JP4774763B2 - Method for producing purified 3-methyl-2-butenyl acetate - Google Patents
Method for producing purified 3-methyl-2-butenyl acetate Download PDFInfo
- Publication number
- JP4774763B2 JP4774763B2 JP2005063455A JP2005063455A JP4774763B2 JP 4774763 B2 JP4774763 B2 JP 4774763B2 JP 2005063455 A JP2005063455 A JP 2005063455A JP 2005063455 A JP2005063455 A JP 2005063455A JP 4774763 B2 JP4774763 B2 JP 4774763B2
- Authority
- JP
- Japan
- Prior art keywords
- methyl
- butenyl acetate
- organic layer
- butenyl
- acetate
- 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.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、不純物の少ない酢酸３−メチル−２−ブテニルの製造方法に関する。 The present invention relates to a method for producing 3-methyl-2-butenyl acetate with less impurities.
酢酸３−メチル−２−ブテニルは、医農薬等の種々の化学品の原料として有用な化合物である。例えば、酢酸３−メチル−２−ブテニルとジアゾ酢酸エステル類とを反応させることにより、合成ピレスロイドの中間体として重要なシクロプロパン化合物を得ることができる（例えば、非特許文献１参照。）。 3-methyl-2-butenyl acetate is a useful compound as a raw material for various chemicals such as medical and agricultural chemicals. For example, by reacting 3-methyl-2-butenyl acetate with diazoacetates, an important cyclopropane compound can be obtained as an intermediate of a synthetic pyrethroid (see, for example, Non-Patent Document 1).
酢酸３−メチル−２−ブテニルの製造法としては、代表的には、３−メチル−２−ブテン−１−オールと無水酢酸とを反応させる方法（例えば、非特許文献２参照。）が知られており、かかる製造法で得られる酢酸３−メチル−２−ブテニルには、通常、酢酸等のカルボン酸類；３−メチル−２−ブテナール等のアルデヒド類；などの、蒸留処理では除去が困難な不純物が含まれており、不純物の少ない酢酸３−メチル−２−ブテニルの効率のよい製造方法の開発が望まれていた。 A typical method for producing 3-methyl-2-butenyl acetate is a method of reacting 3-methyl-2-buten-1-ol with acetic anhydride (see, for example, Non-Patent Document 2). The 3-methyl-2-butenyl acetate obtained by such a production method is usually difficult to remove by distillation treatment such as carboxylic acids such as acetic acid; aldehydes such as 3-methyl-2-butenal; Therefore, it has been desired to develop an efficient production method for 3-methyl-2-butenyl acetate containing a small amount of impurities.
このような状況のもと、本発明者らは、不純物の少ない酢酸３−メチル−２−ブテニルを得る方法について鋭意検討したところ、アルカリ金属亜硫酸水素塩の水溶液および／または塩基の水溶液を用いて粗製の酢酸３−メチル−２−ブテニルを処理することにより、カルボン酸類、アルデヒド類などの不純物を簡便に除去することができ、精製酢酸３−メチル−２−ブテニルが製造できることを見出し、本発明に至った。 Under such circumstances, the present inventors diligently studied a method for obtaining 3-methyl-2-butenyl acetate with less impurities, and using an aqueous solution of alkali metal bisulfite and / or an aqueous solution of base. By treating crude 3-methyl-2-butenyl acetate, it was found that impurities such as carboxylic acids and aldehydes can be easily removed, and purified 3-methyl-2-butenyl acetate can be produced. It came to.
すなわち、本発明は、粗製の酢酸３−メチル−２−ブテニルに工程（Ａ）および／または（Ｂ）を施すことを特徴とする精製酢酸３−メチル−２−ブテニルの製造方法を提供するものである。
（Ａ）アルカリ金属亜硫酸水素塩の水溶液で処理し、有機層を分取し、該有機層から酢酸３−メチル−２−ブテニルを回収する工程
（Ｂ）塩基の水溶液で処理し、有機層を分取し、該有機層から酢酸３−メチル−２−ブテニルを回収する工程
That is, the present invention provides a method for producing purified 3-methyl-2-butenyl acetate, which comprises subjecting crude 3-methyl-2-butenyl acetate to steps (A) and / or (B). It is.
(A) Treatment with an aqueous solution of alkali metal bisulfite, separating the organic layer, and recovering 3-methyl-2-butenyl acetate from the organic layer (B) Treatment with an aqueous base solution, Separating and recovering 3-methyl-2-butenyl acetate from the organic layer
本発明によれば、医農薬等の種々の化学品の原料として有用な酢酸３−メチル−２−ブテニルを効率よく精製することが出来るため、工業的に有利である。 According to the present invention, 3-methyl-2-butenyl acetate useful as a raw material for various chemicals such as medicines and agricultural chemicals can be efficiently purified, and is industrially advantageous.
本発明は、上記のような公知の製造法により得られる粗製の酢酸３−メチル−２−ブテニルに工程（Ａ）および／または（Ｂ）を施すことを特徴とする精製酢酸３−メチル−２−ブテニルの製造することを目的とするものである。
（Ａ）アルカリ金属亜硫酸水素塩の水溶液で処理し、有機層を分取し、該有機層から酢酸３−メチル−２−ブテニルを回収する工程
（Ｂ）塩基の水溶液で処理し、有機層を分取し、該有機層から酢酸３−メチル−２−ブテニルを回収する工程
In the present invention, purified 3-methyl-2 acetate is characterized by subjecting crude 3-methyl-2-butenyl acetate obtained by a known production method as described above to steps (A) and / or (B). -It is intended to produce butenyl.
(A) Treatment with an aqueous solution of alkali metal bisulfite, separating the organic layer, and recovering 3-methyl-2-butenyl acetate from the organic layer (B) Treatment with an aqueous base solution, Separating and recovering 3-methyl-2-butenyl acetate from the organic layer
本発明において、粗製の酢酸３−メチル−２−ブテニルは、これをそのままで、または水と混和しない有機溶媒の溶液として、前記工程（Ａ）および／または（Ｂ）に供する。水と混和しない有機溶媒としては、例えばトルエン、キシレン、メシチレン、クロロベンゼン等の芳香族炭化水素溶媒；ペンタン、ヘキサン、ヘプタン、オクタン、シクロヘキサン等の脂肪族炭化水素溶媒；酢酸エチル、炭酸ジエチル等のエステル溶媒；ジクロロメタン、ジクロロエタン、四塩化炭素等のハロゲン化脂肪族炭化水素溶媒；ジエチルエーテル、ｔｅｒｔ−ブチルメチルエーテル等のエーテル溶媒；などが挙げられる。 In the present invention, the crude 3-methyl-2-butenyl acetate is subjected to the steps (A) and / or (B) as it is or as a solution of an organic solvent immiscible with water. Examples of the organic solvent immiscible with water include aromatic hydrocarbon solvents such as toluene, xylene, mesitylene and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane and cyclohexane; esters such as ethyl acetate and diethyl carbonate Solvents; Halogenated aliphatic hydrocarbon solvents such as dichloromethane, dichloroethane and carbon tetrachloride; Ether solvents such as diethyl ether and tert-butyl methyl ether;
工程（Ａ）において、粗製の酢酸３−メチル−２−ブテニルをアルカリ金属亜硫酸水素塩の水溶液で処理するとは、通常、両者を攪拌・混合することにより実施され、その混合順序は特に限定されず、二層が完全に混合する程度に十分に攪拌することが好ましい。 In the step (A), the treatment of crude 3-methyl-2-butenyl acetate with an aqueous solution of alkali metal bisulfite is usually carried out by stirring and mixing the two, and the mixing order is not particularly limited. It is preferred that the two layers be sufficiently stirred so that they are completely mixed.
アルカリ金属亜硫酸水素塩としては、例えば亜硫酸水素ナトリウム、亜硫酸水素カリウム等が挙げられる。かかるアルカリ金属亜硫酸水素塩の使用量は、含まれるアルデヒド類に対して、通常１モル倍以上であればよく、上限は特に制限されない。 Examples of the alkali metal bisulfite include sodium bisulfite and potassium bisulfite. The amount of the alkali metal bisulfite used is usually 1 mole or more with respect to the aldehydes contained, and the upper limit is not particularly limited.
アルカリ金属亜硫酸水素塩の水溶液の濃度は、通常０．５〜５０重量％の範囲であり、好ましくは１〜４０重量％程度の範囲である。処理温度は、通常０〜１００℃の範囲であり、好ましくは３０〜６０℃程度の範囲である。処理時間は、通常５分〜５時間程度の範囲である。 The concentration of the aqueous solution of alkali metal bisulfite is usually in the range of 0.5 to 50% by weight, preferably in the range of about 1 to 40% by weight. The treatment temperature is usually in the range of 0 to 100 ° C, preferably in the range of about 30 to 60 ° C. The treatment time is usually in the range of about 5 minutes to 5 hours.
粗製の酢酸３−メチル−２−ブテニルをアルカリ金属亜硫酸水素塩の水溶液で処理した後に、有機層と水層を分離することにより、有機層として酢酸３−メチル−２−ブテニルを得ることができる。得られた酢酸３−メチル−２−ブテニルに含まれる３−メチル−２−ブテナール等のアルデヒド類は、通常０．１重量％以下程度である。アルデヒド類の除去をさらに十分に行うため、得られた有機層を水で処理し、有機層と水層を分離して有機層を得ることが好ましい。この場合の水の使用量、処理温度および処理時間は、上記したアルカリ金属亜硫酸水素塩の水溶液での処理に準じて実施すればよい。 After treating crude 3-methyl-2-butenyl acetate with an aqueous solution of an alkali metal hydrogen sulfite, the organic layer and the aqueous layer can be separated to obtain 3-methyl-2-butenyl acetate as the organic layer. . Aldehydes such as 3-methyl-2-butenal contained in the obtained 3-methyl-2-butenyl acetate are usually about 0.1% by weight or less. In order to remove aldehydes more sufficiently, it is preferable to treat the obtained organic layer with water and separate the organic layer and the aqueous layer to obtain an organic layer. The amount of water used, the treatment temperature, and the treatment time in this case may be implemented in accordance with the treatment with the aqueous solution of alkali metal bisulfite described above.
工程（Ｂ）において、粗製の酢酸３−メチル−２−ブテニルを塩基の水溶液で処理するとは、通常、両者を攪拌・混合することにより実施され、その混合順序は特に限定されず、二層が完全に混合する程度に十分に攪拌することが好ましい。 In the step (B), treating the crude 3-methyl-2-butenyl acetate with an aqueous solution of a base is usually carried out by stirring and mixing the two, the mixing order is not particularly limited, and the two layers are formed. It is preferable to stir sufficiently to mix thoroughly.
塩基としては、例えば水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物；例えば炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩；例えば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炭酸水素塩；などが挙げられ、酢酸３−メチル−２−ブテニルの加水分解抑制の観点で、アルカリ金属炭酸水素塩の使用が好ましく、また同様に、かかる塩基の使用量も、カルボン酸類に対して、通常１〜５モル倍程度の範囲で、目的を達成することができる。 Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; From the viewpoint of inhibiting hydrolysis of 3-methyl-2-butenyl acetate, the use of alkali metal hydrogen carbonate is preferable. Similarly, the amount of such base used is usually 1 to 1 relative to carboxylic acids. The object can be achieved within a range of about 5 moles.
塩基の水溶液の濃度は、通常０．５〜５０重量％の範囲であり、好ましくは１〜４０重量％程度の範囲である。処理温度は、通常０〜５０℃の範囲であり、好ましくは５〜３０℃程度の範囲である。処理時間は、通常５分〜２時間程度の範囲である。 The concentration of the aqueous solution of the base is usually in the range of 0.5 to 50% by weight, preferably in the range of about 1 to 40% by weight. The treatment temperature is usually in the range of 0 to 50 ° C, preferably in the range of about 5 to 30 ° C. The treatment time is usually in the range of about 5 minutes to 2 hours.
粗製の酢酸３−メチル−２−ブテニルを塩基の水溶液で処理した後に、有機層と水層を分離することにより、有機層として酢酸３−メチル−２−ブテニルを得ることができる。得られた酢酸３−メチル−２−ブテニルに含まれる酢酸等のカルボン酸類は、通常０．１重量％以下程度である。カルボン酸類の除去をさらに十分に行う目的および残存塩基により酢酸３−メチル−２−ブテニルの加水分解が進行することを抑制する目的において、得られた有機層を水で処理し、有機層と水層を分離して有機層を得ることが好ましい。この場合の水の使用量、処理温度および処理時間は、上記した塩基の水溶液での処理に準じて実施すればよい。 After treating the crude 3-methyl-2-butenyl acetate with an aqueous base solution, the organic layer and the aqueous layer are separated to obtain 3-methyl-2-butenyl acetate as the organic layer. Carboxylic acids such as acetic acid contained in the obtained 3-methyl-2-butenyl acetate are usually about 0.1% by weight or less. For the purpose of sufficiently removing carboxylic acids and suppressing the progress of hydrolysis of 3-methyl-2-butenyl acetate by the remaining base, the obtained organic layer is treated with water, and the organic layer and the water It is preferable to separate the layers to obtain an organic layer. The amount of water used, the treatment temperature, and the treatment time in this case may be carried out in accordance with the treatment with the aqueous base solution described above.
上記工程（Ａ）（Ｂ）は、除去する目的の不純物の種類により、一方の工程のみを施すこともできるし、もちろん両方の工程を施してもよい。つまりアルデヒド類の除去を目的とする場合には工程（Ａ）を施せばよく、カルボン酸類の除去を目的とする場合には工程（Ｂ）を施せばよい。両方の工程を施す場合の工程の順番は特に制限されず、工程（Ａ）を施した後に工程（Ｂ）を施してもよいし、その逆の順番でもよい。ただし、工程（Ａ）においては、アルカリ金属亜硫酸水素塩由来の亜硫酸ガス等の酸性物質が残存する可能性があり、かかる酸性物質を除去する目的で、工程（Ａ）を施した後に工程（Ｂ）を施すことが好ましい。また、工程（Ａ）のみを施す場合には、前記した残存する可能性のある亜硫酸ガス等の酸性物質を除去する目的で、得られた酢酸３−メチル−２−ブテニルに不活性ガスを吹き込んでもよい。 In the steps (A) and (B), depending on the type of impurities to be removed, only one step can be performed or, of course, both steps may be performed. That is, when the purpose is to remove aldehydes, step (A) may be performed, and when the purpose is to remove carboxylic acids, step (B) may be performed. The order of the steps when both steps are performed is not particularly limited, and the step (B) may be performed after the step (A) is performed, or the reverse order may be employed. However, in the step (A), there is a possibility that an acidic substance such as sulfurous acid gas derived from alkali metal hydrogen sulfite may remain. After the step (A) is performed, the step (B ) Is preferable. In addition, when only the step (A) is performed, an inert gas is blown into the obtained 3-methyl-2-butenyl acetate for the purpose of removing acidic substances such as sulfurous acid gas which may remain. But you can.
かくして得られた精製酢酸３−メチル−２−ブテニルは、必要に応じて蒸留処理等の通常の精製方法によって、さらに精製してもよい。 The purified 3-methyl-2-butenyl acetate thus obtained may be further purified by an ordinary purification method such as distillation treatment, if necessary.
以下、実施例により本発明をさらに詳細に説明するが、本発明は実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to an Example.
実施例において、酢酸３−メチル−２−ブテニルおよびそれに含まれる不純物の含量は、いずれもガスクロマトグラフィー面積百分率により求めた。 In Examples, the contents of 3-methyl-2-butenyl acetate and impurities contained therein were both determined by gas chromatography area percentage.
実施例１
窒素雰囲気下に、酢酸３−メチル−２−ブテニル９７．８８％、酢酸０．３４％、３−メチル−２−ブテナール０．６２％を含む粗製の酢酸３−メチル−２−ブテニル２０７ｇに、５％亜硫酸水素ナトリウム水溶液１３５ｇを加え、４０〜５０℃で３０分間攪拌した後、静置分液し、有機層を得た。該有機層に、水１３５ｇを加え、同温度で１０分間攪拌した後、静置分液し、有機層を得た。該有機層を１５〜２５℃に冷却し、５％炭酸水素ナトリウム水溶液１３５ｇを加え、同温度で３０分間攪拌した後、静置分液し、有機層を得た。該有機層に、水１３５ｇを加え、同温度で１０分間攪拌洗浄した後、静置分液した。
得られた有機層を、窒素雰囲気下に単蒸留し、酢酸３−メチル−２−ブテニル１９７ｇを得た。沸点７０〜７１℃／５ｋＰａ。
該精製酢酸３−メチル−２−ブテニルには、酢酸３−メチル−２−ブテニル９９．３１％、３−メチル−２−ブテナール０．０１％が含まれており、酢酸は検出されなかった。
Example 1
Under a nitrogen atmosphere, to 207 g of crude 3-methyl-2-butenyl acetate containing 97.88% 3-methyl-2-butenyl acetate, 0.34% acetic acid, 0.62% 3-methyl-2-butenal, After adding 135 g of 5% aqueous sodium hydrogensulfite solution and stirring at 40 to 50 ° C. for 30 minutes, the solution was allowed to stand still to obtain an organic layer. 135 g of water was added to the organic layer, and the mixture was stirred at the same temperature for 10 minutes, followed by stationary separation to obtain an organic layer. The organic layer was cooled to 15 to 25 ° C., 135 g of 5% aqueous sodium hydrogen carbonate solution was added, and the mixture was stirred at the same temperature for 30 minutes, and then allowed to stand for liquid separation to obtain an organic layer. 135 g of water was added to the organic layer, and the mixture was stirred and washed at the same temperature for 10 minutes.
The obtained organic layer was subjected to simple distillation under a nitrogen atmosphere to obtain 197 g of 3-methyl-2-butenyl acetate. Boiling point 70-71 ° C / 5 kPa.
The purified 3-methyl-2-butenyl acetate contained 99.31% 3-methyl-2-butenyl acetate and 0.01% 3-methyl-2-butenal, and no acetic acid was detected.
参考例１
窒素置換した５０ｍＬシュレンク管に、トリフルオロメタンスルホン酸銅（Ｉ）・トルエン錯体５．２ｍｇ、１，１−ビス［（４Ｓ）−ｔｅｒｔ−ブチル−２−オキサゾリン］シクロプロパン６．７ｍｇおよび実施例１で得た精製後の酢酸３−メチル−２−ブテニル７．５ｍＬを加えた後、２１℃で３０分攪拌し、不斉銅触媒を調製した。その後、ジアゾ酢酸エチル２．３ｇを実施例１で得た精製後の酢酸３−メチル−２−ブテニル３．８ｍＬに溶解した溶液を同温度で４時間かけて滴下し、さらに同温度で３０分間攪拌、反応させたところ、２，２−ジメチル−３−（アセトキシメチル）シクロプロパンカルボン酸エチルを含む溶液を得た。ガスクロマトグラフィー内部標準法により分析を行ったところ、 収率は７２％（ジアゾ酢酸エチル基準）であった。
Reference example 1
To a nitrogen-substituted 50 mL Schlenk tube, 5.2 mg of copper (I) trifluoromethanesulfonate / toluene complex, 6.7 mg of 1,1-bis [(4S) -tert-butyl-2-oxazoline] cyclopropane and Example 1 were added. After adding 7.5 mL of the purified 3-methyl-2-butenyl acetate obtained in the above, the mixture was stirred at 21 ° C. for 30 minutes to prepare an asymmetric copper catalyst. Thereafter, 2.3 g of ethyl diazoacetate dissolved in 3.8 mL of purified 3-methyl-2-butenyl acetate obtained in Example 1 was added dropwise at the same temperature over 4 hours, and further at the same temperature for 30 minutes. When stirred and reacted, a solution containing ethyl 2,2-dimethyl-3- (acetoxymethyl) cyclopropanecarboxylate was obtained. Analysis by gas chromatography internal standard method revealed that the yield was 72% (based on ethyl diazoacetate).
参考例２
実施例１で得た精製後の酢酸３−メチル−２−ブテニルの代わりに、実施例１で用いた粗製の酢酸３−メチル−２−ブテニルを使用すること以外は、参考例１と同様に反応を行った。２，２−ジメチル−３−（アセトキシメチル）シクロプロパンカルボン酸エチルの収率は５７％（ジアゾ酢酸エチル基準）であった。
Reference example 2
Similar to Reference Example 1 except that the crude 3-methyl-2-butenyl acetate used in Example 1 was used instead of the purified 3-methyl-2-butenyl acetate obtained in Example 1. Reaction was performed. The yield of ethyl 2,2-dimethyl-3- (acetoxymethyl) cyclopropanecarboxylate was 57% (based on ethyl diazoacetate).
Claims (4)
（Ａ）アルカリ金属亜硫酸水素塩の水溶液で、３０〜６０℃で５分〜５時間処理し、有機層を分取し、該有機層から酢酸３−メチル−２−ブテニルを回収する工程
（Ｂ）塩基の水溶液で処理し、有機層を分取し、該有機層から酢酸３−メチル−２−ブテニルを回収する工程 Method for producing a purified 3-methyl-2-butenyl acetate, characterized in that applied to crude 3-methyl-2-butenyl acetate Step a (A) and (B).
(A) A process of treating with an aqueous solution of alkali metal bisulfite at 30 to 60 ° C. for 5 minutes to 5 hours, separating an organic layer, and recovering 3-methyl-2-butenyl acetate from the organic layer (B ) A step of treating with an aqueous base solution, separating an organic layer, and recovering 3-methyl-2-butenyl acetate from the organic layer
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005063455A JP4774763B2 (en) | 2004-03-25 | 2005-03-08 | Method for producing purified 3-methyl-2-butenyl acetate |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004088617 | 2004-03-25 | ||
| JP2004088617 | 2004-03-25 | ||
| JP2005063455A JP4774763B2 (en) | 2004-03-25 | 2005-03-08 | Method for producing purified 3-methyl-2-butenyl acetate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005306852A JP2005306852A (en) | 2005-11-04 |
| JP4774763B2 true JP4774763B2 (en) | 2011-09-14 |
Family
ID=35436010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005063455A Active JP4774763B2 (en) | 2004-03-25 | 2005-03-08 | Method for producing purified 3-methyl-2-butenyl acetate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4774763B2 (en) |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4588487A (en) * | 1985-09-16 | 1986-05-13 | Rohm And Haas Company | Process for the preparation of 3'-halodiphenylethers |
| JPH072687B2 (en) * | 1988-02-27 | 1995-01-18 | 三洋化成工業株式会社 | Tolan compound and liquid crystal composition |
| JP2959222B2 (en) * | 1991-08-22 | 1999-10-06 | 住友化学工業株式会社 | Method for producing ketone or tertiary alcohol |
| JP3275399B2 (en) * | 1991-12-25 | 2002-04-15 | 住友化学工業株式会社 | Production method of lactone or ester |
| US5872277A (en) * | 1997-03-10 | 1999-02-16 | Loyola University Of Chicago | Methods for preparing prenyl alcohol |
| DE19748774A1 (en) * | 1997-11-05 | 1999-05-06 | Haarmann & Reimer Gmbh | 8-Ocimenyl esters and their use as fragrances and flavorings |
| US6278016B1 (en) * | 1999-12-09 | 2001-08-21 | Loyola University Of Chicago | Methods for conversion of isoprene to prenyl alcohol and related compounds |
| DE10142659A1 (en) * | 2001-08-31 | 2003-03-20 | Aventis Pharma Gmbh | Use of multiply substituted indan-1-ol. Systems for the preparation of medicaments for the prophylaxis or treatment of obesity |
| JP4453368B2 (en) * | 2003-01-30 | 2010-04-21 | 住友ベークライト株式会社 | Bisaminophenol derivatives |
-
2005
- 2005-03-08 JP JP2005063455A patent/JP4774763B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005306852A (en) | 2005-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1714068A (en) | Method for making carboxylic acids | |
| JP4774763B2 (en) | Method for producing purified 3-methyl-2-butenyl acetate | |
| KR101150056B1 (en) | Processes for producing 3-methyl-2-butenyl acetate | |
| CN100509748C (en) | Preparation method for purified 3-methyl-2-butenyl acetate | |
| JP2008534577A (en) | Method for producing p-toluic acid by liquid phase oxidation of p-xylene in water | |
| CN108144612B (en) | Cobalt-based catalyst for synthesizing carboxylic ester by one-pot method and preparation and application thereof | |
| WO2006066904A1 (en) | Process for decomposing cyclohexylhdroperoxide | |
| JP5076313B2 (en) | Process for producing purified 2,2-dimethyl-3-formylcyclopropanecarboxylic acid ester and intermediate thereof | |
| JP2006045190A (en) | Method for producing 3-methyl-2-butenyl acetate | |
| KR102159227B1 (en) | Novel Menthyl Nicotinate Synthesis Method | |
| JP2007161655A (en) | Method for producing unsaturated fatty acid | |
| JP2676910B2 (en) | Method for producing high-purity 0-toluic acid | |
| JPH05977A (en) | Method for purifying mixture of cyclododecanol and cyclododecanone | |
| JP4045774B2 (en) | Process for producing carboxylic acids and their catalysts | |
| WO2003014055A1 (en) | Method of oxidising hydrocarbons to acids | |
| JP2005306860A (en) | Method for producing (1-alkenyl)cyclopropane compound | |
| Mohapatra et al. | Selective oxidation of cycloalkanes over iron-substituted hexagonal mesoporous aluminophosphate molecular sieves | |
| Hashemi et al. | Oxidation of benzylic methylene compounds to ketones with 4-aminoperoxybenzoic acid supported on silica gel in presence of oxygen or air | |
| JP2007320878A (en) | Method for producing cycloalkanol and cycloalkanone | |
| JP6274573B2 (en) | Process for producing carboxylic acid and ketone and / or alcohol | |
| EP1492754B1 (en) | Method for making carboxylic acids | |
| Yim et al. | Effects of ultrasound on the formation of α-benzoylbenzyl cyanide from benzyl cyanide and alkylphenyl ketone from α-alkylbenzyl cyanide by potassium superoxide in the presence of crown ether | |
| JPS5842180B2 (en) | Cicancyclopropane carbonate methyl ester | |
| JP2005023037A (en) | Method for production of cyclopentene | |
| JPH06135890A (en) | Production of carboxylic acid ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080109 |
|
| RD05 | Notification of revocation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7425 Effective date: 20080131 |
|
| RD05 | Notification of revocation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7425 Effective date: 20080514 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110118 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110315 |
|
| 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: 20110531 |
|
| 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: 20110613 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 4774763 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140708 Year of fee payment: 3 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |