WO1996033994A1 - Amino-substituted derivatives, process for the preparation thereof, and herbicide - Google Patents

Amino-substituted derivatives, process for the preparation thereof, and herbicide Download PDF

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Publication number
WO1996033994A1
WO1996033994A1 PCT/JP1996/001155 JP9601155W WO9633994A1 WO 1996033994 A1 WO1996033994 A1 WO 1996033994A1 JP 9601155 W JP9601155 W JP 9601155W WO 9633994 A1 WO9633994 A1 WO 9633994A1
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Prior art keywords
group
alkyl
optionally substituted
alkoxy
alkyl group
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PCT/JP1996/001155
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French (fr)
Japanese (ja)
Inventor
Akiyoshi Ueda
Yasuyuki Miyazawa
Daisuke Sato
Yoshihiko Hara
Masami Koguchi
Isoko Matsumoto
Takashi Kawana
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Nippon Soda Co., Ltd.
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Publication of WO1996033994A1 publication Critical patent/WO1996033994A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • the present invention relates to novel amino-substituted derivatives, production methods and herbicides.
  • Background art :
  • An object of the present invention is to provide a herbicide which can be synthesized industrially advantageously, is effective at a low dose, has high safety, and has high crop selectivity. Disclosure of the invention:
  • A represents N or CR 3
  • Z represents 0 or S
  • Q is a carbon atom benzene
  • R 2 each independently hydrogen atom, alkyl group, C, - 6 alkoxy groups, halo alkyl groups, halo C 6 alkoxy group, C, - 6 alkylamino amino group, di C DOO 6 alkylamino amino group, C alkylthio group, Represents a halogen atom or a cyano group
  • R 3 represents a hydrogen atom, a C alkyl group, a halogen atom, a nitro group, a formyl group, an acyl group, or may form a ring together with R 2
  • X is wherein NR 4 R 5 (wherein, R 4 and R 5 are each independently a hydrogen atom, alkyl
  • R 4 and R 5 may represent a group, an optionally substituted benzoyl group or an optionally substituted heterocyclic carbonyl group, or may form a ring together. However, R 4 and R 5 are not both ds alkoxycarbonyl groups. ).
  • examples of the heterocycle represented by Q include the following.
  • Upsilon, - 5 is hydrogen, C, - 6 alkyl group, C 3 - 7 cycloalkyl group, halo C
  • examples of the hetero ring formed by R 4 and R 5 together in the group represented by X include a hetero ring represented by the following formula.
  • C have alkyl groups, C 3 - 7 cycloalkyl, C, - 6 alkoxy 6 ⁇ alkyl group, C, - 6 alkylthio C, - 6 alkyl group, C, - Ji 6 alkylsulfonyl, -
  • R 7 represents a hydrogen atom, a C atom, an amino group or a carboxyl
  • Salts of the compound represented by the general formula [1] include deer horticulturally acceptable salts, for example, inorganic salts such as hydrochloride and hydrogen bromide, and organic salts such as acetate, oxalate and formate. Acid salts, etc., and alkali metals, alkaline earth metals, ammonium salts and the like.
  • the compound of the present invention can be produced by the following method.
  • the compound represented by the general formula [2] and the compound represented by the general formula [3] are coupled in an organic solvent in the presence of a suitable base.
  • Bases used in the reaction include metal hydrides such as hydrogenated sodium, carbonates such as carbonated carbon, and organic bases such as triethylamine.
  • the solvent used is DMF. , DMS O, THF, DME and the like. The reaction mixture is stirred at 0 to 90, and sometimes at 120, until the reaction is completed.
  • the 0-heterocyclic-substituted phenol derivative of the starting compound [3] in the above reaction is as follows. It can be manufactured by the method described below.
  • solvents used in the following reactions include alcohols such as methanol, ethanol, and isopropyl alcohol, aromatic hydrocarbons such as benzene and toluene, dichloromethane, and chloroform.
  • Halogenated hydrocarbons such as mouth form, ethers such as getyl ether and THF, ketones such as acetone and MEK, esters such as methyl acetate and ethyl acetate, and non-protons such as DMF and DMS 0 Polar solvents, nitriles such as acetate tritriol, and water.
  • the bases used include sodium carbonate, carbonates such as carbon dioxide, sodium hydroxide, metal hydroxides such as hydroxide, sodium methylate, sodium ethylate and the like.
  • Metal alcoholates such as sodium hydroxide, metal hydrides such as sodium hydride, alkyl metals such as butyllithium, lithium amides such as lithium diisopropylamide, lithium bistrimethylsilylamide, and triethylamido And organic bases such as DBU.
  • the acids used are mineral acids such as hydrochloric acid, nitric acid and sulfuric acid, organic acids such as formic acid and acetic acid, and Lewis acids such as aluminum chloride and boron trifluoride dimethyl ether. The reaction proceeds smoothly within the temperature range of the boiling point of the solvent used since —90.
  • X represents the same meaning as described above, L, represents an alkoxy group, a chlorine atom or a 1-imigzole group, and y, represents an alkyl group, a benzyl group or a p-toluenesulfonyl group.
  • ⁇ 3 is a compound of 1,2.4_triazole-3-yl
  • the compound [7] can be produced by reacting the compound [7] with acid chloride or acid anhydride in DMF at 0 to 120 ° C.
  • X represents the same meaning as described above, and y 2 represents an alkyl group, an aryl group, or a haloalkyl group.
  • 2-substituted — 1, 2, 4 — triazol-3-yl derivatives are prepared according to the method described in J. Org. Chem. 44, vol. 4, page 4160 (1977).
  • the amide [8] is reacted with dimethylformamide dimethyl acetal to synthesize N—C (dimethylamino) methylene] amide [9].
  • [9] is reacted with hydrazines to induce triazole [10].
  • L 2 is a methoxymethoxy or benzyloxy group, it can be obtained by treating [10] with an acid or by a hydrocracking reaction using palladium carbon or the like as a catalyst.
  • L 2 represents a methoxymethoxy group, a benzyloxy group, a nitro group, or a halogen atom
  • L 3 represents an alkyl group or a benzyl group
  • y 3 represents an alkyl group. Represents a benzyl group or a phenyl group.
  • X, L 2 , L 3 and y 5 represent the same meaning as described above, and ys represents an alkyl group, an aryl amino group, an alkyl amino group or an aryl amino group.
  • a derivative in which Q is thiazol-5-yl can also be produced by the same method as described above.
  • L 4 represents a halogen
  • y l 0 represents hydrogen, methyl, Echiru group or alkyl carbonylation Le group
  • y is hydrogen Represents an atom, alkyl group or funinyl group.
  • y 12 represents an alkyl group or a phenyl group
  • y 13 represents a hydrogen atom, an alkyl group, a benzyl group.
  • Ki Hue Represents a nyl group, an alkoxycarbonyl group or a tosyl group, represents a hydrogen atom, an alkyl group or a benzyl group.
  • y 15 represents a hydrogen atom, an alkyl group or a halogen atom.
  • a mixture of the isoxazolin-3-yl and the isoxazolin-5-yl forms can be easily separated by mouth chromatography or recrystallization.
  • y 16 represents a hydrogen atom, an alkyl group or a phenyl group.
  • it can be obtained by reacting benzofuran and hydroxylamine with alcohol at 25 to 80 for 0.5 to 8 hours. Can be done.
  • y 17 is a hydrogen atom, an alkyl group, a benzyl group, an aryl group, a haloalkyl group.
  • An alkoxyalkyl group or an alkylthioalkyl group is represented by X, L,, L 2 or L represents the same meaning as described above.
  • y 18 and y l 9 is Shiano group, an alkoxycarbonyl group, or to display the Fuweniru group, X and L 2 are as defined above.
  • L 4 represents a halogen atom, preferably fluorine
  • the compound of the formula [65] can be produced by a method similar to the above-mentioned phenol derivative synthesis method, by reacting a compound of the general formula [66] with sodium sulfide, thiourea or the like.
  • [65] can also be produced by applying the aniline derivative [69] to the method described in Organic Synthesis Color 1 ect., Vol. 3, page 809. (In the formula, L 4 represents halogen.)
  • the compound of the present invention can also be produced by the following method. 96/33994
  • this is a method for producing [1] by reacting the compound represented by the general formula [55] with an appropriate condensing agent shown in the production method of the above [3].
  • the compound represented by the general formula [56] and sodium azide are placed in a suitable solvent, preferably using DMF, at room temperature to a temperature not higher than the boiling point of the solvent, preferably 80 to 120. It is produced by reacting for 1-2 hours.
  • the solvent used in this reaction include alcohols such as methanol, ethanol and isopropanol, aromatic hydrocarbons such as benzene and toluene, and halogenated carbons such as dichloromethane and chloroform.
  • the compound represented by the general formula [59] is reacted with TosMIC in a suitable solvent in a suitable solvent at a temperature from room temperature to a temperature lower than the boiling point of the solvent for 1 to 24 hours according to a method known in the literature. It is manufactured by
  • the compound of the formula [60] and hydrazines are reacted in the presence or absence of a suitable base in a suitable solvent at a temperature from room temperature to a temperature lower than the boiling point of the solvent for 1 to 24 hours. It is produced by reacting.
  • Solvents used in this reaction include, for example, alcohols such as methanol, ethanol, and isopropanol; aromatic hydrocarbons such as benzene and toluene; dichloromethane; Halogenated hydrocarbons, ethers such as getyl ether and THF, ketones such as acetone and MEK, esters such as methyl acetate and ethyl acetate, and non-protonic polar solvents such as DMF and DMSO , Acetonitrile, water and the like.
  • Examples of the base used in this reaction include carbonates such as sodium carbonate and carbonated carbonate, metal hydroxides such as sodium hydroxide and potassium hydroxide, and sodium hydroxide.
  • the compound represented by the general formula [61] and the promoter [15] are reacted with a suitable base in the presence or absence of a suitable base in a suitable solvent at a temperature from room temperature to a temperature lower than the boiling point of the solvent. Manufactured by reacting for 4 hours.
  • the solvent used for this reaction include methanol, ethanol, and isoprono.
  • Alcohols such as ethanol, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane and chloroform, ethers such as getyl ether and THF, and ketones such as acetate and MEK.
  • the aldehyde represented by the general formula [62] and isonitrile [37] are compared to the aldehyde in the presence of a suitable base of at least 2 S in a suitable solvent at room temperature to below the boiling point of the solvent. It is produced by reacting at a temperature of 1 to 24 hours.
  • the solvent used in this reaction include alcohols such as methanol, ethanol and isopropanol, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane and chloroform, and getyl.
  • Ethers such as ether and THF; non-protonic polar solvents such as DMF and DMS 0; and acetonitrile.
  • Examples of the base used in this reaction include carbonates such as sodium carbonate and potassium carbonate, metal hydroxides such as sodium hydroxide and hydroxylating water, and sodium methylate.
  • Metal alcohols such as sodium and sodium ethyl ethers; metal hydrides such as sodium hydride and potassium hydride; lithium amides such as lithium diisopropyl amide and lithium p-methylsilyl amide; And organic bases such as DBU.
  • [1j] is produced by reacting for 2 hours.
  • the solvent used for this reaction include methanol, ethanol, and isoprono.
  • Alcohols such as ethanol, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane and chloroform, ethers such as getyl ether and THF, and non-hydrocarbons such as DMF and DMS0.
  • Examples include protonic polar solvents and acetonitril.
  • the base used in this reaction include carbonates such as sodium carbonate and carbonated carbonate, metal hydroxides such as sodium hydroxide and hydroxylated phosphate, and sodium hydride.
  • metal hydrides such as tritium and potassium hydride, lithium amides such as lithium diisopropyl amide and lithium bistrimethylsilyl amide, and organic bases such as triethylamine and DBU.
  • the acylimidazole represented by the general formula [63] and the amide oxime [47] are reacted in a suitable solvent in the presence of a suitable base at a temperature of 115 to 140 for 1 to 24 hours.
  • the reaction produces [lk].
  • the solvent used in this reaction include aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as dichloromethane and chloroform; ethers such as getyl ether and THF; Non-protonic polar solvents such as F and DMSO, acetonitrile, and the like.
  • Bases used in this reaction include carbonates such as sodium carbonate and carbonated carbonate, metal hydroxides such as sodium hydroxide and hydroxylated phosphate, and sodium hydride.
  • Metal hydrides such as potassium and potassium hydride; lithium amides such as lithium diisopropylamide; and organic bases such as triethylamine and DBU.
  • the compound represented by the general formula [] can be prepared by a method known in the literature, in the presence of a suitable base or acid, without a solvent or in a suitable solvent, at a temperature lower than the boiling point of the solvent.
  • Z 2 represents oxygen or sulfur
  • y 22 represents alkyl or aryl
  • yl 4 has the same meaning as described above.
  • reaction of the compound of the general formula [1j] with [64] in the presence of a suitable base in a suitable solvent at a temperature of ⁇ 15 to 25 ° C. for 1 to 24 hours yields [11 1 ] Is manufactured.
  • solvent used in this reaction include alcohols such as methanol, ethanol, and isopropanol; aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as dichloromethane and chloroform; Ethers such as tyl ether and THF; ketones such as acetone and MEK; esters such as methyl acetate and ethyl acetate; non-protonic polar solvents such as DMF and DMS 0; Water and the like.
  • Examples of the base used in this reaction include carbonates such as sodium carbonate and potassium carbonate, gold hydroxides such as sodium hydroxide and potassium hydroxide, sodium methylate, and the like.
  • Metal alcohols such as sodium ethylate; metal hydrides such as sodium hydride and potassium hydride; lithium diisopropyl Examples thereof include lithium amides such as amide and lithium bistrimethylsilyl amide, and organic bases such as triethylamine and DBU.
  • a compound of the general formula [70] (wherein R,, R 2 , A and Z represent the same meaning as described above); and a compound of the general formula [66] (wherein Q, X, Y n, L, have the same meaning as described above.))
  • the compound is coupled in an organic solvent in the presence of a base.
  • the base include metal hydrides such as hydrogenated sodium, carbonates such as carbonated lime, and organic bases such as triethylamine.
  • the solvent include DMF, DMS O, and THF. , DME and the like.
  • the reaction mixture is stirred at 0-90 ° C., possibly at 120 ° C., until the reaction is complete.
  • the structure of the compound of the present invention was determined from IR, NMR, MS and the like.
  • n n H H 0 H H H 3H0 3H0 1 0 LZ-Z n u n u
  • HHHH 0 H 3W0 9H0 1 0 9S-Z unnu HHUHH a H0 3 0 I 0
  • OW 1300D-H3 HD H H 3W0 awo 8 ⁇ - ⁇ ⁇ 3 ⁇ 43
  • N3-HD HD H H 3W0 awo
  • the compound of the present invention shows high herbicidal activity under soil cultivation conditions in both soil treatment and foliage treatment, and various compounds such as Aquinoeno korogusa, Ichibi and Inubu, etc. It is effective for field weeds and contains compounds that are selective for crops such as corn, wheat, soybeans, and potatoes.
  • the compound of the present invention also includes a compound that is useful for producing growth suppression for useful plants such as crops, ornamental plants, and fruit trees.
  • the compound of the present invention has excellent herbicidal activity against various paddy weeds such as nobie, evening magayalli, omomodaka and hoyurui, and shows selectivity to rice.
  • the compound of the present invention can be applied to the control of weeds in orchards, lawns, track ends, vacant lots and the like.
  • the compounds of the present invention include those having a plant growth regulating action, and the intermediate compounds of the present compounds also include those having a herbicidal activity.
  • the herbicide of the present invention contains one or more of the compounds of the present invention as an active ingredient.
  • a general pesticide for the purpose of using it as a pesticide that is, a wettable powder, an abductant, a powder, It can also be used in the form of emulsions, aqueous solvents, suspensions, flowables and the like.
  • vegetable powders such as soybean flour and flour, diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, clay and other mineral fine powders
  • Organic and inorganic compounds such as sodium benzoate, urea, and sodium sulfate are used.
  • petroleum fractions such as kerosene, xylene and sorbent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetate, and tris
  • chlorethylene, methylisobutyl ketone, mineral oil, vegetable oil, water, etc. as solvents.
  • a surfactant may be added if necessary.
  • the concentration of the active ingredient in the herbicide of the present invention varies depending on the form of the preparation described above. 5 to 90%, preferably 10 to 85% for wettable powders; 3 to 70%, preferably 5 to 30% for emulsions. %: For abductants, a concentration of 0.01 to 30%, preferably 0.05 to 10% is used.
  • the wettable powder and emulsion thus obtained are diluted with water to a predetermined degree to form a suspension or an emulsion, and the granules are directly sprayed on the soil before or after germination of the weeds. Or mixed. In actually applying the herbicide of the present invention, an appropriate amount of 0.1 g or more of the active ingredient is applied per 10 ares.
  • the herbicide of the present invention can be used in combination with known fungicides, insecticides, acaricides, herbicides, plant growth regulators and the like.
  • the synergistic action of the mixed drug can be expected to have a much higher effect. In that case, a combination with a plurality of known herbicides is also possible.
  • Suitable agents to be used in combination with the herbicide of the present invention include carbamate herbicides such as benthiocarb, molinate, and dimepirate, acid carbohydrate herbicides, butachlor, pretilachlor, and mefenacet. Mid-type herbicides, diphenyl ether-type herbicides such as chrometoxynil, biphenox, etc .; triazine-type herbicides such as atrazine and cyanadine; and sulfonyl-urea-type herbicides such as chlorsulfuron and sulfometurone monomethyl.
  • carbamate herbicides such as benthiocarb, molinate, and dimepirate, acid carbohydrate herbicides, butachlor, pretilachlor, and mefenacet.
  • Mid-type herbicides diphenyl ether-type herbicides such as chrometoxynil, biphenox, etc .
  • triazine-type herbicides such
  • Carboxylic acid herbicides such as MCP, MCPB, etc., phenoxycarboxylic acid herbicides such as diclohop-methyl, etc., and pyridyloxyphenoxypropionic acid such as fludihopbutyl.
  • Dinitroaniline such as herbicides, trifluralin, and pendimethalin Herbicides, urea herbicides such as linuron and diuron, benzoylaminopropionic acid herbicides such as benzoylprophetyl and flavonopetyl, and imidazolinone herbicides such as imazaquin; and others, biverofos , Daimron, Benzozon, Difenzocoat, Nabroanilide, Etobenzanide, Triazophenamide, Kink Mouth Rack, and Xanthion herbicides such as Sethoxydim, Cresodim, etc.
  • Example 3 wettable powder
  • the above components were uniformly mixed and finely pulverized to obtain a wettable powder containing 20% of the active ingredient.
  • the above mixture was uniformly mixed and finely pulverized, and then granulated into particles having a diameter of 0.5 to 10 mm to obtain granules having an active ingredient of 5%.
  • T of the following test examples on the effect of the present invention herbicides The herbicidal effect was investigated according to the following criteria and expressed as a herbicidal index ⁇
  • the numbers 1, 3, 5, 7, and 9 are intermediate values between 0 and 2, 2 and 4, 4 and 6, 6, 8 and 10 respectively.
  • Table 11 1 Compound No.Dose Noviet Tamagayarimodoka transplanted rice g / ha
  • the paddy of the present invention shows high herbicidal activity in any of soil treatment and foliage treatment under upland cropping conditions, and is effective against various field weeds such as Aquinoeno korogusa, Ichibi and Inubu.
  • the compounds of the present invention also include compounds that exhibit a growth-inhibiting effect on useful plants such as crops, ornamental plants, and fruit trees.
  • the compound of the present invention has an excellent herbicidal activity against various paddy weeds such as Nobie, Tamagayari, Omodaka, Hoyurui, etc., and contains fossils showing selectivity to rice. .
  • the compound of the present invention can also be applied to the control of weeds in orchards, lawns, roadsides, vacant lots and the like.
  • composition containing the compound of the present invention is useful as a herbicide.

Abstract

Novel amino-substituted derivatives represented by general formula (I) exhibiting a herbicidal activity higher than those of known analogues thereof, a process for the preparation thereof, and a herbicide comprising the same as the active principle. In said formula, A is N or CR3; Z is O or S; Q is a five- or six-membered heterocycle; R1 and R2 are each independently H, C1-C6 alkyl, C1-C6 alkoxy or the like; R3 is H, C1-C6 alkyl, halogeno or the like; and X is NR4R5 (wherein R4 and R5 are each independently H, C1-C6 alkyl, C3-C7 cycloalkyl, C1-C6 alcoxy, C1-C6 alkyl or the like, or R4 and R5 may together form a ring.

Description

明 細 書 アミ ノ置換誘導体、 製造方法及び除草剤 技術分野：  Description Amino-substituted derivatives, production methods and herbicides
本発明は新規なアミ ノ置換誘導体， 製造方法及び除草剤に関する。 背景技術 ：  The present invention relates to novel amino-substituted derivatives, production methods and herbicides. Background art:
農園芸作物の栽培にあたり、 多大の労力を必要と してきた雑草防除に多くの除 草剤が使用されるようになってきた。 しかし作物に薬害を生じたり、 環境に残留 したり、 汚染したりすることから、 より低い薬量で効果が確実でしかも安全に使 用できる薬剤の開発が望まれている。  Many herbicides have come to be used for weed control, which has required a great deal of effort in cultivating agricultural and horticultural crops. However, there is a need for the development of drugs that can be used safely and safely at lower doses because they cause phytotoxicity, remain in the environment, and pollute crops.
本発明化合物と関連した化合物を開示したものと して、 W O 9 4 Z 1 7 0 5 9 に Xがアミ ノ基であり、 Qが 5 -ォキサゾリル基である化合物の除草活性及びそ の製造法の記載がある。 しかしながらその生物活性は実用的には不十分なもので ある。  Disclosed are compounds related to the compound of the present invention, which include the herbicidal activity of a compound in which X is an amino group and Q is a 5-oxazolyl group in WO94Z17759 and a method for producing the same. There is a description. However, its biological activity is insufficient for practical use.
本発明の目的は、 工業的に有利に合成でき、 より低い薬量で効果の確実な安全 性の高い、 作物との選択性の良い除草剤を提供することである。 発明の開示 ：  An object of the present invention is to provide a herbicide which can be synthesized industrially advantageously, is effective at a low dose, has high safety, and has high crop selectivity. Disclosure of the invention:
本発明は、 一般式 〔 I 〕 で表わされるァミ ノ置換誘導体又はその塩、 その製造 方法及び該化合物を有効成分と して含有することを特徴とする除草剤である。  The present invention is a herbicide characterized by comprising an amino-substituted derivative represented by the general formula [I] or a salt thereof, a method for producing the same, and the compound as an active ingredient.
Figure imgf000003_0001
Figure imgf000003_0001
〔式中、 Aは N又は C R 3 を表し、 Zは 0又は Sを表し、 Qは炭素原子でベンゼ ン環と結合している、 N、 0、 もしく は Sを同一または相異なって 1〜4個含む 置換基を有していてもよい 5~ 6員のへテロ環を表し、 、 R2 は各々独立し て水素原子、 6 アルキル基、 C ,-6 アルコキシ基、 ハロ 6 アルキル基、 ハロ C 6 アルコキシ基、 C ,-6 アルキルアミ ノ基、 ジ Cト 6 アルキルアミ ノ基 、 C アルキルチオ基、 ハロゲン原子又はシァノ基を表し、 R3 は水素原子、 C アルキル基、 ハロゲン原子、 ニ トロ基、 ホルミル基、 ァシル基を表すか、 又は R2 と一緒になって環を形成していても良く、 Xは、 式 NR4 R5 (式中、 R4 及び R5 は各々独立して、 水素原子、 6 アルキル基、 C3-7 シクロアル キル基、 C ^s アルコキシ 6 アルキル基、 C ,-6 アルキルチオ 6 アルキ ル基、 C アルキルスルホニル C ,-6 アルキル基、 C 2 アルケニル基、 C2- アルキニル基、 ヒ ドロキシル C z アルキル基、 6 アルコキシカルボニル 基、 ァミ ノ C ,-6 アルキル基、 アルコキシカルボニル C 6 アルキル基、In the formulas, A represents N or CR 3, Z represents 0 or S, Q is a carbon atom benzene A 5- or 6-membered heterocyclic ring having 1 to 4 N, 0, or S, which are the same or different and which are bonded to a heterocyclic ring, and R 2 each independently hydrogen atom, alkyl group, C, - 6 alkoxy groups, halo alkyl groups, halo C 6 alkoxy group, C, - 6 alkylamino amino group, di C DOO 6 alkylamino amino group, C alkylthio group, Represents a halogen atom or a cyano group; R 3 represents a hydrogen atom, a C alkyl group, a halogen atom, a nitro group, a formyl group, an acyl group, or may form a ring together with R 2 ; , X is wherein NR 4 R 5 (wherein, R 4 and R 5 are each independently a hydrogen atom, alkyl group, C 3 - 7 a cycloalkyl group, C ^ s alkoxy alkyl group, C, - 6 alkylthio 6 alkyl le groups, C alkylsulfonyl C, - 6 alkyl group, C 2 alkenyl group, C 2 - alkyl Group, human Dorokishiru C z alkyl group, 6 alkoxycarbonyl group, § Mi Bruno C, - 6 alkyl group, alkoxycarbonyl C 6 alkyl group,
C 1 - アルキルスルホニル基、 力ルバモイル基、 チォカルバモイル基、 置換され ても良いベンジル基、 置換されても良いフヱニル基、 置換されてもよいへテロ環 基、 置換されても良いフヱニルスルホニル基、 置換されても良いベンゾィル基又 は置換されても良いヘテロ環カルボ二ル基を表すか、 R4 と R5 が一緒になつて 環を形成してもよい。 但し、 R4 と R5 が共に d-s アルコキシカルボニル基、 ではない。 ） を表す。 〕 C 1 -alkylsulfonyl group, carbamoyl group, thiocarbamoyl group, benzyl group which may be substituted, phenyl group which may be substituted, heterocyclic group which may be substituted, phenylsulfonyl which may be substituted R 4 and R 5 may represent a group, an optionally substituted benzoyl group or an optionally substituted heterocyclic carbonyl group, or may form a ring together. However, R 4 and R 5 are not both ds alkoxycarbonyl groups. ). ]
本発明において、 Qで表されるヘテロ環と しては下記式のものが例示される。 In the present invention, examples of the heterocycle represented by Q include the following.
Figure imgf000005_0001
Figure imgf000005_0001
Figure imgf000005_0002
Figure imgf000005_0002
Figure imgf000005_0003
Figure imgf000005_0003
(式中、 Υ,-5 は水素原子、 C ,-6 アルキル基、 C3- 7 シクロアルキル基、 ハロ C(Wherein, Upsilon, - 5 is hydrogen, C, - 6 alkyl group, C 3 - 7 cycloalkyl group, halo C
, -6 アルキル基、 d-6 アルコキシ C S アルキル基、 d-6 アルキルチオ アルキル基、 じ卜6 アルキルスルホニル C , -6 アルキル基、 C2-6 アルケニル基、, -6 alkyl group, d-6 alkoxy CS alkyl group, d-6 alkylthio group, Ji Bok 6 alkylsulfonyl C, -6 alkyl group, C 2 - 6 alkenyl group,
C 2-6 アルキニル基、 ハロゲン原子、 シァノ基、 ニ トロ基、 ア ミ ノ基、 C ,-6 アル キルア ミ ノ基、 ァシルァ ミ ノ基、 C ,-6 アルキルスルホニルァ ミ ノ基、 ヒ ドロキシ ル基、 カルボキシル基、 6 アルコキシカルボニル基、 C ,-6 アルコキシ基、 置 換されても良いベンジルォキシ基、 C 2-6 アルケニルォキシ基、 C 2- c アルキニル ォキシ基、 ハロ C ,-6 アルコキシ基、 6 アルキルチオ基、 C卜 6 アルキルスル ホニル基、 C2-6 アルケニルチオ基、 C2-6 アルキニルチオ基、 ァシルォキシ基、 力ルバモイルォキシ基、 チォカルバモイルォキシ基、 ァミ ノォキシ基、 置換されて も良いベンジル基、 置換されても良いフエニル基、 置換されても良いフ 二ルチオ 基、 置換されても良いフ Xニルスルホニル基、 置換されても良いベンゾィル基、 置 換されても良いヘテロ環ォキシ基又はへテロ環チォ基を表し、 又、 2つの Y, — YC 2-6 alkynyl group, a halogen atom, Shiano group, nitro group, A Mi amino group, C, - 6 Al Killua Mi amino group, Ashirua Mi amino group, C, - 6 alkylsulfonyl § Mi amino group, human Dorokishi group, a carboxyl group, 6 alkoxycarbonyl group, C, - 6 alkoxy groups, location Conversion which may be Benjiruokishi groups, C 2 - 6 Arukeniruokishi groups, C 2 - c alkynyl Okishi group, halo C, - 6 alkoxy groups, 6 alkylthio groups, C WINCH 6 alkylsulfanyl Honiru groups, C 2 - 6 alkenyl thio, C 2 - 6 alkynylthio, Ashiruokishi group, forces Rubamoiruokishi group, Chio carbamoyl O alkoxy group, § Mi Nookishi group, an optionally substituted benzyl group, an optionally substituted phenyl group may be substituted Represents a fluorothio group, an optionally substituted phenylsulfonyl group, an optionally substituted benzoyl group, an optionally substituted heterocyclic oxy group or a heterocyclic thio group, and two Y, — Y
5 で炭素環又はへテロ環を形成してもよい。 ） 5 may form a carbocyclic or heterocyclic ring. )
また、 Xで表される基において R4 と R5 が一緒になって形成するへテロ環と し ては下記式のへテロ環が挙げられる。 Further, examples of the hetero ring formed by R 4 and R 5 together in the group represented by X include a hetero ring represented by the following formula.
X' , X ',
N N
(式中、 Wは 0、 S、 S 0、 S 02 、 C R6 及び NR7 を表し、 X' 及び R6 は水 素原子、 Cい アルキル基、 C3-7 シクロアルキル基、 C ,- 6 アルコキシ 6 ァ ルキル基、 C ,-6 アルキルチオ C ,-6 アルキル基、 C ,-6 アルキルスルホ二ルじ ,―(Wherein, W is 0, S, S 0, S 0 2, represents a CR 6 and NR 7, X 'and R 6 are water atom, C have alkyl groups, C 3 - 7 cycloalkyl, C, - 6 alkoxy 6 § alkyl group, C, - 6 alkylthio C, - 6 alkyl group, C, - Ji 6 alkylsulfonyl, -
6 アルキル基、 C2 -B アルケニル基、 C2-6 アルキニル基、 ヒ ドロキシ C 2-6 アル キル基、 アルコキシカルボニル基、 ァミ ノ C ! -d アルキル基、 アルコ キシカルボ二ルじ C アルキル基、 水酸基、 C ,-c アルコキシ基、 C2- 6 アルケニ ルォキシ基、 ハロ C |- G アルコキシ基、 C 1 -6 アルキルスルホニル基、 ァシルォキ シ基、 力ルバモイル基、 チォカルバモイル基、 置換されても良いベンジル基、 置換 されても良いフエニル基、 置換されてもよいへテロ環、 置換されても良いフヱニル スルホニル基、 置換されても良いベンゾィル基、 又は置換されても良いヘテロ環力 ルポ二ル基、 ァシル基、 アミ ノ基又はカルボキシル基を表し、 R7 は水素原子、 C6 alkyl group, C 2 -B alkenyl group, C 2 - 6 alkynyl group, human Dorokishi C 2 -! 6 Al Kill group, an alkoxycarbonyl group, § Mi Roh C -d alkyl group, Arco Kishikarubo nil Ji C alkyl group , hydroxyl, C, - c alkoxy groups, C 2 - 6 alkenyl Ruokishi group, halo C | - G alkoxy groups, C 1 -6 alkylsulfonyl group, Ashiruoki sheet group, the force Rubamoiru group, Chiokarubamoiru group, optionally substituted Good benzyl group, optionally substituted phenyl group, optionally substituted hetero ring, optionally substituted phenylsulfonyl group, optionally substituted benzoyl group, or optionally substituted heterocyclic group R 7 represents a hydrogen atom, a C atom, an amino group or a carboxyl group.
,-,2アルキル基、 C 3 -7 シクロアルキル基、 d- 6 アルコキシ C ,- S アルキル基、, -, 2 alkyl group, C 3 -7 cycloalkyl group, d-6 alkoxy C, - S alkyl group,
C ,-«,· アルキルチオ C ,-6 アルキル基、 C ,- s アルキルスルホニル C 6 アルキル 基、 C2-6 アルケニル基、 C2-6 アルキニル基、 ヒ ドロキシ C2- u アルキル基、 C アルコキシカルボニル基、 ァ ミ ノ C ,-6 アルキル基、 アルコキシカルボ 二ル 卜^ アルキル基、 C , アルキルスルホニル基、 ァシルォキシ基、 カルバモ ィル基、 チォカルバモイル基、 置換されても良いベンジル基、 置換されても良いフ ェニル基、 置換されてもよいへテロ環、 置換されても良いフヱニルスルホニル基、 置換されても良いベンゾィル基、 又は置換されても良いヘテロ環カルボ二ル基を表 し、 mは 0または 1〜3の整数を表す。 ） C, - «, · alkylthio C, - 6 alkyl groups, C, - s alkylsulfonyl C 6 alkyl groups, C 2 - 6 alkenyl groups, C 2 - 6 alkynyl group, human Dorokishi C 2 - u alkyl groups, C Alkoxycarbonyl group, § Mi Bruno C, - 6 alkyl group, alkoxycarbonyl alkylsulfonyl Bok ^ alkyl, C, alkylsulfonyl group, Ashiruokishi group, Karubamo I group, Chiokarubamoiru group, an optionally substituted benzyl group, a substituted Represents an optionally substituted phenyl group, an optionally substituted hetero ring, an optionally substituted phenylsulfonyl group, an optionally substituted benzoyl group, or an optionally substituted heterocyclic carbonyl group. And m represents 0 or an integer of 1 to 3. )
—般式 〔 1〕 で表される化合物の塩としては、 鹿園芸上許容される塩、 例えば 、 塩酸塩、 臭化水素塩等の無機酸塩類、 酢酸塩、 蓚酸塩、 蟻酸塩等の有機酸塩類 等、 及びアルカリ金属、 アルカリ土類金属、 アンモニゥム塩等が挙げられる。 発明を実施するための最良の形態 ：  — Salts of the compound represented by the general formula [1] include deer horticulturally acceptable salts, for example, inorganic salts such as hydrochloride and hydrogen bromide, and organic salts such as acetate, oxalate and formate. Acid salts, etc., and alkali metals, alkaline earth metals, ammonium salts and the like. BEST MODE FOR CARRYING OUT THE INVENTION
本発明の化合物は、 以下の方法によって製造することができる。  The compound of the present invention can be produced by the following method.
(製造法 - 1 ) 反応式 1  (Production method-1) Reaction formula 1
Figure imgf000007_0001
Figure imgf000007_0001
C2] [3] [la]  C2] [3] [la]
(式中、 A、 R, 、 R2 、 X及び Zは前記と同じ意味を表し、 Lはハロゲン原子 又はアルキルスルホ二ル基を表す。 ） (In the formula, A, R,, R 2 , X and Z represent the same meaning as described above, and L represents a halogen atom or an alkylsulfonyl group.)
一般式 [2 ] で表される化合物と一般式 [ 3] で表される化合物とを有機溶媒 中適当な塩基の存在下カップリ ングさせる。 反応に使用される塩基としては、 水 素化ナ ト リゥム等の水素化金属類、 炭酸力リ ゥム等の炭酸塩類、 卜 リェチルァミ ン等の有機塩基類であり、 溶媒と しては、 DMF、 DMS O、 THF、 DME等 が挙げられる。 反応混合物は反応が完了するまで、 0~9 0て、 場合によっては 1 2 0てで撹拌される。  The compound represented by the general formula [2] and the compound represented by the general formula [3] are coupled in an organic solvent in the presence of a suitable base. Bases used in the reaction include metal hydrides such as hydrogenated sodium, carbonates such as carbonated carbon, and organic bases such as triethylamine.The solvent used is DMF. , DMS O, THF, DME and the like. The reaction mixture is stirred at 0 to 90, and sometimes at 120, until the reaction is completed.
上記反応における原料化合物 [3] の 0—へテロ環置換フエノール誘導体は以 下に述べるような方法により製造することができる。 尚、 特に指定をしていない 場合、 以下の反応において用いられる溶媒は、 メタノール、 エタノール、 イソプ 口ピルアルコール等のアルコール類、 ベンゼン、 トル-ェン等の芳香族炭化水素類 、 ジクロロメ タン、 クロ口ホルム等のハロゲン化炭化水素類、 ジェチルエーテル 、 THF等のエーテル類、 アセ トン、 MEK等のケ トン類、 酢酸メチル、 酢酸ェ チル等のエステル類、 DMF、 DMS 0等の非プロ トン性極性溶媒、 ァセ 卜二 卜 リル等の二ト リル類、 水等である。 又、 用いられる塩基は、 炭酸ナ ト リ ウム、 炭 酸力リゥ厶等の炭酸塩類、 水酸化ナト リ ウム、 水酸化力リ ゥム等の水酸化金属類 、 ナ ト リウムメチラー 卜、 ナ ト リウムェチラー 卜等の金属アルコラー ト類、 水素 化ナ ト リ ウム等の水素化金属類、 ブチルリチウム等のアルキル金属類、 リチウム ジイソプロピルァミ ド、 リチウムビス 卜 リ メチルシリルァミ ド等のリチウムアミ ド類、 ト リェチルァミ ン、 D B U等の有機塩基類等である。 又、 用いられる酸は 塩酸、 硝酸、 硫酸等の鉱酸類、 蟻酸、 酢酸等の有機酸類、 塩化アルミニウム、 ボ ロン ト リフロリ ドジェチルエーテル等のルイス酸類である。 反応は、 — 9 0てか ら用いられる溶媒の沸点の温度範囲で円滑に進行する。 The 0-heterocyclic-substituted phenol derivative of the starting compound [3] in the above reaction is as follows. It can be manufactured by the method described below. Unless otherwise specified, solvents used in the following reactions include alcohols such as methanol, ethanol, and isopropyl alcohol, aromatic hydrocarbons such as benzene and toluene, dichloromethane, and chloroform. Halogenated hydrocarbons such as mouth form, ethers such as getyl ether and THF, ketones such as acetone and MEK, esters such as methyl acetate and ethyl acetate, and non-protons such as DMF and DMS 0 Polar solvents, nitriles such as acetate tritriol, and water. The bases used include sodium carbonate, carbonates such as carbon dioxide, sodium hydroxide, metal hydroxides such as hydroxide, sodium methylate, sodium ethylate and the like. Metal alcoholates such as sodium hydroxide, metal hydrides such as sodium hydride, alkyl metals such as butyllithium, lithium amides such as lithium diisopropylamide, lithium bistrimethylsilylamide, and triethylamido And organic bases such as DBU. The acids used are mineral acids such as hydrochloric acid, nitric acid and sulfuric acid, organic acids such as formic acid and acetic acid, and Lewis acids such as aluminum chloride and boron trifluoride dimethyl ether. The reaction proceeds smoothly within the temperature range of the boiling point of the solvent used since —90.
( 1 ) Qがィ ミダゾリ ン— 2—ィル及びィ ミ ダゾールー 2—ィルの化合物は、 J . Ame r. C h e m. S o c . 9 6巻， 2 4 6 3ページ （ 1 9 7 4年） に記載 の方法を応用して製造することができる。 (1) Compounds in which Q is imidazoline-2-yl and imidazole-2-yl are described in J. Amer. Chem. Soc. 4 years).
OH OH
Figure imgf000009_0001
Figure imgf000009_0001
[3c]  [3c]
(式中、 Xは前記と同じ意味を表し、 L , はアルコキシ基、 塩素原子又は 1 —ィ ミ グゾール基を表し、 y , はアルキル基、 ベンジル基又は p— トルエンスルホニ ル基を表す。 ）  (In the formula, X represents the same meaning as described above, L, represents an alkoxy group, a chlorine atom or a 1-imigzole group, and y, represents an alkyl group, a benzyl group or a p-toluenesulfonyl group. )
( 2 ) Qがイ ミ ダゾールー 4一ィルの化合物は、 J . Am e r. C h e m. S o c. 8 2巻， 3 3 8 6ページ （ 1 9 6 0年） に記載の方法を応用して製造するこ とができる。 (2) Compounds in which Q is imidazole-41-yl are prepared according to the method described in J. Amer. Chem. Soc. 82, pp. 33686 (1966). It can be manufactured by applying.
0CH2Ph
Figure imgf000009_0002
0CH 2 Ph
Figure imgf000009_0002
[5]  [Five]
Figure imgf000009_0003
Figure imgf000009_0003
[3d]  [3d]
(式中、 Xは前記と同じ意味を表す。 ） 又、 J. O r g. C h e m. 4 2巻， 1 1 5 3ページ （ 1 9 7 7年） に記載の 方法で製造することもできる。 (In the formula, X represents the same meaning as described above.) It can also be manufactured by the method described in J. Org. Chem. 42, Vol. 2, page 1153 (1977).
Figure imgf000010_0001
Figure imgf000010_0001
(式中、 X及び y , は前記と同じ意味を表す。 ） (Wherein, X and y, represent the same meaning as described above.)
( 3 ) <3が 1 , 2. 4 _ 卜 リアゾールー 3 -ィルの化合物 (3) <3 is a compound of 1,2.4_triazole-3-yl
化合物 [ 7 ] を酸クロライ ドもしく は、 酸無水物と DM F中、 0〜 1 2 0°Cで 反応させることにより製造することができる。  The compound [7] can be produced by reacting the compound [7] with acid chloride or acid anhydride in DMF at 0 to 120 ° C.
Figure imgf000010_0002
Figure imgf000010_0002
(式中、 Xは前記と同じ意味を表し、 y2 はアルキル基、 ァリール基又はハロ アルキル基を表す。 ） (In the formula, X represents the same meaning as described above, and y 2 represents an alkyl group, an aryl group, or a haloalkyl group.)
2位置換— 1 , 2 , 4 — 卜リアゾールー 3 —ィル誘導体は、 J. O r g. C h e m. 4 4卷、 4 1 6 0ページ （ 1 9 7 9年） に記載の方法に従い、 アミ ド [ 8 ] とジメチルホルムアミ ドジメチルァセタールを反応させて、 N— C (ジメチル ァミ ノ） メチレン] アミ ド [ 9 ] を合成する。 [ 9 ] にヒ ドラジン類を反応させ て、 卜 リアゾール [ 1 0 ] へと誘導する。 L 2 がメ トキシメ トキシ、 ベンジルォ キシ基の場合は、 [ 1 0 ] を酸で処理するか、 パラジウム炭素等を触媒にした加 水素化分解反応によって得られる。 L 2 力 、ロゲン、 二 卜口の場合には、 [ 1 0 ] にナ ト リ ウムアルコラ一卜を反 応させて、 化合物 [ 1 1 ] を合成する。 [ 1 1 ] から [ 3 g] への変換は、 " P r o t e c t i v e G r o u s i n O r g a n i c S y n t h e s i s " T. W. G r e e n e編集、 J OHN W I L EY & S ON S, N. Y . 発行、 第 3章、 8 7ページに記載の方法から、 適切な反応を選択して行われる 。 例えば、 1 ) L i C 1等の塩を DMFや DMS 0等の溶媒中で、 加熱する方法 、 2 ) HB r/酢酸中加熱する方法、 3 ) ピリ ジン塩酸塩中加熱する方法、 4 ) 金属触媒を用いた加水素化分解による方法、 5 ) ボロン ト リハライ ド等のルイス 酸による脱アルキル化等が挙げられる。 2-substituted — 1, 2, 4 — triazol-3-yl derivatives are prepared according to the method described in J. Org. Chem. 44, vol. 4, page 4160 (1977). The amide [8] is reacted with dimethylformamide dimethyl acetal to synthesize N—C (dimethylamino) methylene] amide [9]. [9] is reacted with hydrazines to induce triazole [10]. When L 2 is a methoxymethoxy or benzyloxy group, it can be obtained by treating [10] with an acid or by a hydrocracking reaction using palladium carbon or the like as a catalyst. In the case of L 2 force, logen, and sodium, the compound [11] is synthesized by reacting sodium alcohol with [10]. Conversion from [1 1] to [3g] is described in "Protective G rousin Organic Synthesis" edited by TW Greene, published by JOHN WILEY & S ON S, NY, Chapter 3, 8 7 An appropriate reaction is selected from the methods described on the page. For example, 1) a method of heating a salt such as LiC1 in a solvent such as DMF or DMS0, 2) a method of heating in HBr / acetic acid, 3) a method of heating in pyridine hydrochloride, 4) 5) Dealkylation with a Lewis acid such as boron trihalide.
Figure imgf000011_0001
Figure imgf000011_0001
L2=HalogenL 2 = Halogen
NaOL; or Ni tro NaOL ; or Nitro
Figure imgf000011_0002
Figure imgf000011_0002
[3g] [11]  [3g] [11]
(式中、 Xは前記と同じ意味を表し、 L2 はメ トキシメ 卜キシ基、 ベンジルォキ シ基、 ニトロ基又はハロゲン原子を表し、 L3 はアルキル基又はベンジル基を表 し、 y3 はアルキル基、 ベンジル基又はフヱニル基を表す。 ） (In the formula, X represents the same meaning as described above, L 2 represents a methoxymethoxy group, a benzyloxy group, a nitro group, or a halogen atom, L 3 represents an alkyl group or a benzyl group, and y 3 represents an alkyl group. Represents a benzyl group or a phenyl group.
( 4 ) Qがテ トラゾールー 5 -ィルの誘導体は、 J . Am e r . C h e m. S o c 8 0巻. 3 9 0 8ページ （ 1 9 5 8年） の方法を応用して、 二 卜 リル [ 1 2 ： にアジ化ナ ト リゥムと塩化アンモニゥムを DMF中 8 0〜 1 4 0 °Cで 1〜 4 8 時間反応させることにより製造することができる。 (4) The derivative of Q is tetrazol-5-yl is obtained by applying the method described in J. Amer. Chem. Soc 80, 390, page 198 (1985). Trial [1 2 It can be produced by reacting sodium azide and ammonium chloride in DMF at 80 to 140 ° C for 1 to 48 hours.
Figure imgf000012_0001
Figure imgf000012_0001
また、 J. O r g. C h e m. 5 6卷， 2 3 9 5ページ （ 1 9 9 1年） に記載 される方法により、 スズアジ ドと [ 1 2 ] を反応させても製造することができる  Also, it can be produced by reacting tin azide with [12] according to the method described in J. Org. Chem. Vol. 56, pp. 2395 (1991). Can
Figure imgf000012_0002
Figure imgf000012_0002
( 5 ) Qがチアブール— 2 —ィルの誘導体は下記反応式のようにして合成される (5) Derivatives of Q is thiabool-2-yl are synthesized according to the following reaction formula.
Figure imgf000013_0001
Figure imgf000013_0001
[16]  [16]
Figure imgf000013_0002
Figure imgf000013_0002
(式中、 X、 L 2 及び L 3 は前記と同じ意味を表し、 Ί はアルキル基、 ァリール 基又はハロアルキルを表し、 y5 は水素原子、 アルキル基又はアルコキシカルボ二 ル基を表し、 R 10はアルキル基を表す。 ） (Wherein, X, L 2 and L 3 represent the same meaning as described above, 、 represents an alkyl group, an aryl group or a haloalkyl, y 5 represents a hydrogen atom, an alkyl group or an alkoxycarbonyl group, and R 10 Represents an alkyl group.)
6 ) Qがチアゾール— 4一ィルの誘導体は、 下記反応式のようにして合成される 6) The derivative of Q is thiazole-41-yl is synthesized according to the following reaction formula.
Figure imgf000014_0001
Figure imgf000014_0001
(式中、 X、 L2 、 L3 及び y 5 は前記と同じ意味を表し、 y s はアルキル基、 ァ リール基 アミ ノ基、 アルキルアミ ノ基又はァリールアミ ノ基を表す。 ） (In the formula, X, L 2 , L 3 and y 5 represent the same meaning as described above, and ys represents an alkyl group, an aryl amino group, an alkyl amino group or an aryl amino group.)
( 7 ) Qがチアゾールー 5—ィルの誘導体も、 前述と同様の方法によって製造する ことが出来る。 (7) A derivative in which Q is thiazol-5-yl can also be produced by the same method as described above.
Figure imgf000015_0001
Figure imgf000015_0001
[3k]  [3k]
(式中、 X、 L2 、 L3 及び y6 は前記と同じ意味を表し、 y， は H又はアルキル 基を表す。 ） (In the formula, X, L 2 , L 3 and y 6 represent the same meaning as described above, and y and H represent H or an alkyl group.)
尚、 これらのチアゾール誘導体の合成法は、 C h e m. H e t e r o c y c l i c . C omp o u n d s、 3 4巻、 パー ト 1 ~3 ( 1 9 7 8〜 1 9 7 9年） 、 ある いは、 " H e t e r o c y c l i c C omp o u n d s R . し. E l d e r f i e 1 d編集、 W I L EY. N. Y. 発行、 5卷、 4 8 4〜 7 2 2ページ （ 1 9 5 7年） に記載されている。 The synthesis of these thiazole derivatives is described in Chem. Heterocyclic.Compounds, Vol. 34, parts 1-3 (1978-19779), or "H Eterocyclic Compounds R. Shid. Elderfie 1d, edited by WILEY. NY, Vol. 5, pp. 484-722 (1957).
( 8 ) Qがォキサゾ一ル- 2—ィルの誘導体は、 下記反応式のようにして台成され る。 (8) The derivative of Q is oxazo-2-yl is formed as shown in the following reaction formula.
Figure imgf000016_0001
Figure imgf000016_0001
NaOL5 L2=Halogen NaOL 5 L 2 = Halogen
1 or Ni tro  1 or Ni tro
Figure imgf000016_0002
Figure imgf000016_0002
(式中、 X、 L 2 及び L., は前記と同じ意味を表し、 Y8 は水素原子、 アルキル基 、 フヱニル基又はハロアルキル基を表し、 Υ9 は水素原子、 アルキル基又はフエ二 ル基を表す。 ） ( 9〉 Qがォキサゾールー 4—ィルの誘導体は、 下記反応式のようにして合成され る。 (Wherein, X, L 2 and L., have the same meaning as described above, Y 8 represents a hydrogen atom, an alkyl group, a phenyl group or a haloalkyl group, and 9 represents a hydrogen atom, an alkyl group or a phenyl group. Represents.) (9) A derivative in which Q is oxazole-4-yl is synthesized according to the following reaction formula.
Figure imgf000017_0001
Figure imgf000017_0001
NaOLs L2=Halogen or Ni tro NaOLs L 2 = Halogen or Nitro
Figure imgf000017_0002
Figure imgf000017_0002
(式中、 X、 L2 及び L3 は前記と同じ意味を表し、 L4 はハロゲンを表し、 y l 0 は水素、 メチル、 ェチル基又はアルキルカルボ二ル基を表し、 y ,,は水素原子、 ァ ルキル基又はフニ二ル基を表す。 ） (Wherein, X, L 2 and L 3 are as defined above, L 4 represents a halogen, y l 0 represents hydrogen, methyl, Echiru group or alkyl carbonylation Le group, y ,, is hydrogen Represents an atom, alkyl group or funinyl group.)
96/33994 96/33994
( 1 0 ) Qがォキサゾールー 5 -ィルの誘導体は下記反応式のようにして合成され る。  The derivative of (10) Q is oxazole-5-yl is synthesized according to the following reaction formula.
ogen tro ogen tro
Figure imgf000018_0001
Figure imgf000018_0001
yiz  yiz
Figure imgf000018_0002
Figure imgf000018_0002
[31] [32]  [31] [32]
[30]  [30]
NaOL; L2=Halogen i or Ni tro NaOL ; L 2 = Halogen i or Nitro
Figure imgf000018_0003
Figure imgf000019_0001
Figure imgf000018_0003
Figure imgf000019_0001
Figure imgf000019_0002
Figure imgf000019_0002
Figure imgf000019_0003
Figure imgf000019_0003
NaOL3 L2=Halogen or Ni tro NaOL 3 L 2 = Halogen or Nitro
Figure imgf000019_0004
Figure imgf000019_0004
(式中、 X、 、 L2 、 L3 、 y 7 及び y Mは前記と同じ意味を表し、 y 12はァ ルキル基又はフエ二ル基を表し、 y 13は水素原子、 アルキル基、 ベンジル基、 フエ ニル基、 アルコキシカルボニル基又はトシル基を表し、 は水素原子、 アルキル 基又はベンジル基を表す。 ） (Wherein, X,, L 2 , L 3 , y 7 and y M represent the same meaning as described above, y 12 represents an alkyl group or a phenyl group, and y 13 represents a hydrogen atom, an alkyl group, a benzyl group. Ki, Hue Represents a nyl group, an alkoxycarbonyl group or a tosyl group, represents a hydrogen atom, an alkyl group or a benzyl group. )
( 1 1 ) Qが縮合ォキサゾ一ルー 2—ィルの誘導体は、 下記反応式のようにして合 成される。 (11) A derivative in which Q is a condensed oxazolyl-2-yl is synthesized according to the following reaction formula.
Figure imgf000020_0001
Figure imgf000020_0001
NaOL; L2=Halogen NaOL ; L 2 = Halogen
or i tro  or i tro
Figure imgf000020_0002
Figure imgf000020_0002
(式中、 X、 L 2 及び L:, は前記と同じ意味を表し、 y l5は水素原子、 アルキル 基又はハロゲン原子を表す。 ） (Wherein, X, L 2 and L : , have the same meaning as described above, and y 15 represents a hydrogen atom, an alkyl group or a halogen atom.)
尚、 ォキサゾール誘導体の製造法に関する著害としては多数あるが、 " H e t e r o c y c l i c C omp o u n d s " 4 5巻、 I . J. T u r c h i編集、 J Although there are many harmful effects on the production method of oxazole derivatives, "Heteroc ycli cC omp oun ds" Vol. 45, edited by I.J.Turchhi, J.
0 H N W I L EY, N. Y. 発行 （ 1 9 8 6年） 及び、 " H e t e r o c y c l0 H NW I LEY, N.Y. issued (1996) and "Het e r o c y c l
1 c C omp o u n d s " R. C. E l d e r f i e l d編集、 W I L EY. N . Y. 発行、 5巻、 2 9 8〜4 5 1ページ （ 1 9 5 7年） に記載の方法、 文献を参 考にすることができる。 ( 1 2 ) イ ソォキサゾリ ン— 3—ィル体、 イ ソォキサゾリ ン— 5—ィル体、 イ ソォ キサゾ一ルー 3 -ィル体及びィソォキサゾ一ルー 5—ィル体は 下記反応式のよう にして合成される。 1 c C om pounds "Edited by RC Elderfield, published by WIL EY. N.Y., Vol. 5, pp. 298-451 (1957). Can be. (1 2) Isoxozolin-3-yl, Isosazozolin-5-yl, Isosoxazo-1-3-yl and Isosazozol-1-5-yl, as shown in the following reaction formula. Synthesized.
Figure imgf000021_0001
Figure imgf000021_0001
ィ ソォキサゾリ ンー 3—ィル体とイ ソォキサゾリ ンー 5—ィル体の混合物はク口 マ トグラフィ 一や再結晶により、 容易に分離できる。  A mixture of the isoxazolin-3-yl and the isoxazolin-5-yl forms can be easily separated by mouth chromatography or recrystallization.
( 1 3 ) Qがィソォキサゾールー 4一ィルの誘導体は、 薬学雑誌、 7 9巻、 6 2 3 ページ （ 1 9 5 9年） 記載の方法を参考にして合成される。 (13) The derivative where Q isisoxazole-41-yl is synthesized with reference to the method described in Pharmaceutical Journal, Vol. 79, p. 623 (1959).
0CH3
Figure imgf000021_0002
0CH 3
Figure imgf000021_0002
[43] [44]  [43] [44]
Figure imgf000021_0003
Figure imgf000021_0003
[45] (式中、 y 16は水素原子、 アルキル基又はフヱニル基を表す。 ) あるいは、 ベンゾフランとヒ ドロキシルアミ ンとをアルコール中、 2 5〜 8 0 てで 0. 5〜 8時間反応させることにより得ることが出来る。 [45] (In the formula, y 16 represents a hydrogen atom, an alkyl group or a phenyl group.) Alternatively, it can be obtained by reacting benzofuran and hydroxylamine with alcohol at 25 to 80 for 0.5 to 8 hours. Can be done.
Figure imgf000022_0001
Figure imgf000022_0001
( 1 4 ) <3カく 1 , 2. 4—ォキサジァゾール— 5—ィルの誘導体は、 下記反応式 のようにして合成される。 (14) <3, 1,2.4-oxaziazol-5-yl derivative is synthesized according to the following reaction formula.
Figure imgf000022_0002
Figure imgf000022_0002
NaOL5 し 2=Halogen NaOL 5 2 = Halogen
or Nitro  or Nitro
Figure imgf000022_0003
Figure imgf000022_0003
(式中、 y l 7は水素原子、 アルキル基、 ベンジル基、 ァリール基、 ハロアルキル基 . アルコキシアルキル基又はアルキルチオアルキル基を表し、 X、 L , 、 L 2 又は L は前記と同じ意味を表す。 ） (In the formula, y 17 is a hydrogen atom, an alkyl group, a benzyl group, an aryl group, a haloalkyl group. An alkoxyalkyl group or an alkylthioalkyl group is represented by X, L,, L 2 or L represents the same meaning as described above. )
( 1 5 ) <3が 1 , 2, 4 _ォキサジァゾ一ルー 3—ィルの誘導体は、 下記反応式の ようにして合成される。
Figure imgf000023_0001
A derivative of (1,5) <3, in which 1,2,4-oxoxadiazole-3-yl is synthesized according to the following reaction formula.
Figure imgf000023_0001
NaOL3 L2=Halogen NaOL 3 L 2 = Halogen
or Ni tro  or Ni tro
Figure imgf000023_0002
Figure imgf000023_0002
( 1 6 ) Qがピラゾールー 4—ィルの誘導体は下記反応式のようにして合成され る。(16) A derivative in which Q is pyrazole-4-yl is synthesized according to the following reaction formula.
Figure imgf000023_0003
Figure imgf000023_0003
[46] [3b' ]  [46] [3b ']
(式中、 y 3 は前記と同じ意味を表す。 ） ( 1 7 ) Qがピロ一ルー 2 ―ィルの誘導体は、 下記反応式のようにして合成され る。 (Wherein, y 3 represents the same meaning as described above.) (17) A derivative in which Q is pyrol-2-yl is synthesized according to the following reaction formula.
Figure imgf000024_0001
Figure imgf000024_0001
[51] [52] [53]  [51] [52] [53]
Figure imgf000024_0002
Figure imgf000024_0002
[3c，]  [3c,]
(式中、 y 18及び y l 9はシァノ基、 アルコキシカルボニル基又はフヱニル基を表 し、 X及び L2 は前記と同じ意味を表す。 ） (Wherein, y 18 and y l 9 is Shiano group, an alkoxycarbonyl group, or to display the Fuweniru group, X and L 2 are as defined above.)
( 1 8 ) Qが 3—ピリダジノ ン— 6 —ィルの誘導体は下記反応式のようにして合成 される。 (18) A derivative of 3-pyridazinone-6-yl Q is synthesized according to the following reaction formula.
Figure imgf000024_0003
Figure imgf000024_0003
C3d'] また、 反応式 1における化合物 〔 3〕 において， Zが Sであるチォフエノール 誘導体は、 下記反応式に従って合成される。 C3d '] In the compound [3] in the reaction formula 1, the thiophenol derivative in which Z is S is synthesized according to the following reaction formula.
NMe:
Figure imgf000025_0001
NMe:
Figure imgf000025_0001
[3a] [67] [68]  [3a] [67] [68]
(式中、 X及び Qは前記と同じ意味を表し， L4 はハロゲン原子、 好ま しく はフ ッ素を表す） (Wherein X and Q have the same meanings as above, and L 4 represents a halogen atom, preferably fluorine)
上述のフエ ノール誘導体の合成法に準じた方法で製造する事の出来る、 一般式 [6 6] の化合物に硫化ナ ト リ ウムやチォゥレア等を反応させて、 化合物 [ 6 5 The compound of the formula [65] can be produced by a method similar to the above-mentioned phenol derivative synthesis method, by reacting a compound of the general formula [66] with sodium sulfide, thiourea or the like.
] を製造することが出来る。 この反応の参考文献と しては、 C h em i s t r y L e t t e r s、 1 3 0 7ページ （ 1 9 8 5年） が挙げられる。 ] Can be manufactured. References for this reaction include ChemistryL Letterrors, page 1307 (1989).
あるいは、 [6 5] は、 前述の化合物 [3 a ] を [6 7 ] に誘導した後、 J. Alternatively, [65] induced the aforementioned compound [3a] to [67], and then
O r g. C h em. 3 1巻， 3 9 8 0ページ （ 1 9 6 6年） に記載された、 ニュ 一マン転位反応により [6 8] と して、 これを加水分解する事によっても製造す ることが出来る。 Org. Chem. 31 Vol. 3, pp. 398 (1966), [68] by the Newman rearrangement reaction, and hydrolyzing this Can also be manufactured.
又、 ァニリ ン誘導体 [6 9] を O r g a n i c S y n t h e s e s C o l 1 e c t. 、 3卷、 8 0 9ページに記載の方法を応用しても、 [6 5] を製造す ることが出来る。 （式中、 L4 はハロゲンを表す。 ） [65] can also be produced by applying the aniline derivative [69] to the method described in Organic Synthesis Color 1 ect., Vol. 3, page 809. (In the formula, L 4 represents halogen.)
(製造法— 2 ) (Manufacturing method-2)
又、 次の方法によっても本発明化合物を製造することが出来る。 96/33994 The compound of the present invention can also be produced by the following method. 96/33994
Figure imgf000026_0001
Figure imgf000026_0001
(式中、 A、 R, 、 R 2 、 X、 Ζ及び Qは前記と同じ意味を表し、 Rは下記で表され るいずれかの基を表す。 ） (In the formula, A, R,, R 2, X, Ζ and Q have the same meanings as described above, and R represents any of the groups shown below.)
COL, COCHO CN CHO 0^ . H2 S ^ ΝΠ2 COL, COCHO CN CHO 0 ^. H 2 S ^ Ν Π2
Figure imgf000026_0002
即ち、 一般式 [5 5] で示される化合物と、 上記 [ 3] の製造法で示された、 適 当な縮合剤を反応させることにより [ 1 ] を製造する方法である。
Figure imgf000026_0002
That is, this is a method for producing [1] by reacting the compound represented by the general formula [55] with an appropriate condensing agent shown in the production method of the above [3].
a ) テ 卜ラゾール [ 1 a ] の製造法 a) Method for producing tetrazole [1a]
Figure imgf000027_0001
Figure imgf000027_0001
一般式 〔 5 6〕 で示される化合物とァジ化ナ トリ ゥムを適当な溶媒中、 好ま し く は DMFを用い、 室温〜溶媒の沸点未满の温度、 好ましく は 8 0〜 1 2 0 で 1 - 2 4時間反応させることにより製造される。  The compound represented by the general formula [56] and sodium azide are placed in a suitable solvent, preferably using DMF, at room temperature to a temperature not higher than the boiling point of the solvent, preferably 80 to 120. It is produced by reacting for 1-2 hours.
(以下、 式中、 R , 、 R2 、 A、 Z、 Xは前記の意味を示す。 ） b) ピロール [ l b] 、 [ l c] 、 [ I d] の製造法 (Hereinafter, in the formula, R, R 2 , A, Z, and X have the above-mentioned meanings.) B) Method for producing pyrrole [lb], [lc], [I d]
Figure imgf000027_0002
Figure imgf000027_0002
[57] [57]
Figure imgf000028_0001
Figure imgf000028_0001
[58]  [58]
Figure imgf000028_0002
Figure imgf000028_0002
—般式 〔 5 7〕 あるいは [ 5 8 ] で示される化合物と TosMIC等のィソシァ二 ド 類を、 適当な塩基の存在下、 溶媒中、 室温〜溶媒の沸点の温度範囲で 1〜 2 4時 間反応させることにより製造される。 この反応に用いられる溶媒と しては、 例え ば、 メ タノール、 エタノール、 イ ソプロパノール等のアル一コール類、 ベンゼン 、 トルエン等の芳香族炭化水素類、 ジクロロメタン、 クロ口ホルム等のハロゲン 化炭化水素類、 ジェチルエーテル、 TH F等のエーテル類、 アセ ト ン、 MEK等 のケ 卜ン類、 酢酸メチル、 酢酸ェチル等のエステル類、 DMF、 DMS O等の非 プロ ト ン性極性溶媒、 ァセ トニ ト リル、 水等が挙げられる。 又、 この反応に用い られる塩基と しては、 炭酸ナ 卜 リ ゥム、 炭酸力リゥム等の炭酸塩類、 水酸化ナ 卜 リゥム、 水酸化力リゥ厶等の水酸化金属類、 ナ ト リ ウムメチラー 卜、 ナ ト リ ウム ェチラー 卜等の金属アルコラ一 卜類、 水素化ナ ト リ ウム、 水素化力 リゥム等の水 素化金属類、 リチウムジイソプロピルァミ ド、 リチウムピス トリメチルシリルァ ミ ド等のリチウムァミ ド類、 卜リェチルァミ ン、 D B U等の有機塩基類等が挙げ られる。 c ) イ ミ ダゾール [ 1 e ] の製造法 —The compound of general formula [57] or [58] and an isocyanide such as TosMIC in a solvent in the presence of an appropriate base in a solvent at a temperature ranging from room temperature to the boiling point of the solvent for 1 to 24 hours. It is manufactured by reacting for a while. Examples of the solvent used in this reaction include alcohols such as methanol, ethanol and isopropanol, aromatic hydrocarbons such as benzene and toluene, and halogenated carbons such as dichloromethane and chloroform. Hydrogens, ethers such as getyl ether and THF, ketones such as acetone and MEK, esters such as methyl acetate and ethyl acetate, non-protonic polar solvents such as DMF and DMS O, Acetonitrile, water and the like. Examples of the base used in this reaction include carbonates such as sodium carbonate and carbonated carbonate, metal hydroxides such as sodium hydroxide and hydroxylated phosphate, and sodium methyler. Metal alcohols such as sodium and sodium ethyl ethers, sodium hydride, metal hydrides such as hydrogen hydride, lithium amides such as lithium diisopropylamide, lithium pistrimethylsilyl amide, etc. And organic bases such as triethylamine, DBU and the like. c) Method for producing imidazole [1 e]
Figure imgf000029_0001
文献公知の方法に従い、 一般式 〔 5 9〕 で示される化合物と TosM I Cを適当な塩 基の存在下、 適当な溶媒中、 室温〜溶媒の沸点未満の温度で 1 ~ 2 4時間反応さ せることにより製造される。
Figure imgf000029_0001
The compound represented by the general formula [59] is reacted with TosMIC in a suitable solvent in a suitable solvent at a temperature from room temperature to a temperature lower than the boiling point of the solvent for 1 to 24 hours according to a method known in the literature. It is manufactured by
この反応に用いられる溶媒と しては、 例えば、 メ タノール、 エタノール、 イソ プロパノール等のアルコール類、 ベンゼン、 トルエン等の芳香族炭化水素類、 ジ クロロメタン、 クロ口ホルム等のハロゲン化炭化水素類、 ジェチルエーテル、 T H F等のエーテル類、 アセ ト ン、 M E K等のケ ト ン類、 酢酸メチル、 酢酸ェチル 等のエステル類、 D M F、 D M S 0等の非プロ ト ン性極性溶媒、 ァセ トニ ト リ ル 、 水等が挙げられる。 又、 この反応に用いられる塩基としては、 炭酸ナ ト リ ウム 、 炭酸力リゥム等の炭酸塩類、 水酸化ナ ト リ ウム、 水酸化力リゥム等の水酸化金 属類、 ナ ト リ ウムメチラー ト、 ナ ト リ ウムェチラー 卜等の金属アルコラ一 卜類、 水素化ナ ト リ ウム、 水素化カリ ウム等の水素化金属類、 リチウムジイソプロピル ア ミ ド、 リチウムピス ト リ メチルシ リルア ミ ド等のリチウムア ミ ド類、 ト リェチ ルァミ ン、 D B U等の有機塩基類等が挙げられる。 Examples of the solvent used in this reaction include alcohols such as methanol, ethanol, and isopropanol; aromatic hydrocarbons such as benzene and toluene; and halogenated hydrocarbons such as dichloromethane and chloroform. Ethers such as, dimethyl ether, THF, etc., ketones such as aceton, MEK, esters such as methyl acetate, ethyl acetate, etc., non-protonic polar solvents such as DMF, DMS 0, etc. Trill, water and the like can be mentioned. Examples of the base used in this reaction include sodium carbonate, carbonates such as carbonated lime, sodium hydroxide, metal hydroxides such as hydroxylated lime, sodium methylate, and the like. Metal alcoholates such as sodium ethylate; metal hydrides such as sodium hydride and potassium hydride; lithium amides such as lithium diisopropyl amide and lithium p-methylsilyl amide And organic bases such as triethylamine, DBU and the like.
