JP2000256244A - Production of 4-methyltetrafluorobenzyl alcohol derivative - Google Patents
Production of 4-methyltetrafluorobenzyl alcohol derivativeInfo
- Publication number
- JP2000256244A JP2000256244A JP11061540A JP6154099A JP2000256244A JP 2000256244 A JP2000256244 A JP 2000256244A JP 11061540 A JP11061540 A JP 11061540A JP 6154099 A JP6154099 A JP 6154099A JP 2000256244 A JP2000256244 A JP 2000256244A
- Authority
- JP
- Japan
- Prior art keywords
- group
- alcohol derivative
- general formula
- organic solvent
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyrane Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、４−メチルテトラ
フルオロベンジルアルコール誘導体の製造法に関する。TECHNICAL FIELD The present invention relates to a method for producing a 4-methyltetrafluorobenzyl alcohol derivative.
【０００２】[0002]
【従来の技術および発明が解決しようとする課題】従
来、４−メチルテトラフルオロベンジルアルコールをそ
のアルコール部位として有する、ある種のエステル化合
物が優れた殺虫活性を有することがしられており（特開
昭５６−９７２５１号公報）、４−メチルテトラフルオ
ロベンジルアルコールの効率的な製造方法の確立が切望
されている。2. Description of the Related Art Heretofore, certain ester compounds having 4-methyltetrafluorobenzyl alcohol as its alcohol moiety have been known to have excellent insecticidal activity (Japanese Patent Application Laid-Open (JP-A) No. 2002-110572). There is an urgent need to establish an efficient method for producing 4-methyltetrafluorobenzyl alcohol.
【０００３】[0003]
【課題を解決するための手段】本発明者は、このような
状況下で鋭意検討した結果、下記一般式 化３で示され
るペンタフルオロベンジルアルコール誘導体とメチルリ
チウムとを有機溶媒中で反応させることにより、高収率
で下記一般式 化４で示される４−メチルテトラフルオ
ロベンジルアルコール誘導体が得られることを見出し、
本発明に至った。一般式 化４で示される４−メチルテ
トラフルオロベンジルアルコール誘導体は、脱保護する
ことにより、４−メチルテトラフルオロベンジルアルコ
ールを簡便に収率良く製造し得る。即ち、本発明は、一
般式 化３Means for Solving the Problems The inventors of the present invention have made intensive studies under such circumstances, and have found that a pentafluorobenzyl alcohol derivative represented by the following general formula 3 is reacted with methyllithium in an organic solvent. As a result, a 4-methyltetrafluorobenzyl alcohol derivative represented by the following general formula 4 can be obtained in high yield,
The present invention has been reached. By deprotecting the 4-methyltetrafluorobenzyl alcohol derivative represented by the general formula (4), 4-methyltetrafluorobenzyl alcohol can be easily produced with a high yield. That is, the present invention provides a compound represented by the following general formula:
【化３】 [式中、Ｒはメチルリチウムに対して不活性な保護基を
表わす。]で示されるペンタフルオロベンジルアルコー
ル誘導体とメチルリチウムとを有機溶媒中で反応させる
ことを特徴とする一般式 化４Embedded image [In the formula, R represents a protecting group inert to methyllithium. Wherein the pentafluorobenzyl alcohol derivative represented by the formula [1] is reacted with methyllithium in an organic solvent.
【化４】 [式中、Ｒは前記と同じ意味を表わす。]で示される４−
メチルテトラフルオロベンジルアルコール誘導体の製造
法を提供する。Embedded image [Wherein, R represents the same meaning as described above. 4-
Provided is a method for producing a methyltetrafluorobenzyl alcohol derivative.
【０００４】[0004]
【発明の実施の形態】以下、本発明につき詳細に説明す
る。一般式 化３で示されるペンタフルオロベンジルア
ルコール誘導体とメチルリチウムとの使用割合は、任意
の割合を取り得るが、一般式 化３で示されるペンタフ
ルオロベンジルアルコール誘導体１モルに対してメチル
リチウムを１〜３モルの割合で使用することが好まし
い。該反応は有機溶媒中で行われ、かかる溶媒としては
ジエチルエーテル、テトラヒドロフラン等のエーテル系
溶媒、ｎ−ヘプタン、ｎ−ヘキサン等の脂肪族炭化水素
系溶媒、ベンゼン、トルエン、キシレン、クメン等の芳
香族炭化水素系溶媒およびそれらの混合物があげられ
る。該反応の反応温度としては、特に限定されないが、
０℃から反応に使用する溶媒の沸点の範囲が好ましい。
反応終了後の反応液は、反応液を氷水に注加し、有機溶
媒抽出、濃縮等の通常に行われる後処理操作を行うこと
により目的とする一般式 化４で示される４−メチルテ
トラフルオロベンジルアルコール誘導体を得ることがで
きる。また、目的化合物はクロマトグラフィー、蒸留、
再結晶等の通常に行われる精製操作により精製すること
も可能である。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The ratio of the pentafluorobenzyl alcohol derivative represented by the general formula (3) to methyl lithium can be an arbitrary ratio, but 1 mol of the methyl lithium is added to 1 mol of the pentafluorobenzyl alcohol derivative represented by the general formula (3). Preferably, it is used in a proportion of up to 3 moles. The reaction is carried out in an organic solvent. Examples of such a solvent include ether solvents such as diethyl ether and tetrahydrofuran, aliphatic hydrocarbon solvents such as n-heptane and n-hexane, and aromatic solvents such as benzene, toluene, xylene and cumene. Group hydrocarbon solvents and mixtures thereof. The reaction temperature of the reaction is not particularly limited,
The range of 0 ° C. to the boiling point of the solvent used in the reaction is preferred.
After completion of the reaction, the reaction solution is poured into ice water and subjected to a usual post-treatment operation such as extraction with an organic solvent and concentration to obtain the desired 4-methyltetrafluoro compound represented by the general formula (4). A benzyl alcohol derivative can be obtained. In addition, the target compound is chromatography, distillation,
It is also possible to purify by ordinary purification operations such as recrystallization.
【０００５】尚、本発明において、Ｒで示されるメチル
リチウムに対して不活性な保護基としては、例えば、メ
チル基、ベンジル基、メトキシメチル基、メチルチオメ
チル基、ｔ−ブトキシメチル基、メトキシエトキシメチ
ル基、テトラヒドロピラニル基、ｔ−ブチル基、トリメ
チルシリル基、トリエチルシリル基、ｔ−ブチルジメチ
ルシリル基等があげられる。脱保護の際の簡便性から、
Ｒとしては一般式Ｒ1ＣＨ2−Ｏ−Ｒ2ＣＨ−で示される
基または一般式Ｒ3Ｓｉ(Ｒ4)2−で示される基｛ここ
で、Ｒ1およびＲ2は同一または相異なり、水素原子また
はＣ１−Ｃ５アルキル基を表すか、Ｒ1とＲ2が末端で結
合して、エチレン基、トリメチレン基またはテトラメチ
レン基を表してもよい。Ｒ3およびＲ4は同一または相異
なり、Ｃ１−Ｃ５アルキル基またはフェニル基を表
す。｝が好ましい。In the present invention, examples of the protective group inert to methyllithium represented by R include methyl, benzyl, methoxymethyl, methylthiomethyl, t-butoxymethyl, methoxyethoxy and the like. Examples include a methyl group, a tetrahydropyranyl group, a t-butyl group, a trimethylsilyl group, a triethylsilyl group, and a t-butyldimethylsilyl group. Because of the ease of deprotection,
R is a group represented by the general formula R 1 CH 2 —O—R 2 CH— or a group represented by the general formula R 3 Si (R 4 ) 2 — wherein R 1 and R 2 are the same or different , A hydrogen atom or a C1-C5 alkyl group, or R 1 and R 2 may be bonded at the terminal to represent an ethylene group, a trimethylene group or a tetramethylene group. R 3 and R 4 are the same or different and represent a C1-C5 alkyl group or a phenyl group. ｝ Is preferred.
【０００６】一般式 化３で示されるペンタフルオロベ
ンジルアルコール誘導体は、ペンタフルオロベンジルア
ルコールから、例えば、Protective Groups in Organic
Chemistry (John Wiley & Sons, Inc.)に記載の方法に
より製造することができる。尚、一般式 化３で示され
るペンタフルオロベンジルアルコール誘導体の一部の化
合物については、具体的には以下に示す方法（式 化
５、式 化６または式化７）に準じて、簡便に収率良く
製造することができるThe pentafluorobenzyl alcohol derivative represented by the general formula (3) can be obtained from pentafluorobenzyl alcohol by, for example, Protective Groups in Organic
It can be produced by the method described in Chemistry (John Wiley & Sons, Inc.). It should be noted that some of the compounds of the pentafluorobenzyl alcohol derivative represented by the general formula (3) can be simply collected according to the method shown below (formula 5, 6 or 7). Can be manufactured efficiently
【化５】 Embedded image
【化６】 Embedded image
【化７】 Embedded image
【０００７】また、本発明の方法により得られた一般式
化４で示される４−メチルテトラフルオロベンジルア
ルコール誘導体は、例えば、Protective Groups in Org
anicChemistry (John Wiley & Sons, Inc.)に記載の方
法により、目的とする４−メチルテトラフルオロベンジ
ルアルコールを製造することができる。Further, the 4-methyltetrafluorobenzyl alcohol derivative represented by the general formula (4) obtained by the method of the present invention can be used, for example, in Protective Groups in Org
The desired 4-methyltetrafluorobenzyl alcohol can be produced by the method described in anicChemistry (John Wiley & Sons, Inc.).
【０００８】[0008]
【実施例】以下、製造例をあげて、本発明をさらに詳し
く説明するが、本発明はこれらの例に限定されない。 製造例 窒素雰囲気下、ペンタフルオロベンジル＝テトラヒドロ
ピラン−２−イル＝エーテル１４．２ｇの乾燥ジエチル
エーテル１５０ｍｌ溶液に、攪拌しながら、室温にてメ
チルリチウムのジエチルエーテル溶液（１．１４Ｍ）６
６ｍｌを少しずつ滴下した（滴下中、発熱により温度が
上昇し還流し始める）。その後、還流温度で１時間攪拌
を行った。室温まで冷却後、反応液を砕いた氷を入れた
容器に注加した。これにジエチルエーテル２００ｍｌを
加え、氷が融解した後、分液した。ジエチルエーテル層
を無水硫酸ナトリウムで乾燥した後、減圧下に濃縮し
た。残渣をシリカゲルカラムクロマトグラフィー（酢酸
エチル：ｎ−ヘキサン＝１：１０）に付し、４−メチル
テトラフルオロベンジル＝テトラヒドロピラン−２−イ
ル＝エーテル１３．３ｇ（収率９０％）を得た。1 Ｈ−ＮＭＲ（ＣＤＣｌ3、ＴＭＳ内部標準）δ値 １．４０〜１．９０（ｍ、６Ｈ）、２．３０（ｓ、３
Ｈ）、３．５５（ｍ、１Ｈ）、３．９０（ｍ、１Ｈ）、
４．６０（ｄｄ、１Ｈ）、４．８０（ｄｄ、２Ｈ）EXAMPLES Hereinafter, the present invention will be described in more detail by way of production examples, but the present invention is not limited to these examples. Production Example Under a nitrogen atmosphere, a diethyl ether solution of methyllithium (1.14M) 6 in a solution of 14.2 g of pentafluorobenzyl = tetrahydropyran-2-yl = ether in 150 ml of dry diethyl ether at room temperature with stirring.
6 ml was added dropwise little by little (during the dropwise addition, the temperature rose due to heat generation and reflux started). Thereafter, stirring was performed at a reflux temperature for 1 hour. After cooling to room temperature, the reaction solution was poured into a container containing crushed ice. To this, 200 ml of diethyl ether was added, and after the ice melted, liquid separation was performed. After the diethyl ether layer was dried over anhydrous sodium sulfate, it was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography (ethyl acetate: n-hexane = 1: 10) to obtain 13.3 g (yield 90%) of 4-methyltetrafluorobenzyl = tetrahydropyran-2-yl = ether. 1 H-NMR (CDCl 3 , TMS internal standard) δ value 1.40 to 1.90 (m, 6H), 2.30 (s, 3
H), 3.55 (m, 1H), 3.90 (m, 1H),
4.60 (dd, 1H), 4.80 (dd, 2H)
【０００９】次に、ペンタフルオロベンジルアルコール
から一般式 化４で示されるペンタフルオロベンジルア
ルコール誘導体を製造する方法および一般式 化５で示
される４−メチルテトラフルオロベンジルアルコール誘
導体から４−メチルテトラフルオロベンジルアルコール
を製造する方法を、参考例にて説明する。 参考例１．窒素雰囲気下、ペンタフルオロベンジルアル
コール２０．０ｇ、２，３−ジヒドロ−４Ｈ−ピラン
９．３ｇ及び乾燥ジエチルエーテル２００ｍｌの混合液
に、０〜５℃で、濃塩酸１ｍｌを加えた後、さらに室温
で５時間攪拌を行った。反応液を氷水に注加し、分液し
た。更に、該水層にジエチルエーテル２００ｍｌを加
え、抽出した。ジエチルエーテル層を併せ、飽和炭酸水
素ナトリウム水溶液で洗浄、無水硫酸ナトリウムで乾燥
した後、減圧下に濃縮した。残渣をシリカゲルカラムク
ロマトグラフィー（酢酸エチル：ｎ−ヘキサン＝１：１
０）に付し、ペンタフルオロベンジル＝テトラヒドロピ
ラン−２−イル＝エーテル２６．５ｇ（収率９２％）を
得た。1 Ｈ−ＮＭＲ（ＣＤＣｌ3、ＴＭＳ内部標準）δ値 ４０〜１．９０（ｍ、６Ｈ）、３．５５（ｍ、１Ｈ）、
３．９０（ｍ、１Ｈ）、４．６０（ｄｄ、１Ｈ）、４．
８０（ｄｄ、２Ｈ） 参考例２． ４−メチルテトラフルオロベンジル＝テトラヒドロピラ
ン−２−イル＝エーテル１１．０ｇ及びメタノール１０
０ｍｌの混合液に、０〜５℃で、ｐ−トルエンスルホン
酸一水和物１ｇを加えた後、室温で５時間攪拌を行っ
た。反応液を氷氷に注加し、分液した。該水層に酢酸エ
チル５００ｍｌを加え、抽出した。酢酸エチル層を併
せ、飽和炭酸水素ナトリウム水溶液で洗浄、無水硫酸ナ
トリウムで乾燥した後、減圧下に濃縮した。残渣をシリ
カゲルカラムクロマトグラフィー（酢酸エチル：ｎ−ヘ
キサン＝１：５）に付し、４−メチルテトラフルオロベ
ンジルアルコール６．２ｇ（収率８７％）を得た。1 Ｈ−ＮＭＲ（ＣＤＣｌ3、ＴＭＳ内部標準）δ値 ２．３０（ｓ、３Ｈ）、２．４０（ｂｒｓ、１Ｈ）、
４．８０（ｓ、２Ｈ）Next, a method for producing a pentafluorobenzyl alcohol derivative represented by the general formula (4) from pentafluorobenzyl alcohol and 4-methyltetrafluorobenzyl derivative from the 4-methyltetrafluorobenzyl alcohol derivative represented by the general formula (5) A method for producing alcohol will be described in Reference Examples. Reference Example 1. Under a nitrogen atmosphere, 1 ml of concentrated hydrochloric acid was added to a mixture of 20.0 g of pentafluorobenzyl alcohol, 9.3 g of 2,3-dihydro-4H-pyran and 200 ml of dry diethyl ether at 0 to 5 ° C., and then at room temperature. For 5 hours. The reaction solution was poured into ice water and separated. Further, 200 ml of diethyl ether was added to the aqueous layer for extraction. The diethyl ether layers were combined, washed with a saturated aqueous solution of sodium hydrogen carbonate, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The residue was subjected to silica gel column chromatography (ethyl acetate: n-hexane = 1: 1).
0) to give 26.5 g (92% yield) of pentafluorobenzyl = tetrahydropyran-2-yl = ether. 1 H-NMR (CDCl 3 , TMS internal standard) δ value 40 to 1.90 (m, 6H), 3.55 (m, 1H),
3.90 (m, 1H), 4.60 (dd, 1H),
80 (dd, 2H) Reference Example 2. 11.0 g of 4-methyltetrafluorobenzyl = tetrahydropyran-2-yl = ether and methanol 10
After adding 1 g of p-toluenesulfonic acid monohydrate to 0 ml of the mixture at 0 to 5 ° C, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured on ice and separated. 500 ml of ethyl acetate was added to the aqueous layer for extraction. The ethyl acetate layers were combined, washed with a saturated aqueous solution of sodium hydrogen carbonate, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The residue was subjected to silica gel column chromatography (ethyl acetate: n-hexane = 1: 5) to obtain 6.2 g (yield 87%) of 4-methyltetrafluorobenzyl alcohol. 1 H-NMR (CDCl 3 , TMS internal standard) δ value 2.30 (s, 3H), 2.40 (brs, 1H),
4.80 (s, 2H)
【発明の効果】本発明の方法によれば、４−メチルテト
ラフルオロベンジルアルコールを効率的に製造すること
ができる。According to the method of the present invention, 4-methyltetrafluorobenzyl alcohol can be efficiently produced.
Claims (4)
表わす。]で示されるペンタフルオロベンジルアルコー
ル誘導体とメチルリチウムとを、有機溶媒中で反応させ
ることを特徴とする一般式 化２ 【化２】 [式中、Ｒは前記と同じ意味を表わす。]で示される４−
メチルテトラフルオロベンジルアルコール誘導体の製造
法。1. A compound represented by the general formula: [In the formula, R represents a protecting group inert to methyllithium. Wherein the pentafluorobenzyl alcohol derivative represented by the formula [1] is reacted with methyllithium in an organic solvent. [Wherein, R represents the same meaning as described above. 4-
A method for producing a methyltetrafluorobenzyl alcohol derivative.
ドロフランまたはそれらの混合物である請求項１記載の
製造法。2. The method according to claim 1, wherein the organic solvent is diethyl ether, tetrahydrofuran or a mixture thereof.
Ｈ2−Ｏ−Ｒ2ＣＨ−で示される基または一般式Ｒ3Ｓｉ
(Ｒ4)2−で示される基｛ここで、Ｒ1およびＲ2は同一も
しくは相異なり、水素原子またはＣ１−Ｃ５アルキル基
を表すか、Ｒ1とＲ2が末端で結合して、エチレン基、ト
リメチレン基またはテトラメチレン基を表してもよい。
Ｒ3およびＲ4は各々独立して、Ｃ１−Ｃ５アルキル基ま
たはフェニル基を表す。｝である請求項１または２に記
載の製造法。3. In the general formula 1, R is a group represented by the general formula R 1 C
A group represented by H 2 —O—R 2 CH— or a general formula R 3 Si
A group represented by (R 4 ) 2 — wherein R 1 and R 2 are the same or different and each represent a hydrogen atom or a C1-C5 alkyl group, or R 1 and R 2 are bonded at the terminal to form ethylene May represent a group, a trimethylene group or a tetramethylene group.
R 3 and R 4 each independently represent a C1-C5 alkyl group or a phenyl group. The method according to claim 1 or 2, wherein｝.
ピラン−２−イル基である請求項１または２に記載の製
造法。4. The method according to claim 1, wherein in the general formula 1, R is a tetrahydropyran-2-yl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06154099A JP4399885B2 (en) | 1999-03-09 | 1999-03-09 | Method for producing 4-methyltetrafluorobenzyl alcohol derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06154099A JP4399885B2 (en) | 1999-03-09 | 1999-03-09 | Method for producing 4-methyltetrafluorobenzyl alcohol derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000256244A true JP2000256244A (en) | 2000-09-19 |
| JP4399885B2 JP4399885B2 (en) | 2010-01-20 |
Family
ID=13174059
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06154099A Expired - Fee Related JP4399885B2 (en) | 1999-03-09 | 1999-03-09 | Method for producing 4-methyltetrafluorobenzyl alcohol derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4399885B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007072966A1 (en) * | 2005-12-22 | 2007-06-28 | Sumitomo Chemical Company, Limited | Tetrafluorotoluene compound, method for producing same and use thereof |
| JP2007191472A (en) * | 2005-12-22 | 2007-08-02 | Sumitomo Chemical Co Ltd | 4-alkoxymethyl-2,3,5,6-tetrafluorotoluene, method for producing the same and utilization thereof |
| US7939695B2 (en) | 2005-06-22 | 2011-05-10 | Showa Denko K.K. | Production process of nucleus-halogenated methylbenzyl alcohol |
| CN105399675A (en) * | 2015-12-12 | 2016-03-16 | 常州大学 | Synthetic method for 1,3,5-trimethyl-4-pyrazole methyl formate |
-
1999
- 1999-03-09 JP JP06154099A patent/JP4399885B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7939695B2 (en) | 2005-06-22 | 2011-05-10 | Showa Denko K.K. | Production process of nucleus-halogenated methylbenzyl alcohol |
| WO2007072966A1 (en) * | 2005-12-22 | 2007-06-28 | Sumitomo Chemical Company, Limited | Tetrafluorotoluene compound, method for producing same and use thereof |
| JP2007191472A (en) * | 2005-12-22 | 2007-08-02 | Sumitomo Chemical Co Ltd | 4-alkoxymethyl-2,3,5,6-tetrafluorotoluene, method for producing the same and utilization thereof |
| CN101346334B (en) * | 2005-12-22 | 2013-04-24 | 住友化学株式会社 | Tetrafluorotoluene compound, method for producing same and use thereof |
| CN105399675A (en) * | 2015-12-12 | 2016-03-16 | 常州大学 | Synthetic method for 1,3,5-trimethyl-4-pyrazole methyl formate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4399885B2 (en) | 2010-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8618314B2 (en) | Exo- and diastereo-selective synthesis of himbacine analogs | |
| EP2632889B1 (en) | Intermediate compounds and process for the preparation of fingolimod | |
| US6927300B2 (en) | Process for the preparation of Latanoprost | |
| JP2009522227A (en) | Epoxide intermediates in the synthesis of Tamiflu | |
| JPH05194501A (en) | Process for preparing substituted azetidinone useful as antiinflammatory or antidenaturant | |
| JPH11501313A (en) | Catalytic enantioselective synthesis of spiro-fused azetidinones | |
| JP2000256244A (en) | Production of 4-methyltetrafluorobenzyl alcohol derivative | |
| JP5587350B2 (en) | Preparation of ramelteon | |
| US4395561A (en) | Synthesis of 3-hydroxyoxetane | |
| JP4157361B2 (en) | Method for producing 9-spirofluorene compound | |
| US6291696B2 (en) | Preparation of tris (trimethylsilyl) silylethyl esters | |
| JP2860506B2 (en) | Halogenoallyl alcohol derivatives | |
| JPH08325228A (en) | Production of bicyclohexanamine derivative | |
| JP4267107B2 (en) | Pyridine derivative and method for producing the same | |
| JP3770678B2 (en) | Optically active alcohol and its carboxylic acid ester | |
| JP4330783B2 (en) | Method for producing formylcyclopropanecarboxylic acid ester | |
| JP3632979B6 (en) | Method for producing 2-aminomalonic acid derivative and 2-amino-1,3-propanediol derivative | |
| JPH05229975A (en) | Cyclopentenol derivative | |
| US7319155B2 (en) | 7,7-disubstituted (5H,9H)-6,8-dioxabenzocycloheptene compounds useful in the synthesis of non-steroidal analogues of vitamin D | |
| JP3249847B2 (en) | Method for producing Z-cyclohexylideneacetic acid derivative | |
| JPH07179437A (en) | Production of 4,6-dialkoxy-2-hydroxymethylpyrimidine derivative | |
| JP4800933B2 (en) | Process for producing cyclopropane monoacetal derivative and its intermediate | |
| JPH07252183A (en) | Production of phenol derivative | |
| JPH04305553A (en) | Production of cyclohexylidene acetic acid derivative | |
| JPH027583B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060119 |
|
| RD05 | Notification of revocation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7425 Effective date: 20080125 |
|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20080220 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090619 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090714 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090910 |
|
| 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: 20091006 |
|
| 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: 20091019 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121106 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131106 Year of fee payment: 4 |
|
| LAPS | Cancellation because of no payment of annual fees |