WO1996019470A1 - Procede de preparation d'un derive de pyrazole - Google Patents

Procede de preparation d'un derive de pyrazole Download PDF

Info

Publication number
WO1996019470A1
WO1996019470A1 PCT/JP1995/002581 JP9502581W WO9619470A1 WO 1996019470 A1 WO1996019470 A1 WO 1996019470A1 JP 9502581 W JP9502581 W JP 9502581W WO 9619470 A1 WO9619470 A1 WO 9619470A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
reaction
general formula
alkyl group
integer
Prior art date
Application number
PCT/JP1995/002581
Other languages
English (en)
Japanese (ja)
Inventor
Masashi Sakamoto
Ichiro Nasuno
Original Assignee
Idemitsu Kosan Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Idemitsu Kosan Co., Ltd. filed Critical Idemitsu Kosan Co., Ltd.
Priority to AU41890/96A priority Critical patent/AU4189096A/en
Publication of WO1996019470A1 publication Critical patent/WO1996019470A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/06—Benzothiopyrans; Hydrogenated benzothiopyrans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • the present invention relates to a novel method for producing a virazole derivative useful as a herbicide, and an intermediate thereof.
  • WO 94/01431 does not cause harm to useful crops such as corn, wheat, barley, etc .; Novel virazole derivatives with excellent selectivity that can control both at low doses have been reported.
  • the ⁇ ⁇ ⁇ method of a novel pyrazole derivative described in the IHJ publication requires the synthesis of a carboxylic acid by a Grignard reaction as a [i] -isomer, and the condensation reaction using dicyclohexylcarpo- imide (DCC). However, many steps such as a transfer reaction using a base were required.
  • a thiochroman-41-one derivative which is a raw material of an intermediate carboxylic acid, was prepared by the method described in Japanese Patent Application Laid-Open No. 58-198483, International Publication W088 / 06155 and Can. J. Chem. , 51, 839 (1973).
  • some R-type thiochroman-4-one derivatives require an isomer separation step, resulting in low yield. Will be.
  • the present invention does not require an isomer separation step that results in a low yield as described above and a complicated step of synthesizing carboxylic acid to produce a virazole derivative useful as a herbicide. It is an object of the present invention to provide a method for producing a virazole derivative which is advantageous to the above.
  • the purpose of the Kimi II sword is to provide a new method of producing a wild virulence attractant as a herbicide.
  • a second object of the present invention is to provide a process for producing a novel diazole or a hapogen compound, which is a production intermediate for producing a novel virazole derivative and is a novel compound.
  • a third object of the present invention is to provide a method for producing an amino compound, which is a production intermediate for producing the above-mentioned diazonium or halogen compound and is a novel compound.
  • a fourth object of the present invention is to provide a process for producing a nuclear halogenated amino compound, which is an intermediate for producing the amino compound and is a novel compound.
  • a fifth object of the present invention is to provide a nitro compound which is an intermediate for producing the above-mentioned nucleated halogenated amino compound or amino compound and which is a novel compound.
  • the present inventors have conducted intensive studies to achieve the above objectives, and the results are shown below. ”: It is industrially possible, which does not include the isomer separation process and the synthetic soil of carboxylic acid. The inventors have found an advantageous method for producing a virazole derivative and an intermediate thereof, and have completed the present invention.
  • the first object of the present invention is to provide a compound represented by the general formula (IV)
  • R 1 and X ′ each independently represent a Ci-C 4 alkyl group, X 3 represents a diazodium salt or a halogen atom, and n represents an integer of 0, 1 or 2.
  • a diazonium or halogen compound represented by the following formula hereinafter referred to as “diazonium or halogen compound (IV)”);
  • a virazole compound (hereinafter, referred to as a “birazol compound (V ) ”).
  • the general (VI) which is characterized by the reaction of
  • Vila ′ nol derivative (VI) Is achieved by A second object of the present invention is to provide a compound of the general formula (III)
  • R 1 and X 1 each independently represent a C, to C 4 alkyl group, and n represents an integer of 0, 1 or 2).
  • II I ").
  • the general formula (IV) characterized in that diazotization is carried out and reacted with tetrafluoroboronic acid or cuprous halide.
  • a third object of the present invention is to provide a compound of the general formula ( ⁇ )
  • nuclear halogenated amino compound (II) characterized by the general formula (III)
  • a fourth object of the present invention is to provide a compound represented by the general formula (I)
  • R 1 and X ′ each independently represent a C 4 alkyl group, X 2 represents a halogen atom, and n represents an integer of 0, 1 or 2.
  • FIG. 1 is a diagram showing a process for producing the virazole derivative (VI) of the present invention.
