JPH1112225A - Production of 1,1-cyclopropanedicarboxylic diester - Google Patents
Production of 1,1-cyclopropanedicarboxylic diesterInfo
- Publication number
- JPH1112225A JPH1112225A JP9184315A JP18431597A JPH1112225A JP H1112225 A JPH1112225 A JP H1112225A JP 9184315 A JP9184315 A JP 9184315A JP 18431597 A JP18431597 A JP 18431597A JP H1112225 A JPH1112225 A JP H1112225A
- Authority
- JP
- Japan
- Prior art keywords
- potassium carbonate
- acid diester
- diester
- cyclopropanedicarboxylic
- mol
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、１，１−シクロプ
ロパンジカルボン酸ジエステルの製造法に関する。The present invention relates to a method for producing 1,1-cyclopropanedicarboxylic acid diester.
【０００２】[0002]
【従来の技術】従来より、１，１−シクロプロパンジカ
ルボン酸ジエチルエステルを加水分解して得られるジカ
ルボン酸は、消炎鎮痛剤として、また、還元して得られ
るジメタノールはロイコトリエン拮抗剤として有用で、
１，１−シクロプロパンジカルボン酸ジエチルエステル
から誘導される化合物は医薬中間体として広範囲に利用
されている。かかる１，１−シクロプロパンジカルボン
酸ジエチルエステルの製造法にあたっては、例えば、Ｕ
ＳＰ５，５１０，５０９には、マロン酸ジエステルと炭
酸カリウムと１，２−ジクロロアルカンを反応させ、か
かる炭酸カリウムとして、０．０５ｍｍメシュ以下の粒
子径のものを用いる旨の記載がある。2. Description of the Related Art Hitherto, dicarboxylic acid obtained by hydrolyzing diethyl 1,1-cyclopropanedicarboxylate has been useful as an anti-inflammatory analgesic, and dimethanol obtained by reduction has been useful as a leukotriene antagonist. ,
Compounds derived from 1,1-cyclopropanedicarboxylic acid diethyl ester are widely used as pharmaceutical intermediates. In the production method of 1,1-cyclopropanedicarboxylic acid diethyl ester, for example, U
SP 5,510,509 states that malonic acid diester is reacted with potassium carbonate and 1,2-dichloroalkane, and that potassium carbonate having a particle size of 0.05 mm mesh or less is used.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、本発明
者が上記の炭酸カリウムの粒子径について詳細な検討を
行ったが、ただ単に粒子径を小さくするだけでは、反応
生成率が低くなり、収率が低下する傾向にあるため、
１，１−シクロプロパンジカルボン酸ジエチルエステル
の収率を上げるためには、炭酸カリウムの粒子径をただ
単に粒子径を小さくするだけでは限界があることが判明
した。However, the present inventor has conducted a detailed study on the particle size of potassium carbonate described above. Tends to decrease,
It has been found that there is a limit to increasing the yield of 1,1-cyclopropanedicarboxylic acid diethyl ester simply by reducing the particle size of potassium carbonate.
【０００４】[0004]
【問題を解決するための手段】そこで、本発明者は、上
記の事情に鑑みて鋭意研究した結果、マロン酸ジエステ
ルとｎ，ｍ−ジハロゲン化アルカン（但し、ｎ，ｍは整
数で、ｎ≠ｍ）を比表面積が０．６ｍ2／ｇ以上の炭酸
カリウムの共存下に反応させてなる時、１，１−シクロ
プロパンジカルボン酸ジエステルの収率が向上し、更に
かかる反応後、該炭酸カリウムの３．５倍重量以上の水
を添加して分液することにより、本発明の効果を顕著に
得ることができることを見出し本発明を完成するに至っ
た。In view of the above circumstances, the present inventors have conducted intensive studies and have found that malonic acid diester and n, m-dihalogenated alkane (where n and m are integers and n 整数 m). m) in the co-presence of potassium carbonate having a specific surface area of 0.6 m 2 / g or more, the yield of 1,1-cyclopropanedicarboxylic acid diester is improved. It has been found that the effect of the present invention can be remarkably obtained by adding 3.5 times by weight or more of water and separating the liquid, and the present invention has been completed.
【０００５】[0005]
【発明の実施の形態】以下に、本発明の製造法を詳細に
述べる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the production method of the present invention will be described in detail.
【０００６】本発明の原料となるマロン酸ジエステルと
しては、マロン酸ジメチル、マロン酸ジエチル、マロン
酸ジｎ−ブチル、マロン酸ジｎ−プロピルなどが挙げら
れ、好ましくは、マロン酸ジメチル、マロン酸ジエチル
が用いられる。また、本発明の原料兼溶媒となるｎ，ｍ
−ジハロゲン化アルカン（但し、ｎ，ｍは整数で、ｎ≠
ｍ）としては、具体的には１，２−ジクロロエタン、
１，２−ジクロロブタン、１，２−ジクロロプロパン等
の１，２−ジクロロアルカンや１−ブロモ−３−クロロ
プロパン、１−ブロモ−３−クロロペンタン等の１−ブ
ロモ−３−クロロアルカン、更には１，３−ジクロロプ
ロパン、１，５−ジクロロペンタン等が挙げられ、好適
には１，２−ジクロロエタンが用いられ、上記のマロン
酸ジエステル１モルに対して、１〜１０モル程度使用す
ることが好ましく、１モル未満では未反応物が残留し、
逆に１０モルを越えても経済的に不利になるだけで好ま
しくない。Examples of the malonate diester used as a raw material in the present invention include dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-n-propyl malonate, and the like. Diethyl is used. In addition, n and m serving as the raw material and solvent of the present invention
-Dihalogenated alkane (where n and m are integers and n ≠)
m) specifically includes 1,2-dichloroethane,
1,2-dichloroalkanes such as 1,2-dichlorobutane and 1,2-dichloropropane, and 1-bromo-3-chloroalkanes such as 1-bromo-3-chloropropane and 1-bromo-3-chloropentane; Is 1,3-dichloropropane, 1,5-dichloropentane, etc., and preferably 1,2-dichloroethane is used, and about 1 to 10 mol is used per 1 mol of the malonic acid diester. Is preferably less than 1 mol, unreacted substances remain,
Conversely, if it exceeds 10 moles, it is economically disadvantageous and is not preferred.
【０００７】本発明においては、上記のマロン酸ジエス
テルとｎ，ｍ−ジハロゲン化アルカン（但し、ｎ，ｍは
整数で、ｎ≠ｍ）を比表面積が０．６ｍ2／ｇ以上（更
には０．９〜１．８ｍ2／ｇ）の炭酸カリウムの存在下
で反応させることを最大の特徴とするもので、該炭酸カ
リウムの比表面積が０．６ｍ2／ｇ未満では、反応が完
結せず低収率となって本発明の目的を達成することはで
きない。かかる炭酸カリウムは、上記のマロン酸ジエス
テル１モルに対して、１〜５モル程度使用することが好
ましく、１モル未満では未反応物が残留し、逆に５モル
を越えても経済的に不利になるだけで好ましくない。ま
た、本発明においては、テトラ−ｎ−ブチルアンモニウ
ムブロマイド、テトラ−ｎ−ブチルアンモニウムハイド
ロジエンスルフェイト、テトラ−ｎ−ブチルアンモニウ
ムクロリド、トリエチルベンジルアンモニウムクロリ
ド、トリオクチルメチルアンモニウムクロリド、テトラ
メチルアンモニウムクロリド、ｎ−ヘキシルトリフェニ
ルホスホニウムブロミド等の触媒を上記のマロン酸ジエ
ステル１モルに対して、０．０１〜０．５モル程度使用
することが好ましく、０．０１モル未満では未反応物が
残留し、逆に０．５モルを越えても経済的に不利になる
だけで好ましくない。In the present invention, the above malonic acid diester and n, m-dihalogenated alkane (where n and m are integers and n ≠ m) have a specific surface area of 0.6 m 2 / g or more (furthermore, 0 or more). The most characteristic feature is that the reaction is carried out in the presence of potassium carbonate of 0.9 to 1.8 m 2 / g). When the specific surface area of the potassium carbonate is less than 0.6 m 2 / g, the reaction is not completed. The object of the present invention cannot be achieved with a low yield. Such potassium carbonate is preferably used in an amount of about 1 to 5 mol per mol of the above malonic acid diester, and if less than 1 mol, unreacted substances remain, and if it exceeds 5 mol, it is economically disadvantageous. Is not preferred. Further, in the present invention, tetra-n-butylammonium bromide, tetra-n-butylammonium hydrogen sulfate, tetra-n-butylammonium chloride, triethylbenzylammonium chloride, trioctylmethylammonium chloride, tetramethylammonium chloride, It is preferable to use a catalyst such as n-hexyltriphenylphosphonium bromide in an amount of about 0.01 to 0.5 mol based on 1 mol of the malonic acid diester, and if less than 0.01 mol, unreacted substances remain, Conversely, if it exceeds 0.5 mol, it is not preferable because it is economically disadvantageous.
【０００８】上記の反応を行うに当たっては、マロン酸
ジエステル、ｎ，ｍ−ジハロゲン化アルカン（但し、
ｎ，ｍは整数で、ｎ≠ｍ）、比表面積が０．６ｍ2／ｇ
以上の炭酸カリウム及び必要に応じてテトラ−ｎ−ブチ
ルアンモニウムブロマイド等の触媒を仕込んで、昇温し
て、９０〜１１０℃（更には９５〜１０５℃）で１〜２
０時間（更には３〜１０時間）程度反応させることが好
ましく、かかる反応により、効率よく１，１−シクロプ
ロパンジカルボン酸ジエステルが生成されるのである。In carrying out the above reaction, malonic diester, n, m-dihalogenated alkane (provided that
n and m are integers and n ≠ m), and the specific surface area is 0.6 m 2 / g.
The above-mentioned potassium carbonate and, if necessary, a catalyst such as tetra-n-butylammonium bromide were charged and the temperature was raised to 90 to 110 ° C. (further 95 to 105 ° C.) to 1 to 2
The reaction is preferably carried out for about 0 hours (more preferably for about 3 to 10 hours), and 1,1-cyclopropanedicarboxylic acid diester is efficiently produced by such a reaction.
【０００９】かかる反応液から１，１−シクロプロパン
ジカルボン酸ジエステルを分離するに当たっては、特に
限定されず公知の方法が採用され得るが、本発明では、
かかる反応液に該炭酸カリウムの３．５倍重量以上（更
には３．５〜１０倍重量）の水を添加して分液すること
が好ましく、かかる添加水が３．５倍重量未満では、目
的物の分離が難しくなる傾向にあり好ましくない。かか
る分液された有機層を再度水により水洗して得られた有
機層を濃縮することにより、目的とする１，１−シクロ
プロパンジカルボン酸ジエステルを得ることができるの
である。The separation of 1,1-cyclopropanedicarboxylic acid diester from the reaction solution is not particularly limited, and a known method can be employed.
It is preferable to add 3.5 times by weight or more (more preferably 3.5 to 10 times by weight) of water to the reaction solution to separate the solution, and if the added water is less than 3.5 times by weight, It is not preferable because separation of the target substance tends to be difficult. By washing the separated organic layer with water again and concentrating the obtained organic layer, the desired 1,1-cyclopropanedicarboxylic acid diester can be obtained.
【００１０】[0010]
【実施例】以下、実施例を挙げて本発明を具体的に説明
する。 実施例１ マロン酸ジエチル６４．１０ｇ（０．４００モル）、
１，２−ジクロロエタン２７０ｍｌ（約３．４モル）、
比表面積が１．６ｍ2／ｇの炭酸カリウム１３８．２１
ｇ及びテトラ−ｎ−ブチルアンモニウムブロマイド６．
４ｇ（０．０２モル）を反応器に仕込み、１００℃にて
還流下に５時間撹拌して反応を行った後、室温まで冷却
して、５００ｇの水を加え、有機層を分液し、水層を１
００ｍｌの１，２−ジクロロエタンで抽出して、これを
分液して得られた有機層を上記の有機層に戻した後、濃
縮して、１，１−シクロプロパンジカルボン酸ジエステ
ルを得た。得られた１，１−シクロプロパンジカルボン
酸ジエステルの収率は９８．５％であった。The present invention will be specifically described below with reference to examples. Example 1 64.10 g (0.400 mol) of diethyl malonate,
270 ml (about 3.4 mol) of 1,2-dichloroethane,
Potassium carbonate 138.21 having a specific surface area of 1.6 m 2 / g
g and tetra-n-butylammonium bromide6.
4 g (0.02 mol) was charged into a reactor and stirred at 100 ° C. under reflux for 5 hours to carry out a reaction. After cooling to room temperature, 500 g of water was added, and the organic layer was separated. 1 water layer
The organic layer was extracted with 00 ml of 1,2-dichloroethane, separated, and the resulting organic layer was returned to the above organic layer and concentrated to obtain 1,1-cyclopropanedicarboxylic acid diester. The yield of the obtained 1,1-cyclopropanedicarboxylic acid diester was 98.5%.
【００１１】実施例２ 実施例１において、比表面積が１．３ｍ2／ｇの炭酸カ
リウム１３８．２１ｇを用いた以外は同様に行って１，
１−シクロプロパンジカルボン酸ジエステルを得た。得
られた１，１−シクロプロパンジカルボン酸ジエステル
の収率は９７．５％であった。Example 2 The procedure of Example 1 was repeated, except that 138.21 g of potassium carbonate having a specific surface area of 1.3 m 2 / g was used.
1-Cyclopropanedicarboxylic acid diester was obtained. The yield of the obtained 1,1-cyclopropanedicarboxylic acid diester was 97.5%.
【００１２】実施例３ 実施例１において、マロン酸ジエチル６４．１０ｇ
（０．４００モル）をマロン酸ジメチル５２．８８ｇ
（０．４００モル）とした以外は同様に行って１，１−
シクロプロパンジカルボン酸ジエステルを得た。得られ
た１，１−シクロプロパンジカルボン酸ジエステルの収
率は９７．３％であった。Example 3 In Example 1, 64.10 g of diethyl malonate was used.
(0.400 mol) of dimethyl malonate 52.88 g
(0.400 mol), except that 1,1-
Cyclopropane dicarboxylic diester was obtained. The yield of the obtained 1,1-cyclopropanedicarboxylic acid diester was 97.3%.
【００１３】実施例４ 実施例１において、室温まで冷却した後の水の添加量を
１０００ｇとした以外は同様に行って１，１−シクロプ
ロパンジカルボン酸ジエステルを得た。得られた１，１
−シクロプロパンジカルボン酸ジエステルの収率は９
８．１％であった。Example 4 A 1,1-cyclopropanedicarboxylic acid diester was obtained in the same manner as in Example 1 except that the amount of water added after cooling to room temperature was changed to 1000 g. The resulting 1,1
-The yield of cyclopropanedicarboxylic diester is 9
It was 8.1%.
【００１４】比較例１ 実施例１において、比表面積が０．５ｍ2／ｇで粒子径
が０．０５ｍｍメッシュの炭酸カリウムを用いた以外は
同様に行って１，１−シクロプロパンジカルボン酸ジエ
ステルを得たが、得られた１，１−シクロプロパンジカ
ルボン酸ジエステルの収率は３０％であった。Comparative Example 1 The procedure of Example 1 was repeated, except that potassium carbonate having a specific surface area of 0.5 m 2 / g and a particle size of 0.05 mm mesh was used, to prepare 1,1-cyclopropanedicarboxylic acid diester. Although obtained, the yield of the obtained 1,1-cyclopropanedicarboxylic acid diester was 30%.
【００１５】[0015]
【発明の効果】本発明では、マロン酸ジエステルと１，
２−ジクロロエタン等のｎ，ｍ−ジハロゲン化アルカン
を比表面積が０．６ｍ2／ｇ以上の炭酸カリウムの共存
下に反応させているため、目的とする１，１−シクロプ
ロパンジカルボン酸ジエステルを効率よく得ることがで
きる。According to the present invention, malonic diester and 1,1
Since the n, m-dihalogenated alkane such as 2-dichloroethane is reacted in the presence of potassium carbonate having a specific surface area of 0.6 m 2 / g or more, the desired 1,1-cyclopropanedicarboxylic acid diester can be efficiently produced. Can get well.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification symbol FI // C07B 61/00 300 C07B 61/00 300
Claims (4)
ン化アルカン（但し、ｎ，ｍは整数で、ｎ≠ｍ）を比表
面積が０．６ｍ2／ｇ以上の炭酸カリウムの共存下に反
応させてなることを特徴とする１，１−シクロプロパン
ジカルボン酸ジエステルの製造法。1. A malonic acid diester is reacted with an n, m-dihalogenated alkane (where n and m are integers and n） m) in the presence of potassium carbonate having a specific surface area of 0.6 m 2 / g or more. A method for producing a 1,1-cyclopropanedicarboxylic acid diester, comprising:
ン化アルカン（但し、ｎ，ｍは整数で、ｎ≠ｍ）を比表
面積が０．６ｍ2／ｇ以上の炭酸カリウムの共存下に反
応させた後、該炭酸カリウムの３．５倍重量以上の水を
添加して分液することを特徴とする１，１−シクロプロ
パンジカルボン酸ジエステルの製造法。2. A malonic acid diester is reacted with an n, m-dihalogenated alkane (where n and m are integers and n ≠ m) in the presence of potassium carbonate having a specific surface area of 0.6 m 2 / g or more. And then separating the mixture by adding water at least 3.5 times the weight of the potassium carbonate, followed by liquid separation.
２−ジクロロアルカンまたは１−ブロモ−３−クロロア
ルカンであることを特徴とする請求項１または２記載の
１，１−シクロプロパンジカルボン酸ジエステルの製造
法。3. The method according to claim 1, wherein the n, m-dihalogenated alkane is 1,2.
The method for producing 1,1-cyclopropanedicarboxylic acid diester according to claim 1 or 2, wherein the method is 2-dichloroalkane or 1-bromo-3-chloroalkane.
クロロエタンであることを特徴とする請求項３記載の
１，１−シクロプロパンジカルボン酸ジエステルの製造
法。4. The method for producing 1,1-cyclopropanedicarboxylic acid diester according to claim 3, wherein the 1,2-dichloroalkane is 1,2-dichloroethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18431597A JP3967793B2 (en) | 1997-06-24 | 1997-06-24 | Process for producing 1,1-cyclopropanedicarboxylic acid diester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18431597A JP3967793B2 (en) | 1997-06-24 | 1997-06-24 | Process for producing 1,1-cyclopropanedicarboxylic acid diester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1112225A true JPH1112225A (en) | 1999-01-19 |
| JP3967793B2 JP3967793B2 (en) | 2007-08-29 |
Family
ID=16151195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18431597A Expired - Fee Related JP3967793B2 (en) | 1997-06-24 | 1997-06-24 | Process for producing 1,1-cyclopropanedicarboxylic acid diester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3967793B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006169154A (en) * | 2004-12-15 | 2006-06-29 | Sumitomo Chemical Co Ltd | Method for producing quaternary ammonium salt |
| CN112745219A (en) * | 2019-10-31 | 2021-05-04 | 常州锐博生物科技有限公司 | Preparation method of 1, 1-naphthenic dicarboxylic acid and derivatives thereof |
-
1997
- 1997-06-24 JP JP18431597A patent/JP3967793B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006169154A (en) * | 2004-12-15 | 2006-06-29 | Sumitomo Chemical Co Ltd | Method for producing quaternary ammonium salt |
| CN112745219A (en) * | 2019-10-31 | 2021-05-04 | 常州锐博生物科技有限公司 | Preparation method of 1, 1-naphthenic dicarboxylic acid and derivatives thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3967793B2 (en) | 2007-08-29 |
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