JPH0434986B2 - - Google Patents
Info
- Publication number
- JPH0434986B2 JPH0434986B2 JP2054885A JP2054885A JPH0434986B2 JP H0434986 B2 JPH0434986 B2 JP H0434986B2 JP 2054885 A JP2054885 A JP 2054885A JP 2054885 A JP2054885 A JP 2054885A JP H0434986 B2 JPH0434986 B2 JP H0434986B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- compound
- acetate
- acetylamino
- 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
- 150000001875 compounds Chemical class 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- MWVBVDJUFFMLAR-UHFFFAOYSA-N 3-acetamidoprop-2-enoic acid Chemical compound CC(=O)NC=CC(O)=O MWVBVDJUFFMLAR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- -1 acetate amide Chemical class 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OAKURXIZZOAYBC-UHFFFAOYSA-M 3-oxopropanoate Chemical compound [O-]C(=O)CC=O OAKURXIZZOAYBC-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- AXJDEHNQPMZKOS-UHFFFAOYSA-N acetylazanium;chloride Chemical compound [Cl-].CC([NH3+])=O AXJDEHNQPMZKOS-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000003862 amino acid derivatives Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical class NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
（産業上の利用分野）
本発明は、新規化合物であるβ−（アセチルア
ミノ）アクリル酸エステルに関するものである。
本発明で提供される化合物は新規のアミノ酸誘導
体であり還元によりβ−アラニン誘導体となるな
ど医薬品原料としての利用が期待される化合物で
ある。
（従来技術）
従来アクリル酸エステルのβ位水素がアセチル
アミノ基で置換された化合物は知られていなかつ
た。
（発明の目的）
本発明の目的は新規化合物であるβ−（アセチ
ルアミノ）アクリル酸エステルの一群を提供する
ことにある。
（発明の構成）
この発明の対象とする化合物は一般式(1)で示さ
れる化合物である。
（式中Ｒはアルキル基又はアリール基を意味す
る。）
Ｒを具体的に例示すると、メチル基、エチル
基、ｎ−プロピル基、イソプロピル基、ｎ−ブチ
ル基、イソブチル基、sec−ブチル基、tert−ブ
チル基、ベンジル基、フエニル基などである。
また、一般式(1)で示される化合物には２種の幾何
異性体が存在するが、本発明の範囲には、これら
のいずれの異性体も含まれる。
（製造法）
この発明の化合物(1)は式(2)
MO−CH＝CH−COOR (2)
（式中ＭはNa，ｋ，Liを示す。式中Ｒは先の式
(1)について説明したものと同じである。）で表わ
されるアルカリホルミル酢酸エステルに、式(3)
(Industrial Application Field) The present invention relates to a new compound, β-(acetylamino)acrylic acid ester.
The compound provided by the present invention is a novel amino acid derivative, which becomes a β-alanine derivative upon reduction, and is expected to be used as a pharmaceutical raw material. (Prior Art) Conventionally, no compound was known in which the hydrogen at the β-position of an acrylic acid ester was substituted with an acetylamino group. (Object of the invention) The object of the present invention is to provide a group of novel compounds, β-(acetylamino)acrylic esters. (Structure of the Invention) The compound targeted by this invention is a compound represented by general formula (1). (In the formula, R means an alkyl group or an aryl group.) Specific examples of R include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, Examples include tert-butyl group, benzyl group, and phenyl group. Further, the compound represented by the general formula (1) has two types of geometric isomers, and the scope of the present invention includes any of these isomers. (Production method) Compound (1) of the present invention has the formula (2) MO-CH=CH-COOR (2) (where M represents Na, k, Li. In the formula, R is the formula
This is the same as explained for (1). ) to the alkali formyl acetate represented by formula (3)
【式】（Ｘ：ハロゲン、HSO4，
NO3を示す）で示される酢酸アミドの鉱酸塩と
を溶媒の存在下反応させることにより得ることが
できる。
反応温度は50℃〜150℃が好ましい。反応時間は
用いる原料、反応温度、反応溶媒等の組合せによ
り異なるが、およそ１〜20時間である。
又、反応溶液中の一般式(2)及び(3)の化合物の濃度
はいずれも５〜20wt％が好適である。
溶媒としてはアルカリホルミル酢酸エステルおよ
び酢酸アミドの鉱酸塩に不活性な溶媒例えば
DMF，SMSO，THF，ジエチルエーテルなどが
好適である。原料のアルカリホルシル酢酸エステ
ルは一酸化炭素とアルカリアルコラートと酢酸エ
ステルとの反応によつて得ることができる。
以下この発明を実施例で説明する。
実施例
ジムロート冷却管付き100ml三ツ口フラスコに
ナトリウムホルミル酢酸メチル2.48ｇ（20mmol）
とジメチルホルムアミド50mlを入れ室温で攪拌し
ながら酢酸アミドの塩酸塩1.91ｇ（20mmol）を
加えた。温度を100℃に昇温し４時間攪拌した後、
溶媒を減圧留去し残査をカラムクロマトグラフイ
ーにより分離精製した結果、β−アセチルアミノ
アクリル酸メチルが1.1ｇ（7.7mmol）得られた。
尚、この化合物は、次に示す物性データより同定
した。
・IRスペクトル（kBr，cm-1）
1713cm-1 1690cm-1 1620cm-1
・NMRスペクトル（cDCl3，ppm）
Ha 3.73（１重線）
Hb シス体 5.08〜5.16（２重線）
トランス体 5.40〜5.55（２重線）
Hc シス体 7.61〜7.45（３重線）
トランス体 7.83〜8.13（３重線）
Hd 8.92〜9.34（巾の広いピーク）
He 2.14（１重線）
・元素分析値
計算値 Ｃ：50.35 Ｈ：6.29
Ｏ：33.57 Ｎ：9.79
実測値 Ｃ：50.01 Ｈ：6.41
Ｏ：33.89 Ｎ：9.69It can be obtained by reacting a mineral acid salt of acetate amide represented by the formula (X: halogen, HSO 4 , NO 3 ) in the presence of a solvent. The reaction temperature is preferably 50°C to 150°C. The reaction time varies depending on the combination of raw materials used, reaction temperature, reaction solvent, etc., but is approximately 1 to 20 hours. Further, the concentration of the compounds of general formulas (2) and (3) in the reaction solution is preferably 5 to 20 wt%. Examples of solvents include solvents inert to mineral acid salts of alkali formyl acetate and acetate amide.
DMF, SMSO, THF, diethyl ether, etc. are suitable. The raw material alkali forsylacetate can be obtained by reacting carbon monoxide, an alkali alcoholate, and an acetate. This invention will be explained below with reference to Examples. Example: 2.48 g (20 mmol) of sodium formyl methyl acetate in a 100 ml three-necked flask with a Dimroth condenser.
and 50 ml of dimethylformamide were added thereto, and 1.91 g (20 mmol) of acetic acid amide hydrochloride was added while stirring at room temperature. After raising the temperature to 100℃ and stirring for 4 hours,
The solvent was distilled off under reduced pressure and the residue was separated and purified by column chromatography to obtain 1.1 g (7.7 mmol) of methyl β-acetylaminoacrylate. This compound was identified based on the physical property data shown below.・IR spectrum (kBr, cm -1 ) 1713cm -1 1690cm -1 1620cm -1・NMR spectrum (cDCl 3 , ppm) H a 3.73 (singlet) H b cis 5.08-5.16 (double) trans 5.40-5.55 (double) H c cis 7.61-7.45 (triplet) trans 7.83-8.13 (triplet) line) H d 8.92 to 9.34 (wide peak) H e 2.14 (single line) Elemental analysis value Calculated value C: 50.35 H: 6.29 O: 33.57 N: 9.79 Actual value C: 50.01 H: 6.41 O: 33.89 N:9.69
Claims (1)
す）で表わされるβ−（アセチルアミノ）アクリ
ル酸エステル ２ 一般式(1)のＲが炭素数１〜３のアルキル基で
ある特許請求の範囲第１項記載の化合物[Claims] 1 General formula (1) (In the formula, R represents an alkyl group or an aryl group) β-(acetylamino)acrylic acid ester 2 Claim 1, wherein R in the general formula (1) is an alkyl group having 1 to 3 carbon atoms. Compounds listed in section
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2054885A JPS61180751A (en) | 1985-02-05 | 1985-02-05 | Beta-(acetylamino)acrylic ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2054885A JPS61180751A (en) | 1985-02-05 | 1985-02-05 | Beta-(acetylamino)acrylic ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61180751A JPS61180751A (en) | 1986-08-13 |
| JPH0434986B2 true JPH0434986B2 (en) | 1992-06-09 |
Family
ID=12030202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2054885A Granted JPS61180751A (en) | 1985-02-05 | 1985-02-05 | Beta-(acetylamino)acrylic ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61180751A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5304820A (en) * | 1987-03-27 | 1994-04-19 | Canon Kabushiki Kaisha | Process for producing compound semiconductor and semiconductor device using compound semiconductor obtained by same |
| JPH0634134Y2 (en) * | 1989-02-14 | 1994-09-07 | シャチハタ工業株式会社 | Date stamp |
-
1985
- 1985-02-05 JP JP2054885A patent/JPS61180751A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61180751A (en) | 1986-08-13 |
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