JP2001322983A - Method for producing pyrazole carboxylic acid ester derivative - Google Patents
Method for producing pyrazole carboxylic acid ester derivativeInfo
- Publication number
- JP2001322983A JP2001322983A JP2000144516A JP2000144516A JP2001322983A JP 2001322983 A JP2001322983 A JP 2001322983A JP 2000144516 A JP2000144516 A JP 2000144516A JP 2000144516 A JP2000144516 A JP 2000144516A JP 2001322983 A JP2001322983 A JP 2001322983A
- Authority
- JP
- Japan
- Prior art keywords
- group
- general formula
- carboxylic acid
- acid ester
- producing
- 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.)
- Granted
Links
Abstract
Description
【発明の属する技術分野】本発明は、医薬、農薬の合成
中間体として有用なピラゾールカルボン酸エステル誘導
体の製造法に関する。TECHNICAL FIELD The present invention relates to a method for producing a pyrazolecarboxylic acid ester derivative useful as a synthetic intermediate for pharmaceuticals and agricultural chemicals.
【従来の技術】Jornal of the Chemical Society Chemi
cl Communication,p.2484-2488,(1970).によると、アセ
ト酢酸エステル類にビルスマイヤー反応を行うと、β−
クロロ−α−ホルミルビニルエステル類が得られること
が知られている。しかし、このβ−クロロ−α−ホルミ
ルビニルエステル類を用いたピラゾールカルボン酸誘導
体の合成法については、全く知られていない。[Prior Art] Journal of the Chemical Society Chemi
According to cl Communication, p.2484-2488, (1970), when a Vilsmeier reaction is performed on acetoacetates, β-
It is known that chloro-α-formylvinyl esters can be obtained. However, there is no known method for synthesizing a pyrazole carboxylic acid derivative using the β-chloro-α-formylvinyl ester.
【発明が解決しようとする課題】本発明はβ−クロロ−
α−ホルミルビニルエステル類を用いて、医薬、農薬の
合成中間体として有用なピラゾールカルボン酸エステル
誘導体の製造法を提供することを目的とする。SUMMARY OF THE INVENTION The present invention relates to β-chloro-
An object of the present invention is to provide a method for producing a pyrazole carboxylic acid ester derivative which is useful as a synthetic intermediate for pharmaceuticals and agricultural chemicals using α-formyl vinyl esters.
【課題を解決するための手段】本発明者らは、上記課題
について鋭意検討を行ったところ、β−クロロ−α−ホ
ルミルビニルエステル類とヒドラジン類を反応させるこ
とでピラゾールカルボン酸エステル誘導体を製造するこ
とができることを見いだし、本発明を完成した。すなわ
ち、本発明は、一般式（１）（化４）Means for Solving the Problems The present inventors have made intensive studies on the above-mentioned problems and found that a pyrazole carboxylic acid ester derivative was produced by reacting β-chloro-α-formylvinyl ester with hydrazine. The present invention has been completed. That is, the present invention relates to a compound represented by the general formula (1):
【化４】 （式中、Ｒは炭素数１〜６のアルキル基または炭素数１
〜６のハロアルキル基を示し、Ｒ1は水素原子または炭
素数１〜６のアルキル基を示し、Ｒ2は炭素数１〜６の
アルキル基を示す。）で示されるピラゾールカルボン酸
エステル誘導体の製造法であって、一般式（２）（化
５）Embedded image (Wherein R is an alkyl group having 1 to 6 carbon atoms or 1 carbon atom)
To haloalkyl groups, R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 2 represents an alkyl group having 1 to 6 carbon atoms. A method for producing a pyrazole carboxylic acid ester derivative represented by the general formula (2):
【化５】 （式中Ｒ、Ｒ2は前記と同様）で示される化合物と、一
般式（３）（化６）Embedded image (Wherein R and R 2 are as defined above) and a compound represented by the general formula (3)
【化６】 （式中Ｒ1は前記と同様）で示される化合物を反応させ
て得ることを特徴とする、一般式（１）で示されるピラ
ゾールカルボン酸エステル誘導体の製造法。Embedded image (Wherein R 1 is the same as defined above), which is obtained by reacting a compound represented by the following formula (1):
【発明の実施の形態】本発明において、Ｒで示される炭
素数１〜６のアルキル基としては、例えば、メチル基、
エチル基、プロピル基、イソプロピル基、ブチル基、イ
ソブチル基、sec-ブチル基、tert-ブチル基、ペンチル
基、ヘキシル基、シクロヘキシル基等のアルキル基が挙
げられ、Ｒで示される炭素数１〜６のハロアルキル基と
しては、トリフルオロメチル基、ジフルオロメチル基、
ペンタフルオロエチル基、ヘプタフルオロプロピル基、
トリデカフルオロプロピル等のハロアルキル基が挙げら
れる。Ｒ1は水素原子、Ｒ1で示される炭素数１〜６のア
ルキル基としては、例えば、メチル基、エチル基、プロ
ピル基、イソプロピル基、ブチル基、イソブチル基、se
c-ブチル基、tert-ブチル基、ペンチル基、ヘキシル
基、シクロヘキシル基等のアルキル基が挙げられる。Ｒ
2で示される炭素数１〜６のアルキル基としては、例え
ば、メチル基、エチル基、プロピル基、イソプロピル
基、ブチル基、イソブチル基、sec-ブチル基、tert-ブ
チル基、ペンチル基、ヘキシル基、シクロヘキシル基等
のアルキル基が挙げられる。一般式（２）に示される波
線は一般式（２）の化合物がＥ体、Ｚ体もしくはＥ体と
Ｚ体の混合物のいずれでも良いことを意味する。以下に
本発明の製造法について詳細に説明する。本発明に係わ
る製造方法は以下の反応式１に示される反応により行わ
れる（化７）。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the alkyl group having 1 to 6 carbon atoms represented by R includes, for example, a methyl group,
An alkyl group such as an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, and the like, and having 1 to 6 carbon atoms represented by R Examples of the haloalkyl group include a trifluoromethyl group, a difluoromethyl group,
Pentafluoroethyl group, heptafluoropropyl group,
And haloalkyl groups such as tridecafluoropropyl. R 1 is a hydrogen atom, and examples of the alkyl group having 1 to 6 carbon atoms represented by R 1 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a se.
Examples thereof include an alkyl group such as a c-butyl group, a tert-butyl group, a pentyl group, a hexyl group, and a cyclohexyl group. R
Examples of the alkyl group having 1 to 6 carbon atoms represented by 2 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. And an alkyl group such as a cyclohexyl group. The wavy line represented by the general formula (2) means that the compound of the general formula (2) may be any of E-form, Z-form or a mixture of E-form and Z-form. Hereinafter, the production method of the present invention will be described in detail. The production method according to the present invention is carried out by a reaction represented by the following reaction formula 1 (Chem. 7).
【化７】 （Ｒ、Ｒ1、Ｒ2は前記と同様） 出発物質であるβ−クロロ−α−ホルミルビニルエステ
ル類は、Jornal of the Chemical Society Chemicl Com
munication,p.2484-2488,(1970).に記載された方法、す
なわち以下の反応式２に従い合成することができる（化
８）。Embedded image (R, R 1 and R 2 are the same as described above.) The starting material β-chloro-α-formylvinyl ester is obtained from the Journal of the Chemical Society Chemicl Com.
munication, p. 2484-2488, (1970). That is, it can be synthesized according to the following reaction formula 2 (Chem. 8).
【化８】 （Ｒ、Ｒ2は前記と同様） 本発明は、一般式（２）で示されるβ−クロロ−α−ホ
ルミルビニルエステル類と一般式（３）で示されるヒド
ラジン類とを反応させて、一般式（１）で示されるピラ
ゾールカルボン酸エステルを得る反応である。本反応に
おける一般式（３）で示される化合物の使用量は、通常
一般式（２）で示される化合物１．０モルに対して、
０．２〜２０．０モル、好ましくは０．５〜５．０モ
ル、特に好ましくは１．０〜２．５モルの割合である。
本反応で必要により使用される溶媒としては、通常、ヘ
キサン、石油エーテル等の脂肪族炭化水素、ベンゼン、
トルエン、クロロベンゼン、アニソール等の芳香族類、
メタノール、エタノール等のアルコール類、ジオキサ
ン、テトラヒドロフラン、ジエチルエーテル等のエーテ
ル類、アセトニトリル、プロピオニトリル等のニトリル
類、酢酸エチル等のエステル類、ジクロロメタン、クロ
ロホルム、１，２−ジクロロエタン等のハロゲン化炭化
水素、ジメチルホルムアミド、ジメチルスルホキシド等
の非プロトン性極性溶媒、またこれらの溶媒の混合溶媒
が挙げられ、好ましくは、メタノール、エタノール等の
アルコール類である。本反応における溶媒の使用量は、
一般式（２）で示される化合物１ｇに対して通常０．１
〜２００ｍｌ、好ましくは１〜２０ｍｌである。本反応
は塩基がなくても進行するが、塩基の存在下で反応を行
っても良く、用いられる塩基としては、例えば、水酸化
ナトリウム、水酸化カリウム、水酸化カルシウム等のア
ルカリ金属およびアルカリ土類金属の水酸化物、水素化
ナトリウム、水素化カルシウム等のアルカリ金属および
アルカリ土類金属の水素化物、炭酸ナトリウム、炭酸カ
ルシウム、炭酸マグネシウム等のアルカリ金属およびア
ルカリ土類金属の炭酸塩、炭酸水素ナトリウム、炭酸水
素カリウム等のアルカリ金属およびアルカリ土類金属の
炭酸水素塩、ナトリウムメトキシド、ナトリウムエトキ
シド、カリウム−ｔ−ブトキシド、ジメトキシマグネシ
ウム等のアルカリ金属およびアルカリ土類金属のアルコ
キシド、トリエチルアミン、ピリジン等の種々の有機塩
基類が挙げられる。これらの塩基の使用量は、一般式
（２）で示される化合物１モルに対して、通常０．０１
〜２０．０モル、好ましくは０．１〜２．０モルであ
る。反応温度は通常−７０℃〜２５０℃、好ましくは−
２０℃〜１００℃、特に好ましくは０℃〜４０℃であ
る。反応時間は通常１分間〜７２時間、好ましくは１０
分間〜１０時間である。本反応における種々の条件、即
ち、一般式（２）、一般式（３）で示される化合物の使
用量、溶媒の種類および使用量、塩基の種類および使用
量、反応温度ならびに反応時間各々の設定に際しては、
各々の条件毎に示された通常の範囲の数値と好ましい範
囲の数値と特に好ましい範囲の数値から適宜相互に選択
し、組み合わせることができる。Embedded image (R and R 2 are the same as described above.) In the present invention, a β-chloro-α-formylvinyl ester represented by the general formula (2) is reacted with a hydrazine represented by the general formula (3), and This is a reaction for obtaining a pyrazole carboxylic acid ester represented by the formula (1). The amount of the compound represented by the general formula (3) in this reaction is usually based on 1.0 mol of the compound represented by the general formula (2).
The proportion is 0.2 to 20.0 mol, preferably 0.5 to 5.0 mol, particularly preferably 1.0 to 2.5 mol.
Solvents used as necessary in this reaction are usually hexane, aliphatic hydrocarbons such as petroleum ether, benzene,
Aromatics such as toluene, chlorobenzene, and anisole;
Alcohols such as methanol and ethanol; ethers such as dioxane, tetrahydrofuran and diethyl ether; nitriles such as acetonitrile and propionitrile; esters such as ethyl acetate; halogenated carbonized such as dichloromethane, chloroform and 1,2-dichloroethane. Examples include aprotic polar solvents such as hydrogen, dimethylformamide, and dimethyl sulfoxide, and mixed solvents of these solvents, and preferred are alcohols such as methanol and ethanol. The amount of solvent used in this reaction is
Usually, 0.1 g per 1 g of the compound represented by the general formula (2)
２００200 ml, preferably 1-20 ml. This reaction proceeds without a base, but the reaction may be carried out in the presence of a base. Examples of the base used include alkali metals such as sodium hydroxide, potassium hydroxide and calcium hydroxide and alkaline earths. Alkali metal and alkaline earth metal hydrides such as hydroxides of similar metals, sodium hydride and calcium hydride, alkali metal and alkaline earth metal carbonates such as sodium carbonate, calcium carbonate and magnesium carbonate, hydrogen carbonate Alkali metal and alkaline earth metal bicarbonates such as sodium and potassium bicarbonate, alkali metal and alkaline earth metal alkoxides such as sodium methoxide, sodium ethoxide, potassium-t-butoxide and dimethoxymagnesium, triethylamine, pyridine And various organic bases such as It is. The amount of the base to be used is generally 0.01 mol per 1 mol of the compound represented by the general formula (2).
To 20.0 mol, preferably 0.1 to 2.0 mol. The reaction temperature is usually -70 ° C to 250 ° C, preferably-
20 ° C to 100 ° C, particularly preferably 0 ° C to 40 ° C. The reaction time is generally 1 minute to 72 hours, preferably 10 minutes.
Minutes to 10 hours. Various conditions in this reaction, that is, setting of the amount of the compound represented by the general formula (2) and the formula (3), the type and the amount of the solvent, the type and the amount of the base, the reaction temperature and the reaction time In doing so,
The values can be appropriately selected from the values in the ordinary range, the values in the preferred range, and the values in the particularly preferred range indicated for each condition, and can be combined.
【実施例】本発明を更に具体的に説明するため、以下に
実施例を示すが、本発明はこの実施例に限定されるもの
ではない。 実施例１ ３−トリフルオロメチルピラゾール−４−カ
ルボン酸エチルエステルの合成 ３−クロロ−４，４，４−トリフルオロ−２−ホルミル
−２−ブテン酸エチルエステル３．０ｇ（１３．０ｍｍ
ｏｌ）をエタノール９ｍｌに装入し、８℃まで冷却し
た。反応温度を８〜１０℃に保ちながら、エタノール６
ｍｌに混合させたヒドラジン一水和物１．３ｇ（２６．
０ｍｍｏｌ）を滴下した。室温で４時間攪拌した後、水
を１５ｍｌ加え、減圧下エタノールを留去したところ、
結晶が析出した。これを濾取した後、水で洗浄し、減圧
下乾燥することで、目的物 ２．１２ｇを結晶として得
た。（収率：７９％)。1 H-NMR(CDCl3,ppm):1.39(3H,t,J=7.3Hz),4.37(2H,q,J=
7.3Hz),8.24(1H,s).EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 Synthesis of ethyl 3-trifluoromethylpyrazole-4-carboxylate 3.0 g of ethyl 3-chloro-4,4,4-trifluoro-2-formyl-2-butenoate (13.0 mm
ol) was charged into 9 ml of ethanol and cooled to 8 ° C. While maintaining the reaction temperature at 8 to 10 ° C, ethanol 6
1.3 g of hydrazine monohydrate (26.
0 mmol) was added dropwise. After stirring at room temperature for 4 hours, 15 ml of water was added, and ethanol was distilled off under reduced pressure.
Crystals precipitated. This was collected by filtration, washed with water, and dried under reduced pressure to obtain 2.12 g of the desired product as crystals. (Yield: 79%). 1 H-NMR (CDCl 3 , ppm): 1.39 (3H, t, J = 7.3 Hz), 4.37 (2H, q, J =
7.3Hz), 8.24 (1H, s).
【発明の効果】本発明によれば、一般式（２）の化合物
と一般式（３）の化合物とを反応させると、一般式
（１）で表されるピラゾールカルボン酸誘導体を簡便且
つ高収率で製造できる。According to the present invention, when the compound of the general formula (2) is reacted with the compound of the general formula (3), the pyrazole carboxylic acid derivative represented by the general formula (1) can be obtained easily and with high yield. Can be manufactured at a rate.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小高 建次 千葉県茂原市東郷1144番地 三井化学株式 会社内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kenji Odaka 1144 Togo, Mobara-shi, Chiba Mitsui Chemicals Co., Ltd.
Claims (4)
〜６のハロアルキル基を示し、Ｒ1は水素原子または炭
素数１〜６のアルキル基を示し、Ｒ2は炭素数１〜６の
アルキル基を示す。）で示されるピラゾールカルボン酸
エステル誘導体の製造法であって、一般式（２）（化
２） 【化２】 （式中Ｒ、Ｒ2は前記と同様）で示される化合物と、一
般式（３）（化３） 【化３】 （式中Ｒ1は前記と同様）で示される化合物を反応させ
て得ることを特徴とする、一般式（１）で示されるピラ
ゾールカルボン酸エステル誘導体の製造法。1. A compound represented by the general formula (1): (Wherein R is an alkyl group having 1 to 6 carbon atoms or 1 carbon atom)
To haloalkyl groups, R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 2 represents an alkyl group having 1 to 6 carbon atoms. A method for producing a pyrazole carboxylate derivative represented by the general formula (2): (Wherein R and R 2 are the same as described above) and a compound represented by the following general formula (3): (Wherein R 1 is the same as defined above), which is obtained by reacting a compound represented by the following formula (1):
ピラゾールカルボン酸エステル誘導体の製造法。2. The method for producing a pyrazole carboxylic acid ester derivative according to claim 1, wherein R 1 is a hydrogen atom.
１または２に記載のピラゾールカルボン酸エステル誘導
体の製造法。3. The method for producing a pyrazole carboxylic acid ester derivative according to claim 1, wherein R is a trifluoromethyl group.
求項１、２または３に記載のピラゾールカルボン酸エス
テル誘導体の製造法。4. The method for producing a pyrazole carboxylic acid ester derivative according to claim 1, wherein R 2 is a methyl group or an ethyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000144516A JP4568404B2 (en) | 2000-05-17 | 2000-05-17 | Method for producing pyrazole carboxylic acid ester derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000144516A JP4568404B2 (en) | 2000-05-17 | 2000-05-17 | Method for producing pyrazole carboxylic acid ester derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001322983A true JP2001322983A (en) | 2001-11-20 |
| JP4568404B2 JP4568404B2 (en) | 2010-10-27 |
Family
ID=18651161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000144516A Expired - Fee Related JP4568404B2 (en) | 2000-05-17 | 2000-05-17 | Method for producing pyrazole carboxylic acid ester derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4568404B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011012618A2 (en) | 2009-07-28 | 2011-02-03 | Syngenta Participations Ag | Processes relating to the alkylation of pyrazoles |
| WO2011012620A2 (en) | 2009-07-31 | 2011-02-03 | Syngenta Participations Ag | Processes for the alkylation of pyrazoles |
| WO2012019950A1 (en) | 2010-08-10 | 2012-02-16 | Syngenta Participations Ag | Process for the preparation of 3-haloalkylpyrazoles |
| CN110872255A (en) * | 2019-12-10 | 2020-03-10 | 武威金仓生物科技有限公司 | Preparation method of 3, 4-dimethylpyrazole and phosphate thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000044541A (en) * | 1998-08-03 | 2000-02-15 | Mitsui Chemicals Inc | Production of 1,3-dialkylpyrazole-4-carboxylic acid ester |
| JP2000212166A (en) * | 1999-01-26 | 2000-08-02 | Mitsui Chemicals Inc | Production of 1,3-dialkylpyrazole-4-carboxlic acid ester |
-
2000
- 2000-05-17 JP JP2000144516A patent/JP4568404B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000044541A (en) * | 1998-08-03 | 2000-02-15 | Mitsui Chemicals Inc | Production of 1,3-dialkylpyrazole-4-carboxylic acid ester |
| JP2000212166A (en) * | 1999-01-26 | 2000-08-02 | Mitsui Chemicals Inc | Production of 1,3-dialkylpyrazole-4-carboxlic acid ester |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011012618A2 (en) | 2009-07-28 | 2011-02-03 | Syngenta Participations Ag | Processes relating to the alkylation of pyrazoles |
| WO2011012620A2 (en) | 2009-07-31 | 2011-02-03 | Syngenta Participations Ag | Processes for the alkylation of pyrazoles |
| WO2012019950A1 (en) | 2010-08-10 | 2012-02-16 | Syngenta Participations Ag | Process for the preparation of 3-haloalkylpyrazoles |
| CN110872255A (en) * | 2019-12-10 | 2020-03-10 | 武威金仓生物科技有限公司 | Preparation method of 3, 4-dimethylpyrazole and phosphate thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4568404B2 (en) | 2010-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4725977B2 (en) | Process for producing 2-dihaloacyl-3-amino-acrylic acid ester and 3-dihalomethyl-pyrazole-4-carboxylic acid ester | |
| JPWO2006090778A1 (en) | Process for producing 1-substituted-3-fluoroalkylpyrazole-4-carboxylic acid ester | |
| JP2005247690A (en) | Method for producing 6,6,6-trifluoro-3,5-dioxohexanoic acid ester and its tautomer | |
| JP2001322983A (en) | Method for producing pyrazole carboxylic acid ester derivative | |
| JP2008208111A (en) | Bis(2-alkoxyethyl) azodicarboxylate ester compound and intermediate for producing the same | |
| KR20080031910A (en) | Process for the preparation of 1-[cyano(4-hydroxyphenyl)methyl]cyclohexanol compounds | |
| JP2979358B2 (en) | Phenothiazine derivatives | |
| US20160060225A1 (en) | Method of manufacturing pyridazinone compound | |
| JP2608714B2 (en) | Method for producing 1,2,3-triazole and its derivative | |
| KR102546866B1 (en) | Process for preparing 3-substituted 2-vinylphenyl sulfonates | |
| JP3959178B2 (en) | Method for producing hydrazine derivative, intermediate thereof and method for producing intermediate | |
| JP2006298872A (en) | Manufacturing method of 1-fluoro-1-phenylthioethene | |
| JP2649122B2 (en) | 4,5-Dihalogeno-6- (α-substituted ethyl) pyrimidine and process for producing the same | |
| JP2000344703A (en) | Production of 4-alkoxymethyl-2,3,5,6-tetrafluorobenzyl alcohol | |
| JP3855686B2 (en) | 3,3-dialkoxy-2-hydroxyimino derivative and process for producing the same | |
| JP2004131486A (en) | Method for producing n-alkoxycarbonylpiperidine derivative, raw material compound of the same and method for producing the same | |
| WO2022002116A1 (en) | Preparation method for phenylisoxazoline compound | |
| JP2006124347A (en) | New method for producing phenyl 2-pyrimidinyl ketones and new intermediate therefor | |
| JP2004269376A (en) | Method for producing 1-formyl-3-(3,4-methylenedioxyphenyl)propene derivative | |
| JP3283959B2 (en) | D-biotin intermediate and method for producing the same | |
| JP5148836B2 (en) | Process for producing nicotinic acid derivative or salt thereof | |
| JP5034277B2 (en) | Of 3- (N-acylamino) -3- (4-tetrahydropyranyl) -2-oxopropanoic acid ester and 3- (N-acylamino) -3- (4-tetrahydropyranyl) -2-oxopropanohydrazide Production method | |
| JP2009035508A (en) | Process for producing optically active carboxylic acid | |
| JP2002226431A (en) | Method for producing liquid crystalline compound | |
| JPH07179434A (en) | 4,6-dialkoxy-2-sulfonyloxymethylpyrimidine derivative and its production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060614 |
|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20071018 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100216 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20100318 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100323 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100413 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100415 |
|
| 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: 20100727 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100809 |
|
| 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: 20130813 Year of fee payment: 3 |
|
| LAPS | Cancellation because of no payment of annual fees |