JP3761206B2 - Method for producing 1H-pyrazolo [3,2-C] -1,2,4-triazole compound - Google Patents
Method for producing 1H-pyrazolo [3,2-C] -1,2,4-triazole compound Download PDFInfo
- Publication number
- JP3761206B2 JP3761206B2 JP10785994A JP10785994A JP3761206B2 JP 3761206 B2 JP3761206 B2 JP 3761206B2 JP 10785994 A JP10785994 A JP 10785994A JP 10785994 A JP10785994 A JP 10785994A JP 3761206 B2 JP3761206 B2 JP 3761206B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- pyrazolo
- ethyl acetate
- present
- general formula
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Fee Related
Links
- 0 CC1c2c(*)c(C*)n[n]2C(*)=NC1 Chemical compound CC1c2c(*)c(C*)n[n]2C(*)=NC1 0.000 description 1
Description
【０００１】
【産業上の利用分野】
本発明は、１Ｈ−ピラゾロ［３，２−Ｃ］−１，２，４−トリアゾール系化合物の製造方法に関し、詳しくは、有機溶媒中、鉱酸を添加し、鉱酸塩として高収率、高純度で１Ｈ−ピラゾロ［３，２−Ｃ］−１，２，４−トリアゾール系化合物を製造する方法に関する。
【０００２】
【従来技術】
１Ｈ−ピラゾロ［３，２−Ｃ］−１，２，４−トリアゾール系化合物は、写真用カプラー、特にマゼンタカプラー、あるいは、マゼンタカプラー合成の中間体として有用な化合物である。これらの化合物は、例えば英国特許１，２５２，４１８号、米国特許３，７２５，０６７号或いは、ジャーナル・オブ・ザ・ケミカル・ソサイアティー・パーキンＩ（１９７７年）２０４７−２０５２頁に記載された方法で合成することができる。
【０００３】
すなわち、前記記載に従って反応した１Ｈ−ピラゾロ［３，２−Ｃ］−１，２，４−トリアゾール系化合物は、アルコール系溶媒、アセトニトリル、酢酸エチル、トルエン及びヘキサン等を用いて結晶化、単離することができる。
しかし、低収率であったり、純度も低く、また静電気の発生しやすいｎ−ヘキサン等を用いる等の問題点を有している。
【０００４】
【発明の目的】
本発明は、上記の事情に鑑みてなされたものであり、その目的とするところは、安全性の高い有機溶媒を用い、１Ｈ−ピラゾロ［３，２−Ｃ］−１，２，４−トリアゾール系化合物を高収率、高純度で単離することができる製造方法を提供することである。
【０００５】
【発明の構成】
本発明の上記目的は、下記構成によって達成される。
１．下記一般式［Ｉ］で表わされる１Ｈ−ピラゾロ［３，２−Ｃ］−１，２，４−トリアゾール系化合物を単離する際、有機溶媒として酢酸エチル、酢酸プロピル、アセトニトリル又はトルエンを用い、反応生成物に対し２倍重量から１０倍重量の前記有機溶媒中、反応生成物に対し１倍モルから５倍モル量の鉱酸を添加して、下記一般式［Ｉ］で表わされる１Ｈ−ピラゾロ［３，２−Ｃ］−１，２，４−トリアゾール系化合物の鉱酸塩として単離することを特徴とする製造方法。
【０００６】
【化２】
【０００７】
以下、具体的に本発明を説明する。
一般式［Ｉ］において、Ｒ１としては、例えばメチル基、エチル基、イソプロピル基、ｔｅｒｔ−ブチル基、ペンチル基、ｎ−ドデシル基、ペンタデシル基、ヘキサデシル基、γ−（２，４−ジ−ｔｅｒｔ−アミルフェノキシ）プロピル基、フェニル基、ｐ−ニトロフェニル基、ｎ−ニトロフェニル基、ｏ−クロロフェニル基、（２，４−ジ−ｔｅｒｔ−アミルフェノキシ）アセトアミドフェニル基、ｐ−メトキシフェニル基、ピリジル基、フリル基、チェニル基が挙げられるが、本発明においてはＲ １ はアルキル基を表わす。Ｒ２としては例えば、メチル基、エチル基、γ−（ｐ−ニトロフェニル）プロピル基、ｎ−ドデシル基、γ−（２，４−ジ−ｔｅｒｔ−アミルフェノキシ）プロピル基、（β−ドデシルスルホニル−ｄ−メチル）エチル基、フェニル基、ｐ−ニトロフェニル基、ｍ−クロロフェニル基、ｐ−メトキシフェニル基、ｐ−ドデシルオキシフェニル基、ピリジル基、フリル基、チェニル基が挙げられるが、本発明おいては、Ｒ ２ はアルキルスルホニル基で置換されたアルキル基を表わす。
【０００８】
Ｘで表わされるハロゲン原子としては塩素原子、臭素原子、沃素原子及びフッ素原子が挙げられ、アルキルカルボキシレート基としては、メチルカルボキシレート基、エチルカルボキシレート基、プロピルカルボキシレート基、ベンジルカルボキシレート基、トリフルオロメチルカルボキシレート基、オクチルカルボキシレート基が挙げられ、アリールカルボキシレート基としては、フェニルカルボキシレート基、ｐ−ニトロフェニルカルボキシレート基が挙げられるが、本発明においては、Ｘは水素原子、ハロゲン原子又は無置換のアルキルカルボキシレート基を表す。
【０００９】
次に一般式［Ｉ］で示される化合物の例を以下に例示するが、本発明は、これらに限定されるものではない。但し、下記例示化合物中、請求項１に含まれるもののみが、本発明の化合物となる。
【００１０】
【化３】
【化４】
【化５】
【化６】
【化７】
【化８】
【化９】
【化１０】
【化１１】
本発明において使用される有機溶媒としては、酢酸エチル、酢酸メチル、酢酸プロピル、酢酸イソプロピル、アセトニトリル、酢酸、メタノール、エタノール、イソプロピルアルコール、トルエン、キシレン等が挙げられ、また、これらの溶媒を混合して使用しても良いが、本発明においては、有機溶媒は、酢酸エチル、酢酸プロピル、アセトニトリル、トルエンが挙げられる。
【００２０】
使用する有機溶媒の量としては、反応生成物に対し、２倍重量から１０倍重量である。使用される鉱酸としては、塩酸、硝酸、硫酸、臭化水素酸が挙げられる。好ましくは、塩酸（塩化水素）、硫酸が挙げられる。鉱酸の量としては、反応生成物に対し、１から５倍モル量で、好ましくは、１倍モルから１．５倍モル量である。本発明の方法によって得られる１Ｈ−ピラゾロ［３，２−Ｃ］−１，２，４−トリアゾール系化合物は、無色あるいは黄色を帯びた結晶もしくは油状物である。
この化合物は、写真用カプラーとして有用な中間体及びカプラーである。
【００２１】
【実施例】
本発明の方法を具体的に示すために、以下に実施例を比較例と共に記載するが、本発明は、これら実施例により限定されるものではない。
【００２２】
比較例−１
本発明の製造方法によらない例示化合物Ｉ−１１の合成
エチル−３−メチル−５−（β−イソヘキシルノニルスルホニル）プロピオニルヒドラジノ−１Ｈ−ピラゾール−４−カルボキシレート５２．８ｇとオキシ塩化リン４０ｇを４００ｍｌのベンゼン中２４時間還流攪拌した。反応液を水洗し、硫酸マグネシウムで乾燥後ベンゼンを減圧留去し、残渣をアセトニトリルより再結晶した。風乾して３０ｇ（収率５７％）の例示化合物Ｉ−11を得た。ｍ．ｐ９５〜１００℃、このものは、高速液体カラムクロマトグラフィーで８８．５％の面積比を示した。
【００２３】
比較例−２
本発明の製造方法によらない例示化合物Ｉ−１９の合成
例示化合物Ｉ−１１を５１ｇと濃硫酸１００ｇ及び水５０ｇを１２０℃で４時間攪拌した。反応液を氷水に注ぎ、酢酸エチルで抽出し、水洗後、硫酸マグネシウムで乾燥後、酢酸エチルを減圧留去し、残渣を酢酸エチルとｎ−ヘキサンの混合溶媒より再結晶した。風乾して３２．２ｇ（収率６５％）、ｍ．ｐ１０５〜１１０℃の例示化合物Ｉ−１９を得た。このものは、高速液体カラムクロマトグラフィーで８５％の面積比を示した。
【００２４】
比較例−３
本発明の製造方法によらない例示化合物Ｉ−３６の合成
例示化合物Ｉ−２０の４８ｇをクロロホルム２００ｍｌに溶解後、２５℃から３０℃でＮ−クロルコハク酸イミド１３．１ｇを加え、同温度で１時間攪拌した。反応液を水洗し、硫酸マグネシウムで乾燥し、クロロホルムを減圧留去し、残渣をメタノールより再結晶した。風乾して３０．９ｇ（収率６０％）、ｍ．ｐ４３〜４９℃の例示化合物Ｉ−３６を得た。このものは、高速液体クロマトグラフィーで９０％の面積比を示した。
【００２５】
実施例−１
本発明の製造方法による例示化合物Ｉ−１１の合成
前記比較例−１と同様に反応し、水洗して、ベンゼンを減圧留去し、残渣に酢酸エチル２００ｍｌを加え溶解し、室温で濃硫酸１１ｇを滴下すると、白色結晶が析出する。これを炉取、風乾して５５ｇ（収率９０％）、ｍ．ｐ１７０〜２１０℃の例示化合物Ｉ−１１の硫酸塩を得た。このものは、高速液体クロマトグラフィーで、９８％の面積比を示した。この硫酸塩５５ｇを酢酸エチル３００ｍｌに懸濁し、炭酸ソーダ水溶液で中和し、水洗後、硫酸マグネシウムで乾燥して、酢酸エチルを減圧留去すると、白色結晶４５．９ｇの例示化合物Ｉ−１１を得た。ｍ．ｐ９８〜１００℃。このものは、高速液体カラムクロマトグラフィーで、９８％の面積比を示した。
【００２６】
実施例−２
本発明の製造方法による例示化合物Ｉ−１９の合成
前記比較例−２と同様に反応し、反応液を氷水に注ぎ、酢酸エチル２２０ｍｌで抽出、水洗後、硫酸マグネシウムで乾燥後、硫酸マグネシウムを炉別し、炉液の酢酸エチル溶液に、塩化水素ガス４．４ｇを吹き込んだ。白色結晶が析出、これを炉取し、風乾すると、４０．５ｇ（収率８８％）の例示化合物Ｉ−１９の塩酸塩が得られた。ｍ．ｐ１４０〜１９０℃。このものは、高速液体カラムクロマトグラフィーで９８．５％の面積比を示した。この塩酸塩４０．５ｇを酢酸エチル２５０ｍｌに懸濁し、炭酸ソーダ水溶液で中和し、水洗後、硫酸マグネシウムで乾燥後、酢酸エチルを減圧留去すると、白色ロウ状晶３７ｇの例示化合物Ｉ−１９を得た。ｍ．ｐ１１０〜１１２℃。このものは、高速液体カラムクロマトグラフィーで９８．５％の面積比を示した。
【００２７】
実施例−３
本発明の製造方法による例示化合物Ｉ−３６の合成
比較例−３と同様に反応し、反応液を水洗し、硫酸マグネシウムで乾燥し、クロロホルムを減圧留去し、残渣を酢酸エチル１５０ｍｌに溶解後、塩化水素ガス４．４ｇを吹き込んだ。白色結晶が析出、これを炉取し、風乾すると５０．５ｇ（収率９１．６％）の例示化合物Ｉ−３６の塩酸塩が得られた。ｍ．ｐ１００〜１４５℃。このものは、高速液体カラムクロマトグラフィーで９８．５％の面積比を示した。この塩酸塩５０．５ｇを酢酸エチル２００ｍｌに懸濁し、炭酸ソーダ水溶液で中和、水洗後、硫酸マグネシウムで乾燥し、酢酸エチルを減圧留去して、残渣をメタノールで再結晶すると４４．８ｇ（収率８７％）、ｍ．ｐ４９〜５２℃の例示化合物Ｉ−３６を得た。このものは、高速液体カラムクロマトグラフィーで９９．１％の面積比を示した。
【００２８】
実施例−４
実施例−１、２及び３において有機溶媒を酢酸エチルから酢酸プロピル、アセトニトリル又はトルエンに代えたことのみ異ならせたところ、各々実施例−１、２及び３と同様の結果であった。
【００２９】
その他の化合物も、実施例−１、実施例−２及び実施例−３と同様にして、高収率、高純度で得ることができた。
【００３０】
【発明の効果】
本発明の製造方法によれば、１Ｈ−ピラゾロ［３，２−Ｃ］−１，２，４−トリアゾール系化合物を高収率、高純度で得ることができる。[0001]
[Industrial application fields]
The present invention relates to a method for producing 1H-pyrazolo [3,2-C] -1,2,4-triazole-based compound, and more specifically, a mineral acid is added in an organic solvent to obtain a high yield as a mineral acid salt. The present invention relates to a method for producing a 1H-pyrazolo [3,2-C] -1,2,4-triazole compound with high purity.
[0002]
[Prior art]
The 1H-pyrazolo [3,2-C] -1,2,4-triazole compound is a useful compound as a photographic coupler, particularly a magenta coupler or an intermediate for synthesizing a magenta coupler. These compounds are prepared according to, for example, the methods described in British Patent 1,252,418, US Pat. No. 3,725,067 or Journal of the Chemical Society Parkin I (1977) 2047-2052. Can be synthesized.
[0003]
That is, the 1H-pyrazolo [3,2-C] -1,2,4-triazole compound reacted according to the above description is crystallized and isolated using an alcohol solvent, acetonitrile, ethyl acetate, toluene, hexane or the like. can do.
However, there are problems such as low yield, low purity, and the use of n-hexane or the like that is likely to generate static electricity.
[0004]
OBJECT OF THE INVENTION
The present invention has been made in view of the above circumstances, and the object thereof is to use a highly safe organic solvent and use 1H-pyrazolo [3,2-C] -1,2,4-triazole. It is to provide a production method capable of isolating a system compound with high yield and high purity.
[0005]
[Structure of the invention]
The above object of the present invention is achieved by the following configurations.
1. When isolating 1H-pyrazolo [3,2-C] -1,2,4-triazole compound represented by the following general formula [I], ethyl acetate, propyl acetate, acetonitrile or toluene is used as an organic solvent, the organic solvent 10 times the weight of 2 times by weight relative to the reaction product, with the addition of 5-fold molar amount of mineral acid from 1-fold mole reaction product, represented by the following general formula [I] 1H- A production method comprising isolating as a mineral acid salt of a pyrazolo [3,2-C] -1,2,4-triazole compound.
[0006]
[Chemical 2]
[0007]
Hereinafter, the present invention will be specifically described.
In the general formula [I], as R 1 , for example, methyl group, ethyl group, isopropyl group, tert-butyl group, pentyl group, n-dodecyl group, pentadecyl group, hexadecyl group, γ- (2,4-di-) tert-amylphenoxy) propyl group, phenyl group, p-nitrophenyl group, n-nitrophenyl group, o-chlorophenyl group, (2,4-di-tert-amylphenoxy) acetamidophenyl group, p-methoxyphenyl group, pyridyl group, furyl group, but a thienyl group Ru mentioned, R 1 is in the present invention represents an alkyl group. Examples of R 2 include a methyl group, ethyl group, γ- (p-nitrophenyl) propyl group, n-dodecyl group, γ- (2,4-di-tert-amylphenoxy) propyl group, (β-dodecylsulfonyl). -d-) ethyl group, a phenyl group, p- nitrophenyl group, m- chlorophenyl group, p- methoxyphenyl group, p- dodecyloxyphenyl group, a pyridyl group, a furyl group, there may be mentioned thienyl group, the present invention R 2 represents an alkyl group substituted with an alkylsulfonyl group .
[0008]
Examples of the halogen atom represented by X include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom. Examples of the alkyl carboxylate group include a methyl carboxylate group, an ethyl carboxylate group, a propyl carboxylate group, a benzyl carboxylate group, Examples thereof include a trifluoromethylcarboxylate group and an octylcarboxylate group, and examples of the arylcarboxylate group include a phenylcarboxylate group and a p-nitrophenylcarboxylate group. In the present invention, X represents a hydrogen atom, a halogen atom. Represents an atomic or unsubstituted alkyl carboxylate group .
[0009]
Next, examples of the compound represented by the general formula [I] are illustrated below, but the present invention is not limited thereto. However, among the following exemplified compounds, only those included in claim 1 are the compounds of the present invention.
[0010]
[Chemical 3]
[Formula 4]
[Chemical formula 5]
[Chemical 6]
[Chemical 7]
[Chemical 8]
[Chemical 9]
[Chemical Formula 10]
Embedded image
Examples of the organic solvent used in the present invention include ethyl acetate, methyl acetate, propyl acetate, isopropyl acetate, acetonitrile, acetic acid, methanol, ethanol, isopropyl alcohol, toluene, xylene, and the like. In the present invention, examples of the organic solvent include ethyl acetate, propyl acetate, acetonitrile, and toluene.
[0020]
The amount of the organic solvent used is 2 to 10 times the weight of the reaction product. Examples of the mineral acid used include hydrochloric acid, nitric acid, sulfuric acid, and hydrobromic acid. Preferably, hydrochloric acid (hydrogen chloride) and sulfuric acid are used. The amount of the mineral acid is 1 to 5 times by mole, preferably 1 to 1.5 times by mole with respect to the reaction product. The 1H-pyrazolo [3,2-C] -1,2,4-triazole compound obtained by the method of the present invention is a colorless or yellowish crystal or oily substance.
This compound is an intermediate and coupler useful as a photographic coupler.
[0021]
【Example】
In order to show the method of the present invention concretely, an example is described below with a comparative example, but the present invention is not limited by these examples.
[0022]
Comparative Example-1
Synthesis of Exemplified Compound I-11 Not According to the Production Method of the Present Invention 5-3-g of ethyl-3-methyl-5- (β-isohexylnonylsulfonyl) propionylhydrazino-1H-pyrazole-4-carboxylate and phosphorus oxychloride 40 g was stirred under reflux in 400 ml of benzene for 24 hours. The reaction solution was washed with water, dried over magnesium sulfate, benzene was distilled off under reduced pressure, and the residue was recrystallized from acetonitrile. Air-dried to obtain 30 g (yield 57%) of Exemplified Compound I-11. m. p95-100 ° C., which showed an area ratio of 88.5% by high performance liquid column chromatography.
[0023]
Comparative Example-2
Synthesis of Exemplified Compound I-19 Not According to the Production Method of the Present Invention 51 g of Exemplified Compound I-11, 100 g of concentrated sulfuric acid, and 50 g of water were stirred at 120 ° C. for 4 hours. The reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, ethyl acetate was distilled off under reduced pressure, and the residue was recrystallized from a mixed solvent of ethyl acetate and n-hexane. Air dried to 32.2 g (65% yield), m.p. Exemplified compound I-19 at p105 to 110 ° C was obtained. This product showed an area ratio of 85% by high performance liquid column chromatography.
[0024]
Comparative Example-3
Synthesis of Exemplified Compound I-36 Not According to the Production Method of the Present Invention After dissolving 48 g of Exemplified Compound I-20 in 200 ml of chloroform, 13.1 g of N-chlorosuccinimide was added at 25 to 30 ° C., and 1 at the same temperature. Stir for hours. The reaction solution was washed with water and dried over magnesium sulfate, chloroform was distilled off under reduced pressure, and the residue was recrystallized from methanol. Air-dried to 30.9 g (yield 60%), m.p. Exemplified compound I-36 at p43-49 ° C was obtained. This product showed an area ratio of 90% by high performance liquid chromatography.
[0025]
Example-1
Synthesis of Exemplified Compound I-11 by the Production Method of the Present Invention Reaction was conducted in the same manner as in Comparative Example 1, washed with water, benzene was distilled off under reduced pressure, 200 ml of ethyl acetate was dissolved in the residue and dissolved, and 11 g of concentrated sulfuric acid at room temperature. Is dropped, white crystals are precipitated. This was furnace-dried and air-dried to 55 g (yield 90%), m.p. The sulfate of Exemplified Compound I-11 at p170-210 ° C. was obtained. This product showed an area ratio of 98% by high performance liquid chromatography. 55 g of this sulfate salt was suspended in 300 ml of ethyl acetate, neutralized with an aqueous sodium carbonate solution, washed with water, dried over magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to give 45.9 g of Example Compound I-11 as white crystals. Obtained. m. p98-100 ° C. This product showed an area ratio of 98% by high performance liquid column chromatography.
[0026]
Example-2
Synthesis of Exemplified Compound I-19 by Production Method of the Present Invention Reaction was carried out in the same manner as in Comparative Example-2, and the reaction solution was poured into ice water, extracted with 220 ml of ethyl acetate, washed with water, dried over magnesium sulfate, Separately, 4.4 g of hydrogen chloride gas was blown into the ethyl acetate solution of the furnace liquid. White crystals were precipitated, which were taken up in an oven and air-dried to obtain 40.5 g (yield 88%) of hydrochloride of Exemplified Compound I-19. m. p140-190 ° C. This product showed an area ratio of 98.5% by high performance liquid column chromatography. 40.5 g of this hydrochloride was suspended in 250 ml of ethyl acetate, neutralized with an aqueous sodium carbonate solution, washed with water, dried over magnesium sulfate, and then ethyl acetate was distilled off under reduced pressure to give 37 g of white waxy crystal as exemplified compound I-19. Got. m. p110-112 ° C. This product showed an area ratio of 98.5% by high performance liquid column chromatography.
[0027]
Example-3
Synthesis of Exemplified Compound I-36 by the Production Method of the Present Invention Reaction was carried out in the same manner as Comparative Example-3, the reaction solution was washed with water, dried over magnesium sulfate, chloroform was distilled off under reduced pressure, and the residue was dissolved in 150 ml of ethyl acetate. Then, 4.4 g of hydrogen chloride gas was blown in. White crystals were precipitated, which were taken up in an oven and air-dried to obtain 50.5 g (yield 91.6%) of hydrochloride of Exemplified Compound I-36. m. p100-145 ° C. This product showed an area ratio of 98.5% by high performance liquid column chromatography. 50.5 g of this hydrochloride was suspended in 200 ml of ethyl acetate, neutralized with aqueous sodium carbonate solution, washed with water, dried over magnesium sulfate, ethyl acetate was distilled off under reduced pressure, and the residue was recrystallized from methanol to yield 44.8 g ( Yield 87%), m.p. Exemplified compound I-36 at p49-52 ° C was obtained. This product showed an area ratio of 99.1% by high performance liquid column chromatography.
[0028]
Example-4
When the organic solvent in Examples-1, 2, and 3 was changed from ethyl acetate to propyl acetate, acetonitrile, or toluene, the results were the same as in Examples-1, 2, and 3, respectively.
[0029]
Other compounds could also be obtained in high yield and high purity in the same manner as in Example-1, Example-2, and Example-3.
[0030]
【The invention's effect】
According to the production method of the present invention, a 1H-pyrazolo [3,2-C] -1,2,4-triazole compound can be obtained in high yield and high purity.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10785994A JP3761206B2 (en) | 1994-04-22 | 1994-04-22 | Method for producing 1H-pyrazolo [3,2-C] -1,2,4-triazole compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10785994A JP3761206B2 (en) | 1994-04-22 | 1994-04-22 | Method for producing 1H-pyrazolo [3,2-C] -1,2,4-triazole compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07295172A JPH07295172A (en) | 1995-11-10 |
| JP3761206B2 true JP3761206B2 (en) | 2006-03-29 |
Family
ID=14469885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10785994A Expired - Fee Related JP3761206B2 (en) | 1994-04-22 | 1994-04-22 | Method for producing 1H-pyrazolo [3,2-C] -1,2,4-triazole compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3761206B2 (en) |
-
1994
- 1994-04-22 JP JP10785994A patent/JP3761206B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07295172A (en) | 1995-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0742290B2 (en) | Method for aroylating 5-position of 1,2-dihydro-3H-pyrrolo [1,2-α] pyrrole-1-carboxylic acid ester | |
| WO2008078482A1 (en) | Process for producing intermediate of asenapine synthesis | |
| JP3761206B2 (en) | Method for producing 1H-pyrazolo [3,2-C] -1,2,4-triazole compound | |
| JP2001521498A (en) | Method for producing O- (3-amino-2-hydroxy-propyl) -hydroxymic acid halide | |
| US6861525B2 (en) | Process for the preparation imidazo[1,2-A]pyridine-3-acetamides | |
| JP4373033B2 (en) | Pyrazolo [3,2-c] -1,2,4-triazole compound, 1,2,4-triazolo [3,4-b] thiadiazine compound, and synthesis method thereof | |
| HU192136B (en) | Process for producing a 2-thiophfene-acetic acid derivative | |
| JPH069553A (en) | Preparation of 1-(2s-methyl-3-mercaptopropionyl)- pyrrolidine-2s-carboxylic acid | |
| JP3613657B2 (en) | Process for producing optically active N-substituted α-amino-γ-halobutyric acid ester | |
| JP4059949B2 (en) | Method for producing 1H-1,2,4-triazol-5-yl acetate ester compound | |
| KR100277414B1 (en) | Method for preparing 1,2,3,9-tetrahydro-9-methyl-3-[(2-methyl-1H-imidazol-1-yl) methyl] -4H-carbazol-4-one | |
| JP3855686B2 (en) | 3,3-dialkoxy-2-hydroxyimino derivative and process for producing the same | |
| JP4673313B2 (en) | Process for producing 1,2,3,9-tetrahydro-9-methyl-3-[(2-methyl-1H-imidazol-1-yl) methyl] -4H-carbazol-4-one or a salt thereof | |
| JP3961049B2 (en) | 3-Amino-4- (1-hydroxyalkyl) pyrazoline compound, method for producing the same and method for producing the same | |
| JP3711625B2 (en) | Method for producing 1H-pyrazolo [3,2-c] -1,2,4-triazole compound | |
| JPH04211664A (en) | 5-phenyl-1h-pyrazole-4-propionic acid derivative, process for producing same and use thereof | |
| JPS5916879A (en) | Production of n-substituted imidazole | |
| JPWO2002085880A1 (en) | Method for producing nitrile compound | |
| JP2743441B2 (en) | Cyclopenta [1,2-C] -3-pyrazolecarboxylic acid derivative | |
| JPH0987288A (en) | Purification method for 1,3-bis(3-aminopropyl)-1,1,3,3-tetraorganodisiloxane | |
| JP4013772B2 (en) | 2-Hydroxyimino-3-oxopropionitrile and process for producing the same | |
| JP2002503648A (en) | Methods and intermediates useful for producing antifolates | |
| JPH0613478B2 (en) | 5-hydrazino-1H-pyrazole compound | |
| PL176485B1 (en) | Method of obtaining n-/2-chlorobenzyl/-2-/2-thienyl/ethylamine | |
| JPH09278758A (en) | Production of n-pyrazolylamidoxime compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040914 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050308 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050428 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050906 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20051031 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20051220 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20060110 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090120 Year of fee payment: 3 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100120 Year of fee payment: 4 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |