JPH0655699B2 - Method for producing amino acid hydrochloride - Google Patents
Method for producing amino acid hydrochlorideInfo
- Publication number
- JPH0655699B2 JPH0655699B2 JP8423385A JP8423385A JPH0655699B2 JP H0655699 B2 JPH0655699 B2 JP H0655699B2 JP 8423385 A JP8423385 A JP 8423385A JP 8423385 A JP8423385 A JP 8423385A JP H0655699 B2 JPH0655699 B2 JP H0655699B2
- Authority
- JP
- Japan
- Prior art keywords
- amino acid
- amount
- reaction
- acid hydrochloride
- slurry
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- -1 amino acid hydrochloride Chemical class 0.000 title claims description 6
- 150000001413 amino acids Chemical class 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 239000012320 chlorinating reagent Substances 0.000 claims description 2
- 235000001014 amino acid Nutrition 0.000 description 16
- 229940024606 amino acid Drugs 0.000 description 16
- 239000002002 slurry Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZGUNAGUHMKGQNY-SSDOTTSWSA-N D-alpha-phenylglycine Chemical compound OC(=O)[C@H](N)C1=CC=CC=C1 ZGUNAGUHMKGQNY-SSDOTTSWSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- IAZPUJDTYUZJMI-OGFXRTJISA-N (2r)-2-amino-2-phenylacetic acid;hydrochloride Chemical compound Cl.OC(=O)[C@H](N)C1=CC=CC=C1 IAZPUJDTYUZJMI-OGFXRTJISA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 description 1
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 1
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 150000001370 alpha-amino acid derivatives Chemical class 0.000 description 1
- 235000008206 alpha-amino acids Nutrition 0.000 description 1
- ZGUNAGUHMKGQNY-UHFFFAOYSA-N alpha-phenylglycine Chemical compound OC(=O)C(N)C1=CC=CC=C1 ZGUNAGUHMKGQNY-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 1
- 229960000310 isoleucine Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 〈産業上の利用分野〉 本発明は医薬品等の原料として用途の広いアミノ酸塩酸
塩の製造法の改良に係る。さらに詳しくは本発明は中性
又は塩基性アミノ酸を、水分を含有した不活性有機溶媒
中で塩化水素ガスと反応せしめることを特徴とするアミ
ノ酸塩酸塩の製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to an improvement in a method for producing an amino acid hydrochloride, which has a wide range of uses as a raw material for pharmaceuticals and the like. More specifically, the present invention relates to a method for producing an amino acid hydrochloride, which comprises reacting a neutral or basic amino acid with hydrogen chloride gas in an inert organic solvent containing water.
本発明でいう中性又は塩基性アミノ酸とはカルボニル基
以外に三塩化リン等の塩素化剤と反応する反応基、例え
ばヒドロキシル基、メルカプト基を含まないアミノ酸を
いう。具体的には、グリシン、α−フエニルグリシン、
アラニン、バリン、ロイシン、イソロイシン、リジン、
フエニルアラニン、プロリン及び上記の如き反応性官能
基を含有しない長鎖アミノ酸が挙げられる。このアミノ
酸は必ずしもα−アミノ酸である必要はなく、又、その
光学活性体及びラセミ体の双方が用いられる。The neutral or basic amino acid in the present invention means an amino acid which does not contain a reactive group that reacts with a chlorinating agent such as phosphorus trichloride in addition to a carbonyl group, for example, a hydroxyl group or a mercapto group. Specifically, glycine, α-phenylglycine,
Alanine, valine, leucine, isoleucine, lysine,
Examples include phenylalanine, proline and long chain amino acids that do not contain reactive functional groups such as those mentioned above. This amino acid does not necessarily have to be an α-amino acid, and both its optically active form and its racemic form are used.
〈従来の技術及び問題点〉 従来、アミノ酸塩酸塩は大量の不活性有機溶媒にアミノ
酸を懸濁させ塩化水素ガスを吹き込んで合成している
が、溶媒量がアミノ酸に対して８重量倍以下では反応途
中で系内のスラリー状態が変化し、この攪拌（→均一
化）（以下、略す。）が不能となる。従つて溶媒量を８
重量倍以上使用することになるがこれでは製造能力の低
下を招き、工業的製造には極めて不利である。<Conventional Technology and Problems> Conventionally, amino acid hydrochloride is synthesized by suspending an amino acid in a large amount of an inert organic solvent and blowing hydrogen chloride gas, but if the amount of solvent is 8 times or less by weight of the amino acid, During the reaction, the slurry state in the system changes and this stirring (→ homogenization) (hereinafter abbreviated) becomes impossible. Therefore, the amount of solvent is 8
Although it will be used in an amount of more than the weight, this causes a decrease in production capacity and is extremely disadvantageous for industrial production.
ところで、一般に、その工業化において本発明の如き、
スラリー状態を伴う反応系ではこの攪拌問題が化学的に
も、又、物理的（労力さらには機械設備）にも、極めて
重要な要素を占め、当業者が対策にもつとも、苦慮する
ところである。By the way, in general, as in the present invention in its industrialization,
In a reaction system involving a slurry state, this stirring problem occupies a very important factor both chemically and physically (labor and mechanical equipment), and it is difficult for those skilled in the art to take countermeasures.
〈問題点を解決するための手段及び効果〉 本発明者らは上記の欠点を無くすべく鋭意検討を重ね工
業的に有利なアミノ酸塩酸塩の製造法を見い出したもの
である。<Means and Effects for Solving Problems> The present inventors have conducted intensive studies to eliminate the above-mentioned drawbacks and found an industrially advantageous method for producing an amino acid hydrochloride.
即ち、本発明はアミノ酸を不活性有機溶媒に懸濁させ水
を存在させたのちに、攪拌下で塩化水素ガスとの反応を
行なわせるものであるが、驚くべきことに溶媒に対し、
0.1重量％程度の少量の水であつても系内のスラリー状
態が大幅に改善され、反応が非常に円滑に進行するので
溶媒量をアミノ酸に対して３〜４重量倍にまで下げるこ
とが可能となり、工業的製造を考えた時には２倍もの能
力アツプとなつたのである。That is, in the present invention, the amino acid is suspended in an inert organic solvent and water is allowed to exist, and then the reaction with hydrogen chloride gas is performed under stirring.
Even with a small amount of water of about 0.1% by weight, the slurry state in the system is greatly improved, and the reaction proceeds very smoothly, so it is possible to reduce the amount of solvent to 3 to 4 times the weight of amino acid. Therefore, when considering industrial manufacturing, the capacity was doubled.
本発明に於いて反応系に存在させる水は制限は無いが、
反応後の処理等を考えれば少ない方が良い。幸いなこと
に少量でも極めて大きな効果が見られるので、溶媒の種
類、量によつても異なるが、溶媒に対して0.01〜1.0重
量％の範囲で選択される。In the present invention, the water present in the reaction system is not limited,
Considering the treatment after the reaction, the smaller the amount, the better. Fortunately, an extremely large effect can be seen even in a small amount, so it is selected in the range of 0.01 to 1.0% by weight with respect to the solvent, although it depends on the kind and amount of the solvent.
また、溶媒としては反応物及び生成物に不活性な有機溶
媒であれば特に制限は無く、例えば、ベンゼン、トルエ
ン、ｎ−ヘキサン、シクロヘキサン等の炭化水素類、ジ
クロルメタン、ジクロルエタン、四塩化炭素、トリクレ
ン、パークレン等のハロゲン化炭化水素類等が好適に使
用される。なお、これらの２種以上を混合して使用して
も構わない。溶媒の使用量はアミノ酸に対し２〜６重量
倍の範囲が適当である。The solvent is not particularly limited as long as it is an organic solvent inert to the reaction product and the product, and examples thereof include hydrocarbons such as benzene, toluene, n-hexane and cyclohexane, dichloromethane, dichloroethane, carbon tetrachloride and trichlene. Halogenated hydrocarbons such as perchlorene and the like are preferably used. In addition, you may use these 2 or more types in mixture. The amount of the solvent used is appropriately in the range of 2 to 6 times by weight of the amino acid.
アミノ酸に対する塩化水素ガスの割合は通常、１〜1.1
倍モル程度であつて大過剰に用いる必要はない。反応温
度は通常、０〜２０℃の範囲から選ばれる。反応及びそ
れに伴う反応熱は塩化水素ガスの通気量によつて、好適
に制御することが出来る。The ratio of hydrogen chloride gas to amino acids is usually 1 to 1.1.
It is not necessary to use it in a large excess, although it is about twice the molar amount. The reaction temperature is usually selected from the range of 0 to 20 ° C. The reaction and the heat of reaction associated therewith can be suitably controlled by adjusting the aeration amount of hydrogen chloride gas.
生成物の単離方法は必要に応じて、公知の手段、例え
ば、過、遠心分離、傾瀉等の固液分離によつて達成す
ることが出来る。The method for isolating the product can be achieved by known means, for example, solid-liquid separation such as filtration, centrifugation, or decantation.
〈実施例〉 以下、実施例により本発明を具体的に説明する。<Examples> Hereinafter, the present invention will be specifically described with reference to Examples.
なお、実施例でいうスラリーの流動角とは円筒回転法に
よる安息角測定器（筒井理化学器械株式会社製作）を利
用して測定したものをいう。即ち、反応で得られたスラ
リーを、該ガラス製容器に入れ、ゆつくり回転させて、
スラリーが動き始めた時の液面の傾きを流動角とした。
ここで、流動角３０°が工業的にはスラリー攪拌の可能
範囲と判定された。In addition, the flow angle of the slurry referred to in the examples refers to that measured using a repose angle measuring device (manufactured by Tsutsui Rikagaku Kikai Co., Ltd.) by a cylindrical rotation method. That is, the slurry obtained by the reaction, put in the glass container, and gently spin,
The inclination of the liquid surface when the slurry started to move was defined as the flow angle.
Here, the flow angle of 30 ° was industrially determined to be within the range where slurry stirring was possible.
実施例１ Ｄ−α−フエニルグリシン30.0ｇをジクロルメタン120
ｇに懸濁し、これに水0.093ｇを加えた。懸濁液を１０
℃に冷却した後、攪拌下で塩化水素ガス8.4ｇを１時間
かけて供給した。Example 1 D-α-phenylglycine (30.0 g) was dissolved in dichloromethane 120
g, and 0.093 g of water was added thereto. 10 suspensions
After cooling to 0 ° C., 8.4 g of hydrogen chloride gas was supplied with stirring over 1 hour.
結果、スラリーの流動角は9゜であつた。攪拌は良好であ
り、反応は極めて円滑に終始した。As a result, the flow angle of the slurry was 9 °. The stirring was good and the reaction started very smoothly.
続いて、別して、生成したＤ−α−フエニルグリシン
塩酸塩（結晶）37.1ｇを得た。収率99.5％。Subsequently, separately, 37.1 g of the produced D-α-phenylglycine hydrochloride (crystal) was obtained. Yield 99.5%.
次に水を加えないで同様な操作を行なつた結果、流動角
は測定不能（→200゜以上）（以下略す。）、系内は綿菓
子状態となりスラリーは流動せず工業的には攪拌不可で
あつた。反応は途中から進行せず、完結しないまま、未
反応のＤ−α−フエニルグリシンを相当量残した。（比
較例） 加える水を表−１に示した量で同様な操作を行ない、次
の結果（表−１）を得た。Next, as a result of performing the same operation without adding water, the flow angle cannot be measured (→ 200 ° or more) (abbreviated below), the inside of the system becomes a cotton candy state, and the slurry does not flow and is industrially stirred. It was impossible. The reaction did not proceed from the middle, and unreacted D-α-phenylglycine remained in a considerable amount. (Comparative Example) The same operation was performed with the amount of water added shown in Table 1 to obtain the following result (Table 1).
実施例２ 実施例１においてジクロルメタンを255ｇとし、同様な
操作を行なつた結果スラリーの流動角は2゜であつた。系
内のスラリー攪拌は良好であり、反応は極めて円滑に終
始した。 Example 2 Dichloromethane was added to 255 g in Example 1 and the same operation was performed. As a result, the flow angle of the slurry was 2 °. Stirring of the slurry in the system was good, and the reaction started extremely smoothly.
次に水を加えないで同様な操作を行なつた結果流動角は
30゜であつた。系内のスラリー攪拌は漸く可能な状態で
あり（→ほぼ限界値）、反応は円滑に進行せず、この完
結にはさらに数時間を要した。（比較例） 又加える水を表−２に示した量で同様な操作を行ない、
次の結果（表−２）を得た。As a result of performing the same operation without adding water next, the flow angle is
It was 30 degrees. It was possible to agitate the slurry in the system (→ almost the limit value), the reaction did not proceed smoothly, and it took several hours to complete the reaction. (Comparative Example) Further, the same operation was performed with the amount of water to be added shown in Table-2,
The following results (Table-2) were obtained.
実施例３ 実施例１において表−３に示した溶媒量、添加水量を変
えた以外同様な操作を行ない、次の結果（表−３）を得
た。 Example 3 The same operation as in Example 1 was carried out except that the amount of solvent and the amount of added water shown in Table 3 were changed, and the following result (Table 3) was obtained.
実施例４〜７ 実施例１において表−４に示したアミノ酸、溶媒種類、
溶媒量、添加水量を変えた以外、同様な操作を行ない、
次の結果（表−４）を得た。 Examples 4 to 7 The amino acids and solvent types shown in Table 4 in Example 1,
Perform the same operation except changing the amount of solvent and the amount of added water,
The following results (Table 4) were obtained.
Claims (1)
応基を有さない中性又は塩基性アミノ酸を、水分を含有
した不活性有機溶媒中で塩化水素ガスと反応せしめるこ
とを特徴とするアミノ酸塩酸塩の製造法。1. A neutral or basic amino acid having no reactive group other than a carbonyl group that reacts with a chlorinating agent is reacted with hydrogen chloride gas in an inert organic solvent containing water. Method for producing amino acid hydrochloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8423385A JPH0655699B2 (en) | 1985-04-19 | 1985-04-19 | Method for producing amino acid hydrochloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8423385A JPH0655699B2 (en) | 1985-04-19 | 1985-04-19 | Method for producing amino acid hydrochloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61243050A JPS61243050A (en) | 1986-10-29 |
| JPH0655699B2 true JPH0655699B2 (en) | 1994-07-27 |
Family
ID=13824753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8423385A Expired - Lifetime JPH0655699B2 (en) | 1985-04-19 | 1985-04-19 | Method for producing amino acid hydrochloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0655699B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4988789A (en) * | 1990-01-05 | 1991-01-29 | Sandoz Ltd. | Process for preparing glycine hydrochloride |
| US8853446B2 (en) | 2010-11-30 | 2014-10-07 | Green Products & Technologies, L.L.C. | Synthetic acid and associated methods |
| CN103145572A (en) * | 2013-03-20 | 2013-06-12 | 康化（上海）新药研发有限公司 | Asymmetric synthesis method for natural product chlorinated gamma-norvaline hydrochloride |
-
1985
- 1985-04-19 JP JP8423385A patent/JPH0655699B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61243050A (en) | 1986-10-29 |
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