JPH0680037B2 - Method for racemizing carboxymethyl cysteine - Google Patents
Method for racemizing carboxymethyl cysteineInfo
- Publication number
- JPH0680037B2 JPH0680037B2 JP60188478A JP18847885A JPH0680037B2 JP H0680037 B2 JPH0680037 B2 JP H0680037B2 JP 60188478 A JP60188478 A JP 60188478A JP 18847885 A JP18847885 A JP 18847885A JP H0680037 B2 JPH0680037 B2 JP H0680037B2
- Authority
- JP
- Japan
- Prior art keywords
- scmc
- acid
- heated
- present
- racemizing
- 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 - Fee Related
Links
- 238000000034 method Methods 0.000 title claims description 4
- JJVXHDTWVIPRBZ-VKHMYHEASA-N (2r)-2-[carboxy(methyl)amino]-3-sulfanylpropanoic acid Chemical compound OC(=O)N(C)[C@@H](CS)C(O)=O JJVXHDTWVIPRBZ-VKHMYHEASA-N 0.000 title 1
- GBFLZEXEOZUWRN-VKHMYHEASA-N S-carboxymethyl-L-cysteine Chemical compound OC(=O)[C@@H](N)CSCC(O)=O GBFLZEXEOZUWRN-VKHMYHEASA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 10
- 230000006340 racemization Effects 0.000 claims description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 150000003934 aromatic aldehydes Chemical class 0.000 description 3
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 2
- ASBJGPTTYPEMLP-UHFFFAOYSA-N 3-chloroalanine Chemical compound ClCC(N)C(O)=O ASBJGPTTYPEMLP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- XYZZJOZOPGGIJR-UHFFFAOYSA-N ClBr(=O)=O Chemical compound ClBr(=O)=O XYZZJOZOPGGIJR-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 本発明は、光学活性Ｓ−カルボキシメチルシステインの
ラセミ化法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for racemizing optically active S-carboxymethyl cysteine.
イ．産業上の利用分野 Ｓ−カルボキシメチル−Ｌ−システインは去たん剤等と
して有用な化合物である。I. Industrial field of application S-carboxymethyl-L-cysteine is a compound useful as a stripping agent and the like.
Ｓ−カルボキシメチルシステイン（以下SCMCと略す）
は、工業的に安価なβ−クロロアラニンとチオグリコー
ル酸から容易に合成できる（特開昭59−193867）。原料
のβ−クロロアラニンが光学的に不活性な場合は、SCMC
はDL体として得られ、これを光学分割することにより医
薬として非常に重要なＬ−SCMCを得ることができる。こ
のとき必然的にＤ−SCMCが得られるので、これをラセミ
化することは工業的に大きな意義がある。S-carboxymethyl cysteine (abbreviated as SCMC below)
Can be easily synthesized from industrially inexpensive β-chloroalanine and thioglycolic acid (JP-A-59-193867). If the raw material β-chloroalanine is optically inactive, SCMC
Is obtained as DL form, and by optically resolving this, L-SCMC, which is very important as a drug, can be obtained. Since D-SCMC is inevitably obtained at this time, it is industrially significant to racemize it.
ロ．従来の技術及び問題点 従来の技術としては、アルデヒド基に対してオルト位に
１個のヒドロキシ基を有する芳香族アルデヒドを含有す
る酸性を水性媒体中で加熱する方法が知られている。
（特開昭58−167562）が、芳香族アルデヒドが高価で
ある、アルデヒドの水溶性が低いために、ラセミ化時
やSCMC回収時に有機溶媒を使用する必要がある、アル
デヒドの回収が困難である等の工業的に不利な点が多い
ものであった。B. 2. Description of the Related Art As a conventional technique, a method is known in which an acid containing an aromatic aldehyde having one hydroxy group at the ortho position with respect to an aldehyde group is heated in an aqueous medium.
(JP-A-58-167562) shows that aromatic aldehydes are expensive, the water solubility of aldehydes is low, it is necessary to use an organic solvent during racemization or SCMC recovery, and recovery of aldehydes is difficult. There were many industrial disadvantages such as.
ハ．問題点を解決するための手段 本発明者らは、鋭意検討の結果芳香族アルデヒドを使用
しなくても、鉱酸の存在下に光学活性SCMC水溶液を密閉
容器中で加熱すれば、容易に高収率でラセミ化が進行す
ることを見い出し本発明を完成するに至った。C. Means for Solving the Problems As a result of earnest studies, the inventors of the present invention have found that even if an aromatic aldehyde is not used, if an optically active SCMC aqueous solution is heated in a closed container in the presence of a mineral acid, a high temperature can be easily obtained. The present invention was completed by finding that the racemization proceeded in yield.
本発明における鉱酸濃度は0.5〜2.0当量/100g水であ
り、好ましくは、0.8〜1.5当量/100g水である。酸濃度
が大きいとSCMCの分解が多くなり、逆に酸濃度が小さい
と十分なラセミ化速度が得られない。The mineral acid concentration in the present invention is 0.5 to 2.0 equivalent / 100 g water, preferably 0.8 to 1.5 equivalent / 100 g water. When the acid concentration is high, SCMC is decomposed a lot. On the contrary, when the acid concentration is low, a sufficient racemization rate cannot be obtained.
鉱酸としては、塩酸、硫酸、燐酸、クロルスルホン酸、
塩化臭素酸等を単独あるいはこれらを混合したものを使
用できる。Mineral acids include hydrochloric acid, sulfuric acid, phosphoric acid, chlorosulfonic acid,
It is possible to use chlorobromic acid or the like alone or as a mixture thereof.
温度は100〜140℃がよい。140℃を越える温度ではSCMC
の分解が多く、100℃より低い温度ではラセミ化が遅く
好ましくない。The temperature is preferably 100-140 ° C. SCMC above 140 ° C
Is often decomposed, and racemization is slow at temperatures lower than 100 ° C, which is not preferable.
加熱は、酸や溶媒の蒸発を防ぐ意味で密閉容器中で行な
うのが好ましい。Heating is preferably performed in a closed container in order to prevent evaporation of acid and solvent.
SCMC濃度については特に規制はないが、10〜30wt％が適
当である。The SCMC concentration is not particularly limited, but 10 to 30 wt% is appropriate.
加熱時間は鉱酸の種類及び酸濃度により異なるが、２〜
80時間が適当である。The heating time varies depending on the type of mineral acid and the acid concentration.
80 hours is appropriate.
ニ．実施例 以下、実施例を挙げて本発明を更に詳細に説明するが、
これらは単なる例示であり本発明はこれらにより何ら制
限されない。D. EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples.
These are merely examples and the present invention is not limited thereto.
実施例 １ Ｄ−SCMC500mgを35％塩酸2.0gにとかして封管し、130℃
にて30時間加熱した。冷却後開管し、光学分割カラムを
用いて分析したところ、Ｄ−SCMCが255mg及びＬ−SCMC
が229mg存在していた。（ラセミ化率94.4％、SCMCの残
存率96.8％） 但し、 ＜ラセミ化率＞ ＜SCMCの残存率＞ とする。Example 1 500 mg of D-SCMC was dissolved in 2.0 g of 35% hydrochloric acid, and the tube was sealed and heated to 130 ° C.
It was heated for 30 hours. After cooling, the tube was opened and analyzed using an optical resolution column to find that D-SCMC was 255 mg and L-SCMC.
Was present at 229 mg. (Racemization rate 94.4%, SCMC residual rate 96.8%) <SCMC survival rate> And
実施例 ２ Ｄ−SCMC500mgを25％塩酸2.0gにとかして封管し、130℃
にて70時間加熱した。冷却後開管し、光学分割カラムを
用いて分析したところ、Ｄ−SCMCが269mg及びＬ−SCMC
が222mg存在していた。（ラセミ化率90.4％、SCMCの残
存率98.1％） 実施例 ３ Ｄ−SCMC500mgを30％硫酸2.0gにとかして封管し、130℃
にて50時間加熱した。冷却後開管し、光学分割カラムを
用いて分析したところ、Ｄ−SCMCが256mg及びＬ−SCMC
が226mg存在していた。（ラセミ化率93.6％、SCMCの残
存率96.3％） 実施例 ４ Ｄ−SCMC500mgを29％硫酸2.0gにとかして封管し、130℃
にて４時間加熱した。冷却後開管し、光学分割カラムを
用いて分析したところ、Ｄ−SCMCが250mg及びＬ−SCMC
が223mg存在していた。Example 2 500 mg of D-SCMC was dissolved in 2.0 g of 25% hydrochloric acid, and the tube was sealed and heated to 130 ° C.
It was heated for 70 hours. After cooling, the tube was opened and analyzed using an optical resolution column to find that D-SCMC was 269 mg and L-SCMC.
Was present at 222 mg. (Racemization rate: 90.4%, SCMC residual rate: 98.1%) Example 3 D-SCMC (500 mg) was dissolved in 30% sulfuric acid (2.0 g), sealed, and sealed at 130 ° C.
It was heated for 50 hours. After cooling, the tube was opened and analyzed using an optical resolution column to find that D-SCMC was 256 mg and L-SCMC
Was present at 226 mg. (Racemization rate 93.6%, SCMC residual rate 96.3%) Example 4 D-SCMC (500 mg) was dissolved in 29% sulfuric acid (2.0 g), sealed, and sealed at 130 ° C.
It was heated for 4 hours. After cooling, the tube was opened and analyzed using an optical resolution column to find that D-SCMC was 250 mg and L-SCMC
Was present at 223 mg.
（ラセミ化率94.5％、SCMCの残存率94.5％） 実施例 ５ Ｄ−SCMC500mgを50％クロルスルホン酸2.0gにとかして
封管し、130℃にて20時間加熱した。冷却後開管し、光
学分割カラムを用いて分析したところ、Ｄ−SCMCが255m
g及びＬ−SCMCが228mg存在していた。(Racemization rate 94.5%, SCMC residual rate 94.5%) Example 5 D-SCMC (500 mg) was dissolved in 50% chlorosulfonic acid (2.0 g), sealed, and heated at 130 ° C for 20 hours. After cooling, the tube was opened and analyzed using an optical resolution column.
228 mg of g and L-SCMC were present.
（ラセミ化率94.％、SCMCの残存率96.5％）(Racemization rate 94.%, SCMC residual rate 96.5%)
Claims (1)
を0.8〜1.5当量/100g水の濃度の鉱酸の水溶液とし、該
水溶液を密閉容器中100〜140℃にて加熱することを特徴
とする光学活性Ｓ−カルボキシメチルシステインのラセ
ミ化法。1. Optically active S-carboxymethylcysteine is used as an aqueous solution of a mineral acid having a concentration of 0.8 to 1.5 equivalents / 100 g of water, and the aqueous solution is heated at 100 to 140 ° C. in a closed container. A racemization method of S-carboxymethyl cysteine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60188478A JPH0680037B2 (en) | 1985-08-29 | 1985-08-29 | Method for racemizing carboxymethyl cysteine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60188478A JPH0680037B2 (en) | 1985-08-29 | 1985-08-29 | Method for racemizing carboxymethyl cysteine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6251658A JPS6251658A (en) | 1987-03-06 |
| JPH0680037B2 true JPH0680037B2 (en) | 1994-10-12 |
Family
ID=16224428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60188478A Expired - Fee Related JPH0680037B2 (en) | 1985-08-29 | 1985-08-29 | Method for racemizing carboxymethyl cysteine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0680037B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0521982U (en) * | 1991-09-10 | 1993-03-23 | 住友ゴム工業株式会社 | Sports competition hat |
| CN1483515B (en) | 2002-07-16 | 2010-07-28 | M技术株式会社 | Fluid processing apparatus, fluid processing method, and deaerator with micronizing apparatus |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3209232A1 (en) * | 1982-03-13 | 1983-09-22 | Degussa Ag, 6000 Frankfurt | METHOD FOR RACEMIZING OPTICALLY ACTIVE S- (CARBOXYMETHYL) CYSTEIN |
| JPS58185556A (en) * | 1982-04-26 | 1983-10-29 | Hiroyuki Nohira | Racemization of optically active cysteine |
-
1985
- 1985-08-29 JP JP60188478A patent/JPH0680037B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6251658A (en) | 1987-03-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |