JPH052659B2 - - Google Patents
Info
- Publication number
- JPH052659B2 JPH052659B2 JP1027884A JP1027884A JPH052659B2 JP H052659 B2 JPH052659 B2 JP H052659B2 JP 1027884 A JP1027884 A JP 1027884A JP 1027884 A JP1027884 A JP 1027884A JP H052659 B2 JPH052659 B2 JP H052659B2
- Authority
- JP
- Japan
- Prior art keywords
- trans
- cis
- acid
- crystals
- isomer
- 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.)
- Expired - Lifetime
Links
- 239000013078 crystal Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 11
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 8
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 7
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229930016911 cinnamic acid Natural products 0.000 claims description 4
- 235000013985 cinnamic acid Nutrition 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- WBYWAXJHAXSJNI-VOTSOKGWSA-N trans-cinnamic acid Chemical compound OC(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- -1 alkaline earth metal salt Chemical class 0.000 claims 1
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HJBWJAPEBGSQPR-GQCTYLIASA-N 3,4-dimethoxycinnamic acid Chemical compound COC1=CC=C(\C=C\C(O)=O)C=C1OC HJBWJAPEBGSQPR-GQCTYLIASA-N 0.000 description 6
- HJBWJAPEBGSQPR-UHFFFAOYSA-N DMCA Natural products COC1=CC=C(C=CC(O)=O)C=C1OC HJBWJAPEBGSQPR-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- AFDXODALSZRGIH-UHFFFAOYSA-N p-coumaric acid methyl ether Natural products COC1=CC=C(C=CC(O)=O)C=C1 AFDXODALSZRGIH-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- AFDXODALSZRGIH-QPJJXVBHSA-N (E)-3-(4-methoxyphenyl)prop-2-enoic acid Chemical compound COC1=CC=C(\C=C\C(O)=O)C=C1 AFDXODALSZRGIH-QPJJXVBHSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
Description
【発明の詳細な説明】
本発明は各種有機薬品製造の際にしばしば合成
原料として用いられる桂皮酸およびその誘導体の
それぞれの幾何異性体を高純度でその混合物から
採取する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for collecting highly pure geometric isomers of cinnamic acid and its derivatives from a mixture thereof, which are often used as synthetic raw materials in the production of various organic drugs.
本発明によれば、桂皮酸およびその誘導体のシ
ス−トランス混合物を金属塩として水溶液中に溶
解せしめる。溶解しにくい場合には加熱すること
により溶解が促進される。この場合使用される金
属塩としては、炭酸ナトリウム、炭酸水素ナトリ
ウム、苛性ソーダなどのナトリウム塩、炭酸カリ
ウム、水酸化カリウムなどのカリウム塩、水酸化
バリウム、炭酸バリウムなどのバリウム塩などが
通常である。次にこの溶液中にトランス体含量に
対応したグラム当量の鉱酸を加えて30分間から数
時間0°〜室温で攪拌し、そして析出するトランス
−桂皮酸およびその誘導体を取する。液には
さらに酸を加えてPH1.0付近とすることによりシ
ス体の結晶が析出する。これを過することによ
りシス−桂皮酸およびその誘導体を得ることがで
きる。得られたシス体およびトランス体の純度は
95％以上である。上記の操作をくり返して行なう
ことによりほとんど純粋なシス体およびトランス
体を得ることができる。 According to the invention, a cis-trans mixture of cinnamic acid and its derivatives is dissolved in an aqueous solution as a metal salt. If it is difficult to dissolve, dissolution is promoted by heating. The metal salts used in this case usually include sodium salts such as sodium carbonate, sodium bicarbonate, and caustic soda, potassium salts such as potassium carbonate and potassium hydroxide, and barium salts such as barium hydroxide and barium carbonate. Next, a gram equivalent of mineral acid corresponding to the content of the trans isomer is added to this solution and stirred at 0° to room temperature for 30 minutes to several hours, and the precipitated trans-cinnamic acid and its derivatives are collected. By further adding acid to the solution to bring the pH to around 1.0, cis-isomer crystals precipitate. Through this process, cis-cinnamic acid and its derivatives can be obtained. The purity of the obtained cis isomer and trans isomer is
More than 95%. By repeating the above operations, almost pure cis and trans isomers can be obtained.
従来桂皮酸誘導体ばかりでなく、１対の幾何異
性体では一般に各幾何異性体相互の間に融点、溶
解度などの物理的性質の差があることが知られて
いた。このなかでも特に精製の面では溶解度の差
を利用した分別結晶法を用いることが行なわれて
いた。 Conventionally, it has been known that not only cinnamic acid derivatives but also a pair of geometric isomers generally have differences in physical properties such as melting point and solubility between each geometric isomer. Particularly in terms of purification, a fractional crystallization method that takes advantage of the difference in solubility has been used.
本発明の特徴は溶解度差を利用する方法と異な
り、シス体とトランス体のpKaの違いを利用した
精製方法である。すなわち、シス体がトランス体
よりもpKaが小さいことからその金属塩が酸と反
応する際に酸の量を規制することにより選択的に
トランス体のみを遊離させ、シス体と分離するこ
とを特徴としている。以下に実施例を示す。 A feature of the present invention is a purification method that utilizes the difference in pKa between the cis and trans forms, unlike methods that utilize differences in solubility. In other words, since the pKa of the cis form is smaller than that of the trans form, when the metal salt reacts with acid, by regulating the amount of acid, only the trans form is selectively released and separated from the cis form. It is said that Examples are shown below.
実施例 １
３，４−ジメトキシ桂皮酸（シス：トランス＝
70：30）20g（0.0962モル）と炭酸ナトリウム10g
（0.0943モル）とを水1000mlに加熱溶解する。室
温下に濃塩酸（12N）10.1mlを加えて30分間攪拌
し、析出した結晶を過しそしてこの結晶を乾燥
するとトランス−３，４−ジメトキシ桂皮酸5.0g
（シス：トランス＝２：98）が得られる。液に
濃塩酸を加えてPH1.0とし析出結晶を過する。
結晶は乾燥することによりシス−３，４−ジメト
キシ桂皮酸12.8g（シス：トランス＝96：４）を得
る。シス体はm.p.98.2〜100℃、そしてトランス
体はm.p.180〜180.5℃である。Example 1 3,4-dimethoxycinnamic acid (cis:trans=
70:30) 20g (0.0962 mol) and 10g of sodium carbonate
(0.0943 mol) in 1000 ml of water by heating. Add 10.1 ml of concentrated hydrochloric acid (12N) at room temperature, stir for 30 minutes, filter the precipitated crystals, and dry the crystals to obtain 5.0 g of trans-3,4-dimethoxycinnamic acid.
(cis:trans=2:98) is obtained. Add concentrated hydrochloric acid to the solution to adjust the pH to 1.0 and filter out the precipitated crystals.
By drying the crystals, 12.8 g of cis-3,4-dimethoxycinnamic acid (cis:trans=96:4) was obtained. The cis form has a mp of 98.2 to 100°C, and the trans form has a mp of 180 to 180.5°C.
実施例 ２
３，４−ジメトキシ桂皮酸（シス：トランス＝
64：36）15.85g（0.0762モル）と炭酸カリウム
20.2g（0.145モル）とを水500mlに加熱溶解する。
室温下に6N塩酸40.2mlを加えて30分間攪拌し、
析出した結晶を過しそして乾燥するとトランス
−３，４−ジメトキシ桂皮酸5.2g（シス：トラン
ス＝４：96）が得られる。このときの溶液のPHは
約4.1である。液に6N塩酸を加えてPH1.0にし、
析出した結晶を過しそして乾燥することにより
シス−３，４−ジメトキシ桂皮酸7.4g（シス：ト
ランス＝95：５）を得る。最後の母液を酢酸エチ
ルで抽出し、酢酸エチル層を水および飽和食塩水
で順次洗浄した後、乾燥濃縮して粗結晶3.0gを得
た。この結晶もトランス体を多く含む（シス：ト
ランス＝88.9：11.1）。Example 2 3,4-dimethoxycinnamic acid (cis:trans=
64:36) 15.85g (0.0762mol) and potassium carbonate
Heat and dissolve 20.2g (0.145mol) in 500ml of water.
Add 40.2ml of 6N hydrochloric acid at room temperature and stir for 30 minutes.
The precipitated crystals are filtered and dried to yield 5.2 g of trans-3,4-dimethoxycinnamic acid (cis:trans=4:96). The pH of the solution at this time is approximately 4.1. Add 6N hydrochloric acid to the solution to adjust the pH to 1.0.
The precipitated crystals were filtered and dried to obtain 7.4 g of cis-3,4-dimethoxycinnamic acid (cis:trans=95:5). The final mother liquor was extracted with ethyl acetate, and the ethyl acetate layer was washed successively with water and saturated brine, and then dried and concentrated to obtain 3.0 g of crude crystals. This crystal also contains a large amount of trans isomer (cis:trans = 88.9:11.1).
実施例 ３
３，４−ジメトキシ桂皮酸（シス：トランス＝
75：25）10.0g（0.048モル）と水酸化バリウム８
水和物20.0g（0.063モル）を水500mlに溶解し、こ
の中に6N硫酸15.1mlを加えて室温下に30分間攪
拌した。析出した結晶を過乾燥するとトランス
−３，４−ジメトキシ桂皮酸2.7g（シス：トラン
ス＝２：98）が得られる。このときの溶液のPHは
約4.1である。液にさらに6N硫酸を加えてPH1.0
とする。析出する結晶を取乾燥してシス−３，
４−ジメトキシ桂皮酸4.2g（シス：トランス＝
96：４）を得る。母液を酢酸エチルで抽出した
後、濃縮して粗結晶3.0g（シス：トランス＝90：
10）を得る。Example 3 3,4-dimethoxycinnamic acid (cis:trans=
75:25) 10.0g (0.048mol) and barium hydroxide 8
20.0 g (0.063 mol) of the hydrate was dissolved in 500 ml of water, 15.1 ml of 6N sulfuric acid was added thereto, and the mixture was stirred at room temperature for 30 minutes. When the precipitated crystals are overdried, 2.7 g of trans-3,4-dimethoxycinnamic acid (cis:trans=2:98) is obtained. The pH of the solution at this time is approximately 4.1. Add 6N sulfuric acid to the solution to adjust the pH to 1.0.
shall be. The precipitated crystals were dried to obtain cis-3,
4-dimethoxycinnamic acid 4.2g (cis:trans=
96:4). After extracting the mother liquor with ethyl acetate, it was concentrated to give 3.0 g of crude crystals (cis: trans = 90:
10) get.
実施例 ４
桂皮酸（シス：トランス＝78：22）10g（0.0676
モル）と炭酸ナトリウム10g（0.0943モル）とを水
1000mlに溶解する。室温下に塩酸11.3ml（0.1358
モル）を加えて５分間攪拌し、析出した結晶を
過し、そしてこの結晶を乾燥するとトランス−桂
皮酸1.7g（シス：トランス＝４：96）が得られる。
液に濃塩酸を加えてPH2.0に調整する。この溶
液を酢酸エチル各100mlを使用して２回抽出する。
酢酸エチル層を水洗し、さらに飽和食塩水で洗浄
した後硫酸マグネシウムで乾燥し濃縮して油状の
シス−桂皮酸8.0g（シス：トランス＝91：９）を
得る。Example 4 Cinnamic acid (cis:trans=78:22) 10g (0.0676
mol) and 10g (0.0943 mol) of sodium carbonate in water.
Dissolve in 1000ml. 11.3 ml of hydrochloric acid (0.1358
1.7 g of trans-cinnamic acid (cis:trans=4:96) is obtained by adding 1.7 g of trans-cinnamic acid (cis:trans=4:96).
Add concentrated hydrochloric acid to the solution to adjust the pH to 2.0. This solution is extracted twice using 100 ml each of ethyl acetate.
The ethyl acetate layer was washed with water, further washed with saturated saline, dried over magnesium sulfate, and concentrated to obtain 8.0 g of oily cis-cinnamic acid (cis:trans=91:9).
実施例 ５
Ｐ−メトキシ桂皮酸（シス：トランス＝79：
21）10g（0.0562モル）と炭酸ナトリウム10g
（0.0943モル）とを水1000mlに溶解する。室温下
に塩酸11.0ml（0.1324モル）を加えて析出する結
晶を過しそしてこの結晶を乾燥するとトランス
−ｐ−メトキシ桂皮酸2.8g（シス：トランス＝
13：87）が得られる。液に塩酸8.3ml（0.100モ
ル）を加えて約PH2.0に調整し析出する結晶を
過し、この結晶を乾燥するとシス−ｐ−メトキシ
桂皮酸4.6g（シス：トランス＝99：１）を得る。
さらに液を減圧濃縮して50ml程度にした後静置
すると結晶が析出する。この結晶を過して乾燥
しシス−ｐ−メトキシ桂皮酸2.0g（シス：トラン
ス＝95：５）を得る。Example 5 P-methoxycinnamic acid (cis:trans=79:
21) 10g (0.0562 mol) and 10g of sodium carbonate
(0.0943 mol) in 1000 ml of water. Add 11.0 ml (0.1324 mol) of hydrochloric acid at room temperature, filter the precipitated crystals, and dry the crystals to obtain 2.8 g of trans-p-methoxycinnamic acid (cis:trans=
13:87) is obtained. Add 8.3 ml (0.100 mol) of hydrochloric acid to the solution to adjust the pH to approximately 2.0, filter out the precipitated crystals, and dry the crystals to obtain 4.6 g of cis-p-methoxycinnamic acid (cis: trans = 99:1). obtain.
Further, when the liquid is concentrated under reduced pressure to about 50 ml and left to stand, crystals will precipitate. The crystals were filtered and dried to obtain 2.0 g of cis-p-methoxycinnamic acid (cis:trans=95:5).
Claims (1)
コキシ基を示す）で表わされる桂皮酸およびその
誘導体のシス体およびトランス体の混合物を水溶
液中でアルカリ金属またはアルカリ土類金属の塩
とした後、この溶液中にトランス体含量に対応し
た酸を加えることによりトランス体のみを水溶液
中から析出させて回収し、そして分離された液
を酸性にすることによりシス体の結晶を析出させ
て回収することを特徴とする、シス−およびトラ
ンス−桂皮酸およびその誘導体の採取方法。[Claims] 1 Formula (1) (In the formula, R 1 and R 2 represent a hydrogen atom or a lower alkoxy group) A mixture of cis and trans forms of cinnamic acid and its derivatives is made into an alkali metal or alkaline earth metal salt in an aqueous solution. By adding an acid corresponding to the trans-isomer content to this solution, only the trans-isomer is precipitated from the aqueous solution and recovered, and by making the separated liquid acidic, crystals of the cis-isomer are precipitated and recovered. A method for collecting cis- and trans-cinnamic acid and derivatives thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1027884A JPS60156639A (en) | 1984-01-25 | 1984-01-25 | Method for collecting geometric isomer of cinnamic acid compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1027884A JPS60156639A (en) | 1984-01-25 | 1984-01-25 | Method for collecting geometric isomer of cinnamic acid compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60156639A JPS60156639A (en) | 1985-08-16 |
| JPH052659B2 true JPH052659B2 (en) | 1993-01-13 |
Family
ID=11745837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1027884A Granted JPS60156639A (en) | 1984-01-25 | 1984-01-25 | Method for collecting geometric isomer of cinnamic acid compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60156639A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5206430A (en) * | 1990-10-31 | 1993-04-27 | Mitsui Toatsu Chemicals, Incorporated | Method for obtaining high-purity cinnamic acid |
-
1984
- 1984-01-25 JP JP1027884A patent/JPS60156639A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60156639A (en) | 1985-08-16 |
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