emulsion that the compound of above-mentioned formula (I) forms according to the formulation method of routine and weigh regulation active ingredient amount, be diluted to the water that is equivalent to per 1 hectare 300 or 500 liters and (, contain MSO Concentrate:CognisCorporation system or Network サリノ one: Nihon Nihyaku Co., Ltd's system) as the agricultural spreader-sticker.The spreading liquid of modulation is carried out the cauline leaf processing with miniaturised nebuliser.

The growth conditions of the 18th～24 day each plant species of perusal after chemicals treatment is estimated herbicidal effect with the growth inhibition ratio (%) of 0 (being equal to the non-processor district)～100 (withered fully killing), thereby is obtained the result of table 5～table 7.

[table 5]

(the agricultural spreader-sticker: MSO Concentrate 0.5 capacity %, scatter the water yield: the 300L/ hectare)

[table 6]

(the agricultural spreader-sticker: Network サリノ one 0.1 capacity %, scatter the water yield: the 500L/ hectare)

[table 7]

Then, record formulation example.

Formulation example 1

(1) compound 75 weight portions of above-mentioned formula (I)

(2) ゲロ Port Application T-77 (trade name, ロ one ヌプ one ラ Application society system) 14.5 weight portions

(3) NaCl 10 weight portions

(4) dextrin 0.5 weight portion

Above each composition is added mixed at high speed fine-graining machine, and then the water that adds 20 weight % therein carries out granulation, dry and obtain the particle hydrating agents.

Formulation example 2

(1) kaolin 78 weight portions

(2) ラベリ Application FAN (trade name, the first industrial pharmacy (strain) system) 2 weight portions

(3) ソ Le Port one Le 5039 (trade name, eastern nation chemical industry (strain) system) 5 weight portions

(4) カ one プレ Star Network ス (trade name, Shionogi (strain) system) 15 weight portions

The mixture of ingredients of above (1)～(4) is mixed with 9: 1 weight ratio with the compound of above-mentioned formula (I) and obtain hydrating agents.

Formulation example 3

(1) Ha イ Off イラ one No.10 (trade name, loose village industry (strain) system) 33 weight portions

(2) ソ Le Port one Le 5050 (trade name, eastern nation chemical industry (strain) system) 3 weight portions

(3) ソ Le Port one Le 5073 (trade name, eastern nation chemical industry (strain) system) 4 weight portions

(4) compound 60 weight portions of above-mentioned formula (I)

Each compositions of above (1)～(4) mixed and obtain hydrating agents.

Formulation example 4

(1) compound 4 weight portions of above-mentioned formula (I)

(2) bentonite 30 weight portions

(3) calcium carbonate 61.5 weight portions

(4) トキサノ Application GR-31A (trade name, Sanyo changes into industry (strain) system) 3 weight portions

(5) lignin sulfonic acid calcium salt 1.5 weight portions

(1), (2) and (3) of pulverizing are in advance mixed, add (4), (5) and water therein and mix, carry out extruding pelletization.Then, dry, whole grain and obtain granula.

Formulation example 5

(1) compound 30 weight portions of above-mentioned formula (I)

(2) ジ one Network ライト (trade name, ジ one Network ライト (strain) system) 60 weight portions

(3) ニユ one カ Le ゲ WG-1 (trade name, this grease of bamboo (strain) system) 5 weight portions

(4) ニユ one カ Le ゲ Application FS-7 (trade name, this grease of bamboo (strain) system) 5 weight portions

(1), (2) and (3) are mixed, by cracker, add then (4) mixing after, carry out extruding pelletization.Then, dry, whole grain and obtain the particle hydrating agents.

Formulation example 6

(1) compound 28 weight portions of above-mentioned formula (I)

(2) ソプロ Port one Le FL (trade name, ロ one ヌプ one ラ Application society system) 2 weight portions

(3) ソ Le Port one Le 355 (trade name, eastern nation chemical industry (strain) system) 1 weight portion

(4) IP ソ Le ベ Application ト 1620 (trade name, bright dipping petrochemistry (strain) system) 32 weight portions

(5) ethylene glycol 6 weight portions

(6) water 31 weight portions

The composition of above (1)～(6) is mixed, use wet crushing mill (ball mill) to pulverize and obtain the aqueous suspension agent.

The industry utilizability

Herbicidal composition of the present invention has excellent herbicidal effect, its range of application relates to the many-sides such as non-agricultural cultivated land such as the crop lands such as paddy field, dry land, fruit tree garden, mulberry field, mountain forest, road, farmland, place, factory place, in addition, application process also can suitably be selected soil treatment, cauline leaf processing, submerging treatment etc., and industrial utilizability is high.

In addition, here quote and all the elements of Japanese patent application 2007-195420 number specification, claim, accompanying drawing and summary of application on July 27th, 2007 Japanese patent application 2007-155359 number of application on June 12nd, Japanese patent application 2006-351617 number 1 of on December 27th, 2006 application, comprise as the disclosed content of specification of the present invention that they are whole.

Claims

1. weed killer herbicide that contains the benzoylpyrazole compound shown in the formula (I) or its salt as active ingredient,

2. the weed killer herbicide that contains benzoylpyrazole compound or its salt as active ingredient according to claim 1, R ⁴It is alkyl; R ⁵Be cyano group, cyanoalkyl, halo alkoxy alkyl, can be selected from alkyl, cyano group, cyanoalkyl, (alkylthio group) carbonylic alkyl, alkyl (thiocarbonyl) alkyl ,-C (O) OR ⁷With-C (O) SR ⁷In amino (thiocarbonyl) alkyl that replaces of at least 1 substituting group; the thiocyanate groups alkyl; the halogen alkoxyl; the alkoxyl alkoxyl; alkyl sulphonyl, alkyl sulphonyl alkyl, alkoxy carbonyl alkyl; the alkoxy carbonyl alkoxyl, the heterocyclic radical alkyl or can be selected from alkyl, cyano group, cyanoalkyl, (alkylthio group) carbonylic alkyl, alkyl (thiocarbonyl) alkyl ,-C (O) OR ⁷With-C (O) SR ⁷In the aminoalkyl that replaces of at least 1 substituting group.

3. a Herbicidal composition contains the described benzoylpyrazole compound of claim 1 or its salt and agricultural adjuvant.

4. method of preventing and kill off undesired plants or suppressing its growth is applied to the herbicidally effective amount of the described benzoylpyrazole compound of claim 1 or its salt in the place of undesired plants or its growth.

5. method according to claim 4 is prevented and kill off noxious plant in corn plantation field.

6. method according to claim 5, corn are the corns through transforming.

7. the manufacture method of the compound shown in the formula (I-a), be to make compound and the alkali reaction shown in compound shown in the formula (I-b) and the formula (VIII), perhaps make the reacting metal salt of the compound shown in compound shown in the described formula (I-b) and the described formula (VIII), thereby the method for the compound shown in the manufacturing formula (I-a)

In the following formula, R ¹It is alkyl or cycloalkyl; R ²Be hydrogen atom or alkyl; R ³It is hydroxyl; R ⁴Be alkyl, alkylhalide group, alkoxyl, halogen, nitro, cyano group, alkylthio group, alkyl sulphinyl or alkyl sulphonyl; R ^5-a-1Be alkoxyl, halogen alkoxyl, alkoxyl alkoxyl, halogen alkoxyl alkoxyl, alkoxyl halogen alkoxyl, halogen alkoxyl halogen alkoxyl, heterocyclyloxy base, heterocyclic radical alkoxyl, cycloalkyl oxy ,-OC (O) SR ⁷,-OC (O) OR ⁷, alkylthio group alkoxyl, alkoxy carbonyl alkoxyl, thiazolinyl oxygen base or alkynyloxy base; R ⁶Be alkylhalide group, halogen, nitro, cyano group, alkylthio group, alkyl sulphinyl or alkyl sulphonyl; R ⁷Be alkyl, alkylhalide group, alkoxyalkyl, thiazolinyl, haloalkenyl, alkynyl or can be by R ⁸The aryl alkyl that replaces; R ⁸Be halogen, alkyl or alkoxyl;

HO-R ^α(VIII)

In the following formula, R ^αBe alkyl, alkylhalide group, alkoxyalkyl, halo alkoxy alkyl, alkoxyl alkylhalide group, halogen alkoxyl alkylhalide group, heterocyclic radical, heterocyclic radical alkyl, cycloalkyl ,-C (O) SR ⁷,-C (O) OR ⁷, alkylthio alkyl, alkoxy carbonyl alkyl, alkenyl or alkynyl; R ⁷As mentioned above.

8. the manufacture method of the compound shown in the formula (I-a-Hal-3), be that compound or its salt shown in the compound shown in the formula (XXXIII), the formula (III) and carbon monoxide or its equivalents are reacted in the presence of catalyzer and alkali, thereby the method for the compound shown in the manufacturing formula (I-a-Hal-3)

In the following formula, R ¹And R ²As mentioned above.

9. the manufacture method of the compound shown in the formula (XXXIII) is to make compound shown in the formula (XXXIV) and formula (R ^6-a-3) (Hal-3) or (R ^6-a-3) ₂Compound shown in the O reacts in the presence of acid, thus the method for the compound shown in the manufacturing formula (XXXIII),

In the following formula, R ⁴, Hal-1 and Hal as mentioned above;

10. the manufacture method of the compound shown in the formula (V-a-1-3) is to make the compound shown in the formula (XXXII) and carbon monoxide or its equivalents and H ₂O reacts in the presence of catalyzer and alkali, thus the method for the compound shown in the manufacturing formula (V-a-1-3),

In the following formula, R ⁴Be alkyl, alkylhalide group, alkoxyl, halogen, nitro, cyano group, alkylthio group, alkyl sulphinyl or alkyl sulphonyl; R ^5-a-1Be alkoxyl, halogen alkoxyl, alkoxyl alkoxyl, halogen alkoxyl alkoxyl, alkoxyl halogen alkoxyl, halogen alkoxyl halogen alkoxyl, heterocyclyloxy base, heterocyclic radical alkoxyl, cycloalkyl oxy ,-OC (O) SR ⁷,-OC (O) OR ⁷, alkylthio group alkoxyl, alkoxy carbonyl alkoxyl, thiazolinyl oxygen base or alkynyloxy base; R ^6-a-3It is alkyl sulphonyl; R ⁷Be alkyl, alkylhalide group, alkoxyalkyl, thiazolinyl, haloalkenyl, alkynyl or can be by R ⁸The aryl alkyl that replaces; R ⁸Be halogen, alkyl or alkoxyl;

11. the manufacture method of the compound shown in the formula (XXXII), be make the compound shown in the formula (XXXIII), with formula (VIII) shown in compound in the presence of alkali, react, perhaps make the reacting metal salt of the compound shown in compound shown in the described formula (XXXIII) and the described formula (VIII), thereby the method for the compound shown in the manufacturing formula (XXXII)

In the following formula, R ⁴And R ^6-a-3As mentioned above; Hal-1 and Hal are halogens, and Hal-1 and Hal can be the same or different each other;

HO-R ^α(VIII)

12. the compound shown in the formula (XXXII-a),