d ) ピラゾロン [ 1 f ] の製造法 d) Preparation of pyrazolone [1 f]
Figure imgf000030_0001
Figure imgf000030_0001
—般式 〔 6 0〕 で示される化合物とヒ ドラジン類を適当な塩基の存在下、 若し くは非存在下、 適当な溶媒中、 室温〜溶媒の沸点未満の温度で 1〜 2 4時間反応 させることにより製造される。 この反応に用いられる溶媒と しては、 例えば、 メ タ ノ一ル、 エタノール、 イ ソプロパノール等のアルコール類、 ベンゼン、 トルェ ン等の芳香族炭化水素類、 ジクロロメ タ ン、 クロ口ホルム等のハロゲン化炭化水 素類、 ジェチルエーテル、 T H F等のエーテル類、 アセ ト ン、 M E K等のケ 卜ン 類、 酢酸メチル、 酢酸ェチル等のエステル類、 D M F、 D M S O等の非プロ トン 性極性溶媒、 ァセ 卜二 ト リル、 水等が挙げられる。 又、 この反応に用いられる塩 基と しては、 炭酸ナ ト リウム、 炭酸力リ ゥム等の炭酸塩類、 水酸化ナ ト リ ゥム、 水酸化カ リ ウム等の水酸化金属類、 ナ ト リウムメチラー 卜、 ナ ト リ ウムェチラー 卜等の金属アルコラー ト類、 水素化ナ ト リ ウム、 水素化カ リ ウム等の水素化金属 類、 リチウムジイソプロピルアミ ド、 リチウムピス ト リメチルシリルアミ ド等の リチウムアミ ド類、 卜 リエチルァミ ン、 D B U等の有機塩基類等が挙げられる。 —The compound of the formula [60] and hydrazines are reacted in the presence or absence of a suitable base in a suitable solvent at a temperature from room temperature to a temperature lower than the boiling point of the solvent for 1 to 24 hours. It is produced by reacting. Solvents used in this reaction include, for example, alcohols such as methanol, ethanol, and isopropanol; aromatic hydrocarbons such as benzene and toluene; dichloromethane; Halogenated hydrocarbons, ethers such as getyl ether and THF, ketones such as acetone and MEK, esters such as methyl acetate and ethyl acetate, and non-protonic polar solvents such as DMF and DMSO , Acetonitrile, water and the like. Examples of the base used in this reaction include carbonates such as sodium carbonate and carbonated carbonate, metal hydroxides such as sodium hydroxide and potassium hydroxide, and sodium hydroxide. Metal alcoholates such as sodium methylate and sodium ethylate; metal hydrides such as sodium hydride and potassium hydride; lithium such as lithium diisopropylamide and lithium pristylmethylsilyl amide Examples include amides, triethylamine, and organic bases such as DBU.
e ) チアゾ一ル [ 1 g] の製造法 e) Preparation of thiazole [1 g]
Figure imgf000031_0001
Figure imgf000031_0001
—般式 〔6 1〕 で示される化合物とプロモケ ト ン [ 1 5] を適当な塩基の存在 下、 若しく は非存在下、 適当な溶媒中、 室温〜溶媒の沸点未満の温度で 〜 2 4 時間反応させることにより製造される。 この反応に用いられる溶媒と しては、 例 えば、 メ タ ノール、 エタ ノール、 イソプロノ、。ノール等のアルコール類、 ベンゼン 、 トルエン等の芳香族炭化水素類、 ジクロロメ タン、 クロ口ホルム等のハロゲン 化炭化水素類、 ジェチルエーテル、 THF等のエーテル類、 アセ ト ン、 MEK等 のケ ト ン類、 酢酸メチル、 酢酸ェチル等のエステル類、 DMF、 DMSO等の非 プロ ト ン性極性溶媒、 ァセ トニ 卜 リル等が挙げられる。 又、 この反応に用いられ る塩基としては、 炭酸ナ ト リ ウム、 炭酸力リ ゥム等の炭酸塩類、 水酸化ナ 卜 リ ゥ ム、 水酸化力 リ ゥム等の水酸化金属類、 ナ ト リ ウムメチラー ト、 ナ 卜 リ ゥムェチ ラー ト等の金属アルコラ一 卜類、 水素化ナト リ ウム、 水素化力リ ゥ厶等の水素化 金属類、 リチウムジイソプロピルア ミ ド等のリチウムア ミ ド類、 卜 リエチルア ミ ン、 D B U等の有機塩基類等が挙げられる。 —The compound represented by the general formula [61] and the promoter [15] are reacted with a suitable base in the presence or absence of a suitable base in a suitable solvent at a temperature from room temperature to a temperature lower than the boiling point of the solvent. Manufactured by reacting for 4 hours. Examples of the solvent used for this reaction include methanol, ethanol, and isoprono. Alcohols such as ethanol, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane and chloroform, ethers such as getyl ether and THF, and ketones such as acetate and MEK. And esters such as methyl acetate and ethyl acetate; non-protonic polar solvents such as DMF and DMSO; and acetonitrile. Examples of the base used in this reaction include sodium carbonate, carbonate carbonate and the like, sodium hydroxide, hydroxide hydroxide and the like, and metal hydroxide. Metal alcohols such as sodium methylate and sodium permethylate; metal hydrides such as sodium hydride and hydrogen hydride; lithium amides such as lithium diisopropylamide; Organic bases such as triethylamine and DBU are exemplified.
f ) ォキサゾ一ル [ 1 h ] の製造法 f) Production method of oxazole [1h]
Figure imgf000032_0001
Figure imgf000032_0001
—般式 〔 6 2〕 で示されるアルデヒ ドとイソ二ト リル [ 3 7 ] をアルデヒ ドに 対して 2等 S以上の適当な塩基の存在下、 適当な溶媒中、 室温〜溶媒の沸点未満 の温度で 1 ~ 2 4時間反応させることにより製造される。 この反応に用いられる 溶媒と しては、 例えば、 メタノール、 エタノール、 イソプロパノール等のアルコ —ル類、 ベンゼン、 トルエン等の芳香族炭化水素類、 ジクロロメタン、 クロロホ ルム等のハロゲン化炭化水素類、 ジェチルエーテル、 T H F等のエーテル類、 D M F、 D M S 0等の非プロ 卜ン性極性溶媒、 ァセ トニトリル等が挙げられる。 又 、 この反応に用いられる塩基と しては、 炭酸ナ ト リ ウム、 炭酸カリ ウム等の炭酸 塩類、 水酸化ナト リ ウム、 水酸化力リ ゥム等の水酸化金属類、 ナ ト リウムメチラ 一卜、 ナ ト リウムェチラー 卜等の金属アルコラ一卜類、 水素化ナ ト リウム、 水素 化カリ ウム等の水素化金属類、 リチウムジイソプロピルアミ ド、 リチウムピス ト リ メチルシリルァミ ド等のリチウムアミ ド類、 卜 リェチルァミ ン、 D B U等の有 機塩基類等が挙げられる。 ) ォキサゾ一ル [ 1 i ] の製造法 —The aldehyde represented by the general formula [62] and isonitrile [37] are compared to the aldehyde in the presence of a suitable base of at least 2 S in a suitable solvent at room temperature to below the boiling point of the solvent. It is produced by reacting at a temperature of 1 to 24 hours. Examples of the solvent used in this reaction include alcohols such as methanol, ethanol and isopropanol, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane and chloroform, and getyl. Ethers such as ether and THF; non-protonic polar solvents such as DMF and DMS 0; and acetonitrile. Examples of the base used in this reaction include carbonates such as sodium carbonate and potassium carbonate, metal hydroxides such as sodium hydroxide and hydroxylating water, and sodium methylate. Metal alcohols such as sodium and sodium ethyl ethers; metal hydrides such as sodium hydride and potassium hydride; lithium amides such as lithium diisopropyl amide and lithium p-methylsilyl amide; And organic bases such as DBU. ) Production method of oxazole [1 i]
Figure imgf000033_0001
Figure imgf000033_0001
—般式 〔 6 3〕 で示されるァシルイ ミ ダゾールとィソニト リル類を適当な塩基 の存在下、 適当な溶媒中、 一 7 8 ~ 8 0 °Cの温度で 1〜 2 4時間反応させること により [ 1 i ] が製造される。 この反応に用いられる溶媒と しては、 例えば、 ベ ンゼン、 トルエン等の芳香族炭化水素類、 ジクロロメタン、 クロ口ホルム等のハ ロゲン化炭化水素類、 ジェチルエーテル、 T H F等のエーテル類、 D M F、 D M S O等の非プロ トン性極性溶媒、 ァセ トニ ト リル等が挙げられる。 又、 この反応 に用いられる塩基と しては、 炭酸ナ 卜 リゥ厶、 炭酸力リゥム等の炭酸塩類、 水酸 化ナ ト リウム、 水酸化力リ ゥム等の水酸化金属類、 水素化ナ ト リ ウム、 水素化力 リ ウム等の水素化金属類、 リチウムジイソプロピルアミ ド、 リチウムピス ト リメ チルシリルァミ ド等のリチウムア ミ ド類、 卜 リェチルァミ ン、 D B U等の有機塩 基類等が挙げられる。 — By reacting the acylimidazole represented by the general formula [63] with isonitriles in a suitable solvent in a suitable solvent at a temperature of 178 to 80 ° C for 1 to 24 hours. [1 i] is manufactured. Examples of the solvent used in this reaction include aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane and chloroform, ethers such as getyl ether and THF, and DMF. And non-protonic polar solvents such as DMSO and acetonitril. Examples of the base used in this reaction include carbonates such as sodium carbonate and carbon dioxide, metal hydroxides such as sodium hydroxide and hydroxyladium, and sodium hydride. Examples include metal hydrides such as tritium and hydrogen hydride, lithium amides such as lithium diisopropylamide and lithium p-trimethylsilyl amide, and organic salts such as triethylamine and DBU.
h ) ォキサゾリ ン [ 1 j ] の製造法 h) Method for producing oxazoline [1j]
Figure imgf000034_0001
Figure imgf000034_0001
—般式 〔 6 2〕 で示されるアルデヒ ドとイソ二卜 リル [ 3 7 ] をアルデヒ ドに 対してほぼ等量の適当な塩基の存在下、 適当な溶媒中、 0て〜室温の温度で 1 ~ —The aldehyde represented by the general formula [62] and isonitrile [37] are reacted with an aldehyde at a temperature of 0 to room temperature in a suitable solvent in the presence of a nearly equivalent amount of a suitable base. 1 to
2時間反応させることにより [ 1 j ] が製造される。 この反応に用いられる溶媒 としては、 例えば、 メタノール、 エタノール、 イソプロノ、。ノール等のアルコール 類、 ベンゼン、 トルエン等の芳香族炭化水素類、 ジクロロメ タ ン、 クロ口ホルム 等のハロゲン化炭化水素類、 ジェチルエーテル、 TH F等のエーテル類、 DMF 、 DMS 0等の非プロ トン性極性溶媒、 ァセ トニト リル等が挙げられる。 又、 こ の反応に用いられる塩基と しては、 炭酸ナ 卜 リゥム、 炭酸力リゥム等の炭酸塩類 、 水酸化ナ ト リ ウム、 水酸化力リ ゥム等の水酸化金属類、 水素化ナ ト リ ウム、 水 素化カリウム等の水素化金属類、 リチウムジイ ソプロピルアミ ド、 リチウムビス 卜 リ メチルシリルアミ ド等のリチウムアミ ド類、 卜 リエチルァミ ン、 D B U等の 有機塩基類等が挙げられる。 [1j] is produced by reacting for 2 hours. Examples of the solvent used for this reaction include methanol, ethanol, and isoprono. Alcohols such as ethanol, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane and chloroform, ethers such as getyl ether and THF, and non-hydrocarbons such as DMF and DMS0. Examples include protonic polar solvents and acetonitril. Examples of the base used in this reaction include carbonates such as sodium carbonate and carbonated carbonate, metal hydroxides such as sodium hydroxide and hydroxylated phosphate, and sodium hydride. Examples include metal hydrides such as tritium and potassium hydride, lithium amides such as lithium diisopropyl amide and lithium bistrimethylsilyl amide, and organic bases such as triethylamine and DBU.
i ) ォキサジァゾ一ル [ l k] の製造法 i) Production process of oxaziazole [lk]
Figure imgf000035_0001
一般式 〔6 3〕 で示されるァシルイ ミ ダゾールとァミ ドキシ厶 [ 4 7 ] を適当 な塩基の存在下、 適当な溶媒中、 一 1 5 ~ 1 4 0ての温度で 1〜 2 4時間反応さ せることにより [ l k] が製造される。 この反応に用いられる溶媒と しては、 例 えば、 ベンゼン、 トルエン等の芳香族炭化水素類、 ジクロロメタン、 クロ口ホル ム等のハロゲン化炭化水素類、 ジェチルエーテル、 THF等のエーテル類、 DM F、 DMS O等の非プロ 卜ン性極性溶媒、 ァセ トニ ト リル等が挙げられる。 又、 この反応に用いられる塩基としては、 炭酸ナ 卜 リゥム、 炭酸力リゥム等の炭酸塩 類、 水酸化ナ ト リ ウム、 水酸化力リ ゥム等の水酸化金属類、 水素化ナ ト リ ウム、 水素化カリ ウム等の水素化金属類、 リチウムジイソプロピルアミ ド等のリチウム アミ ド類、 卜 リエチルァミ ン、 D B U等の有機塩基類等が挙げられる。 R
Figure imgf000035_0001
The acylimidazole represented by the general formula [63] and the amide oxime [47] are reacted in a suitable solvent in the presence of a suitable base at a temperature of 115 to 140 for 1 to 24 hours. The reaction produces [lk]. Examples of the solvent used in this reaction include aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as dichloromethane and chloroform; ethers such as getyl ether and THF; Non-protonic polar solvents such as F and DMSO, acetonitrile, and the like. Bases used in this reaction include carbonates such as sodium carbonate and carbonated carbonate, metal hydroxides such as sodium hydroxide and hydroxylated phosphate, and sodium hydride. Metal hydrides such as potassium and potassium hydride; lithium amides such as lithium diisopropylamide; and organic bases such as triethylamine and DBU. R
(製造法一 3 ) (Production method 3)
Figure imgf000035_0002
Figure imgf000035_0002
(式中、 、 R2 、 A、 Q、 X、 Zは前記と同じ意味を表し、 Q' 、 X' はそ れぞれ Q、 Xと同意味を示す。 ） —般式 〔 〕 で示される化合物を、 文献公知の方法に従い、 適当な塩基、 も しく は酸の存在下、 無溶媒叉は適当な溶媒中、 - 7 8て〜溶媒の沸点未満の温度 で、 適当な試剤 （例えば、 ヨウ化メチル等のアルキル化剤、 ァセチルクロリ ドの ようなァシル化剤、 メタンスルホニルクロリ ドのようなスルホ二ル化剤等） と、 1〜2 4時間反応させ、 ヘテロ環 Q上の置換基もしく はベンゼン環上の置換基 X ' を変換して [ 1 ] を合成する。 a ) ォキサゾリ ン (Wherein, R 2 , A, Q, X, and Z have the same meanings as described above, and Q ′ and X ′ have the same meanings as Q and X, respectively.) The compound represented by the general formula [] can be prepared by a method known in the literature, in the presence of a suitable base or acid, without a solvent or in a suitable solvent, at a temperature lower than the boiling point of the solvent. Reacting with an appropriate reagent (eg, an alkylating agent such as methyl iodide, an acylating agent such as acetyl chloride, a sulfonylating agent such as methanesulfonyl chloride) for 1 to 24 hours, [1] is synthesized by converting the substituent on ring Q or the substituent X 'on the benzene ring. a) Oxazoline
Figure imgf000036_0001
Figure imgf000036_0001
(式中、 Z2 は酸素、 硫黄を表し、 y22はアルキル、 ァリールを表し、 y l 4は前 記と同じ意味を表す。 ） (In the formula, Z 2 represents oxygen or sulfur, y 22 represents alkyl or aryl, and yl 4 has the same meaning as described above.)
—般式 [ 1 j ] の化合物と [ 6 4 ] を適当な塩基の存在下、 適当な溶媒中、 - 1 5 - 2 5 °Cの温度で 1〜 2 4時間反応させることにより [ 1 1 ] が製造される 。 この反応に用いられる溶媒としては、 例えば、 メタノール、 エタノール、 イソ プロパノール等のアルコール類、 ベンゼン、 トルエン等の芳香族炭化水素類、 ジ クロロメ タ ン、 クロ口ホルム等のハロゲン化炭化水素類、 ジェチルエーテル、 T H F等のエーテル類、 アセ トン、 ME K等のケ トン類、 酢酸メチル、 酢酸ェチル 等のエステル類、 DMF、 DMS 0等の非プロ トン性極性溶媒、 ァセ 卜二 卜リル 、 水等が挙げられる。 又、 この反応に用いられる塩基としては、 炭酸ナ ト リ ウム 、 炭酸カリ ウム等の炭酸塩類、 水酸化ナ ト リ ウム、 水酸化カリ ウム等の水酸化金 厲類、 ナ ト リ ウムメチラー ト、 ナ ト リ ウムェチラー ト等の金属アルコラ一卜類、 水素化ナ ト リ ウム、 水素化カ リ ウム等の水素化金属類、 リチウムジイソプロピル アミ ド、 リチウムビス 卜 リ メチルシ リ ルア ミ ド等のリチウムア ミ ド類、 卜 リエチ ルァミ ン、 D B U等の有機塩基類等が挙げられる。 —Reaction of the compound of the general formula [1j] with [64] in the presence of a suitable base in a suitable solvent at a temperature of −15 to 25 ° C. for 1 to 24 hours yields [11 1 ] Is manufactured. Examples of the solvent used in this reaction include alcohols such as methanol, ethanol, and isopropanol; aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as dichloromethane and chloroform; Ethers such as tyl ether and THF; ketones such as acetone and MEK; esters such as methyl acetate and ethyl acetate; non-protonic polar solvents such as DMF and DMS 0; Water and the like. Examples of the base used in this reaction include carbonates such as sodium carbonate and potassium carbonate, gold hydroxides such as sodium hydroxide and potassium hydroxide, sodium methylate, and the like. Metal alcohols such as sodium ethylate; metal hydrides such as sodium hydride and potassium hydride; lithium diisopropyl Examples thereof include lithium amides such as amide and lithium bistrimethylsilyl amide, and organic bases such as triethylamine and DBU.
(製造法一 4 ) (Production method 4)
Figure imgf000037_0001
一般式 [ 7 0 ] (式中、 R, 、 R2 、 A、 Zは前記と同じ意味を表す。 ） の化 合物と、 一般式 [ 6 6 ] (式中、 Q、 X、 Y、 n、 L , は前記と同じ意味を表す 。 ） の化合物を、 有機溶媒中で塩基の存在下カップリ ングさせる。 塩基と しては 、 水素化ナ 卜 リゥム等の水素化金属類、 炭酸力リゥム等の炭酸塩類、 卜 リェチル Ύミ ン等の有機塩基類であり、 溶媒としては、 DMF、 DMS O、 TH F、 DM E等が挙げられる。 反応混合物は反応が完了するまで、 0〜9 0 °C、 場合によつ ては 1 2 0てで撹拌される。 本発明化合物の構造は、 I R, NMR、 MS等から決定した。 実施例 ：
Figure imgf000037_0001
A compound of the general formula [70] (wherein R,, R 2 , A and Z represent the same meaning as described above); and a compound of the general formula [66] (wherein Q, X, Y n, L, have the same meaning as described above.)) The compound is coupled in an organic solvent in the presence of a base. Examples of the base include metal hydrides such as hydrogenated sodium, carbonates such as carbonated lime, and organic bases such as triethylamine. Examples of the solvent include DMF, DMS O, and THF. , DME and the like. The reaction mixture is stirred at 0-90 ° C., possibly at 120 ° C., until the reaction is complete. The structure of the compound of the present invention was determined from IR, NMR, MS and the like. Example :
以下、 本発明を実施例によりさらに詳細に説明する。  Hereinafter, the present invention will be described in more detail with reference to Examples.
実施例 1 Example 1
2— [ 2— ( 4 , 6 —ジメ 卜キシー 2—ピリ ミ ジルォキシ） 一 6— （ 4 —モルホ リ ノ） フエニル] テ トラヒ ドロべンズォキサゾール （化合物 2— 5 ) の合成 Synthesis of 2— [2— (4,6—Dimethoxy-2-pyrimidyloxy) -1 6— (4—morpholino) phenyl] tetrahydrobenzoxazole (Compound 2—5)
Figure imgf000038_0001
Figure imgf000038_0001
2 — 〔 2 — ヒ ドロキシー 6— ( 4 —モルホリ ノ） フヱニル〕 テ 卜ラ ヒ ドロベン ズォキサゾ一ル 4 0 m g、 4 , 6—ジメ トキシ _ 2 —メ タ ンスルホニルピリ ミ ジン 3 2 m g、 及び炭酸カ リ ウム 5 5 m gの DMF ( 1 m 1 ) 混合物を 8 0 てで 4時間撹拌した。 反応後、 水を加え、 次いで酢酸ェチルで抽出した。 有機雇 を水洗、 飽和食塩水で洗浄、 次いで無水硫酸マグネシウムで乾燥した。 溶媒を减 圧下留去し、 得られた残留物をカラムクロマ ト （シリカゲル ； 溶出液 へキサン 一酢酸ェチル = 1 一 1 ) で精製し目的物 5 0 mg、 mp - 1 5 4 — 6 °Cを得た 実施例 2 2— [2—Hydroxy 6— (4—morpholino) phenyl] tetrahydrobenzobenzoxazole 40 mg, 4,6-dimethoxy_2-2-methansulfonylpyrimidine 32 mg, and A mixture of 55 mg of potassium carbonate and DMF (1 m 1) was stirred at 80 ° C. for 4 hours. After the reaction, water was added, followed by extraction with ethyl acetate. The organic layer was washed with water, saturated saline, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by column chromatography (silica gel; eluent hexane / monoethyl acetate = 11/11) to give 50 mg of the desired product, mp-154--6 ° C. Example 2 obtained
2 - [ 2 — ( 4 , 6 —ジメ トキシ一 2 —ピリ ミ ジルォキシ） 一 6 — (N. N—ジ ェチルァミ ノ） フヱニル] テ 卜ラヒ ドロベンズォキサゾ一ル （化合物番号 1 一 2 ) の合成  2-[2 — (4, 6-dimethoxy- 1 2-pyrimidyloxy) 1-6-(NN-diethylamino) phenyl] tetrahydrodrobenzaxazol (Compound No. 1-2) Synthesis of
Figure imgf000038_0002
Figure imgf000038_0002
OMe  OMe
2 - 〔 2 — ヒ ドロキシー 6— （N, N—ジェチルァ ミ ノ） フエニル〕 テ トラヒ ドロべンズォキサゾール 1 1 0 mg、 4. 6—ジメ トキシー 2 —メ タンスルホ ニルピリ ミ ジン 8 4 m g、 及び炭酸カ リ ウム 1 0 6012の01^ （ 1 1 〉 混合物を 6 0 °Cで 1 5時間撹拌した。 反応後、 水を加え、 次いで酢酸ェチルで抽 出した。 有機層を水洗、 飽和食塩水で洗浄、 次いで無水硫酸マグネシウムで乾燥 した。 溶媒を'减圧下留去し、 得られた残留物をカラムクロマ 卜 （シ リ力ゲル ； 溶 出液 へキサン一酢酸ェチル = 3 — 1 ) で精製し目的物 7 0 m gを得た。 上記実施例を含め本発明の化合物の代表例を以下の第 1表〜第 9表に示す。 2-[2-Hydroxy 6-(N, N-getylamino) phenyl] Tetrahi-Drobenzoxazole 110 mg, 4.6-Dimethoxy 2-methanesulfo A mixture of 84 mg of nilpyrimidine and 01 ^ (11) of potassium carbonate 10602 was stirred for 15 hours at 60 ° C. After the reaction, water was added, followed by extraction with ethyl acetate. The organic layer was washed with water, washed with saturated saline, and then dried over anhydrous magnesium sulfate.The solvent was distilled off under reduced pressure, and the obtained residue was subjected to column chromatography (silica gel; eluent hexane monoethyl acetate). = 3-1) to give 70 mg of the desired product Representative examples of the compounds of the present invention including the above Examples are shown in Tables 1 to 9 below.
Figure imgf000040_0001
Figure imgf000040_0001
*a物性値は融点、 もしくは屈折率o. X l 2 R3 yl y2 y3 y4 y5 y6 y7 y8 A l 物性値 *a-1 画 e OMeOMeH H H H H „ H H H CR30 123-5-2 NMeZ OHe OMe II H II 11 II II H II CR30 88-90-3 NEt2 OHe OHe H H H H H H II H CR30 1 5378(29)-4 N(n-Pr)2 OMe OHe )1 11 II II H 11 11 11 CR30 1 5448(29)-5 N(i-Pr)2 OHe OHe 11 H H H H II H 11 CR30* a Physical properties are melting point or refractive index o.X l 2 R3 yl y2 y3 y4 y5 y6 y7 y8 A l Physical properties * a-1 Drawing e OMeOMeH HHHH „HHH CR30 123-5-2 NMeZ OHe OMe II H II 11 II II H II CR30 88-90-3 NEt2 OHe OHe HHHHHH II H CR30 1 5378 (29) -4 N (n-Pr) 2 OMe OHe) 1 11 II II H 11 11 11 CR30 1 5448 (29)- 5 N (i-Pr) 2 OHe OHe 11 HHHH II H 11 CR30
-6 N(n-Bu)2 OMeOMeH H H H H H H H CR30-6 N (n-Bu) 2 OMeOMeH H H H H H H H CR30
-7 N(i-Bu)2 OMe OHe H II 11 11 H 11 II 11 CR30-7 N (i-Bu) 2 OMe OHe H II 11 11 H 11 II 11 CR30
-8 fi(n-Hex)2 OMeOMeH H H II 11 11 II II C 30-8 fi (n-Hex) 2 OMeOMeH H H II 11 11 II II C 30
-9 N(n-C8HI7)2 OMeOMeH H H H H 11 H H C 301 5198(27)-10 N(He)Et OMeOMeH H i( H 11 H H H C30-9 N (n-C8HI7) 2 OMeOMeH H H H H 11 H H C 301 5198 (27) -10 N (He) Et OMeOMeH Hi (H 11 H H H C30
-11 N(Me)CH20Me ONeOHeH H H H II H H H H C 30-11 N (Me) CH20Me ONeOHeH H H H II H H H H C 30
-12 N(Me)Ph OMeOMeH H 11 H H H 11 H 11 C 30 119-120-13 N(Ne)Bn OMeOMeH H H H !1 H H 11 H CR30-12 N (Me) Ph OMeOMeH H 11 H H H 11 H 11 C 30 119-120 -13 N (Ne) Bn OMeOMeH H H H! 1 H H 11 H CR30
-14 N(Ne)CII0 OMeOMeH H H 11 II H H II II CR30-14 N (Ne) CII0 OMeOMeH H H 11 II H H II II CR30
-15 N(He)C0He OMeOMeH H H H 11 H 11 II H CR30 113-5-16 N(Me)C00Ne OMeOMeH H H H H H H H H CR30-15 N (He) C0He OMeOMeH H H H 11 H 11 II H CR30 113-5-16 N (Me) C00Ne OMeOMeH H H H H H H H H CR30
-17 N(Me)C0Ph OMeOMeH 11 H II H H II H H C 30 第 1 表 (統き） -17 N (Me) C0Ph OMeOMeH 11 H II HH II HHC 30 Table 1 (Guide)
No. X Rl 2 R3 yl yl v3 y5 y6 y8 A Z 物性値 *a No. X Rl 2 R3 yl yl v3 y5 y6 y8 A Z Physical properties * a
1-18 NHe2 OHe OHe H He H H H H H H H CR30 卜 19 NMeZ OMe OHe H H H H H H H H CR30 卜 20 NHe2 OHe OHe H H H H H He H H H CR30 1-18 NHe2 OHe OHe H He H H H H H H H H CR30 No. 19 NMeZ OMe OHe H H H H H H H H CR30 No. 20 NHe2 OHe OHe H H H H H He H H H CR30
1-21 NHe2 OMe OHe H H H H H H H Me H CR30  1-21 NHe2 OMe OHe H H H H H H H Me Me H CR30
1-22 NMe2 OMe OMe H Me Me H H H H H CR30  1-22 NMe2 OMe OMe H Me Me H H H H H CR30
1-23 NHe2 OHe OHe H H H Up Up H H H H CR30  1-23 NHe2 OHe OHe H H H Up Up H H H H CR30
1-24 NMe2 OMeOKeH H H H He Me H H CR30  1-24 NMe2 OMeOKeH H H H He Me H H CR30
1-25 NMe2 OMe OMe H H H H H H Ne Me C 30  1-25 NMe2 OMe OMe H H H H H H Ne Me C 30
1-26 NMe2 OHe OMe H Et H H H H H H H CR30  1-26 NMe2 OHe OMe H Et H H H H H H H CR30
1-27 NMe2 OMe OHe H H H Et H H H H H CR30  1-27 NMe2 OMe OHe H H H Et H H H H H CR30
I -28 NMe2 OMe OHe H H H H H Et H H H C 30  I -28 NMe2 OMe OHe H H H H H Et H H H C 30
I - 29 NHe2 OMeOMe H H H H H H H Et H C 30  I-29 NHe2 OMeOMe H H H H H H H Et H C 30
1-30 NMe2 OMe OHe H i-Pr H H H H H Et H CR30  1-30 NMe2 OMe OHe Hi i-Pr H H H H H Et H CR30
I -31 NNeZ OHe OHe H H H i-Pr H H H II H CR30 卜 32 NMe2 OHe OMe H H H H H i-Pr H H H C 30  I -31 NNeZ OHe OHe H H H i-Pr H H H II H CR30 Table 32 NMe2 OHe OMe H H H H H i-Pr H H H C 30
I - 33 NMe2 OHe OHe H =0 H H H H H H CR30  I-33 NMe2 OHe OHe H = 0 H H H H H H CR30
1-34 NMe2 OHe OHe H H H =0 H H H H CR30  1-34 NMe2 OHe OHe H H H = 0 H H H H CR30
1 - 35 NHe2 OMe OHe H H H H H =0 H H CR30  1-35 NHe2 OMe OHe H H H H H = 0 H H CR30
1-36 NMe2 OHe OMe H H H H H H H =0 CR30  1-36 NMe2 OHe OMe H H H H H H H = 0 CR30
1-37 NMe2 OMe OHe K =0 H H Me H H H CR30  1-37 NMe2 OMe OHe K = 0 H H Me H H H CR30
1-38 NHe2 OMe OMe H H H =0 H H H H CR30  1-38 NHe2 OMe OMe H H H = 0 H H H H CR30
1-39 NHe2 OMeOMe H H H H H =0 H H CR30  1-39 NHe2 OMeOMe H H H H H = 0 H H CR30
1-40 NKe2 OMeOMe H =0 H H Ne Me H fl C 30  1-40 NKe2 OMeOMe H = 0 H H Ne Me H fl C 30
HI NMeZ OMeOMe H =0 Ne He H H H H C 30  HI NMeZ OMeOMe H = 0 Ne He H H H H C 30
I -42 NHe2 OMeOMe H Me H H H H H H H C 30  I -42 NHe2 OMeOMe H Me H H H H H H H C 30
I -43 NNe2 OMe OMe H H H Me H H H H H CR30 第 1 表 (統き) I -43 NNe2 OMe OMe HHH Me HHHHH CR30 Table 1 (Guide)
n t no DO  n t no DO
No. X Kl Ko yi i y3 y4 yo yo y* yo A Z 物性値 *a u u  No. X Kl Ko yi i y3 y4 yo yo y * yo A Z Physical properties * a u u
1-44 NMe2 OHe OMe H H n H H He Π Π Π CR30  1-44 NMe2 OHe OMe H H n H H He Π Π Π CR30
u  u
1-45 NHeZ OMe OMe H H H H H n Π Me u  1-45 NHeZ OMe OMe H H H H H n Π Me u
Π C 30 Π C 30
-46 NMe2 OMe OHe H H H H H Ά n n n N 0  -46 NMe2 OMe OHe H H H H H Ά n n n N 0
u u u  u u u
1-47 NMe2 OHe OMe H H H H H H n Π CR3NH  1-47 NMe2 OHe OMe H H H H H H n Π CR3NH
1-48 NHe2 OMe OMe H H H H H H H H H CR3S  1-48 NHe2 OMe OMe H H H H H H H H H CR3S
1-49 *1 OMe OHe H H H H H H H H H C 30 gun 1-49 * 1 OMe OHe H H H H H H H H H C 30 gun
1-50 *2 OHe OMe H H H H H it 1-50 * 2 OHe OMe H H H H H it
H H H H CR30 1.5495(27) H H H H CR30 1.5495 (27)
1-51 *3 OHe OMe H H H H H H H H H CR30 gum1-51 * 3 OHe OMe H H H H H H H H H CR30 gum
1-52 OMe OHe H H H H H ti Π Π Π CR30 1-52 OMe OHe H H H H H ti Π Π Π CR30
u u u U  u u u U
1-53 N(C0Me)Ph OHe OMe H n ti H H n Π H Π CR30 143-4 u u u u u  1-53 N (C0Me) Ph OHe OMe H n ti H H n Π H Π CR30 143-4 u u u u u
I -04 NHrn Ufie UHe u  I -04 NHrn Ufie UHe u
n Π H H H ti Π n CR30 166-8
Figure imgf000042_0001
n Π HHH ti Π n CR30 166-8
Figure imgf000042_0001
u u u I] u  u u u I] u
|-bb UHe UNe H Π H H H H n 11 n CR30 gun | -bb UHe UNe H Π H H H H n 11 n CR30 gun
1-57 N(£t tH2Cn 0Ne n Oil** U u u u u1-57 N (£ t tH2Cn 0Ne n Oil ** U u u u u
Me OHe n Π H H H Π n Π H CR30 1.5465(24) u  Me OHe n Π H H H Π n Π H CR30 1.5465 (24) u
1-58 N(PnCHZCHZOHe OHe OMe H n Π H H H Π n H CR30 1.5452(24.5) n―  1-58 N (PnCHZCHZOHe OHe OMe H n Π H H H Π n H CR30 1.5452 (24.5) n―
卜 59 N(Pr-i)CH2CH20He OHe OMe n H H H H n H ti H CR30 1.5230(22.5)U 59 N (Pr-i) CH2CH20He OHe OMe n H H H H n H ti H CR30 1.5230 (22.5)
1-60 NHPh (4 -CI) OMe OHe H H H H H H H H H CR30 47-52 u 1-60 NHPh (4-CI) OMe OHe H H H H H H H H H CR30 47-52 u
1-61 NHPh (4 -He) O e OMe H H H H H H H H Π C 30 144-6 ί*ο nun. u u u U  1-61 NHPh (4 -He) O e OMe H H H H H H H H Π C 30 144-6 ί * ο nun.u u u U
1-6Z NHBn OMe One H H H H H n n n CR30 135-7 u u u  1-6Z NHBn OMe One H H H H H n n n CR30 135-7 u u u
1-63 NHPn (3-Cl OMe OHe H U u u u  1-63 NHPn (3-Cl OMe OHe H U u u u
H n n Π Π Π C 30 169-170 H n n Π Π Π C 30 169-170
1-64 N(Me)Bn OHeOMeH H H H H H H H H C 30 90-21-64 N (Me) Bn OHeOMeH H H H H H H H H C 30 90-2
1-65 *5 OMeOMeH H H H H H H H H CR30 1.5804(33)1-65 * 5 OMeOMeH H H H H H H H H H CR30 1.5804 (33)
1-66 NHPh (2-Me) ONeOHeH H H H H H H H H CR30 149-1521-66 NHPh (2-Me) ONeOHeH H H H H H H H H CR30 149-152
1-67 NHCONHEt OMeOMeH H H H H H H H H C 30 135-71-67 NHCONHEt OMeOMeH H H H H H H H H H C 30 135-7
1-68 NHCONHPh OMeOHeH H H H H H H H H CR30 190-21-68 NHCONHPh OMeOHeH H H H H H H H H H CR30 190-2
1-69 NHCONHPh (3-C1.4-CI) OMeOMeH H H H H H H H H C 30 194-6 (9Z)8 S 1 H H H H H H H H H 3H03H0 SI* S6-I IOLS I H H H H H H H H H aH09W0 HOZHOZHDHN 6-11-69 NHCONHPh (3-C1.4-CI) OMeOMeH HHHHHHHHC 30 194-6 (9Z) 8 S 1 HHHHHHHHH 3 H0 3 H0 SI * S6-I IOLS IHHHHHHHHH a H0 9 W0 HOZHOZHDHN 6-1
(S So) OSS I H H H H H H H H H 3H0 aH0 H* £6-1(S So) OSS IHHHHHHHHH 3 H0 a H0 H * £ 6-1
Ulli H H H H H H H H H aH0 aH0 ει* Z6-1Ulli HHHHHHHHH a H0 a H0 ει * Z6-1
Z61-881 H H H H H H H H 61* 16- 1Z61-881 H H H H H H H H 61 * 16-1
?9-Sr H H H H H H H H H a 0 aH0 11* 06-1? 9-Sr HHHHHHHHH a 0 a H0 11 * 06-1
9-0Z1 om H H H H H H H H H ΘΗ09H0 01* 68-19-0Z1 om HHHHHHHHH Θ Η0 9 H0 01 * 68-1
Z-OM OSHD H H H H H H H H H ¾H0 dW0 6本 88-1Z-OM OSHD HHHHHHHHH ¾ H0 d W0 6 pcs 88-1
1-091 o H H H H 11 H H H (IJ-S IJ-t) HdHN 8-11-091 o H H H H 11 H H H (IJ-S IJ-t) HdHN 8-1
01)3 H H H H H H H H H aH0 a«0 98-101) 3 HHHHHHHHH a H0 a «0 98-1
Z-Oil 0E¾3 H H H H H ii H Ii H 9«0 aH0 8* 98-1Z-Oil 0E¾3 HHHHH ii H Ii H 9 «0 a H0 8 * 98-1
ZSI-6H om H H H H H H H H H 9H09H0 ^8-1ZSI-6Hom HHHHHHHHH 9 H09H0 ^ 8-1
( ) 2885Ί OW H H H H H H H H H 9H03K0 i* £8-1 om H H H H H H H H H 9H03H0 卜 J細 Z8-I() 2885Ί OW HHHHHHHHH 9 H03K0 i * £ 8-1 om HHHHHHHHH 9 H0 3 H0
WOI ΟΖΏ H H H H H H H H H 3K03H0 13HN 18-1WOI ΟΖΏ HHHHHHHHH 3 K03H0 13HN 18-1
6-Ail OW H H H H H H H H H 3H09H0 9本 08-16-Ail OW HHHHHHHHH 3 H0 9 H0 9 pcs 08-1
OA 1-891 ΟΖΏ H H H H H H H H H 9H0 ΘΗ0 (3JH) HdH OA 1-891 ΟΖΏ HHHHHHHHH 9 H0 Θ Η0 (3JH) HdH
Z-08! OCHD H H H H H H H H H ΘΚ09K0 (IJ-Z) HdHN 2L-\Z-08! OCHD HHHHHHHHH Θ Κ0 9 K0 (IJ-Z) HdHN 2L- \
( o H H H H H H H H H ΘΚ0 ΘΗ0 l nniiki(o HHHHHHHHH Θ Κ0 Θ Η0 l nniiki
-N8HN LL-\ ε-ιοζ om H H H H H H H HdHO 3W0 (I3-£)^HN03HN 9i-l 歸 o H H H H H H H H H 3H03W0 SL-I ε-ζοζ ow H H H H H H H H H3H03H0 (13- WHNCDHN U-\ - N 8HN LL- \ ε-ιοζ om HHHHHHH HdHO 3W0 (I3- £) ^ HN03HN 9i-l unto o HHHHHHHHH 3 H03W0 SL-I ε -ζοζ ow HHHHHHHH H3H03H0 (13- WHNCDHN U- \
00Z-661 om H H H H H H H H H3H03W0 (2J3-£)¾ HN03HN Si- 1 Ζ)999Ί H H H H H H H H H3H09K0 (ng-細 N ZL-\00Z-661 om H H H H H H H H H3H03W0 (2J3- £) ¾ HN03HN Si- 1 Ί) 999Ί H H H H H H H H H3H09K0 (ng-fine N ZL- \
A-9ZI o H H H H H H H H H3H03W0 (3W(H)删 \L-\A-9ZI o H H H H H H H H H3H03W0 (3W (H) 删 \ L- \
ISI-6H 0EH3 H H H H H H H H H9H09H0 13HNS3HN OM z v Sx μ CH ZH 1H X ON 拏 I ISI-6H 0EH3 HHHHHHHH H9H09H0 13HNS3HN OM zv S x μ CH ZH 1H X ON Halla I
SSU0/96df/XDd f66€€/96 O/A
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* a物 値は 点、 もしくは屈折率* a value is point or refractive index
No. n Rl R2 R3 yl 2 y3 y4 y5 y6 y7 y8 A Z物性値 *a-1 CH2 0 OMe OMe H H H H H H H II H C 30 137-9-2 CH2 1 OMe OHe H H H H H H H H H C 30 108-110-3 CH2 2 OMe OMe H H H H H H H H H CR30 1.5656(32)-4 □2 3 OHe OMe H H H H H H H H H CR30No. n Rl R2 R3 yl 2 y3 y4 y5 y6 y7 y8 AZ Physical properties * a-1 CH2 0 OMe OMe HHHHHHH II HC 30 137-9-2 CH2 1 OMe OHe HHHHHHHHHC 30 108-110-3 CH2 2 OMe OMe HHHHHHHHHH CR30 1.5656 (32) -4 □ 23 OHe OMe HHHHHHHHH CR30
-5 0 1 OHe OHe H H H H H H H H H C 30 155-7-6 S 1 OMe OHe H H H H H H H H H C 30 129-131-7 SO 1 OMe OMe H H H H H H H H H CR30 2-4-8 S02 1 OHe OMe H H H H H H H H H CR30 156-9-9 NH 1 OMe OMe H H H H H H H H H CR30 52-5-10 NMe 1 OMe OHe H H H H H H H H H C 30-5 0 1 OHe OHe HHHHHHHHHC 30 155-7-6 S 1 OMe OHe HHHHHHHHHC 30 129-131-7 SO 1 OMe OMe HHHHHHHHH CR30 2-4-8 S02 1 OHe OMe HHHHHHHHH CR30 156-9-9 NH 1 OMe OMe HHHHHHHHH CR30 52-5-10 NMe 1 OMe OHe HHHHHHHHHC 30
-11 NEt 1 OHe OMe H H H H H H H H H CR30-11 NEt 1 OHe OMe H H H H H H H H H H CR30
-12 N(n-Hex) 1 OMe OHe H H H H H H H H H CR30-12 N (n-Hex) 1 OMe OHe H H H H H H H H H CR30
-13 N(n-C8H17) 1 OMe OHe H H H H H H H H H CR30-13 N (n-C8H17) 1 OMe OHe H H H H H H H H H CR30
-14 N(CH20Me) 1 OMe OMe H H H K H H H H H C 30-14 N (CH20Me) 1 OMe OMe H H H K H H H H H C 30
-15 NPh 1 OHe OMe H H H H H H H H H C 30-15 NPh 1 OHe OMe H H H H H H H H H H C 30
-16 NBn 1 OMe OHe H H H H H H H H H CR30-16 NBn 1 OMe OHe H H H H H H H H H H CR30
-17 NCHO 1 OMe OMe H H H H H H H H K CR30 159-160 f -17 NCHO 1 OMe OMe HHHHHHHHK CR30 159-160 f
0 N H H 3H 9H H H 0= 3K0 3W0 1 0 ε卜 z om H H 9H 9H H H 0= H 9H0 aWO I 0 - 2 omo H H ajj 9H 0= H H H 3H0 3X0 I 0 1ト z ow H H H H 9K 9H 0= H 9H0 3H0 1 0 0ト 2 οε¾3 0= H H H H H H H 9H0 9H0 1 0 6E-Z u 0 NHH 3H 9H HH 0 = 3K0 3W0 1 0 ε o z om HH 9H 9H HH 0 = H 9H0 aWO I 0-2 omo HH ajj 9H 0 = HHH 3H0 3X0 I 0 1 o z ow HHHH 9K 9H 0 = H 9H0 3H0 1 0 0 to 2 οε¾3 0 = HHHHHHH 9H0 9H0 1 0 6E-Z u
QW n u n 0= H H H H H 3H0 3H0 1 0 8S-Z u u  QW n u n 0 = H H H H H 3H0 3H0 1 0 8S-Z u u
n n H H 0= H H H 3H0 3H0 1 0 LZ-Z n u n u  n n H H 0 = H H H 3H0 3H0 1 0 LZ-Z n u n u
H H H H 0= H 3W0 9H0 1 0 9S-Z u n n u H H U H H aH0 3 0 I 0 HHHH 0 = H 3W0 9H0 1 0 9S-Z unnu HHUHH a H0 3 0 I 0
ow u n u Π u Π u U H H H 3H0 3H0 I 0 z-z om u n Uひ u Π H H HJd-! H 9H0 3W0 1 0 ii-Z o u  ow u n u Π u Π u U H H H 3H0 3H0 I 0 z-z om u n UHI u Π H H HJd-! H 9H0 3W0 1 0 ii-Z o u
a id H H n u H u H H H 9M0 1 0 ζε-ζ
Figure imgf000046_0001
a id HH nu H u HHH 9M0 1 0 ζε-ζ
Figure imgf000046_0001
ow n n  ow n n
Π Π H H H H H 13 H 9H0 1 0 6Ζ-Ζ aw a H H H H H H H 9H0 aWO I 0 n u n u H H H H H 3H0 1 0 ιι-ι o H H H H aw H H H 9H0 ! 0 sz-z Π Π H H H H H 13 H 9H0 10 6Ζ-Ζ aw a H H H H H H H H 9H0 aWO I 0 n u n u H H H H H 3H0 1 0 ιι-ι o H H H H aw H H H 9H0! 0 sz-z
H H H H H H H 3H0 9H0 1 0 SZ-Z om H aw H H H H H H H 9H0 I 0 η-ζH H H H H H H 3H0 9H0 1 0 SZ-Z om H aw H H H H H H H H 9H0 I 0 η-ζ
H H H H H H H Π u dun
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I C 070-7 υHHHHHHH Π u dun
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IC 070-7 υ
H H H H H H H H H aH0 3H0 1 ζζ-ζ om H H H H H H H H H 3H0 9H0 1 WHN03N \ζ-ζ οεω H H H H H H H H H 9H0 9H0 1 >1續 οζ-ζ om H H H H H H H H H 9H0 3H0 1 9H003N 6Ι-Ζ ow H H H H H H H H H 3H0 3H0 1 3議 8Ι-Ζ z V 8人 ΙΛ 9人 H Τ 11 X •ON HHHHHHHHH a H0 3 H0 1 ζζ-ζ om HHHHHHHHHH 3H0 9H0 1 WHN03N \ ζ-ζ οεω HHHHHHHHHH 9H0 9H0 1> 1 continued οζ-ζ om HHHHHHHHH 9H0 3H0H 3H0H 3H0H 3H0H 3H0H V 8 people ΙΛ 9 people H Τ 11 XON
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OA! 08H3 H H H H H H H H H N3 1 0 £9-ZOA! 08H3 H H H H H H H H H N3 1 0 £ 9-Z
0 SH3 H H H H H H H H H H I 0 Z9-Z0 SH3 H H H H H H H H H H I 0 Z9-Z
£-181 H H Ά H H H H H H Z刚 【 0 I9-Z £ -181 H H Ά H H H H H H Z 刚 [0 I9-Z
O bHJ H H H H H H H H H 13 3H0 1 0 09-Z O bHJ H H H H H H H H H 133 3H0 1 0 09-Z
O EHJ H H H H H H H H a薩 9 1 0 6S-ZO EHJ H H H H H H H H a Sat 9 1 0 6S-Z
9- 91 0 £H3 H H H H H H H H H 13 13 1 0 8S-Z nnQ 9- 91 0 £ H3 H H H H H H H H H 13 13 1 0 8S-Z nnQ
DlU 0 S¾3 H H H H H Vna H H H 9H0 3H0 1 0 s-z DlU 0 S¾3 HHHHHV n a HHH 9H0 3H0 1 0 sz
H H H H H H H H H HZiDO HZJ30 I 0 9S-Z H H H H H H H H H H ZiDO HZJ30 I 09S-Z
H H H H H H H H H 9H0 9H0 1 13003N S9-ZH H H H H H H H H 9H0 9H0 1 13003N S9-Z
L-SL H H H H H H H H H 3H0 3H0 1 13H議 n-zL-SL H H H H H H H H H 3H0 3H0 1 13H discussion n-z
S-S9 U H H H H H H H H ajio 9H0 I ト n8画 es-z c gin u n n XI u n u Π H H n u u n H 9H0 3H0 I u P-7S-S9 UHHHHHHHH ajio 9H0 I to n 8 es-z c gin unn XI unu Π HH nuun H 9H0 3H0 I u P-7
H H H H H H H H H 9H0 3H0 ！ 0 IS-ZH H H H H H H H H 9H0 3H0! 0 IS-Z
0 N H H H H H H H H 9H0 9H0 1 ZHD 0S-20 N H H H H H H H H 9H0 9H0 1 ZHD 0S-2
0 N H H H H H H H H 3H0 3K0 I 0 6ト Z0 N H H H H H H H H 3H0 3K0 I 06 To Z
0 N H an H H H H H H 3H0 9H0 1 ZH3 8ト Z0 N H an H H H H H H 3H0 9H0 1 ZH3 8 G Z
0 N H H H H H H H m 1 ZHO L -Z0 N H H H H H H H m 1 ZHO L -Z
0 N H H H H H aw H H 3W0 1 ZH30 N H H H H H aw H H 3W0 1 ZH3
0 N H H H H H H H 9M 9H0 ! ZH30 N H H H H H H H 9M 9H0! ZH3
0 N H H H H 0= a«0 1 0 ョ * I V 8^ 9^ μ X •ON 0 N H H H H 0 = a «0 1 0 * I V 8 ^ 9 ^ μ XON
¾f) 拏 s ¾  ¾f) Halla s ¾
SSIIO/96dT/X3d ½6εε/96 OM SSIIO / 96dT / X3d ½6εε / 96 OM
Figure imgf000048_0001
Figure imgf000048_0001
*a物性値は融点、 もしくは屈折率o. X Rl R2 R3 R4 R5 A Z 物性値 *a-1 NH2 OMeOMeH H H CR30 * a Physical properties are melting point or refractive index o.X Rl R2 R3 R4 R5 AZ Physical properties * a-1 NH2 OMeOMeH H H CR30
-2 NHe2 OMeOMeH H H CR30-2 NHe2 OMeOMeH H H CR30
-3 NEt2 OMeOMeH H H CR30-3 NEt2 OMeOMeH H H CR30
-4 N(n-Pr)2 OMeOMeH H H C 30-4 N (n-Pr) 2 OMeOMeH H H C 30
-5 N(i-Pr)2 OMeOMeH H H C 30-5 N (i-Pr) 2 OMeOMeH H H C 30
-6 N(n-Bu)2 OMeOMeH H H CR30-6 N (n-Bu) 2 OMeOMeH H H CR30
-7 N(i-Bu)2 OMeOMeH H H CR30-7 N (i-Bu) 2 OMeOMeH H H CR30
-8 N(n-Hex)2 OMeOMeH H H CR30-8 N (n-Hex) 2 OMeOMeH H H CR30
-9 N(n-C8H17)2 OMeOMeH H H CR30-9 N (n-C8H17) 2 OMeOMeH H H CR30
-10 N(He)Et OMeOMeH H H C 30-10 N (He) Et OMeOMeH H H C 30
-11 N(He)CH20He OMeOMeH H H CR30-11 N (He) CH20He OMeOMeH H H CR30
-12 N(He)P OMeOMeH H H CR30-12 N (He) P OMeOMeH H H CR30
-13 N(He)Bn OMeOMeH H H CR30-13 N (He) Bn OMeOMeH H H CR30
-14 N(Me)CH0 OMeOMeH H H CR30-14 N (Me) CH0 OMeOMeH H H CR30
-15 N(He)C0Me OMeOMeH H H CR30-15 N (He) C0Me OMeOMeH H H CR30
-16 N(He)C00He OMeOMeH H H CR30-16 N (He) C00He OMeOMeH H H CR30
-17 N(Me)C0Ph OMeOMeH H H CR30 0 N ά H awoaHO z i卜 ε-17 N (Me) C0Ph OMeOMeH HH CR30 0 N ά H awoaHO zi ε
(5*9Z)895S'l 0 H aw 3W z oト ε (5 * 9Z) 895S'l 0 H aw 3W z o ε
0 H H H 9H09W0 z 6ε-ε 0 H H H 9H09W0 z 6ε-ε
OW H H HaWOawO 9* 8ε - εOW H H HaWOawO 9 * 8ε-ε
0£Ώ H H H 9W03W0 5* LZ-Z0 £ Ώ H H H 9W03W0 5 * LZ-Z
DW H H H9H0aW0 η 9ε-εDW HH H9H0 a W0 η 9ε-ε
OW H H HsH03H0 ζ* 5ε-εOW HHH s H0 3 H0 ζ * 5ε-ε
OW H H H 9H0 aH0 ι* - εOW HHH 9 H0 a H0 ι *-ε
OW 9H-H3=H3 H H aH03W0 Ζ3ΗΝ ΖΖ-ΖOW 9H-H3 = H3 HH a H03W0 Ζ 3 ΖΖ ΖΖ-Ζ
OW 9H-HD=(9H)D H H 9W0 aW0 z zz-zOW 9H-HD = (9H) D H H 9W0 aW0 z zz-z
OW ί3 H H3W03W0 zm ιε-εOW ί3 H H3W03W0 zm ιε-ε
OW U8 H H3W03W0 z οε-εOW U8 H H3W03W0 z οε-ε
O HO H
OW 1300D-H3=HD H H 3W0 awo 8ζ-ε οε¾3 N3-HD=HD H H 3W0 awo OW 1300D-H3 = HD H H 3W0 awo 8ζ-ε οε¾3 N3-HD = HD H H 3W0 awo
OEHD 9HOO0 H H 3W09H0  OEHD 9HOO0 H H 3W09H0
OHD H H 9W03W0  OHD H H 9W03W0
4d-HD=HD H H 3W03W0  4d-HD = HD H H 3W03W0
7UU_b_UJ H u aun aun 7dUJ om ト H HawOSKO z ζζ-ζ
Figure imgf000049_0001
7UU_b_UJ H u aun aun 7dUJ om H HawOSKO z ζζ-ζ
Figure imgf000049_0001
o H HaWOawO zm οζ-ε o H HaWOawO zm οζ-ε
OW m H3W03W0 z 6卜 ε aw H3H03W0 zm 8ト ε 郾¾ l V μ EH ΖΆ IH X 。Ν OW m H3W03W0 z 6 ε aw H3H03W0 zm 8 ε 郾 ¾ V l V μ EH ΖΆ IH X. Ν
SSII0/96dT/JL3d Μ6εε/96 ΟΛλ 第 3 表 （統き）SSII0 / 96dT / JL3d Μ6εε / 96 ΟΛλ Table 3 (Guide)
o. X Rl R2 R3 yl _y2 A Z 物性値 *a-42 NHe2 OHe OHe H Ph-4-CI N 0o. X Rl R2 R3 yl _y2 A Z Physical properties * a-42 NHe2 OHe OHe H Ph-4-CI N 0
-43 NMe2 OMeOMe H Ph-4-OMe N 0-43 NMe2 OMeOMe H Ph-4-OMe N 0
-44 NMe2 OHe OHe H Ph-4-NH2 N 0-44 NMe2 OHe OHe H Ph-4-NH2 N 0
-45 NHe2 OHeOHe H CH=CH-Ph N 0-45 NHe2 OHeOHe H CH = CH-Ph N 0
-46 NMe2 OMe OMe H CHO N 0-46 NMe2 OMe OMe H CHO N 0
-47 NHe2 OMe OMe H COOMe N 0-47 NHe2 OMe OMe H COOMe N 0
-48 NMe2 OMeOMe H CH=CH-CN N 0-48 NMe2 OMeOMe H CH = CH-CN N 0
-49 NMe2 OHeOHe H CH=CH-C00Et N 0-49 NMe2 OHeOHe H CH = CH-C00Et N 0
-50隱 OMeOMe H 3-Pyridyl N 0-50 Hidden OMeOMe H 3-Pyridyl N 0
-51 NHe2 OHe OMe H Bn N 0-51 NHe2 OHe OMe H Bn N 0
-52 NHe2 OMe OMe H Et N 0-52 NHe2 OMe OMe H Et N 0
-53 NNe2 OHe OMe H C(Me)=CH-He N 0-53 NNe2 OHe OMe H C (Me) = CH-He N 0
-54 NHe2 OHe OHe H CH=CH-Me N 0 -54 NHe2 OHe OHe H CH = CH-Me N 0
Figure imgf000050_0001
Figure imgf000050_0001
Figure imgf000050_0002
Figure imgf000051_0001
Figure imgf000050_0002
Figure imgf000051_0001
*a物性値は融点、 もしくは屈折率 o. I n Rl R2 R3 4 R5 A Z * a Physical properties are melting point or refractive index o.In Rl R2 R3 4 R5 AZ
-1 CH2 0 OMeOMeH H H CR30-1 CH2 0 OMeOMeH H H CR30
-2 CH2 1 OHeOHeH H H CR30-2 CH2 1 OHeOHeH H H CR30
-3 CH2 2 OMeOHeH H H CR30-3 CH2 2 OMeOHeH H H CR30
-4 CH2 3 OHeOHeH H H CR30-4 CH2 3 OHeOHeH H H CR30
-5 0 OMeOHeH H H CR30 148-9-6 S OMeOHeH H H CR30-5 0 OMeOHeH H H CR30 148-9-6 S OMeOHeH H H CR30
-7 NH OHeOHeH H H CR30-7 NH OHeOHeH H H CR30
-8 NNe OHeOHeH H H CR30 oil-9 NEt OHeOHeH H H CR30-8 NNe OHeOHeH H H CR30 oil-9 NEt OHeOHeH H H CR30
-10 N(n-Hex) OMeOMeH H H CR30-10 N (n-Hex) OMeOMeH H H CR30
-11 N(n-C8H17) OMeOHeH H H CR30-11 N (n-C8H17) OMeOHeH H H CR30
-12 N(CH20He) OHeOHeH H H CR30-12 N (CH20He) OHeOHeH H H CR30
-13 NPh OMeOHeH H H CR30-13 NPh OMeOHeH H H CR30
-14 NBn OMeOHeH H H CR30-14 NBn OMeOHeH H H CR30
-15 NCHO OMeOMeH H H C 30-15 NCHO OMeOMeH H H C 30
-16 NCOMe OMeOMeH H H CR30-16 NCOMe OMeOMeH H H CR30
-17 NCOOHe OHeOHeH H H CR30 第 4 表 （統き）-17 NCOOHe OHeOHeH HH CR30 Table 4 (Guide)
o. X Rl R2 R3 4 R5 A Z 物性値 *a-18 NCOPh 1 OHeOHeH H H CR30o.X Rl R2 R3 4 R5 AZ Physical properties * a-18 NCOPh 1 OHeOHeH H H CR30
-19 NCONHPh 1 OHeOHeH H H CR30-19 NCONHPh 1 OHeOHeH H H CR30
-20 NCSNHPh 1 OHeOMeH H H CR30-20 NCSNHPh 1 OHeOMeH H H CR30
-210 1 OMeOMeH Me He C 30 gUD)-220 1 OMeOMeH H Ph C 30-210 1 OMeOMeH Me He C 30 gUD) -220 1 OMeOMeH H Ph C 30
-230 1 OHeOMeH H Ph-4-Cl CR30 159-161-240 ! OHeOHeH H Ph-4-OMe CR30-230 1 OHeOMeH H Ph-4-Cl CR30 159-161-240! OHeOHeH H Ph-4-OMe CR30
-250 1 OHeOHeH H Ph-4-NH2 CR30-250 1 OHeOHeH H Ph-4-NH2 CR30
-260 1 OHeOMeH H Ph-4-NHAc CR30-260 1 OHeOMeH H Ph-4-NHAc CR30
-270 1 OMeOMeH H CH=CH - Ph C 30-270 1 OMeOMeH H CH = CH-Ph C 30
-280 1 OHeOHeH H CHO CR30-280 1 OHeOHeH H CHO CR30
-290 1 OMeOHeH H COOMe CR30-290 1 OMeOHeH H COOMe CR30
-300 1 OMeOHeH H CH=CH-CN CR30-300 1 OMeOHeH H CH = CH-CN CR30
-310 1 OHeOHeH H CH=CH-COOEt CR30-310 1 OHeOHeH H CH = CH-COOEt CR30
-320 1 OHeOMeH H 3-Pyridy! CR30 147-151-330 1 OMeOHeH H Bn CR30-320 1 OHeOMeH H 3-Pyridy! CR30 147-151-330 1 OMeOHeH H Bn CR30
-340 1 OMeOMeH H Et CR30-340 1 OMeOMeH H Et CR30
-350 1 OHeOHeH H C(He)=CH-He p Loa U n -360 1 OMeOHeH H CH=CH-Me C 30-350 1 OHeOHeH H C (He) = CH-He p Loa Un -360 1 OMeOHeH H CH = CH-Me C 30
-370 1 OMeOHeH He H CR30-370 1 OMeOHeH He H CR30
-380 1 OHeOMeH Et H C 30-380 1 OHeOMeH Et H C 30
-390 1 OHeOHeH He Ph CR30-390 1 OHeOHeH He Ph CR30
-400 1 OMeOHeH Me Ph-4-CI CR30-400 1 OMeOHeH Me Ph-4-CI CR30
-410 1 OHeONe H H N 0 第 4 表 き）-410 1 OHeONe HHN 0 Table 4)
o. X Rl R2 R3 R4 R5 A Z 物性値 *a-420 1 OMeOMe Me H N 0 o.X Rl R2 R3 R4 R5 A Z Physical properties * a-420 1 OMeOMe Me H N 0
-43 CH2 1 OHeOHe H He CR30-43 CH2 1 OHeOHe H He CR30
-44 CH2 1 OHeOHe Me He CR30-44 CH2 1 OHeOHe Me He CR30
-45 CH2 1 OHeOHe H Ph CR30-45 CH2 1 OHeOHe H Ph CR30
-46 CH2 1 OMeOHe H Ph-4-Cl CR30-46 CH2 1 OMeOHe H Ph-4-Cl CR30
-47 CH2 1 OMeOHe H CH=CH-Ph CR30-47 CH2 1 OMeOHe H CH = CH-Ph CR30
-48 CH2 1 OHeOMe H CH=CH-COOEt C 30-48 CH2 1 OHeOMe H CH = CH-COOEt C 30
-490 1 ONeOHe H H CR3 NH-490 1 ONeOHe H H CR3 NH
-500 1 OHeOMe H H C 3S-500 1 OHeOMe H H C 3S
-510 1 OMeOMeH H *1 CR30 gum-520 1 OMeOHeH H *2 CR30 1.5918(32)-530 1 OHeOMeH H CH=CHCOOEt CR30 1.5872(26)-540 1 OHeOMeH H CH20C0NHPh (3-C DC 30 1.5676 (27) -510 1 OMeOMeH H * 1 CR30 gum-520 1 OMeOHeH H * 2 CR30 1.5918 (32) -530 1 OHeOMeH H CH = CHCOOEt CR30 1.5872 (26) -540 1 OHeOMeH H CH20C0NHPh (3-C DC 30 1.5676 (27)
Figure imgf000053_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000054_0001
*a物性値は融点、 もしくは屈折率o. X Rl R2 R3 R4 R5 A Z 物性値 *a-1 HHe OMeOMeH H H CR30 * a Physical properties are melting point or refractive index o.X Rl R2 R3 R4 R5 AZ Physical properties * a-1 HHe OMeOMeH H H CR30
-2 NMe2 OMeOHeH H H CR30-2 NMe2 OMeOHeH H H CR30
-3 NEt2 OMeOHeH H H CR30-3 NEt2 OMeOHeH H H CR30
-4 N(n-Pr)2 OMeOMeH H H CR30-4 N (n-Pr) 2 OMeOMeH H H CR30
-5 N(i-Pr)2 OMeOHe H H H CR30-5 N (i-Pr) 2 OMeOHe H H H CR30
-6 N(n-Bu)2 OMeOHeH H H C 30-6 N (n-Bu) 2 OMeOHeH H H C 30
-7 N(i-Bu)2 OMeOHeH H H C 30-7 N (i-Bu) 2 OMeOHeH H H C 30
-8 N(n-Hex)2 OHeOMeH H H CR30-8 N (n-Hex) 2 OHeOMeH H H CR30
-9 N(n-C8H17)2 OMeOHe H H H CR30-9 N (n-C8H17) 2 OMeOHe H H H CR30
-10 N(Me)Et OMeOHeH H H CR30-10 N (Me) Et OMeOHeH H H CR30
-11 N (Me)画 Me OHeOMeH H H CR30-11 N (Me) picture Me OHeOMeH H H CR30
-12 N(Me)Ph OMeOHeH H H CR30-12 N (Me) Ph OMeOHeH H H CR30
-13 N(Me)Bn OMeOHe H H H CR30-13 N (Me) Bn OMeOHe H H H CR30
-H N(Me)CH0 OMeOHeH H H CR30-H N (Me) CH0 OMeOHeH H H CR30
-15 N(Me)C0He OHeOMe H H H CR30-15 N (Me) C0He OHeOMe H H H CR30
-16 N(He)C00He OMeOMeH H H CR30-16 N (He) C00He OMeOMeH H H CR30
-17 N(He)C0Ph OMeOMeH H H CR30 第 5 表 （統き）-17 N (He) C0Ph OMeOMeH HH CR30 Table 5 (Guide)
o. X Rl R2 R3 R4 R5 A Z 物性値 *a-18 NMe2 OMeOMeH Me He CR30o.X Rl R2 R3 R4 R5 AZ Physical properties * a-18 NMe2 OMeOMeH Me He CR30
-19 NHe2 OMeOMeH He Ph CR30-19 NHe2 OMeOMeH He Ph CR30
-20 NNe2 OMeOMeH H Ph CR30-20 NNe2 OMeOMeH H Ph CR30
-21 NHe2 OMeOMeH H Ph-4-CI CR30-21 NHe2 OMeOMeH H Ph-4-CI CR30
-22 NHe2 OMeOMeH H Ph-4-OMe C 30-22 NHe2 OMeOMeH H Ph-4-OMe C 30
-23 NHe2 OMeOMeH H Ph-4-NH2 C 30-23 NHe2 OMeOMeH H Ph-4-NH2 C 30
-24 NMe2 OMeOMeH H CH=CH-Ph CR30-24 NMe2 OMeOMeH H CH = CH-Ph CR30
-25 NHe2 OMeOMeH H CHO CR30-25 NHe2 OMeOMeH H CHO CR30
-26 NHe2 OMeOMeH H COOMe CR30-26 NHe2 OMeOMeH H COOMe CR30
-27 NNe2 OMeOMeH H CH=CH-CN CR30-27 NNe2 OMeOMeH H CH = CH-CN CR30
-28 NNe2 OMeOMeH H CH=CH-COOEt CR30-28 NNe2 OMeOMeH H CH = CH-COOEt CR30
-29 NHe2 OMeOMeH H 3-Pyridyl CR30-29 NHe2 OMeOMeH H 3-Pyridyl CR30
-30 NNe2 OMeOMeH H Bn CR30-30 NNe2 OMeOMeH H Bn CR30
-31 NMe2 OMeOMeH H Et CR30-31 NMe2 OMeOMeH H Et CR30
-32 NNe2 OMeOMeH H C(Me)=CH-He CR30-32 NNe2 OMeOMeH H C (Me) = CH-He CR30
-33 NMe2 OMeOMeH H CH=CH-He CR30-33 NMe2 OMeOMeH H CH = CH-He CR30
-34 *1 OMeOMeH H H CR30-34 * 1 OMeOMeH H H CR30
-35 *2 OMeOMeH H H CR30-35 * 2 OMeOMeH H H CR30
-36 *3 OMeOMeH H H C 30-36 * 3 OMeOMeH H H C 30
-37 *4 OMeOMeH H H CR30-37 * 4 OMeOMeH H H CR30
-38 *5 OMeOMeH H H CR30-38 * 5 OMeOMeH H H CR30
-39 *6 OMeOMeH H H CR30-39 * 6 OMeOMeH H H CR30
-40 *7 OMeOMeH H H CR30-40 * 7 OMeOMeH H H CR30
-41 *8 OMeOMeH H H CR30 -41 * 8 OMeOMeH HH CR30
Figure imgf000056_0001
Figure imgf000056_0001
第 6 表 Table 6
No. X No. X
6-1 NHNe  6-1 NHNe
6-2 隱 6-2
6-3 NEt2 6-3 NEt2
6-4 N(n-Pr)2 6-4 N (n-Pr) 2
6-5 N(i-Pr)2 6-5 N (i-Pr) 2
6-6 N(n-Bu)2 6-6 N (n-Bu) 2
6-7 N(i-Bu)2 6-7 N (i-Bu) 2
6-8 N(n-Hex)2 6-8 N (n-Hex) 2
6-9 N(n-C8H17)2 6-9 N (n-C8H17) 2
6-10 N(He)Et 6-10 N (He) Et
6-11 N(Me)CH20He6-11 N (Me) CH20He
Figure imgf000057_0001
Figure imgf000057_0001
6-12 N(He)Ph OHe OMe H H Me CR30 6-13 N(He)Bn OMe OMe H H He CR30 6-12 N (He) Ph OHe OMe HH Me CR30 6-13 N (He) Bn OMe OMe HH He CR30
第 6 表 (統き Table 6
No. X l R2 R3 R4  No. X l R2 R3 R4
6-18 NHe2 OMeOMeH Me  6-18 NHe2 OMeOMeH Me
6-19 NHe2 OHeOHeH He 6-19 NHe2 OHeOHeH He
6-20 NHe2 OMeOHeH H 6-20 NHe2 OMeOHeH H
6-21 NMe2 OMeOMeH H 6-21 NMe2 OMeOMeH H
6-22 NHe2 OMeOHeH H 6-22 NHe2 OMeOHeH H
6-23 NHe2 OMeOMeH H 6-23 NHe2 OMeOMeH H
6-24 NHe2 OHeOHeH H 6-24 NHe2 OHeOHeH H
6-25 NHe2 OMeOHeH H 6-25 NHe2 OMeOHeH H
6-26 NMe2 OMeOMeH H 6-26 NMe2 OMeOMeH H
6-27 NHe2 OMeOMeH H 6-27 NHe2 OMeOMeH H
6-28 NHe2 OHeOHeH H 6-28 NHe2 OHeOHeH H
6-29 NMe2 OMeOMeH H 6-29 NMe2 OMeOMeH H
6-30 NMe2 OMeOHeH H 6-30 NMe2 OMeOHeH H
6-31 NHe2 OHeOHeH H 6-31 NHe2 OHeOHeH H
6-32 NHe2 OMeOHeH H 6-32 NHe2 OMeOHeH H
6-33 NHe2 OHeOHeH H 6-33 NHe2 OHeOHeH H
6-34 *1 OMeOHeH H6-34 * 1 OMeOHeH H
Figure imgf000058_0001
Figure imgf000058_0001
6-35 *2 OMeOHeH H 6-35 * 2 OMeOHeH H
6-36 *3 OMeOMeH H Ne C 30 6-36 * 3 OMeOMeH H Ne C 30
L 9 L 9
s- οε¾3 ω-ε) ID H3W09H0 \* S9-9 ト29 m (!D-nD-9)¾HN0D0ZHD H3W03W0 1* 9-9s-οε¾3ω-ε) ID H3W09H0 \ * S9-9 to 29 m (! D-nD-9) ¾HN0D0ZHD H3W03W0 1 * 9-9
0 -S9 (9dD-e)¾HN030ZHD H3W03W0 I* £9-9 -^9 (!3-S)¾dHN0D0ZH3 H¾)3W0 1* Z9-90 -S9 (9dD-e) ¾HN030ZHD H3W03W0 I * £ 9-9-^ 9 (! 3-S) ¾dHN0D0ZH3 H¾) 3W0 1 * Z9-9
8-9ZI ow H0ZH3 H9H03K0 I* 19-9 8-9ZI ow H0ZH3 H9H03K0 I * 19-9
OSHD 0I*-0ZH3 H3H03W0 1* 09-9 OSHD 0I * -0ZH3 H3H03W0 1 * 09-9
Z-16 m ΘΗ HSH03H0 1* 65-9 Z-16 m ΘΗ HSH03H0 1 * 65-9
0 N 9H-H0=HD H Z 85-9 0 N 9H-H0 = HD H Z 85-9
0 N 3W-HD=(9H)D H 3W03H0 z - 90 N 3W-HD = (9H) D H 3W03H0 z-9
0 N 13 H 3W03W0 z 95-90 N 13 H 3W03W0 z 95-9
0 N H z 55-90 N Hz 55-9
0 N H 9H09W0 Z ^9-90 N H 9H09W0 Z ^ 9-9
0 N ^300D-HD=HD H 3W03W0 Z £5-90 N ^ 300D-HD = HD H 3W03W0 Z £ 5-9
0 N ND-HD=HD H 3W03W0 z zs-90 N ND-HD = HD H 3W03W0 z zs-9
0 N ■3 H 3H09H0 Z 15-90 N 3H 3H09H0 Z 15-9
0 K 0H3 H z os-90 K 0H3 H z os-9
0 N Md-HD=HD H z 6卜 90 N Md-HD = HD H z 6 9
0 N H z 8卜 90 N H z 8 u 9
0 N H 3W03W0 z - 90 N H 3W03W0 z-9
0 N H 3 0 z 9卜 90 N H 3 0 z 9 9
0 N H ¾)aW0 z sト 90 N H ¾) aW0 z s 9
0 aw aw 3W03W0 z - 90 aw aw 3W03W0 z-9
0 N 3H H ^HOaWO z ε卜 90 N 3H H ^ HOaWO z ε 卜 9
0ΖΏ aw H 6* Zf-90ΖΏ aw H 6 * Zf-9
¾郾 C¾ I V sa sa ZH 1H X OH ¾ 郾 C¾ I V sa sa ZH 1H X OH
9  9
SSllO/96dT/XDd ^66£€/96 OAV 第 6 表 (統き）SSllO / 96dT / XDd ^ 66 £ € / 96 OAV Table 6 (Guide)
o Y Rl R2 R3 -R5 A Z 物 ti値 *a-66 t\ OMe OMe H Ph CH20C0NHPh CR30 gum-67 *l OMe ONe H Ph CH20C0Ph(3-CI) CR30 oil-68 *l OMeOHeH Ph Ph CR30 52-6-69 *| OMe OMe H Me Ph CR30 178-180-70 *i OMe OMe H He H CR30 99-100.5-71 *l OMe OMe H Ph H CR30 gum-72 *l OMeOMeH H H CR30 148.5-9.5-73 *l OMeOHeH Me Me CR30 153-74 *l OMeOMeH Bu-t H CR30 1.5512(25)-75 OMeOMeH OEt Pr-i CR30 93-4 o Y Rl R2 R3 -R5 AZ value ti value * a-66 t \ OMe OMe H Ph CH20C0NHPh CR30 gum-67 * l OMe ONe H Ph CH20C0Ph (3-CI) CR30 oil-68 * l OMeOHeH Ph Ph CR30 52- 6-69 * | OMe OMe H Me Ph CR30 178-180-70 * i OMe OMe H He H CR30 99-100.5-71 * l OMe OMe H Ph H CR30 gum-72 * l OMeOMeH HH CR30 148.5-9.5-73 * l OMeOHeH Me Me CR30 153-74 * l OMeOMeH Bu-t H CR30 1.5512 (25) -75 OMeOMeH OEt Pr-i CR30 93-4
Figure imgf000060_0001
Figure imgf000060_0002
e
Figure imgf000060_0001
Figure imgf000060_0002
e
Figure imgf000060_0003
第 7 表
Figure imgf000061_0001
Figure imgf000060_0003
Table 7
Figure imgf000061_0001
*a 物性値は融点、 もしくは屈折率 o. R R4 R5 Rl R2 R3 A Z物性値 *a-1 H H H OMeOHeH CR30* a Physical properties are melting point or refractive index o.R R4 R5 Rl R2 R3 AZ Physical properties * a-1 H H H OMeOHeH CR30
-2 H CF3 H ONeOMeH CR30 141-3-3 *1 CF3 H OHeOMeH C 30 54-7-4 CH(Me)0Et CF3 H OHeOHeH C 30 122-4-5 CH20C0Bu-t H CF3 OHeOHeH CR30 gum-6 COOEt CF3 H OHeOMeH CR30 126-7-7 CH(Me)0C0N(He)2 CF3 H OHeOHeH C 30 1.5618(26) -2 H CF3 H ONeOMeH CR30 141-3-3 * 1 CF3 H OHeOMeH C 30 54-7-4 CH (Me) 0Et CF3 H OHeOHeH C 30 122-4-5 CH20C0Bu-t H CF3 OHeOHeH CR30 gum-6 COOEt CF3 H OHeOMeH CR30 126-7-7 CH (Me) 0C0N (He) 2 CF3 H OHeOHeH C 30 1.5618 (26)
Figure imgf000061_0002
第 8 表
Figure imgf000062_0001
Figure imgf000061_0002
Table 8
Figure imgf000062_0001
*a 物性値は融点、 もしくは屈折率 o. R R4 R5 Rl R2 R3 A Z物性値 *a-1 H H H OKeOMeH C 30* a Physical properties are melting point or refractive index o.R R4 R5 Rl R2 R3 A Z Physical properties * a-1 H H H OKeOMeH C 30
-2 H CF3 H OHeOHeH CR30 193-5-3 CH(Me)0Et CF3 H OMeOHeH CR30 1.506(24)-4 *1 CF3 H OMeOMeH CR30 1.5443(28) -2 H CF3 H OHeOHeH CR30 193-5-3 CH (Me) 0Et CF3 H OMeOHeH CR30 1.506 (24) -4 * 1 CF3 H OMeOMeH CR30 1.5443 (28)
Figure imgf000062_0002
Figure imgf000062_0002
第 9 表
Figure imgf000063_0001
Table 9
Figure imgf000063_0001
*a 物性値は融点、 もしくは屈折率 o. Rl R2 R3 A Z物性値 *a-1 H OMeOMeH CR30 80-84-2 *1 (卜 ft 2 - mixture) OHeOHeH CR30 112-4-3 l-CH20C0Et OMeOMeH CR30 131-133.5-4 2-CH20C0Et OHeOHeH CR30 gum-5 1-CH2CH2CN OHeOMeH CR30 149-151-6 l-CH20C0He OHeOMeH CR30 gum * a Physical properties are melting point or refractive index o.Rl R2 R3 AZ physical properties * a-1 H OMeOMeH CR30 80-84-2 * 1 (Ft ft 2-mixture) OHeOHeH CR30 112-4-3 l-CH20C0Et OMeOMeH CR30 131-133.5-4 2-CH20C0Et OHeOHeH CR30 gum-5 1-CH2CH2CN OHeOMeH CR30 149-151-6 l-CH20C0He OHeOMeH CR30 gum
Figure imgf000063_0002
Figure imgf000063_0002
本発明化合物 （式 〔 I ； で表される化合物又はその塩） は畑作条件で、 土堉処 理、 茎葉処理のいずれの方法でも高い除草活性を示し、 アキノエノ コログサ、 ィ チビ、 ィヌビュ等の各種畑雑草に有効で、 トウモロコシ、 ムギ、 大豆、 ヮタ等の 作物に選択性を示す化合物も含まれている。 The compound of the present invention (the compound represented by the formula [I; or a salt thereof) shows high herbicidal activity under soil cultivation conditions in both soil treatment and foliage treatment, and various compounds such as Aquinoeno korogusa, Ichibi and Inubu, etc. It is effective for field weeds and contains compounds that are selective for crops such as corn, wheat, soybeans, and potatoes.
また、 本発明化合物は、 作物、 観赏用植物、 果樹等の有用植物に対し、 生育抑 制作用を示す化合物も含まれている。  In addition, the compound of the present invention also includes a compound that is useful for producing growth suppression for useful plants such as crops, ornamental plants, and fruit trees.
また本発明化合物は、 ノ ビエ、 夕マガヤッリ、 ォモダカ、 ホ夕ルイ等の各種水 田雑草に対し、 優れた殺草効力を有し、 イネに選択性を示す。  In addition, the compound of the present invention has excellent herbicidal activity against various paddy weeds such as nobie, evening magayalli, omomodaka and hoyurui, and shows selectivity to rice.
更に本発明化合物は果樹園、 芝生、 線路端、 空き地等の雑草の防除にも適用す ることができる。  Further, the compound of the present invention can be applied to the control of weeds in orchards, lawns, track ends, vacant lots and the like.
本発明化合物には植物成長調節作用を有するものも含まれ、 また本発明化合物 の中間体化合物の中には除草活性を有するものも含まれる。 本発明の除草剤は、 本発明化合物の 1種又は 2種以上を有効成分として含有す る。 本発明化合物を実際に施用する際には他成分を加えず純粋な形で使用できる し、 また農薬として使用する目的で一般の農薬のとり得る形態、 即ち、 水和剤、 拉剤、 粉剤、 乳剤、 水溶剤、 懸濁剤、 フロアブル等の形態で使用することもでき る。 添加剤および担体としては固型剤を目的とする場合は、 大豆粉、 小麦粉等の 植物性粉末、 珪藻土、 燐灰石、 石こう、 タルク、 ベン トナイ ト、 パイロフィ ライ 卜、 ク レイ等の鉱物性微粉末、 安息香酸ソーダ、 尿素、 芒硝等の有機及び無機化 合物が使用される。 液体の剤型を目的とする場合は、 ケロシン、 キシレンおよび ソルベン トナフサ等の石油留分、 シクロへキサン、 シクロへキサノ ン、 ジメチル ホルムア ミ ド、 ジメチルスルホキシ ド、 アルコール、 アセ ト ン、 ト リ クロルェチ レン、 メチルイソプチルケ トン、 鉱物油、 植物油、 水等を溶剤として使用する。 これらの製剤において均一かつ安定な形態をとるために、 必要ならば界面活性剤 を添加することもできる。  The compounds of the present invention include those having a plant growth regulating action, and the intermediate compounds of the present compounds also include those having a herbicidal activity. The herbicide of the present invention contains one or more of the compounds of the present invention as an active ingredient. When the compound of the present invention is actually applied, it can be used in a pure form without adding other components, and can be in a form that can be taken by a general pesticide for the purpose of using it as a pesticide, that is, a wettable powder, an abductant, a powder, It can also be used in the form of emulsions, aqueous solvents, suspensions, flowables and the like. When solid additives are used as additives and carriers, vegetable powders such as soybean flour and flour, diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, clay and other mineral fine powders Organic and inorganic compounds such as sodium benzoate, urea, and sodium sulfate are used. For liquid dosage forms, petroleum fractions such as kerosene, xylene and sorbent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetate, and tris Use chlorethylene, methylisobutyl ketone, mineral oil, vegetable oil, water, etc. as solvents. In order to obtain a uniform and stable form in these preparations, a surfactant may be added if necessary.
本発明除草剤における有効成分瀠度は前述した製剤の形により種々の濃度に変 化するものである力く、 例えば、 水和剤に於いては、 5 ~ 9 0 好ましく は 1 0 - 8 5 % : 乳剤に於いては、 3 ~ 7 0 %、 好ま しく は 5 ~ 3 0 % ： 拉剤に於いて は、 0 . 0 1 ~ 3 0 %、 好ましく は、 0 . 0 5 %〜 1 0 %の濃度が用いられる。 このようにして得られた水和剤、 乳剤は水で所定の澳度に希釈して懸濁液或い は乳濁液として、 粒剤はそのまま雑草の発芽前又は発芽後に土壌に散布処理もし く は混和処理される。 実際に本発明除草剤を適用するに当たっては 1 0アール当 たり有効成分 0 . 1 g以上の適当量が施用される。 The concentration of the active ingredient in the herbicide of the present invention varies depending on the form of the preparation described above. 5 to 90%, preferably 10 to 85% for wettable powders; 3 to 70%, preferably 5 to 30% for emulsions. %: For abductants, a concentration of 0.01 to 30%, preferably 0.05 to 10% is used. The wettable powder and emulsion thus obtained are diluted with water to a predetermined degree to form a suspension or an emulsion, and the granules are directly sprayed on the soil before or after germination of the weeds. Or mixed. In actually applying the herbicide of the present invention, an appropriate amount of 0.1 g or more of the active ingredient is applied per 10 ares.
又、 本発明除草剤は公知の殺菌剤、 殺虫剤、 殺ダニ剤、 除草剤、 植物成長調整 剤等と混合して使用することも出来る。 特に、 除草剤と混合使用することにより 、 使用薬量を減少させることが可能である。 又、 省力化をもたらすのみな ず、 混合薬剤の相乗作用により一履高い効果も期待できる。 その場合、 複数の公知除 草剤との組合せも可能である。  Further, the herbicide of the present invention can be used in combination with known fungicides, insecticides, acaricides, herbicides, plant growth regulators and the like. In particular, it is possible to reduce the amount of drug used by mixing and using herbicides. In addition to the labor saving, the synergistic action of the mixed drug can be expected to have a much higher effect. In that case, a combination with a plurality of known herbicides is also possible.
本発明除草剤と混合使用するにふさわしい薬剤としては、 ベンチォカーブ、 モ リネー ト、 ジメ ピぺレー 卜等のカーバメィ 卜系除草剤、 チォカーバメイ 卜系除草 剤、 ブタクロール、 プレチラクロール、 メ フヱナセッ ト等の酸ァ ミ ド系除草剤、 クロメ 卜キシニル、 ビフエノ ッ クス等のジフエニルエーテル系除草剤、 ア トラジ ン、 シアナジン等の 卜 リアジン系除草剤、 クロルスルフロン、 スルホメ チュロン 一メチル等のスルホニルゥ レア系除草剤、 M C P、 M C P B等のフエノキシアル 力ンカルボン酸系除草剤、 ジクロホップ一メチル等のフヱ ノキシフヱノキシプロ ピオン酸系除草剤、 フルァジホップブチル等のピリ ジルォキシフエノキシプロピ オン酸系除草剤、 卜 リフルラリ ン、 ペンジメ タ リ ン等のジニトロアニリ ン系除草 剤、 リニュロン、 ジゥロン等のウ レァ系除草剤、 ベンゾィルプロ ップェチル、 フ ランプロップェチル等のベンゾィルァミ ノプロピオン酸系除草剤、 ィマザキン等 のイ ミ ダゾリ ノ ン系除草剤、 その他と して、 ビベロホス、 ダイムロン、 ベン夕ゾ ン、 ダイフェ ンゾコー ト、 ナブロアニリ ド、 エ トベンザニ ド、 卜 リアゾフエナ ミ ド、 キンク口ラッ ク、 更に、 セ トキシジム、 ク レソジム等のシク口へキサンジォ ン系の除草剤等が挙げられる。 又、 これらの組み合わせた物に植物油及び油濃縮 物を添加することも出来る, 次に、 本発明除草剤に関する製剤例を若干示すが、 有効成分化合物、 添加物及 び添加割合は、 本実施例にのみ限定されることなく、 広い範囲で変更可能である 。 製剤実施例中の部は重量部を示す。 Suitable agents to be used in combination with the herbicide of the present invention include carbamate herbicides such as benthiocarb, molinate, and dimepirate, acid carbohydrate herbicides, butachlor, pretilachlor, and mefenacet. Mid-type herbicides, diphenyl ether-type herbicides such as chrometoxynil, biphenox, etc .; triazine-type herbicides such as atrazine and cyanadine; and sulfonyl-urea-type herbicides such as chlorsulfuron and sulfometurone monomethyl. , Carboxylic acid herbicides such as MCP, MCPB, etc., phenoxycarboxylic acid herbicides such as diclohop-methyl, etc., and pyridyloxyphenoxypropionic acid such as fludihopbutyl. Dinitroaniline such as herbicides, trifluralin, and pendimethalin Herbicides, urea herbicides such as linuron and diuron, benzoylaminopropionic acid herbicides such as benzoylprophetyl and flavonopetyl, and imidazolinone herbicides such as imazaquin; and others, biverofos , Daimron, Benzozon, Difenzocoat, Nabroanilide, Etobenzanide, Triazophenamide, Kink Mouth Rack, and Xanthion herbicides such as Sethoxydim, Cresodim, etc. Can be Vegetable oil and oil concentrate Next, some formulation examples of the herbicide of the present invention are shown, but the active ingredient compounds, additives and the ratio of addition are not limited only to this example, but can be changed over a wide range. It is possible. Parts in Formulation Examples are parts by weight.
実施例 3 水和剤 Example 3 wettable powder
本発明化合物 2 0部  Compound of the present invention 20 parts
ホワイ トカーボン 2 0部  White carbon 20 parts
ケイソゥ土 5 2部  Diatomaceous earth 5 2 parts
アルキル硫酸ソーダ 8部  Sodium alkyl sulfate 8 parts
以上を均一に混合、 微細に粉砕して、 有効成分 2 0 %の水和剤を得た。  The above components were uniformly mixed and finely pulverized to obtain a wettable powder containing 20% of the active ingredient.
実施例 4 乳剤 Example 4 Emulsion
本発明化合物 2 0部  Compound of the present invention 20 parts
キシレン 5 5部  Xylene 5 5 parts
ジメチルホルムアミ ド 1 5部  Dimethylformamide 15 parts
ポリオキシエチレンフエニルエーテル 1 0部  Polyoxyethylene phenyl ether 10 parts
以上を混合、 溶解して有効成分 2 0 %の乳剤を得た。  The above ingredients were mixed and dissolved to obtain an emulsion containing 20% of the active ingredient.
実施例 5 粒剤 Example 5 granules
本発明化合物 5部  5 parts of the compound of the present invention
タルク 4 0部  Talc 40 parts
ク レー 3 8部  Cray 3 8 copies
ベン トナイ 卜 1 0部  Bentonite 10 copies
アルキル硫酸ソーダ 7部  Sodium alkyl sulfate 7 parts
以上を均一に混合して微細に粉砕後、 直径 0 . 5〜 1 0 m mの粒状に造粒し て有効成分 5 %の粒剤を得た。 次に本発明除草剤の効果に関する試験例を示す t 除草効果は下記の調査基準に従って調査し、 殺草指数で表した < The above mixture was uniformly mixed and finely pulverized, and then granulated into particles having a diameter of 0.5 to 10 mm to obtain granules having an active ingredient of 5%. T of the following test examples on the effect of the present invention herbicides The herbicidal effect was investigated according to the following criteria and expressed as a herbicidal index <
調査基準 Survey criteria
殺 草 率 殺 草 指 数  Killing rate killing index
0 % 0  0% 0
2 0〜 2 9 % 2  20 to 29% 2
4 0 - 4 9 % 4  4 0-4 9% 4
6 0〜 6 9 % 6  6 0 to 6 9% 6
8 0 - 8 9 % 8  8 0-8 9% 8
1 0 0 % 1 0  1 0 0% 1 0
また、 1 、 3、 5、 7、 9の数値は、 各々 0と 2、 2 と 4 , 4 と 6、 6と 8 8 と 1 0の中間の値を示す  The numbers 1, 3, 5, 7, and 9 are intermediate values between 0 and 2, 2 and 4, 4 and 6, 6, 8 and 10 respectively.
(無処理区の地上部生草重 -処理区の地上部生草重） 殺草率 （％) =· X 1 0 0 無処理区の地上部生草重 試験例 1 畑作土壌処理 (Aboveground fresh grass weight in untreated area-Aboveground fresh grass weight in treated area) Herbicidal rate (%) =
表面椟が 2 5 0 c m2 のプラスチックポッ 卜に畑土壌を充填し、 これにアキノ エノコログサ、 ィヌ ビュ、 ィチビの種子を播種し、 その上に 0. 5 c mの?^土を した。 翌日実施例 3に示した水和剤の希釈液を、 その有効成分が h a当り 2 5 0 gとなるように土壌表面に均一に散布し、 処理 3週間後に除草効果を調査し、 そ の結果を第 1 0表に示した。 第 1 0 表 化合物番号 薬 量 アキノ エノ ィヌ ビュ ィチビ Field soil was filled into a plastic pot with a surface of 250 cm 2 , and seeds of Aquino enokologa, Inubu and Ichibi were sown, and 0.5 cm of soil was put on it. The next day, the diluent of the wettable powder shown in Example 3 was evenly sprayed on the soil surface so that the active ingredient amounted to 250 g / ha, and three weeks after the treatment, the herbicidal effect was investigated, and the results were obtained. Are shown in Table 10. Table 10 Compound No.Dose Aquino enoine buichibi
g/h a コログサ  g / h a
1一 1 2 5 0 1 1 1 2 5 0
1一 2 1 1 2
1一 9 1 9
2 -5 1 0 比較剤 A 2 -5 1 0 Comparative agent A
比絞例 A Comparative example A
Figure imgf000068_0001
Figure imgf000068_0001
WO 9 4 / 1 7 0 5 9記載の化合物 試験例 2 水田茎葉処理 Compounds described in WO 94/17095 Test Example 2 Paddy foliage treatment
表面穣が 1 0 0 c m2 のポッ トに水田土壌を充塡し、 代搔き後、 ノ ビエ、 タマ ガヤッリおよびォモダカの種子を播種したのち、 2葉期のイネを移植した。 これ を温室内で生育させ. 各雑草が〗〜 1. 5葉期になった時点で水深 3 c mに湛水 した後、 各供試化台物の実施例 3で示した水和剤の水希釈液を、 有効成分が 6 2 - 5 g / h aとなるように滴下処理した。 処理 3週間後に除草効果およびイネの 薬害程度を調査し、 その結果を第 1 1表に示した。 Pots with a surface yield of 100 cm 2 were filled with paddy soil, and after replacement, seeds of Novier, Tama Gayarri and Omodaka were sown, and rice plants at the two leaf stage were transplanted. This is grown in a greenhouse. When each weed reaches the〗 -1.5 leaf stage, it is flooded to a depth of 3 cm. After that, a water diluent of the wettable powder shown in Example 3 of each test platform was dropped so as to have an active ingredient of 62-5 g / ha. Three weeks after the treatment, the herbicidal effect and the degree of phytotoxicity of rice were investigated. The results are shown in Table 11.
第 1 1 表 化合物番号 薬量 ノ ビエ タマガヤッリ ォモダカ 移植イネ g / h a Table 11 1 Compound No.Dose Noviet Tamagayarimodoka transplanted rice g / ha
1 - 1 6 2. 5 1-1 6 2.5
1 一 2 1 0 1 1 2 1 0
1 一 3 1 one 3
1 一 9 1 one 9
1 一 49 1 one 49
1 - 50 1 0 1-50 1 0
2 - 2 1 0 2-2 1 0
2 一 5 1 0 比絞剤 A 6 2. 5 2 1 5 10 Specific agent A 6 2.5
1 2 5 1 2 5
産業上の利用可能性： Industrial applicability:
本発明化台物は畑作条件で、 土壌処理、 茎葉処理のいずれの方法でも高い除草 活性を示し、 アキノエノ コログサ、 ィチビ、 ィヌ ビュ等の各種畑雑草に有効で、 トウモロコシ、 ムギ、 大豆、 ヮ夕等の作物に選択性を示す化合物が含まれている 。 また、 本発明化合物には、 作物、 観貧用植物、 果樹等の有用植物に対し、 生育 抑制作用を示す化合物も含まれている。 また本発明化合物は、 ノ ビエ、 タマガヤ ッリ、 ォモダカ、 ホ夕ルイ等の各種水田雑草に対し、 優れた殺草効力を有し、 ィ ネに選択性を示す化台物が含まれている。 更に本発明化合物は果樹園、 芝生、 線 路端、 空き地等の雑草の防除にも適用することができる。 The paddy of the present invention shows high herbicidal activity in any of soil treatment and foliage treatment under upland cropping conditions, and is effective against various field weeds such as Aquinoeno korogusa, Ichibi and Inubu. Contains compounds that are selective for crops such as corn, wheat, soybeans, and soybeans. The compounds of the present invention also include compounds that exhibit a growth-inhibiting effect on useful plants such as crops, ornamental plants, and fruit trees. Further, the compound of the present invention has an excellent herbicidal activity against various paddy weeds such as Nobie, Tamagayari, Omodaka, Hoyurui, etc., and contains fossils showing selectivity to rice. . Further, the compound of the present invention can also be applied to the control of weeds in orchards, lawns, roadsides, vacant lots and the like.
従って、 本発明化合物を含有する組成物は除草剤と して有用である。  Therefore, a composition containing the compound of the present invention is useful as a herbicide.

Claims

i青 求 の 範 囲 l . —般式 〔 1〕 で表される化合物又はその農園芸学上許容される塩。 i The range of blue demand l. —A compound represented by the general formula [1] or a salt thereof that is acceptable in agriculture and horticulture.
Figure imgf000072_0001
Figure imgf000072_0001
〔式中、 Aは N又は CR3 を表し、 Zは◦又は Sを表し、 Qは炭素原子でベンゼ ン環と結合している、 N、 0、 もしく は Sを同一または相異なって 1 ~ 4個含む 置換基を有していてもよい 5〜 6員のへテロ環基を表し、 、 R2 は各々独立 して水素原子、 Cい fi アルキル基、 C ,-u アルコキシ基、 ハロ -" アルキル基、 ハロ C u アルコキシ基、 C アルキルアミ ノ基、 ジ κ アルキルアミ ノ基、 C アルキルチオ基、 ハロゲン原子又はシァノ基を表し、 R3 は水素原子、 C ,-6 アルキル基、 ハロゲン原子、 ニトロ基、 ホルミル基、 ァシル基を表すか、 又 は R2 と一緒になって環を形成していても良く、 Xは、 式 NR4 Rs (式中、 R , 及び R5 は各々独立して、 C アルキル基、 C:1-7 シクロアルキル基、 C ,- e アルコキシ アルキル基、 C2- B アルケニル基、 C2-e アルキニル基、 ヒ ドロキシル アルキル基、 C ,- s アルコキシカルボニル基、 C ,-" アルキル スルホニル基、 ァシルォキシ基、 力ルバモイル基、 チォカルバモイル基、 置換さ れても良いベンジル基、 置換されても良いフ ニル基、 置換されてもよいへテロ 環基、 置換されても良いフヱニルスルホニル基、 置換されても良いベンゾィル基(Wherein A represents N or CR 3 , Z represents ◦ or S, and Q represents a carbon atom bonded to the benzene ring. Represents a 5- to 6-membered heterocyclic group which may have a substituent (s), wherein R 2 is each independently a hydrogen atom, a C- fialkyl group, a C, -u alkoxy group, a halo - "alkyl group, halo C u alkoxy groups, C alkylamino amino group, di-κ alkylamino Roh groups, C alkylthio group, a halogen atom or a Shiano group, R 3 is a hydrogen atom, C, - 6 alkyl group, a halogen atom, X may represent a nitro group, a formyl group, an acyl group, or may form a ring together with R 2 , wherein X is a group represented by the formula NR 4 R s , wherein R, and R 5 are each independently to, C alkyl, C: 1 - 7 cycloalkyl group, C, - e alkoxy group, C 2 - B alkenyl groups, C 2 - e Arukini Alkyl group, hydroxyalkyl group, C, -s alkoxycarbonyl group, C,-"alkylsulfonyl group, acyloxy group, carbamoyl group, thiocarbamoyl group, benzyl group which may be substituted, benzyl group which may be substituted, An optionally substituted heterocyclic group, an optionally substituted phenylsulfonyl group, an optionally substituted benzoyl group
、 又は置換されても良いヘテロ環カルボ二ル基を表すか、 と R5 が一緒にな つて環を形成してもよい。 但し、 と R5 が共に B アルコキシカルボニル 基、 水酸基、 C ,； アルコキシ基、 C2-fi アルケニルォキシ基、 ハロ C , -" アル コキシ甚又はァシルォキシ基ではない。 ） を表す。 〕 Or represents an optionally substituted heterocyclic carboxy group, or and R 5 may be taken together to form a ring. However, and R5 are both B alkoxycarbonyl group, a hydroxyl group, C,; alkoxy group, C 2 - fi Arukeniruokishi group, halo C, - "alkoxy甚又represents not) in Ashiruokishi group]..
2. —般式 〔 1〕 において、 Qが式 2. —In the general formula [1], Q is the formula
Figure imgf000073_0001
Figure imgf000073_0001
〔式中、 〜Υ5 は、 水素原子、 C ,-« アルキル基、 C3-7 シクロアルキル基Wherein, ～Upushiron 5 is a hydrogen atom, C, - «alkyl group, C 3 - 7 cycloalkyl group
、 ハロ アルキル基、 d-6 アルコキシ C，— 6 アルキル基、 アルキルチ ォじ 《 アルキル基、 アルキルスルホ二ルじ (i アルキル基、 C2-« ァルケ ニル基、 C 2 〜(！ アルキニル基、 ハロゲン原子、 シァノ基、 ニ トロ基、 ア ミ ノ基、 C 1 -C アルキルア ミ ノ基、 ァシルァ ミ ノ基、 C卜 (！ アルキルスルホニルァ ミ ノ基、 ヒ ドロキシル基、 カルボキシル基、 κ アルコキシカルボニル基、 C , -" アルコ キシ基、 置換されても良いベンジルォキシ基、 C B アルケニルォキシ基、 C 2 -" アルキニルォキシ基、 ハロ C " アルコキシ基、 « アルキルチオ基、 C i-r; ァ ルキルスルホニル基、 C 2- (； アルケニルチオ基、 C2-B アルキニルチオ基、 ァシル ォキシ基、 力ルバモイルォキシ基、 チォカルバモイルォキシ基、 アミ ノォキシ基、 置換されても良いベンジル基、 置換されても良いフ ニル基、 置換されても良い フエ二ルチオ基、 置換されても良いフエニルスルホニル基、 置換されても良いベ • ンゾィル基、 又は置換されても良いヘテロ環ォキシ基およびへテロ環チォ基を表 し、 又、 2つの Y T ~Υ 5 で炭素環、 又はへテロ環を形成してもよい。 〕 で表さ れるヘテロ環基の群から選ばれる 1種である請求項 1 に記載の化合物。 , Haloalkyl group, d-6 alkoxy C, -! 6 alkyl group, alkylthio Oji "alkyl group, an alkylsulfonyl Ji (i alkyl, C2-« Aruke alkenyl group, C 2 ~ (alkynyl group, a halogen atom , Cyano, nitro, amino, C 1 -C alkylamino, acylamino, C (! Alkylsulfonylamino, hydroxy, carboxyl, κ-alkoxycarbonyl, C,-"Arco Alkoxy group, may be substituted Benjiruokishi group, C B Arukeniruokishi groups, C 2 - "Arukiniruokishi group, halo C" alkoxy group, «alkylthio group, C ir; § alkylsulfonyl group, C 2-(; alkenylthio group, C 2 - B alkynylthio, Ashiru Okishi group, forces Rubamoiruokishi group, Chio carbamoyl O alkoxy group, amino Nookishi group, an optionally substituted benzyl group, an optionally substituted off group, substituted A phenylthio group, a phenylsulfonyl group which may be substituted, a benzoyl group which may be substituted, or a heterocyclic oxy group or a heterocyclic thio group which may be substituted; May form a carbocycle or a heterocycle with two Y T to Υ5.] The heterocyclic group represented by the formula:
3. —般式 〔 1〕 において、 Xが式 N R であり、 R 4 及び R5 は各々独 立して、 Cい 12アルキル基である力、、 又は一緒になつて、 式 3. In the general formula [1], X is the formula NR, and R 4 and R 5 are each independently a C 12 alkyl group, or together,
Figure imgf000074_0001
Figure imgf000074_0001
(式中、 Wは 0、 S、 S 0、 S 02 、 C RG 及び N R 7 を表し、 X ' 及び RB は 水素原子、 C ,-12アルキル基、 C 3- 7 シクロアルキル基、 C -r, アルコキシ C卜(Wherein, W is 0, S, S 0, S 0 2, represents a C RG and NR 7, X 'and RB is hydrogen, C, - 12 alkyl group, C 3 - 7 cycloalkyl, C - r, alkoxy C
6 アルキル基、 （： ,-(! アルキルチオ C ,— ti アルキル基、 C ^li アルキルスルホ二 ル C ,； アルキル基、 C 2-« アルケニル基、 C 2-« アルキニル基、 ヒ ドロキシ C 2-0 アルキル基、 アルコキシカルボニル基、 ァミ ノ C，- fi アルキル基、 C ,-6 アルコキシカルボ二ル C アルキル基、 水酸基、 6 アルコキシ基、 C6 alkyl group, (:!, - (alkylthio C, - ti alkyl, C ^ li alkyl sulfonyl Le C,; alkyl group, C 2 - «alkenyl group, C 2 -« alkynyl group, human Dorokishi C 2- 0 alkyl group, an alkoxycarbonyl group, § Mi Bruno C, - fi alkyl, C, - 6 alkoxycarbonyl alkylsulfonyl C alkyl group, a hydroxyl group, 6 alkoxy group, C
2_6 アルケニルォキシ基、 ハロ C !-li アルコキシ基、 C !-O アルキルスルホニル 基、 ァシルォキシ基、 力ルバモイル基、 チォカルバモイル基、 置換されても良い ベンジル基、 置換されても良いフエニル基、 置換されてもよいへテロ環基、 置換 されても良いフヱニルスルホニル基、 置換されても良いベンゾィル基、 又は置換 されても良いヘテロ環カルボニル基、 ァシル基、 ァミ ノ基又はカルボキシル基、 置換されても良いベンゾィル基、 又は置換されても良いヘテロ環カルボ二ル基を 表し、 R7 は水素原子、 C アルキル基、 C シクロアルキル基、 C ,-« ァ ルコキシ C ,-*; アルキル基、 C ,-" アルキルチオ C，- G アルキル基、 d- « アル キルスルホニル C ,-" アルキル基、 Cii-d アルケニル基、 C;;- 1; アルキニル基、 ヒ ドロキシ C 2-6 アルキル基、 C ,-!! アルコキシカルボニル基、 ァミ ノ C，-《 ァ ルキル基、 C，-B アルコキシカルボニル C I - (i アルキル基、 C i- S アルキ ルス ルホニル基、 ァシルォキシ基、 力ルバモイル基、 チォカルバモイル基、 置換され ても良いベンジル基、 置換されても良いフヱニル基、 置換されてもよいへテロ環 基、 置換されても良いフ ニルスルホニル基、 置換されても良いベンゾィル基、 又は置換されても良いヘテロ環カルボ二ル基を表し、 mは 0または 1 ~ 3の整数 を表す。 ） である請求項 1 に記載の化合物。 2 _ 6 alkenyloxy group, halo C! -Li alkoxy group, C! -O alkylsulfonyl group, acyloxy group, carbamoyl group, thiocarbamoyl group, optionally substituted benzyl group, optionally substituted phenyl group An optionally substituted heterocyclic group, an optionally substituted phenylsulfonyl group, an optionally substituted benzoyl group, or an optionally substituted heterocyclic carbonyl group, an acyl group, an amino group or a carboxyl group Group, an optionally substituted benzoyl group, or an optionally substituted heterocyclic carbonyl group And R 7 represents a hydrogen atom, a C alkyl group, a C cycloalkyl group, a C,-<alkoxy C,-*; an alkyl group, a C,-"alkylthio C, -G alkyl group, a d-« alkylsulfonyl C ,-"Alkyl group, Cii-d alkenyl group, C ;;- 1; alkynyl group, hydroxy C 2-6 alkyl group, C,-!! alkoxycarbonyl group, amino C,-<< alkyl group, C, -B alkoxycarbonyl CI-(i alkyl group, C i-S alkylsulfonyl group, acyloxy group, carbamoyl group, thiocarbamoyl group, optionally substituted benzyl group, optionally substituted phenyl group, substituted Represents an optionally substituted heterocyclic group, an optionally substituted phenylsulfonyl group, an optionally substituted benzoyl group, or an optionally substituted heterocyclic carbonyl group, and m is 0 or 1-3 Represents an integer.) Of the compound.
4. 一般式 〔 2〕 4. General formula [2]
Figure imgf000075_0001
Figure imgf000075_0001
[2]  [2]
(式中、 Aは N、 又は C R3 を表し、 R， R2 は各々独立して水素原子、 d- ϋ アルキル基、 C 1 -6 アルコキシ基、 C l-β アルキル基、 ヽロ C l-B アルコ キシ基、 C ,-6 アルキルァミ ノ基、 ジ C アルキルァミ ノ基、 C , -6 アルキル チォ基、 ハロゲン原子又はシァノ基を表し、 R3 は水素原子、 C ,-B アルキル基 、 ハロゲン原子、 ニトロ基、 ホルミル基， ァシル基を表すか、 又は R2 と一緒に なって環を形成していても良く、 Lはハロゲン原子又はアルキルスルホ二ル基を 表す。 ） で表される化合物と、 一般式 〔 3〕
Figure imgf000076_0001
(Wherein, A represents N or CR 3 , R and R 2 each independently represent a hydrogen atom, d-ϋalkyl group, C 1-6 alkoxy group, C 1-β alkyl group, alkoxy groups, C, - 6 Arukiruami amino group, di C Arukiruami amino group, C, -6 alkyl Chiomoto, a halogen atom or a Shiano group, R 3 is a hydrogen atom, C, - B alkyl group, a halogen atom, May represent a nitro group, a formyl group, an acyl group, or may form a ring together with R 2, and L represents a halogen atom or an alkylsulfonyl group. General formula (3)
Figure imgf000076_0001
[3]  [3]
〔式中、 Qは炭素原子でベンゼン環と結合している、 N、 0、 もしく は Sを同一 または相異なって 1 ~4個含む置換基を有していてもよい 5〜6員のへテロ環を 表し、 Xは、 式 NR4 R5 (式中、 R4 及び R5 は各々独立して、 水素原子、(In the formula, Q is a carbon atom bonded to a benzene ring, N or 0, or S is the same or different and may have a 5- or 6-membered substituent having 1 to 4 substituents. X represents a heterocyclic ring, wherein X is a group represented by the formula NR 4 R 5 , wherein R 4 and R 5 are each independently a hydrogen atom,
C 1 -6 アルキル基、 C3 -7 シクロアルキル基、 C , -ti アルコキシ C β アルキル 基、 C -S アルキルチオ C ^K アルキル基、 C ,-fi アルキルスルホニル C fi ァ ルキル基、 C2- « アルケニル基、 C2-B アルキニル基、 ヒ ドロキシル C2 " アル キル基、 C ,- 6 アルコキシカルボニル基、 ァ ミ ノ C ,-6 アルキル基、 β アル コキシカルボニル C ,—« アルキル基、 C ! -G アルキルスルホニル基、 力ルバモイ ル基、 チォカルバモイル基、 置換されても良いベンジル基、 置換されても良いフ ェニル基、 S換されてもよいへテロ環、 置換されても良いフヱニルスルホニル基 、 置換されても良いベンゾィル基、 又は S換されても良いヘテロ環カルボニル基 を表すか、 R4 と R5 が一緒になって環を形成してもよい。 但し、 R4 と R5 が 共に水素原子、 C，- 6 アルコキシカルボニル基ではない。 ） を表し、 Zは 0又は Sを表す。 〕 で表される化合物とを反応させることを特徴とする、 式 〔 1 〕 C 1 -6 alkyl group, C 3 -7 cycloalkyl group, C, -ti alkoxy C beta alkyl group, C -S alkylthio C ^ K alkyl, C, - fi alkylsulfonyl C fi § alkyl group, C 2 - «alkenyl group, C 2 - B alkynyl, human Dorokishiru C 2" Al kill group, C, - 6 alkoxycarbonyl group, § Mi Bruno C, - 6 alkyl group, beta alkoxides aryloxycarbonyl C, - «alkyl group, C! -G alkylsulfonyl group, carbamoyl group, thiocarbamoyl group, benzyl group which may be substituted, phenyl group which may be substituted, heterocyclic ring which may be substituted, Represents a benzylsulfonyl group, a benzoyl group which may be substituted, or a heterocyclic carbonyl group which may be S-substituted, or R 4 and R 5 may form a ring together, provided that R 4 and R 5 are both hydrogen atoms, C, - 6 alkoxy Not a carbonyl group.) Represent, Z is characterized by reacting a compound represented by the representative.] 0 or S, wherein (1)
Figure imgf000077_0001
Figure imgf000077_0001
(式中、 A, Q, X, Z， R , および R2 は前記と同一の意味を表す。 (Wherein, A, Q, X, Z, R, and R 2 represent the same meaning as described above.
で表される化合物の製造方法。 A method for producing a compound represented by the formula:
5. —般式 〔 1〕 5. —General formula [1]
Figure imgf000077_0002
Figure imgf000077_0002
〔式中、 Aは N又は C R3 を表し、 Zは 0又は Sを表し、 Qは炭素原子でベンゼ ン環と結合している、 N、 0、 もしく は Sを同一または相異なって 1〜4個含む 置換基を有していてもよい 5~6員のへテロ環を表し、 R, 、 R2 は各々独立し て水素原子、 C ,-6 アルキル基、 C i-K アルコキシ基、 ハロ C . -li アルキル基、 ハロ d-fi アルコキシ基、 アルキルアミ ノ基、 ジ アルキルアミ ノ基 、 C , -e アルキルチオ基、 ハロゲン原子又はシァノ基を表し、 R3 は水素原子、 C . -6 アルキル基、 ハロゲン原子、 ニトロ基、 ホルミル基、 ァシル基を表すか、 又は R2 と一緒になって環を形成していても良く、 Xは、 式 NR4 R5 (式中、 R4 及び R5 は各々独立して、 水素原子、 d-ti アルキル基、 C:,-7 シクロアル キル基、 C !- 6 アルコキシ C，- G アルキル基、 C ,—e アルキルチオ 6 アルキ ル基、 C，- 6 アルキルスルホニル C ,-6 アルキル基、 C2-ti アルケニル基、 C2- ϋ アルキニル基、 ヒ ドロキシル C2- 8 アルキル基、 C -K アルコキシカルボニル 基、 ァミ ノ C !-li アルキル基、 C i-e アルコキシカルボ二ル , -6 アルキル基、 C , -C アルキルスルホニル基、 力ルバモイル基、 チォカルバモイル基、 置換され ても良いベンジル基、 置換されても良いフヱニル基、 置換されてもよいへテロ環 基、 置換されても良いフエニルスルホニル基、 換されても良いベンゾィル基、 又は置換されても良いヘテロ環カルボ二ル基を表すか、 R , と が一緒になつ てへテロ環を形成してもよい。 但し、 と Rs が共に水素原子、 C ,； アルコ キシカルボニル基、 水酸基、 アルコキシ基、 C 2- 6 アルケニルォキシ基、 ハロ アルコキシ基又はァシルォキシ基ではない。 ） を表す。 〕 で表される 化合物又はその農園芸学上許容される塩を有効成分と して含有することを特徴と する除草剤。 In the formulas, A represents N or CR 3, Z represents 0 or S, Q is bound to benzene ring carbon atoms, N, 0, Moshiku the same or different and S 1 Represents a 5- to 6-membered heterocyclic ring which may have a substituent, wherein R, R 2 are each independently a hydrogen atom, a C 6 alkyl group, a C iK alkoxy group, a halo C. -li alkyl group, halo d-fi alkoxy groups, alkylamino amino group, di-alkylamino cyano group, C, -e alkylthio group, a halogen atom or a Shiano group, R 3 is a hydrogen atom, C. -6 alkyl group , A halogen atom, a nitro group, a formyl group, an acyl group, or may form a ring together with R 2 , X is a group represented by the formula NR 4 R 5 (wherein R 4 and R 5 are each independently represent a hydrogen atom, d-ti alkyl group, C:!, - 7 a cycloalkyl group, C - 6 alkoxy C, - G alkyl, C, - e alkyl Thio 6 alkyl le group, C, - 6 alkylsulfonyl C, - 6 alkyl group, C 2 -ti alkenyl group, C 2 - ϋ alkynyl group, human Dorokishiru C 2 - 8 alkyl group, C -K alkoxycarbonyl group, § Mino C! -Li alkyl group, C ie alkoxycarbonyl, -6 alkyl group, C, -C alkylsulfonyl group, carbamoyl group, thiocarbamoyl group, optionally substituted benzyl group, optionally substituted A phenyl group, an optionally substituted heterocyclic group, an optionally substituted phenylsulfonyl group, an optionally substituted benzoyl group, Or a heterocyclic carbonyl group which may be substituted, or R and may form a heterocycle together. However, the R s are both hydrogen atoms, C,; alkoxycarbonyl group, a hydroxyl group, an alkoxy group, C 2 - 6 Arukeniruokishi group, not a halo alkoxy or Ashiruokishi group. ). ] The herbicide characterized by containing the compound represented by these, or its agriculturally and horticulturally acceptable salt as an active ingredient.
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