JPS6241233B2 - - Google Patents
Info
- Publication number
- JPS6241233B2 JPS6241233B2 JP9405478A JP9405478A JPS6241233B2 JP S6241233 B2 JPS6241233 B2 JP S6241233B2 JP 9405478 A JP9405478 A JP 9405478A JP 9405478 A JP9405478 A JP 9405478A JP S6241233 B2 JPS6241233 B2 JP S6241233B2
- Authority
- JP
- Japan
- Prior art keywords
- caprolactam
- amino
- chloro
- chloroform
- present
- 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
- -1 α-Substituted amino-ε-caprolactam Chemical class 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- BOWUOGIPSRVRSJ-UHFFFAOYSA-N 2-aminohexano-6-lactam Chemical compound NC1CCCCNC1=O BOWUOGIPSRVRSJ-UHFFFAOYSA-N 0.000 description 4
- KDRVILWORUDEID-UHFFFAOYSA-N 3-[(3-chloro-2-hydroxypropyl)amino]azepan-2-one Chemical compound ClCC(O)CNC1CCCCNC1=O KDRVILWORUDEID-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UDFAYULBRXIBLR-UHFFFAOYSA-N 3-(oxiran-2-ylmethylamino)azepan-2-one Chemical compound O=C1NCCCCC1NCC1OC1 UDFAYULBRXIBLR-UHFFFAOYSA-N 0.000 description 3
- XTXSOEFUFDVJDT-UHFFFAOYSA-N 3-[bis(3-chloro-2-hydroxypropyl)amino]azepan-2-one Chemical compound ClCC(CN(C1C(=O)NCCCC1)CC(CCl)O)O XTXSOEFUFDVJDT-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007033 dehydrochlorination reaction Methods 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CFZGIDYCUWFUJR-UHFFFAOYSA-N 3-(dimethylamino)azepan-2-one Chemical compound CN(C)C1CCCCNC1=O CFZGIDYCUWFUJR-UHFFFAOYSA-N 0.000 description 1
- NDXGCVGKTPQXFA-UHFFFAOYSA-N 3-chloroazepan-2-one Chemical compound ClC1CCCCNC1=O NDXGCVGKTPQXFA-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003974 aralkylamines Chemical class 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000003951 lactams Chemical group 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- XXEWFEBMSGLYBY-SSDOTTSWSA-N n-dimethyl-lysine Chemical compound CN(C)CCCC[C@@H](N)C(O)=O XXEWFEBMSGLYBY-SSDOTTSWSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Plural Heterocyclic Compounds (AREA)
- Polyamides (AREA)
- Epoxy Resins (AREA)
Description
本発明は一般式 （ここでR1は The present invention is based on the general formula (Here R 1 is
【式】R2は水素又は[Formula] R 2 is hydrogen or
【式】を示す。）
で表わされる新規なα−置換アミノ−ε−カプロ
ラクタムに関する。
本発明の化合物は農薬、ポリマー原料、または
これらの中間体、もしくはその他化合物の中間体
として有用な物質である。
従来から知られているα−置換アミノ−ε−カ
プロラクタムとしてはアルキルまたはアラルキル
アミノ置換体がある。α−ジメチルアミノ−ε−
カプロラクタムはα−アミノ−ε−カプロラクタ
ムにホルマリンとパラジウムで処理して製造し、
Ｎ〓−ジメチルリジン金属塩合成の中間体として
報告されている（特公昭42−11926号公報）。また
α−クロル−ε−カプロラクタムとアルキルまた
はアラルキルアミンを反応させてα−アルキルま
たはα−アラルキルアミノ−ε−カプロラクタム
を製造し、殺菌剤としても報告されている（フラ
ンス特許第1441071号）。
本発明者らはα−アミノ−ε−カプロラクタム
に活性な官能基を導入することにより、さらに有
用な物質を合成すべく鋭意研究を重ねた結果、本
発明に到達した。
即ち本発明のα−置換アミノ−ε−カプロラク
タムは前記一般式で表わされる化合物であるが、
具体的には次のような化合物である。
α−グリシジルアミノ−ε−カプロラクタム、
α−ジグリシジルアミノ−ε−カプロラクタムお
よびこれらの塩。
本発明の化合物の製造法は特に限定されるもの
ではないが、たとえば下式に示すごとくα−（３
−クロル−２−ヒドロキシプロピルアミノ）−ε
−カプロラクタム、α−〔ビス−（３−クロル−２
−ヒドロキシプロピル）アミノ〕−ε−カプロラ
クタムを脱塩酸することにより得ることができ
る。
出発物質であるα−（３−クロル−２−ヒドロ
キシプロピルアミノ）−ε−カプロラクタム、お
よびα−〔ビス−（３−クロル−２−ヒドロキシプ
ロピル）アミノ〕−ε−カプロラクタムはα−ア
ミノ−ε−カプロラクタムとエピクロルヒドリン
を反応させることにより製造することができる。
反応温度は高温になるとラクタム環が加水分解
したり、製造したエポキシ環が反応してしまうの
で０゜〜40℃が好ましい。
反応溶媒はアルカリの溶解性、生成した物質の
単離等を考慮して水と有機溶媒、例えばクロロホ
ルム、エーテル、ベンゼン等の２層間反応が行な
える溶媒が好ましい。
脱塩酸剤はアルカリ金属の水酸化物、ナトリウ
ムアルコキシド等、塩基性化合物なら何でもよい
が反応操作を簡便にするにはアルカリ金属の水酸
化物が好ましい。
以下、実施例により本発明を更に詳細に説明す
るが、本発明の化合物は特にこの製造法によつて
限定されるものではない。
実施例 １
（α−（３−クロル−２−ヒドロキシプロピルア
ミノ）−ε−カプロラクタムの製造）
特公昭41−18089号公報に示された方法により
α−アミノシクロヘキサノンオキシム塩酸塩をベ
ツクマン転位して得たα−アミノ−ε−カプロラ
クタム3.8ｇとエピクロルヒドリン16.7ｇを還流
管と撹拌装置を装着したフラスコに仕込み、室温
中で撹拌した。２時間位で結晶が析出してくる
が、反応は４時間継続した。
析出した結晶をろ別し、酢酸エチルで洗浄し、
粗生成物6.3ｇを得た。
ベンゼンで再結晶し、精α−（３−クロル−２
−ヒドロキシプロピルアミノ）−ε−カプロラク
タム5.6ｇを得た。分解点120℃[Formula] is shown. ) It relates to a novel α-substituted amino-ε-caprolactam. The compound of the present invention is a substance useful as a pesticide, a polymer raw material, or an intermediate thereof, or an intermediate for other compounds. Conventionally known α-substituted amino-ε-caprolactams include alkyl- or aralkylamino-substituted products. α-dimethylamino-ε-
Caprolactam is produced by treating α-amino-ε-caprolactam with formalin and palladium.
It has been reported as an intermediate in the synthesis of N-dimethyllysine metal salts (Japanese Patent Publication No. 11926/1983). It has also been reported that α-chloro-ε-caprolactam is reacted with an alkyl or aralkylamine to produce α-alkyl or α-aralkyl amino-ε-caprolactam as a fungicide (French Patent No. 1441071). The present inventors have conducted intensive research to synthesize a more useful substance by introducing an active functional group into α-amino-ε-caprolactam, and have thus arrived at the present invention. That is, the α-substituted amino-ε-caprolactam of the present invention is a compound represented by the above general formula,
Specifically, the following compounds are used. α-glycidylamino-ε-caprolactam,
α-diglycidylamino-ε-caprolactam and salts thereof. Although the method for producing the compound of the present invention is not particularly limited, for example, α-(3
-chloro-2-hydroxypropylamino)-ε
-Caprolactam, α-[bis-(3-chloro-2
-Hydroxypropyl)amino]-ε-caprolactam can be obtained by dehydrochlorination. The starting materials α-(3-chloro-2-hydroxypropylamino)-ε-caprolactam and α-[bis-(3-chloro-2-hydroxypropyl)amino]-ε-caprolactam are α-amino-ε-caprolactam. - It can be produced by reacting caprolactam and epichlorohydrin. The reaction temperature is preferably 0° to 40°C, since at high temperatures the lactam ring will be hydrolyzed or the produced epoxy ring will react. The reaction solvent is preferably a solvent capable of performing a two-layer reaction with water and an organic solvent, such as chloroform, ether, benzene, etc., taking into consideration the solubility of the alkali and the isolation of the produced substance. The dehydrochlorination agent may be any basic compound such as alkali metal hydroxide, sodium alkoxide, etc., but alkali metal hydroxide is preferable in order to simplify the reaction operation. Hereinafter, the present invention will be explained in more detail with reference to Examples, but the compounds of the present invention are not particularly limited by this production method. Example 1 (Production of α-(3-chloro-2-hydroxypropylamino)-ε-caprolactam) α-Aminocyclohexanone oxime hydrochloride was obtained by Becmann rearrangement according to the method disclosed in Japanese Patent Publication No. 18089/1989. 3.8 g of α-amino-ε-caprolactam and 16.7 g of epichlorohydrin were placed in a flask equipped with a reflux tube and a stirring device, and the mixture was stirred at room temperature. Although crystals began to precipitate in about 2 hours, the reaction continued for 4 hours. The precipitated crystals were filtered and washed with ethyl acetate.
6.3 g of crude product was obtained. Recrystallize from benzene to obtain purified α-(3-chloro-2
5.6 g of -hydroxypropylamino)-ε-caprolactam was obtained. Decomposition point 120℃
【表】
実施例 ２
（α−グリシジルアミノ−ε−カプロラクタム
の製造）
実施例１で製造したα−（３−クロル−２−ヒ
ドロキシプロピルアミノ）−ε−カプロラクタム
５ｇをクロロホルム10mlにとかし、還流管を装着
した三角フラスコに仕込み、44％水酸化ナトリウ
ム水溶液５mlを加え、室温中で３時間撹拌した。
次いでクロロホルム層を分離し、水層はクロロホ
ルム20mlで２回抽出し、分離したクロロホルム層
と合わせた。硫酸マグネシウムで脱水後、クロロ
ホルムを減圧で除去した。残渣を酢酸エチルで再
結晶して精α−グリシジルアミノ−ε−カプロラ
クタム3.5ｇを得た。収率83.9％、mp98〜９℃[Table] Example 2 (Production of α-glycidylamino-ε-caprolactam) 5 g of α-(3-chloro-2-hydroxypropylamino)-ε-caprolactam produced in Example 1 was dissolved in 10 ml of chloroform, and the mixture was poured into a reflux tube. 5 ml of 44% aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 3 hours.
The chloroform layer was then separated, and the aqueous layer was extracted twice with 20 ml of chloroform and combined with the separated chloroform layer. After dehydration with magnesium sulfate, chloroform was removed under reduced pressure. The residue was recrystallized from ethyl acetate to obtain 3.5 g of purified α-glycidylamino-ε-caprolactam. Yield 83.9%, mp98~9℃
【表】
にて行なつた。
実施例 ３
（α−ジグリシジルアミノ−ε−カプロラクタ
ムの製造）
α−〔ビス−（３−クロル−２−ヒドロキシプロ
ピル）アミノ〕−ε−カプロラクタム５ｇを実施
例１と同様にして反応させ、クロロホルムを減圧
で除去したところシロツプ状のα−ジグリシジル
アミノ−ε−カプロラクタム3.7ｇを得た。収率
96.4％[Table]
Example 3 (Production of α-diglycidylamino-ε-caprolactam) 5 g of α-[bis-(3-chloro-2-hydroxypropyl)amino]-ε-caprolactam was reacted in the same manner as in Example 1, and chloroform was removed under reduced pressure to obtain 3.7 g of syrupy α-diglycidylamino-ε-caprolactam. yield
96.4%
【表】
IRで3300cm-1付近のOH吸収の消滅、1670cm-1
のアミド吸収の存在、NMRによる−OHの共鳴ピ
ークの消滅およびバイルシユタインハロゲン確認
試験によるハロゲン陰性結果よりα−ジグリシジ
ルアミノ−ε−カプロラクタムと同定した。
この化合物は非常に不安定で薄層クロマトグラ
フイーによる分析では室温中５時間でRf値が変
化した。[Table] Disappearance of OH absorption near 3300cm -1 in IR, 1670cm -1
The substance was identified as α-diglycidylamino-ε-caprolactam based on the presence of amide absorption, the disappearance of the -OH resonance peak by NMR, and the negative result for halogen by the Weilstein Halogen Confirmation Test. This compound was very unstable, and when analyzed by thin layer chromatography, the Rf value changed within 5 hours at room temperature.
Claims (1)
ム。[Claims] 1. General formula (Here, R 1 is [Formula] and R 2 is hydrogen or [Formula].) α-Substituted amino-ε-caprolactam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9405478A JPS5520742A (en) | 1978-08-01 | 1978-08-01 | Alpha-substituted amino-epsilon-caprolactam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9405478A JPS5520742A (en) | 1978-08-01 | 1978-08-01 | Alpha-substituted amino-epsilon-caprolactam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5520742A JPS5520742A (en) | 1980-02-14 |
| JPS6241233B2 true JPS6241233B2 (en) | 1987-09-02 |
Family
ID=14099823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9405478A Granted JPS5520742A (en) | 1978-08-01 | 1978-08-01 | Alpha-substituted amino-epsilon-caprolactam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5520742A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1680406A1 (en) | 2003-10-29 | 2006-07-19 | Elan Pharmaceuticals, Inc. | N-substituted benzene sulfonamides |
-
1978
- 1978-08-01 JP JP9405478A patent/JPS5520742A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5520742A (en) | 1980-02-14 |
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