  • ⁇ -alkyl group in R ′, R 2 , R 3 and X 1 in the above compound examples include propyl groups such as methyl group, ethyl group, n-propyl group and i-propyl group. And butyl groups such as n-butyl group, i-butyl group and the like.
  • halogen atom in X 2 and X 3 include chlorine.
  • the method for producing the birazol derivative (VI), which is the first object of the present invention, comprises a reaction scheme
  • the amount of the catalyst is generally from 0.01 to 1.0 equivalent relative to the diazonium or the halogen compound (IV), but preferably from 0.05 to 0.5 equivalent.
  • the ligand used for the catalyst metal is not particularly limited, but an organophosphine compound of triphenylphosphine or tri-n-butylphosphine is preferred.
  • the ⁇ of the ligand is 2.0 to 10.0 equivalents, preferably 2.0 to 4.0 equivalents to the metal catalyst.
  • Examples of the base coexisting in the reaction system include organic bases such as pyridine, triethylamine, N, N-dimethylaniline, and inorganic bases such as sodium carbonate, potassium carbonate, and sodium hydroxide, and preferably potassium carbonate.
  • the amount of base is diazo It is 1.0 to 20.0 equivalents, preferably 1.0 to 10.0, relative to the nickel or halogen compound (IV).
  • a phase transfer catalyst such as a tetra-n-butylamine in combination with these salts from the viewpoint of improving the reactivity.
  • This reaction is carried out in a carbon monoxide atmosphere.
  • the pressure of carbon monoxide is generally from normal pressure to 200 kg / cm 2 , but is preferably about 50 to 150 kg / cm 2 .
  • the reaction temperature is generally room temperature to 200 ° C, preferably 50 to 180 ° C.
  • the reaction time is generally 30 minutes to 200 hours, but is usually completed in 1 to 100 hours.
  • the reaction medium is not particularly limited as long as it does not hinder the reaction, but it is usually preferable to use 1,4-dioxane, acetonitrile and the like.
  • the amount of the bisazole compound (V) used in the reaction is generally 1.0 to: I 0.0 equivalent, preferably 1.0 to 5.0 equivalent, relative to diazonium or halide (IV). -Go.
  • the virazole derivative (VI), which is the target product obtained in this reaction is filtered off insolubles according to a conventional method, the solvent is distilled off, and the resulting residue is subjected to a suitable solvent such as ethyl acetate. It can be isolated by separating the liquid with a suitable '' I aqueous medium '' of the aqueous medium and the aqueous medium of W acidified lime, and drying the precipitate from the water.
  • the crude crystal of the birazol derivative (VI) obtained here can be further purified by means such as column chromatography to obtain a sample for identification data.
  • the method for producing a diazonium compound (IVa) wherein X 3 is a diazonium salt comprises a reaction formula
  • Solvents that can be used in this reaction include acetic acid and aqueous hydrochloric acid, and acetic acid is preferred.
  • the diazotization reaction in the first stage can be carried out by a usual method.
  • an aqueous solution of sodium nitrite is added dropwise to a solution of the amino compound (III) and hydrohalic acid in a solvent such as acetic acid. Do by doing.
  • hydrohalic acid examples include hydrobromic acid and hydrochloric acid.
  • the hydrohalic acid is generally used in an amount of 1.0 to 5.0 equivalents, preferably 1.0 to 2.0 equivalents, relative to the amino compound (III).
  • Sodium nitrite is generally used in an amount of 1.0 to 1.5 equivalents, preferably 1.0 to 1.2 equivalents, relative to the amino compound (III).
  • the reaction temperature of the diazotization reaction is generally in the range of 20 ° C to 20 ° C, but is preferably 0 ° C or lower.
  • the latter reaction for obtaining the diazonium salt is carried out by gradually dropping the solution after the first diazotization reaction (hereinafter referred to as “diazonium solution j”) into a tetrafluoroboronic acid solution.
  • the diazonium compound (IVa) can be obtained
  • the tetrafluoroboric acid used in the present reaction is a concept including a salt of tetrafluoroboric acid, and a specific example thereof is tetrafluoroborough. Acids, sodium borofluoride, ammonium fluoride, and the like, with tetrafluoroboric acid being preferred.
  • tetrafluoroboronic acid is generally from 2.0 to 5.0, 1 , A (preferably from 2.0 to 3.0) for the amino compound (III).
  • the reaction temperature of the reaction for obtaining the diazodium salt is generally in the range of 20 to 100 ° C, preferably 0 ° C to room temperature.
  • the reaction time is generally 30 minutes to 2 hours.
  • the diazonium compound (IVa) thus obtained is a novel compound and is useful as an intermediate for producing the virazole derivative (VI).
  • the second object of the present invention that is, diazonium or halogen compound (IV)
  • the method for producing the halogen compound (IVb) wherein X 3 is a halogen atom comprises the reaction scheme
  • the diazonium solution obtained by the first diazotization reaction is converted into a halogenated aqueous solution containing a cuprous halide, such as hydrobromic acid or hydrochloric acid. It is carried out by gradually shaking to obtain the desired halide (IVb). At this time, it is also effective to add a small amount of ethyl acetate to suppress foaming of the reaction solution.
  • a cuprous halide such as hydrobromic acid or hydrochloric acid
  • Cuprous halide which can be used in this reaction includes cuprous chloride, cuprous bromide and the like.
  • the cuprous halide is generally used in an amount of 1.0 to 3.0 equivalents, preferably 1.0 to 2.0 equivalents, based on the amino compound (III).
  • Hydrohalic acid is generally 1.0 to 5.0 equivalents, preferably 1.0 to 2.0 equivalents to the amino compound (III).
  • the reaction temperature is generally 0 ° (: up to 80, preferably 35 ° (: up to 45 ° C.)
  • the reaction time is usually 10 minutes to 1 hour.
  • a solution prepared in advance by reacting copper sulfate with sodium halide may be used.
  • dissolve copper sulfate in warm water at 50 ° C to 60 ° C add 1.0 to: L.2 equivalent of sodium hacogenide, 0.5 to 1.0
  • the target halogen compound (IVb) can also be obtained by dropping a diazonium solution into this solution. It is also effective to add a small amount of ethyl acetate in order to suppress foaming of the reaction solution. After extraction, washing and drying of the organic layer, the solvent can be distilled off and isolated.
  • the thus-obtained halogen compound (IVb) is a novel compound and is useful as an intermediate for producing the virazole derivative (VI).
  • the step C-a for obtaining the compound (IVa) and the step C-b for obtaining the compound (IVb) are defined as (i) using the same starting compound (III), and (ii) diazotization reaction. including, (iii) the obtained compound (IVa) and (IVb), except that the kind of X 1 is different from the same structure, when reacted with the compound (V) in a subsequent step D, have In each case, the group X 3 is eliminated to give the same compound (VI). Therefore, these steps C-a and C-b are positioned as equivalent steps to each other.
  • the method for producing the amino compound (III) starting from the nucleated halogenated amino compound (II) is represented by the following reaction scheme.
  • the hydrogenation catalyst that can be used include palladium and platinum, but palladium is preferable.
  • the amount of the catalyst is generally 0.01 to 1.0 times, preferably 0.05 to 0.5 times, the weight of the nuclear halogenated amino compound (II).
  • a base together with the hydrogenation catalyst.
  • the base there are no particular restrictions on the base that can be used, but inorganic bases such as carbonated sodium, sodium carbonate and sodium hydroxide, and organic bases such as triethylamine and pyridine can be used, with pyridine being particularly preferred.
  • the amount of the base to be used is generally 1.0 to 5.0 equivalents, preferably 1.0 to 3.0 equivalents to 3b-s o with respect to the nuclear halogenated amino compound (II).
  • the solvent used in this reaction is not particularly limited as long as it does not hinder the reaction, but methanol, ethanol and the like are preferable.
  • the reaction pressure of the hydrogen is not particularly restricted to normal pressure ⁇ 100 kg / cm 2, preferably 3 ⁇ 30 kg / cm 2.
  • the reaction temperature is usually from room temperature to 60 ° (: particularly preferably room temperature.
  • the reaction time is generally from 30 minutes to 60 hours, preferably from 2 to 30 hours.
  • the amino compound (III) obtained in this reaction is removed from the reaction mixture by a conventional method after removing the catalyst, the solvent is distilled off, and the obtained residue is dissolved in an appropriate organic solvent such as ethyl acetate. After dissolving, washing and drying the organic layer, the solvent can be distilled off and isolated.
  • the amino compound (III) thus obtained is a novel compound and is useful as a compound during the production of the diazodimide compound (IVa) and the halogenated r compound (IVb).
  • the production method of the compound (III) is a method in which a nuclear halogenated amino compound (II) is subjected to a reduction treatment, and a raw material nuclear halogenated amino compound (II) is produced by a reduction reaction of a nitro compound (I) described later. It can be obtained separately, but the nitro compound (I) is used as a raw material, and the nucleated halogenated amino compound ( ⁇ ) generated by reduction of the nitro compound ( ⁇ ) is continuously separated from the nitro compound (I) without isolation. It is also possible to obtain compound (III).
  • the method for producing the amino compound (III) in one pot from the toro compound (I) is as follows:
  • the one-step reaction of this reaction is a reaction for obtaining a nucleated halogenated amino compound (II) based on a nitrate (I).
  • a fourth object of the present invention to be described later is a nucleated halogenated amino compound. This reaction corresponds to the production method of compound (II), and this reaction is also shown by step A in FIG.
  • the first-stage reduction reaction is achieved by hydrogenating the nitro compound (I) in the presence of a hydrogenation catalyst.
  • the catalyst that can be used here is not particularly limited, but palladium, platinum and the like can be used, and palladium is preferable.
  • the reaction pressure of the hydrogen is not particularly limited to atmospheric pressure ⁇ 1 00 kg / cm 2, the child preferable 3 ⁇ 30 kg / cm 2.
  • the reaction temperature is usually room temperature to 100 ° C, preferably room temperature to 60 ° C.
  • the reaction time is from 1 hour to 24 hours, but usually about 8 hours.
  • the subsequent primary reaction is carried out without releasing the nucleated halogenated amino compound (II) obtained in the previous reduction reaction.
  • the latter il elementary reaction is a reaction in which the above-mentioned nucleated halogenated amino compound (II) is converted to an amino compound (III). This is also the reaction indicated by Bl.
  • the details of the reaction and the method for post-treatment of the target amino compound (III) are as described above.
  • the method for producing a nucleated halogenated amino compound (II), which is the fourth object of the present invention, comprises a reaction scheme
  • the details of this reaction are not particularly limited in the method of reduction in the previous reduction reaction, but a method using a reducing agent such as iron or tin is simple.
  • a method using a reducing agent such as iron or tin is simple.
  • the reduction method there is a method such as reduction with iron in the presence of a mineral acid.
  • the mineral acid used here include hydrochloric acid, sulfuric acid and the like.
  • the amount of the reducing agent for example, in the case of iron, is generally 2 to 5 equivalents, preferably 2.5 to 4 equivalents to the nitro compound (I).
  • the solvent that can be used in the H-stage reaction ( ⁇ 'stage) is not particularly limited as long as it does not hinder the reaction.Ethanol and water are preferred, and ethanol is particularly preferred in consideration of the ill-stage reaction in the latter stage. .
  • the reaction temperature of the first-stage reduction reaction is not particularly limited from room temperature to the reflux temperature of the solvent, but the reflux temperature of the solvent is preferred.
  • the reaction time is usually 30 minutes to 24 hours, but preferably about 4 hours.
  • the nucleated halogenated amino compound (II) obtained by this reaction is washed with a suitable organic solvent such as ethyl acetate according to a conventional method to remove impurities.
  • a suitable organic solvent such as ethyl acetate according to a conventional method to remove impurities.
  • the water W is made alkaline with sodium hydroxide and extracted with ethyl acetate or the like.
  • nucleated halogenated amino compound (II) thus obtained is a novel compound and is useful as an intermediate for producing the amino compound (III).
  • a nitro compound (I) which is an intermediate for producing a nucleated halogenated amino compound (II) and is a novel compound, is represented by the following reaction scheme:
  • the nitrated platform (I) is prepared by adding a thiochroman 4-one compound (VII) and an alkoxyamine (NH 2 ⁇ R ′) in water or an organic solvent (eg, ethanol, methanol, acetic acid, etc.) in an acid catalyst (eg, , Hydrochloric acid, etc.) or in the presence of a base catalyst (eg, pyridine, valine, sodium hydroxide, sodium carbonate, etc.). It is obtained by reacting at C to the reflux temperature of the solvent. Preferably, the reaction is carried out in ethanol in the presence of pyridine at the reflux temperature of the solvent.
  • a thiochroman 4-one compound (VII) and an alkoxyamine (NH 2 ⁇ R ′) in water or an organic solvent (eg, ethanol, methanol, acetic acid, etc.) in an acid catalyst (eg, , Hydrochloric acid, etc.) or in the presence of a base catalyst (eg, pyridine, va
  • the reaction can be 30 minutes to 8 IK'fl'J, but M '1 hour to 4 li ⁇ . In degrees; 7U; S9.
  • the oxidizing agent used in the present oxidation reaction is not particularly limited, and examples thereof include hydrogen peroxide, peracetic acid, and sodium metaperiodate. Hydrogen peroxide is preferable.
  • the solvent to be used is not particularly limited as long as it does not interfere with the reaction. Examples thereof include acetic acid, water, and methanol, and acetic acid is preferable.
  • the obtained nitro compound (I) can be isolated by adding water to the reaction mixture, collecting the precipitated crystals, washing and drying according to a conventional method.
  • the resulting acid Echiru and 5% K 2 C0 3 aqueous solution was separated by adding to the residue.
  • the aqueous layer was neutralized with 5% hydrochloric acid, and the precipitated crystals were collected by filtration and air-dried to obtain 2.5 g (yield 70%) of the desired product.
  • the obtained crystals were purified by column chromatography (elution solvent: black-mouthed form) to obtain 1.6 g (yield 46%) of the target compound (virazole derivative (VI)) as yellow crystals.
  • Table 1 shows the structural formula and N.M.R. data of the obtained target compound (Compound 4).
  • an industrially advantageous virazole derivative which does not require a step of separating isomers which leads to a low yield and a complicated step of synthesizing a carboxylic acid is not required for producing a birazol derivative useful as a herbicide.
  • a manufacturing method was provided.
  • the present invention provides a production intermediate useful for producing a virazole derivative and a production method thereof.

Abstract

La présente invention concerne un procédé, avantageux du point de vue industriel, de préparation d'un dérivé de pyrazole utile comme herbicide, pouvant se passer de la séparation des isomères souffrant d'un faible rendement et de la préparation d'acide carboxylique, qui nécessite des opérations complexes. Le dérivé en question est représenté par les formules (IV), (V), (VI), dans laquelle R?1, R2 et X1¿ sont chacun, indépendamment, un alkyle C¿1?-C4; R?3¿ est H ou un alkyle C¿1?-C4; X?2¿ est un halogène; X3 est un sel de diazonium ou un halogène, et n est 0, 1 ou 2.
PCT/JP1995/002581 1994-12-19 1995-12-15 Procede de preparation d'un derive de pyrazole WO1996019470A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU41890/96A AU4189096A (en) 1994-12-19 1995-12-15 Process for the preparation of pyrazole derivative

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP31466494A JPH08176146A (ja) 1994-12-19 1994-12-19 ピラゾール誘導体の製造法
JP6/314664 1994-12-19

Publications (1)

Publication Number Publication Date
WO1996019470A1 true WO1996019470A1 (fr) 1996-06-27

Family

ID=18056062

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1995/002581 WO1996019470A1 (fr) 1994-12-19 1995-12-15 Procede de preparation d'un derive de pyrazole

Country Status (4)

Country Link
JP (1) JPH08176146A (fr)
AR (1) AR000385A1 (fr)
AU (1) AU4189096A (fr)
WO (1) WO1996019470A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0860441A1 (fr) * 1997-02-24 1998-08-26 E.I. Du Pont De Nemours And Company Dérivés de 1,4-dithiino(2,3c)benzothiopyran comme herbizides

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56142262A (en) * 1980-04-08 1981-11-06 Nippon Shinyaku Co Ltd Piperazine derivative
JPH03503056A (ja) * 1988-12-29 1991-07-11 ノバルティス　アクチエンゲゼルシャフト アクリル酸誘導体
WO1994008988A1 (fr) * 1992-10-15 1994-04-28 Idemitsu Kosan Co., Ltd. Derive de cyclohexanedione
WO1995013275A1 (fr) * 1993-11-09 1995-05-18 Idemitsu Kosan Co., Ltd. Derives de pyrazole et herbicide les contenant

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56142262A (en) * 1980-04-08 1981-11-06 Nippon Shinyaku Co Ltd Piperazine derivative
JPH03503056A (ja) * 1988-12-29 1991-07-11 ノバルティス　アクチエンゲゼルシャフト アクリル酸誘導体
WO1994008988A1 (fr) * 1992-10-15 1994-04-28 Idemitsu Kosan Co., Ltd. Derive de cyclohexanedione
WO1995013275A1 (fr) * 1993-11-09 1995-05-18 Idemitsu Kosan Co., Ltd. Derives de pyrazole et herbicide les contenant

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0860441A1 (fr) * 1997-02-24 1998-08-26 E.I. Du Pont De Nemours And Company Dérivés de 1,4-dithiino(2,3c)benzothiopyran comme herbizides

Also Published As

Publication number Publication date
AU4189096A (en) 1996-07-10
JPH08176146A (ja) 1996-07-09
AR000385A1 (es) 1997-06-18

Similar Documents

Publication Publication Date Title
US7361759B2 (en) Method for producing L-biopterin
JP3981153B2 (ja) Ｎ−置換３−ヒドロキシピラゾールの製造方法
JPH06199763A (ja) 殺虫性ｎ′−置換−ｎ，ｎ′−ジアシルヒドラジン
DE60010682T2 (de) Verfahren zur herstellung von zwischenprodukten für pestizide
US20030187233A1 (en) Perfluoroisopropybenzene derivative
EA001630B1 (ru) Способ получения n-замещенных 3-гидроксипиразолов
WO1996019470A1 (fr) Procede de preparation d'un derive de pyrazole
US4313000A (en) Process for preparing 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro-N-alkanesulphonyl benzamides from a toluene derivative and intermediates
JP3919215B2 (ja) カルボキシアレーンスルホン酸およびそのカルボン酸誘導体の製造法
JP2928044B2 (ja) ブロモニトロアルコール化合物の製造法
CN110563641B (zh) 一种邻位卤代苯基吡啶甲酮类化合物及其制备方法
CA1052383A (fr) Derives de triazole-1,2,4
JP3116171B2 (ja) ピラゾール誘導体の製法及びその中間体並びにその製法
JPH0529215B2 (fr)
JP3059007B2 (ja) １−（２−カルボキシフェニル）インダゾール誘導体の製造方法
JP3052358B2 (ja) 置換ピラゾール―４―カルボン酸の製造法
JPH09188637A (ja) ３−ブロモ−２−（置換フェニル）−１−プロペン類の製造法
JP3244560B2 (ja) アミノ基を有するピラゾロトリアゾール類の製造方法
HUT72169A (en) Process for the preparation of phenylbenzamide derivatives
JPS58185535A (ja) ハロゲノ−３−フエニルブチルアルデヒド及びその製造方法
JP2740959B2 (ja) スレオ―３―（３，４―ジアルコキシフェニル）セリン誘導体の選択的製造方法
JPS61161269A (ja) ２−フエニルベンゾトリアゾ−ル類の製造方法
JP3864996B2 (ja) 新規なイミダゾピロロキノリン化合物
JPS63303958A (ja) ２−アミノ−４，６−ジクロル−５−アルキルフェノ−ルの製造法
AU610015B2 (en) 3-(substituted phenyl) pyrazole derivatives, salts thereof, herbicides therefrom, and process for producing said derivatives or salts

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR BY CA CN HU KR KZ MX PL RU UA US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA