JPH0717899A - Production of carboxylic acid chloride - Google Patents
Production of carboxylic acid chlorideInfo
- Publication number
- JPH0717899A JPH0717899A JP16342693A JP16342693A JPH0717899A JP H0717899 A JPH0717899 A JP H0717899A JP 16342693 A JP16342693 A JP 16342693A JP 16342693 A JP16342693 A JP 16342693A JP H0717899 A JPH0717899 A JP H0717899A
- Authority
- JP
- Japan
- Prior art keywords
- trans
- chloride
- acid chloride
- isopropylcyclohexanecarboxylic
- carboxylic acid
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title abstract description 5
- YRQKWRUZZCBSIG-UHFFFAOYSA-N 4-propan-2-ylcyclohexane-1-carboxylic acid Chemical compound CC(C)C1CCC(C(O)=O)CC1 YRQKWRUZZCBSIG-UHFFFAOYSA-N 0.000 claims abstract description 10
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 10
- YXGDSBSUTMGHOL-KYZUINATSA-N CC(C)[C@H]1CC[C@H](C(Cl)=O)CC1 Chemical compound CC(C)[C@H]1CC[C@H](C(Cl)=O)CC1 YXGDSBSUTMGHOL-KYZUINATSA-N 0.000 claims abstract description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OELFLUMRDSZNSF-OFLPRAFFSA-N (2R)-2-[[oxo-(4-propan-2-ylcyclohexyl)methyl]amino]-3-phenylpropanoic acid Chemical compound C1CC(C(C)C)CCC1C(=O)N[C@@H](C(O)=O)CC1=CC=CC=C1 OELFLUMRDSZNSF-OFLPRAFFSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000002218 hypoglycaemic effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- CKMXAIVXVKGGFM-UHFFFAOYSA-N p-cumic acid Chemical compound CC(C)C1=CC=C(C(O)=O)C=C1 CKMXAIVXVKGGFM-UHFFFAOYSA-N 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- COLNVLDHVKWLRT-MRVPVSSYSA-N D-phenylalanine Chemical compound OC(=O)[C@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-MRVPVSSYSA-N 0.000 description 1
- 229930182832 D-phenylalanine Natural products 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- -1 trans-4-isopropylcyclohexylcarbonyl Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、血糖降下作用を示し、
医薬品として有用なＮ−（トランス−４−イソプロピル
シクロヘキシルカルボニル）−Ｄ−フェニルアラニンの
合成中間体の製造法に関するものである。The present invention shows a hypoglycemic effect,
The present invention relates to a method for producing a synthetic intermediate of N- (trans-4-isopropylcyclohexylcarbonyl) -D-phenylalanine useful as a medicine.
【０００２】[0002]
【従来の技術】Ｎ−（トランス−４−イソプロピルシク
ロヘキシルカルボニル）−Ｄ−フェニルアラニンは特公
平４−１５２２１号に記載されており、血糖降下作用を
示し、医薬品として有用な化合物であることが知られて
いる。この公報によると該化合物の原料であるトランス
−４−イソプロピルシクロヘキサンカルボン酸クロリド
は、トランス−４−イソプロピルシクロヘキサンカルボ
ン酸にチオニルクロリドを反応させて製造している。2. Description of the Related Art N- (trans-4-isopropylcyclohexylcarbonyl) -D-phenylalanine is described in JP-B-4-15221 and is known to be a compound having a hypoglycemic action and useful as a pharmaceutical. ing. According to this publication, trans-4-isopropylcyclohexanecarboxylic acid chloride, which is a raw material of the compound, is produced by reacting trans-4-isopropylcyclohexanecarboxylic acid with thionyl chloride.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、チオニ
ルクロリドを用いて反応を行った場合、シス体への異性
化が起こり、少量のシス−４−イソプロピルシクロヘキ
サンカルボン酸クロリド（シス体）が副生し、これをそ
の後の精製等により除去することは困難であることがわ
かった。さらには、反応に有毒な亜硫酸ガスが発生する
という問題点もあった。本発明の目的は、シス体への異
性化を抑えたトランス−４−イソプロピルシクロヘキサ
ンカルボン酸クロリドの製造法を提供することである。However, when the reaction is carried out using thionyl chloride, isomerization to a cis form occurs, and a small amount of cis-4-isopropylcyclohexanecarboxylic acid chloride (cis form) is produced as a by-product. However, it was found that it is difficult to remove this by subsequent purification. Further, there is a problem that toxic sulfurous acid gas is generated in the reaction. An object of the present invention is to provide a method for producing trans-4-isopropylcyclohexanecarboxylic acid chloride in which isomerization to a cis form is suppressed.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、カルボン
酸クロリドの製造法について鋭意研究を行った結果、チ
オニルクロリドに代えてリン塩化物を用いればシス体へ
の異性化を起こすことなく、収率的にもチオニルクロリ
ドを用いたときと同程度の結果を得ることを見いだし本
発明を完成した。Means for Solving the Problems As a result of earnest studies on a method for producing a carboxylic acid chloride, the present inventors have found that the use of phosphorus chloride in place of thionyl chloride does not cause isomerization to a cis isomer. The present invention has been completed by finding that the yield is similar to that obtained by using thionyl chloride.
【０００５】すなわち、本発明は、トランス−４−イソ
プロピルシクロヘキサンカルボン酸にリン塩化物を反応
させることを特徴とするトランス−４−イソプロピルシ
クロヘキサンカルボン酸クロリドの製造法に関するもの
である。That is, the present invention relates to a method for producing trans-4-isopropylcyclohexanecarboxylic acid chloride, which comprises reacting trans-4-isopropylcyclohexanecarboxylic acid with phosphorus chloride.
【０００６】本発明において用いられるトランス−４−
イソプロピルシクロヘキサンカルボン酸は、クミン酸ま
たはそのエステルを水素添加し製造することができる。
本発明において用いられるリン塩化物としては、三塩化
リン、五塩化リン、オキシ塩化リン等があげられる。リ
ン塩化物の使用量は、トランス−４−イソプロピルシク
ロヘキサンカルボン酸に対して、０．９〜１．５当量、
好ましくは１．０〜１．２当量である。Transformer-4-used in the present invention
Isopropylcyclohexanecarboxylic acid can be produced by hydrogenating cumic acid or its ester.
Examples of the phosphorus chloride used in the present invention include phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and the like. The amount of phosphorus chloride used is 0.9 to 1.5 equivalents relative to trans-4-isopropylcyclohexanecarboxylic acid,
It is preferably 1.0 to 1.2 equivalents.
【０００７】反応は無溶媒あるいは溶媒中で行われる。
溶媒を用いる場合にはリン塩化物に不活性なものを用い
ればよく、例えばジクロロメタン、クロロホルム、１，
２−ジクロロエタン、ベンゼン、トルエン、エーテル等
があげられる。反応を溶媒中で行う場合のトランス−４
−イソプロピルシクロヘキサンカルボン酸の濃度は、通
常、２〜２５重量％、好ましくは５〜２０重量％であ
る。反応は０℃以上リン塩化物あるいは溶媒の沸点以下
の温度で行うことができるが、好ましくは室温から５０
℃である。反応時間は反応温度によっても異なるが、通
常、３０分〜１０時間、好ましくは１〜５時間である。The reaction is carried out without solvent or in a solvent.
When a solvent is used, one that is inert to phosphorous chloride may be used, and for example, dichloromethane, chloroform, 1,
Examples thereof include 2-dichloroethane, benzene, toluene and ether. Trans-4 when the reaction is carried out in a solvent
The concentration of -isopropylcyclohexanecarboxylic acid is usually 2 to 25% by weight, preferably 5 to 20% by weight. The reaction can be carried out at a temperature not lower than 0 ° C. and not higher than the boiling point of the phosphorus chloride or solvent, but preferably from room temperature to 50.
℃. The reaction time varies depending on the reaction temperature, but is usually 30 minutes to 10 hours, preferably 1 to 5 hours.
【０００８】反応終了後は、必要に応じて、水洗、溶媒
留去して目的とするカルボン酸クロリドを得ることがで
きる。After completion of the reaction, the desired carboxylic acid chloride can be obtained by washing with water and distilling off the solvent, if necessary.
【０００９】[0009]
【発明の効果】本発明の方法を用いればトランス−４−
イソプロピルシクロヘキサンカルボン酸クロリドをシス
体の副生なしに製造することができる。また有毒な亜硫
酸ガスの発生しない製造法である。According to the method of the present invention, the transformer-4-
Isopropylcyclohexanecarboxylic acid chloride can be produced without cis-form by-product. In addition, it is a manufacturing method that does not generate toxic sulfurous acid gas.
【００１０】[0010]
【実施例】次に、実施例によって本発明をさらに詳細に
説明する。尚、本実施例で用いた分析方法を以下に示
す。トランス−４−イソプロピルシクロヘキサンカルボ
ン酸クロリド約１００ｍｇを１０ｍｌふた付き試験管へ
正確に秤り採り、メタノール１ｍｌと１Ｎ−水酸化ナト
リウム水溶液２ｍｌを加えた。６０℃のヒートブロック
上で液が均一になるまで充分加熱した。全量を１００ｍ
ｌメスフラスコに移し、正確に１００ｍｌとした。この
溶液１０μｌをＨＰＬＣにより分析した。EXAMPLES Next, the present invention will be described in more detail by way of examples. The analysis method used in this example is shown below. About 100 mg of trans-4-isopropylcyclohexanecarboxylic acid chloride was accurately weighed into a 10 ml test tube with a lid, and 1 ml of methanol and 2 ml of 1N-sodium hydroxide aqueous solution were added. It was sufficiently heated on a heat block at 60 ° C until the liquid became uniform. 100m in total
1 Transferred to a measuring flask to make exactly 100 ml. 10 μl of this solution was analyzed by HPLC.
【００１１】実施例１ トランス−４−イソプロピルシクロヘキサンカルボン酸
１．７０ｇ（１０ｍｍｏｌ）と五塩化リン２．１７ｇ
（１０ｍｍｏｌ）に１，２−ジクロロエタン１０ｍｌを
加え、オイルバスにて４０℃で３時間反応させた。減圧
下溶媒と生成したオキシ塩化リンを留去し、目的とする
カルボン酸クロリドを無色オイルとして１．８３ｇ（収
率９４％）得た。シス体は検出されなかった。得られた
トランス−４−イソプロピルシクロヘキサンカルボン酸
クロリドを特公平４−１５２２１号記載の実施例にした
がい、Ｄ−フェニルアラニンとアルカリ水性溶媒中で縮
合させることにより、Ｎ−（トランス−４−イソプロピ
ルシクロヘキシルカルボニル）−Ｄ−フェニルアラニン
を収率よく得ることができた。Example 1 1.70 g (10 mmol) of trans-4-isopropylcyclohexanecarboxylic acid and 2.17 g of phosphorus pentachloride.
10 ml of 1,2-dichloroethane was added to (10 mmol), and the mixture was reacted in an oil bath at 40 ° C for 3 hours. The solvent and the generated phosphorus oxychloride were distilled off under reduced pressure to obtain 1.83 g (yield 94%) of the desired carboxylic acid chloride as a colorless oil. No cis form was detected. The obtained trans-4-isopropylcyclohexanecarboxylic acid chloride was condensed with D-phenylalanine in an alkaline aqueous solvent according to the example described in JP-B-4-15221 to give N- (trans-4-isopropylcyclohexylcarbonyl). ) -D-phenylalanine could be obtained in good yield.
【００１２】実施例２ トランス−４−イソプロピルシクロヘキサンカルボン酸
１．７０ｇ（１０ｍｍｏｌ）の１，２−ジクロロエタン
（１０ｍｌ）溶液に、氷冷攪拌下三塩化リン０．８８ｍ
ｌ（１０ｍｍｏｌ）を滴下し、オイルバスにて４０℃で
３時間反応させた。１，２−ジクロロエタンを４０ｍｌ
加え、５％炭酸水素ナトリウム水溶液と水で洗浄し、硫
酸ナトリウムで乾燥した。減圧下溶媒を留去し、目的と
するトランス−４−イソプロピルシクロヘキサンカルボ
ン酸クロリドを無色オイルとして１．８０ｇ（収率９３
％）得た。シス体は検出されなかった。Example 2 A solution of 1.70 g (10 mmol) of trans-4-isopropylcyclohexanecarboxylic acid in 1,2-dichloroethane (10 ml) was mixed with 0.88 m of phosphorus trichloride with stirring under ice cooling.
1 (10 mmol) was added dropwise, and the mixture was reacted in an oil bath at 40 ° C. for 3 hours. 40 ml of 1,2-dichloroethane
The mixture was added, washed with a 5% aqueous sodium hydrogen carbonate solution and water, and dried over sodium sulfate. The solvent was distilled off under reduced pressure, and 1.80 g of the target trans-4-isopropylcyclohexanecarboxylic acid chloride was obtained as a colorless oil (yield 93
%)Obtained. No cis form was detected.
【００１３】比較例 トランス−４−イソプロピルシクロヘキサンカルボン酸
２０ｇを２００ｍｌの１，２−ジクロロエタンに溶解
し、塩化チオニル２１ｇ（１．５当量）を室温下で直接
滴下し、滴下終了後８０℃温浴中で２時間加熱攪拌しな
がら反応させた。反応終了後、減圧下未反応の塩化チオ
ニルを留去し、無色澄明液体約２３ｇを得た。シス体含
有量は１．０％、反応収率は９３．６％であった。Comparative Example 20 g of trans-4-isopropylcyclohexanecarboxylic acid was dissolved in 200 ml of 1,2-dichloroethane, and 21 g (1.5 equivalents) of thionyl chloride was directly added dropwise at room temperature. After completion of the addition, in a 80 ° C. hot bath. The mixture was reacted for 2 hours with heating and stirring. After the reaction was completed, unreacted thionyl chloride was distilled off under reduced pressure to obtain about 23 g of a colorless clear liquid. The cis-form content was 1.0%, and the reaction yield was 93.6%.
Claims (1)
サンカルボン酸にリン塩化物を反応させることを特徴と
するトランス−４−イソプロピルシクロヘキサンカルボ
ン酸クロリドの製造法。1. A method for producing trans-4-isopropylcyclohexanecarboxylic acid chloride, which comprises reacting trans-4-isopropylcyclohexanecarboxylic acid with phosphorus chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16342693A JPH0717899A (en) | 1993-07-01 | 1993-07-01 | Production of carboxylic acid chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16342693A JPH0717899A (en) | 1993-07-01 | 1993-07-01 | Production of carboxylic acid chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0717899A true JPH0717899A (en) | 1995-01-20 |
Family
ID=15773682
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16342693A Pending JPH0717899A (en) | 1993-07-01 | 1993-07-01 | Production of carboxylic acid chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0717899A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004018408A1 (en) * | 2002-08-26 | 2004-03-04 | Glenmark Pharmaceuticals Limited | Synthesis and purification of nateglinide |
| US7208622B2 (en) * | 2000-10-18 | 2007-04-24 | Ajinomoto Co., Inc. | Methods for producing nateglinide crystals |
| WO2007119580A1 (en) | 2006-03-31 | 2007-10-25 | Ajinomoto Co., Inc. | Process for production of carboxylic acid chloride compound |
| US7659428B2 (en) * | 2000-10-18 | 2010-02-09 | Ajinomoto Co., Inc. | Methods for producing acylphenylalanine |
| CN109369443A (en) * | 2018-11-05 | 2019-02-22 | 扬子江药业集团江苏海慈生物药业有限公司 | A kind of preparation method of new Nateglinide H crystal form |
-
1993
- 1993-07-01 JP JP16342693A patent/JPH0717899A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7208622B2 (en) * | 2000-10-18 | 2007-04-24 | Ajinomoto Co., Inc. | Methods for producing nateglinide crystals |
| US7459582B2 (en) | 2000-10-18 | 2008-12-02 | Ajinomoto Co., Inc. | Methods for producing nateglinide crystals |
| US7659428B2 (en) * | 2000-10-18 | 2010-02-09 | Ajinomoto Co., Inc. | Methods for producing acylphenylalanine |
| WO2004018408A1 (en) * | 2002-08-26 | 2004-03-04 | Glenmark Pharmaceuticals Limited | Synthesis and purification of nateglinide |
| WO2007119580A1 (en) | 2006-03-31 | 2007-10-25 | Ajinomoto Co., Inc. | Process for production of carboxylic acid chloride compound |
| CN109369443A (en) * | 2018-11-05 | 2019-02-22 | 扬子江药业集团江苏海慈生物药业有限公司 | A kind of preparation method of new Nateglinide H crystal form |
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