JPH0322379B2 - - Google Patents
Info
- Publication number
- JPH0322379B2 JPH0322379B2 JP22739982A JP22739982A JPH0322379B2 JP H0322379 B2 JPH0322379 B2 JP H0322379B2 JP 22739982 A JP22739982 A JP 22739982A JP 22739982 A JP22739982 A JP 22739982A JP H0322379 B2 JPH0322379 B2 JP H0322379B2
- Authority
- JP
- Japan
- Prior art keywords
- acid amide
- carbamoylamino
- methanol
- reaction
- aminobutyric 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.)
- Expired
Links
- MVEPJLNIXKEKMI-UHFFFAOYSA-N 4-aminobutanamide;hydrochloride Chemical compound Cl.NCCCC(N)=O MVEPJLNIXKEKMI-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- CBNWAQVRBGQPGJ-UHFFFAOYSA-N 4-(carbamoylamino)butanamide Chemical compound NC(=O)CCCNC(N)=O CBNWAQVRBGQPGJ-UHFFFAOYSA-N 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims 1
- 230000000321 decarbamoylating effect Effects 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 9
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QYTWIMMLQKHPGL-UHFFFAOYSA-N 4-(carbamoylamino)butanoic acid Chemical compound NC(=O)NCCCC(O)=O QYTWIMMLQKHPGL-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- -1 (benzylamino)-butyronitrile Chemical compound 0.000 description 2
- HDBMIDJFXOYCGK-UHFFFAOYSA-N 2-aminobutanamide;hydrochloride Chemical compound Cl.CCC(N)C(N)=O HDBMIDJFXOYCGK-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229940059260 amidate Drugs 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical compound CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 description 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- YKAWOJYVXDCFDP-UHFFFAOYSA-N 3-cyanopropanamide Chemical compound NC(=O)CCC#N YKAWOJYVXDCFDP-UHFFFAOYSA-N 0.000 description 1
- WCVPFJVXEXJFLB-UHFFFAOYSA-N 4-aminobutanamide Chemical compound NCCCC(N)=O WCVPFJVXEXJFLB-UHFFFAOYSA-N 0.000 description 1
- ZFCFBWSVQWGOJJ-UHFFFAOYSA-N 4-chlorobutanenitrile Chemical compound ClCCCC#N ZFCFBWSVQWGOJJ-UHFFFAOYSA-N 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- MNZMECMQTYGSOI-UHFFFAOYSA-N acetic acid;hydron;bromide Chemical compound Br.CC(O)=O MNZMECMQTYGSOI-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 229940124277 aminobutyric acid Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229960003692 gamma aminobutyric acid Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000000401 methanolic extract Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
Description
【発明の詳細な説明】
本発明は４−アミノ酪酸アミド塩酸塩の工業的
に有利な新規製造法に関するものである。４−ア
ミノ酪酸アミドは脳代謝促進作用を有し医薬品あ
るいは医薬中間体として有用な化合物でありその
従来公知の製造法としては、
(1) ４−アミノ酪酸抵級アルキルエステルをアン
モニア水または液体アンモニアでアミド化する
方法（J.of Medicinal＆Pharmaceutical
Chemistry，４巻，31頁、1961年）
(2) ４−ベンジルオキシカルボニルアミノ）−酪
酸アミドを臭化水素酸−酢酸またはパラジウ
ム／硫酸バリウム−触媒で脱ベンジルオキシカ
ルボニル化する方法（J.of Medicinal
Chemistry，22巻，81頁，1979年）
(3) ３−シアノプロピオン酸アミドを酸化白金触
媒により接触還元する方法（Angew.Chem.，
92巻，640頁，1980年）
(4) ４−クロロブチロニトリルを原料とし４−
（ベンジルアミノ）−ブチロニトリルとし、これ
を加水分解後白金族触媒により接触還元する方
法（特開昭57−128664号）
が知られている。しかしながら(1)の方法は副反応
のため収率が著しく低く(2)，(3)，(4)の方法も高価
な原料を必要とし且高価な触媒を使用して接触還
元する等の欠点があり工業的に満足し得る方法と
は云い難い。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new industrially advantageous method for producing 4-aminobutyric acid amide hydrochloride. 4-Aminobutyric acid amide is a compound that promotes brain metabolism and is useful as a drug or a pharmaceutical intermediate. Conventionally known production methods include: (1) 4-aminobutyric acid lower alkyl ester is mixed with aqueous ammonia or liquid ammonia; How to amidate with (J.of Medicinal & Pharmaceutical
Chemistry, Vol. 4, p. 31, 1961) (2) Method for debenzyloxycarbonylation of 4-benzyloxycarbonylamino)-butyric acid amide with hydrobromic acid-acetic acid or palladium/barium sulfate catalyst (J.of Medicinal
Chemistry, Vol. 22, p. 81, 1979) (3) Catalytic reduction of 3-cyanopropionic acid amide using a platinum oxide catalyst (Angew.Chem.,
92, p. 640, 1980) (4) Using 4-chlorobutyronitrile as a raw material, 4-
A method is known in which (benzylamino)-butyronitrile is hydrolyzed and then catalytically reduced using a platinum group catalyst (Japanese Patent Application Laid-open No. 128664/1983). However, method (1) has extremely low yields due to side reactions.Methods (2), (3), and (4) also have drawbacks such as requiring expensive raw materials and using expensive catalysts for catalytic reduction. However, it is difficult to say that this method is industrially satisfactory.
そこで本発明者等は公知方法の欠点を改良した
工業的に有利な４−アミノ酪酸アミド塩酸塩の製
造法について鋭意検討した結果，４−（カルバモ
イルアミノ）−酪酸アミドに水溶液中亜硝酸ソー
ダと塩酸を作用させせることにより高収率で４−
アミノ酪酸アミド塩酸塩を生成することを知見し
て本発明を完成した。本発明を化学反応式で示せ
ば下記のとおりである。 Therefore, the present inventors conducted intensive studies on an industrially advantageous method for producing 4-aminobutyric acid amide hydrochloride that improves the drawbacks of known methods. By reacting with hydrochloric acid, 4-
The present invention was completed by discovering that aminobutyric acid amide hydrochloride is produced. The chemical reaction formula of the present invention is as follows.
H2NCONH（CH2）3CONH2HNO2＋HCl
――――――――→
HCl・H2N（CH2）3CONH2
本発明において原料として使用する４−（カル
バモイルアミノ）−酪酸アミドは、工業的に安価
に入手できる２−ピロリドンを苛性アルカリ水溶
液で加水分解したのちシアン酸ナトリウムあるい
は尿素を反応させる等の公知方法で高収率で得ら
れる４−（カルバモイルアミノ）酪酸をエステル
化およびアミド化して容易に収率良く製造するこ
とができる。 H 2 NCONH (CH 2 ) 3 CONH 2 HNO 2 +HCl ――――――――→ HCl・H 2 N (CH 2 ) 3 CONH 24-(Carbamoylamino)-butyric acid amide used as a raw material in the present invention is an esterification of 4-(carbamoylamino)butyric acid obtained in high yield by a known method such as hydrolyzing 2-pyrrolidone, which is industrially available at low cost, with an aqueous caustic alkali solution and then reacting it with sodium cyanate or urea. and can be easily produced in good yield by amidation.
本発明を実施する場合脱カルバモイル化の反応
は水溶液中で４−（カルバモイルアミノ）−酪酸ア
ミドに塩酸酸性下、亜硝酸ソーダを作用させるこ
とにより進行するが反応温度が低過ぎるとニトロ
ソ中間体が析出して反応の進行が遅くなり、又、
反応温度や塩酸濃度が高すぎると酸アミドの加水
分解が起こるため、高収率を得るためには適当な
条件を選ぶことが必要である。 When carrying out the present invention, the decarbamoylation reaction proceeds by reacting sodium nitrite with 4-(carbamoylamino)-butyric acid amide in an aqueous solution under the acidity of hydrochloric acid, but if the reaction temperature is too low, the nitroso intermediate is produced. It precipitates and slows down the progress of the reaction, and
If the reaction temperature or hydrochloric acid concentration is too high, hydrolysis of the acid amide will occur, so it is necessary to select appropriate conditions in order to obtain a high yield.
亜硝酸ソーダは当モル以上あれば良いが、当モ
ル〜1.5モル程度が好ましく、塩酸は２倍モル以
上あれば良いが２〜３倍モル程度が好ましい。反
応は０℃でも進行するが、ニトロソ中間体の析出
量の少い20〜50℃程度が好ましい。 Sodium nitrite may be present in an amount equal to or more than the equivalent mole, preferably from approximately the same mole to 1.5 moles, and hydrochloric acid may be present in an amount equal to or more than 2 times the mole, preferably approximately 2 to 3 times the mole. Although the reaction proceeds even at 0°C, a temperature of about 20 to 50°C is preferred because the amount of nitroso intermediate precipitated is small.
反応終了後、反応液を減圧濃縮し、残渣にメタ
ノールを添加して無機塩を除去し、メタノール抽
出液を濃縮してイソプロピルアルコールあるいは
アセトン等の溶媒で結晶化させることにより、４
−アミノ酪酸アミド塩酸塩を高収率で得ることが
できる。 以上の如く、本発明は安価に且つ容易
に入手できる原料を用いて簡単な操作で高収率で
４−アミノ酪酸アミド塩酸塩を得ることができる
工業的に有利な製造法である。 After the reaction is completed, the reaction solution is concentrated under reduced pressure, methanol is added to the residue to remove inorganic salts, and the methanol extract is concentrated and crystallized with a solvent such as isopropyl alcohol or acetone.
-Aminobutyric acid amide hydrochloride can be obtained in high yield. As described above, the present invention is an industrially advantageous production method that can obtain 4-aminobutyric acid amide hydrochloride in high yield with simple operations using inexpensive and easily available raw materials.
次に参考例及び実施例をあげて本発明を具体的
に説明する。 Next, the present invention will be specifically explained with reference to reference examples and examples.
参考例
４−（カルバモイルアミノ）−酪酸100ｇをメタ
ノール438ｇ、濃硫酸6.7ｇ中で６時間加熱還流し
たのちメタノールを減圧留去すると４−（カルバ
モイルアミノ）−酪酸メチルエステルを得る。収
量、ほぼ定量的、融点100〜102℃。Reference Example 100 g of 4-(carbamoylamino)-butyric acid is heated under reflux in 438 g of methanol and 6.7 g of concentrated sulfuric acid for 6 hours, and then the methanol is distilled off under reduced pressure to obtain 4-(carbamoylamino)-butyric acid methyl ester. Yield, almost quantitative, melting point 100-102℃.
次に28％アンモニア水411mlを冷却しつつ加え
15時間攬拌してアミド化する。反応終了後減圧下
に濃縮してアンモニアを回収後、一旦加熱して析
出結晶を溶解させた後、冷却し、析出する結晶を
取、冷水で洗浄したのち乾燥、４−（カルバモ
イルアミノ）−酪酸アミド73.2ｇを得る。収率74
％、融点168〜171℃
実施例 １
４−（カルバモイルアミノ）−酪酸アミド14.5ｇ
を水360ml、30％亜硝酸ソーダ水溶液24mlに溶解
する。室温で２規定塩酸120mlを滴下し、同温度
で４時間反応後、炭酸ソーダ水溶液でpH3に調整
し40℃以下で減圧濃縮する。濃縮残渣にメタノー
ル100mlを加えて無機塩を過し、母液を40℃以
下で減圧濃縮して濃縮残渣にメタノール15mlとイ
ソプロピルアルコール80mlを加えて結晶化させ
る。冷却後過して粗４−アミノ酪酸アミド塩酸
塩9.7ｇを得る。融点125〜129℃、収率70.0％。
メタノールより再結晶して白色針状晶を得る。融
点138〜140℃。この結晶は公知合成法で得られた
４−アミノ酪酸アミド塩酸塩と、IR，NMRで完
全に一致した。 Next, add 411ml of 28% ammonia water while cooling.
Stir for 15 hours to amidate. After the reaction is completed, concentrate under reduced pressure to recover ammonia, heat once to dissolve the precipitated crystals, cool, collect the precipitated crystals, wash with cold water, dry, and prepare 4-(carbamoylamino)-butyric acid. 73.2 g of amide is obtained. Yield 74
%, melting point 168-171°C Example 1 4-(carbamoylamino)-butyric acid amide 14.5 g
Dissolve in 360 ml of water and 24 ml of 30% sodium nitrite aqueous solution. Add 120 ml of 2N hydrochloric acid dropwise at room temperature, react at the same temperature for 4 hours, adjust the pH to 3 with an aqueous sodium carbonate solution, and concentrate under reduced pressure at below 40°C. Add 100 ml of methanol to the concentrated residue to filter out inorganic salts, concentrate the mother liquor under reduced pressure below 40°C, and add 15 ml of methanol and 80 ml of isopropyl alcohol to the concentrated residue to crystallize. After cooling, the mixture was filtered to obtain 9.7 g of crude 4-aminobutyric acid amide hydrochloride. Melting point 125-129℃, yield 70.0%.
Recrystallize from methanol to obtain white needle crystals. Melting point 138-140℃. This crystal completely matched 4-aminobutyric acid amide hydrochloride obtained by a known synthesis method by IR and NMR.
実施例 ２
水225ml、濃塩酸17.5mlの溶液中に４−（カルバ
モイルアミノ）−酪酸アミド14.5ｇを溶解し、30
〜35℃で30％亜硝酸ソーダ水溶液24mlを滴下す
る。滴下後40〜50℃で３時間反応した後減圧濃縮
し、実施例１と同様に後処理して粗４−アミノ酪
酸アミド塩酸塩9.8ｇを得る。融点121〜126℃、
収率70.7％。Example 2 14.5 g of 4-(carbamoylamino)-butyric acid amide was dissolved in a solution of 225 ml of water and 17.5 ml of concentrated hydrochloric acid.
Add 24 ml of 30% sodium nitrite aqueous solution dropwise at ~35°C. After the dropwise addition, the reaction mixture was reacted at 40 to 50°C for 3 hours, then concentrated under reduced pressure, and post-treated in the same manner as in Example 1 to obtain 9.8 g of crude 4-aminobutyric acid amide hydrochloride. Melting point 121-126℃,
Yield 70.7%.
メタノールより再結晶し白色針状結晶、融点
138〜140℃、この結晶は公知合成法で得られた４
−アミノ酪酸アミド塩酸塩とIR.NMRで完全に
一致した。 Recrystallized from methanol, white needle-like crystals, melting point
138-140℃, this crystal was obtained by a known synthesis method.
- Completely matched with aminobutyric acid amide hydrochloride by IR.NMR.
Claims (1)
硝酸により脱カルバモイル化することを特徴とす
る４−アミノ酪酸アミド塩酸塩の製造法1. A method for producing 4-aminobutyric acid amide hydrochloride, which comprises decarbamoylating 4-(carbamoylamino)-butyric acid amide with nitrous acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22739982A JPS59122444A (en) | 1982-12-28 | 1982-12-28 | Preparation of 4-aminobutyric acid amide hydrochloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22739982A JPS59122444A (en) | 1982-12-28 | 1982-12-28 | Preparation of 4-aminobutyric acid amide hydrochloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59122444A JPS59122444A (en) | 1984-07-14 |
| JPH0322379B2 true JPH0322379B2 (en) | 1991-03-26 |
Family
ID=16860211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22739982A Granted JPS59122444A (en) | 1982-12-28 | 1982-12-28 | Preparation of 4-aminobutyric acid amide hydrochloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59122444A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5652159B2 (en) * | 2009-11-30 | 2015-01-14 | 住友化学株式会社 | Process for producing 5- (aminomethyl) -2-chlorothiazole |
-
1982
- 1982-12-28 JP JP22739982A patent/JPS59122444A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59122444A (en) | 1984-07-14 |
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