JPH0468306B2 - - Google Patents
Info
- Publication number
- JPH0468306B2 JPH0468306B2 JP23446285A JP23446285A JPH0468306B2 JP H0468306 B2 JPH0468306 B2 JP H0468306B2 JP 23446285 A JP23446285 A JP 23446285A JP 23446285 A JP23446285 A JP 23446285A JP H0468306 B2 JPH0468306 B2 JP H0468306B2
- Authority
- JP
- Japan
- Prior art keywords
- mercaptoethyl
- methacrylamide
- present
- polymers
- bond
- 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
- UMPKRXLFDLLLHC-UHFFFAOYSA-N 2-methyl-n-(2-sulfanylethyl)prop-2-enamide Chemical compound CC(=C)C(=O)NCCS UMPKRXLFDLLLHC-UHFFFAOYSA-N 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- OGMADIBCHLQMIP-UHFFFAOYSA-N 2-aminoethanethiol;hydron;chloride Chemical compound Cl.NCCS OGMADIBCHLQMIP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229940097265 cysteamine hydrochloride Drugs 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229960003151 mercaptamine Drugs 0.000 description 2
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
〈産業上の利用分野〉
本発明は上記式（）で示される新規なＮ−
（２−メルカプトエチル）メタクリルアミドに関
する。
本発明によつて提供される上記式（）で示さ
れる新規なＮ−（２−メルカプトエチル）メタク
リルアミドはそれ自体で重合させるかまたは各種
のオレフイン性二重結合を有する化合物と共重合
させることによつて側鎖の末端にＳ−Ｈ基をもつ
ポリマーやオリゴマー、付加重合によつてスルフ
イド結合をもつポリマーやオリゴマーとなる可能
性をもつ。Ｓ−Ｈ基をもつオリゴマーは光、熱等
の種々の硬化プロセスが適用でき、たとえばエポ
キシ硬化剤等の用途がある。更にＳ−Ｈ基をもつ
ポリマーは金属との接着性の向上、キレート形成
能の向上が期待されている。また、Ｓ−Ｈ結合は
適当な酸化剤によつて容易に酸化され−Ｓ−Ｓ−
結合を形成し、架橋型となり、またその−Ｓ−Ｓ
−結合は適当な還元剤によつて容易に切断されＳ
−Ｈ結合にもどすことができることから、上記ポ
リマーは非架橋型と架橋型の相互変換が自由な特
異な機能をもつポリマーとなる。
このようなポリマーは、たとえばアミノ酸や核
酸のような生体物質の分離精製用ゲルや生分解性
や光分解性の良好な高分子材料等広い応用分野が
期待されている。
〈従来の技術〉
本発明による上記式（）で示されるＮ−（２
−メルカプトエチル）メタクリルアミドの製造方
法は今まで全く報告されていない。
〈本発明が解決しようとする問題点〉
本発明は、側鎖の末端にＳ−Ｈ基をもつポリマ
ーや上記のような特異な機能をもつ架橋型のポリ
マーとなり得るモノマー成分としてきわめて有用
な新規なＮ−（２−メルカプトエチル）メタクリ
ルアミドを提供することを目的とするものであ
る。
〈問題点を解決するための手段おび作用〉
本発明者等は、上記（）で示される新規なＮ
−（２−メルカプトエチル）メタクリルアミドの
製造方法を検討した結果、システアミンまたはシ
ステアミン塩酸塩もしくは硫酸塩とメタクリル酸
クロライドとの反応において、脱塩酸剤としてア
ルカリ金属酸化物の水溶液を用いる方法によつて
容易に製造できることを見出した。
なお、本発明化合物（）の製造方法が上記の
ものに限定されないことは勿論である。
以下、本発明における新規物質の製造方法を実
施例により具体的に説明し、得られた新規物質を
構造決定するための分析結果をも同時に示す。
実施例 １
撹拌機、温度計、ジムロート型冷却管および滴
下漏斗を備えた容量２のガラス製フラスコにシ
ステアミン塩酸塩25.0gr（0.220モル）を仕込み、
フラスコを冷却しながら10重量％水酸化ナトリウ
ム水溶液280.0grを徐々に加えながら系内を撹拌
し続けた。内温を10℃まで冷却した後、ジクロロ
メタン750ml、フエノチアジン25mgを加えた。内
温を20℃以下に保ちがらメタクリル酸クロライド
25.3gr（0.242モル）を75分間で滴下した。滴下終
了後、更に120分間同じ温度で撹拌した後、二層
分液した。得られた有機層中のジクロロメタンを
留去し、Ｎ−（２−メルカプトエチル）メタクリ
ルアミド31.4gr（収率98.3％）を得た。このもの
は更に蒸留によつて精製した。沸点106.5〜108.0
℃／２mmHg。
下記に得られたこの新規物質の構造決定のため
の分析結果を示した。
Γ沸 点 106.5〜108.0℃／２mmHg
Γ元素分析値
Ｃ(%) Ｈ(%) Ｎ(%) Ｓ(%)
理論値 49.63％ 7.64％ 9.65％ 22.08％
分析値 49.82％ 7.62％ 9.56％ 21.89％
Γ1H−NMR（溶媒：CDCl3、内部標準物質：
TMS）
δ＝7.65ppm（broad singlet 1HNH）
＝5.76ppm（singlet 1H
<Industrial Application Field> The present invention provides a novel N-
(2-Mercaptoethyl)methacrylamide. The novel N-(2-mercaptoethyl) methacrylamide represented by the above formula () provided by the present invention can be polymerized by itself or copolymerized with various compounds having an olefinic double bond. By polymerization, polymers and oligomers having an S--H group at the end of the side chain can be produced, and by addition polymerization, polymers and oligomers having a sulfide bond can be produced. Oligomers having S--H groups can be subjected to various curing processes such as light and heat, and are used, for example, as epoxy curing agents. Furthermore, polymers having S--H groups are expected to have improved adhesion to metals and improved chelate-forming ability. In addition, the S-H bond is easily oxidized by an appropriate oxidizing agent -S-S-
forms a bond, becomes a cross-linked type, and its -S-S
- The bond is easily cleaved by a suitable reducing agent.
Since it can be converted back into a -H bond, the above-mentioned polymer has a unique function of being free to mutually convert between a non-crosslinked type and a crosslinked type. Such polymers are expected to have a wide range of applications, such as gels for separating and purifying biological substances such as amino acids and nucleic acids, and polymeric materials with good biodegradability and photodegradability. <Prior art> N-(2
-Mercaptoethyl)methacrylamide has not been reported at all so far. <Problems to be Solved by the Present Invention> The present invention provides novel monomer components that are extremely useful as polymers having S-H groups at the terminals of side chains and cross-linked polymers having the above-mentioned unique functions. The object of the present invention is to provide N-(2-mercaptoethyl) methacrylamide. <Means and effects for solving the problems> The present inventors have proposed the novel N shown in () above.
- (2-Mercaptoethyl)methacrylamide was studied and found that a method using an aqueous solution of an alkali metal oxide as a dehydrochlorination agent in the reaction of cysteamine or cysteamine hydrochloride or sulfate with methacrylic acid chloride. It has been found that it can be easily manufactured. It goes without saying that the method for producing the compound () of the present invention is not limited to the above method. Hereinafter, the method for producing the novel substance according to the present invention will be specifically explained using Examples, and the analysis results for determining the structure of the obtained novel substance will also be shown at the same time. Example 1 A 2 capacity glass flask equipped with a stirrer, thermometer, Dimroth condenser and addition funnel was charged with 25.0 gr (0.220 mol) of cysteamine hydrochloride.
While cooling the flask, 280.0 gr of a 10% by weight aqueous sodium hydroxide solution was gradually added while stirring the system. After cooling the internal temperature to 10°C, 750 ml of dichloromethane and 25 mg of phenothiazine were added. Methacrylic acid chloride while keeping the internal temperature below 20℃
25.3 gr (0.242 mol) was added dropwise over 75 minutes. After the dropwise addition was completed, the mixture was stirred at the same temperature for an additional 120 minutes, and then separated into two layers. Dichloromethane in the obtained organic layer was distilled off to obtain 31.4 gr (yield 98.3%) of N-(2-mercaptoethyl)methacrylamide. This material was further purified by distillation. Boiling point 106.5-108.0
℃/2mmHg. The analytical results for determining the structure of this new substance obtained are shown below. Γ Boiling point 106.5-108.0℃/2mmHg Γ Elemental analysis value C(%) H(%) N(%) S(%) Theoretical value 49.63% 7.64% 9.65% 22.08% Analysis value 49.82% 7.62% 9.56% 21.89% Γ 1 H-NMR (solvent: CDCl 3 , internal standard:
TMS) δ = 7.65ppm (broad singlet 1HNH) = 5.76ppm (singlet 1H
【式】 ＝5.35ppm（singlet 1H【formula】 = 5.35ppm (singlet 1H
【式】
＝3.45ppm（quartet 2HＮ−CH2−）
＝2.70ppm（quartet 2H−CH2−Ｓ−）
＝1.96ppm（singlet 3H−CH3）
＝1.54ppm（triplet 1H−SH）
Γ13C−NMR（溶媒：CDCl3、内部標準物質：
CDCl3）
δ＝168.0ppm（Ｃ＝Ｏ）
＝138.9ppm（[Formula] = 3.45ppm (quartet 2HN−CH 2 −) = 2.70ppm (quartet 2H−CH 2 −S−) = 1.96ppm (singlet 3H−CH 3 ) = 1.54ppm (triplet 1H−SH) Γ 13 C− NMR (solvent: CDCl 3 , internal standard:
CDCl 3 ) δ = 168.0ppm (C = O) = 138.9ppm (
【式】）
＝118.9ppm（＝CH2）
＝42.0ppm（＝Ｎ−CH2−）
＝23.1ppm（−Ｓ−CH2−）
＝17.8ppm（−CH3）
ΓMS ｍ／ｅ＝145（M+）
ΓIR 3300cm-1（アミドνＮ−Ｈ）
2551cm-1（メルカプトν−Ｓ−Ｈ）
1669cm-1
1617cm-1（アミドνＣ＝Ｏ）
なお、この赤外線吸収スペクトルを第１図に示
す。
実施例 ２
システアミン塩酸塩の代わりにシステアミン
17.0grを用いた他は実施例１と同様に操作し、Ｎ
−（２−メルカプトエチル）メタクリルアミド
30.9gr（収率96.6％）を得た。このものは更に蒸
留によつて精製した。得られた新規物質の構造決
定のための分析結果は実施例１と同じであつた。[Formula]) = 118.9ppm (=CH 2 ) = 42.0ppm (=N-CH 2 -) = 23.1ppm (-S-CH 2 -) = 17.8ppm (-CH 3 ) ΓMS m/e = 145 (M + ) ΓIR 3300cm -1 (amide νN-H) 2551cm -1 (mercapto ν-S-H) 1669cm -1 1617cm -1 (amide νC=O) The infrared absorption spectrum is shown in FIG. Example 2 Cysteamine instead of cysteamine hydrochloride
The operation was the same as in Example 1 except that 17.0gr was used, and N
-(2-mercaptoethyl)methacrylamide
30.9gr (yield 96.6%) was obtained. This material was further purified by distillation. The analysis results for determining the structure of the obtained new substance were the same as in Example 1.
第１図は実施例１でえられたＮ−（２−メルカ
プトエチル）メタクリルアミドの赤外線吸収スペ
クトルである。
FIG. 1 is an infrared absorption spectrum of N-(2-mercaptoethyl)methacrylamide obtained in Example 1.
Claims (1)
トエチル）メタクリルアミド。 [Claims] 1. N-(2-mercaptoethyl)methacrylamide represented by the following formula ().
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23446285A JPS6296461A (en) | 1985-10-22 | 1985-10-22 | N-(2-mercaptethyl)methacrylamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23446285A JPS6296461A (en) | 1985-10-22 | 1985-10-22 | N-(2-mercaptethyl)methacrylamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6296461A JPS6296461A (en) | 1987-05-02 |
| JPH0468306B2 true JPH0468306B2 (en) | 1992-11-02 |
Family
ID=16971380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23446285A Granted JPS6296461A (en) | 1985-10-22 | 1985-10-22 | N-(2-mercaptethyl)methacrylamide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6296461A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6382547A (en) * | 1986-09-26 | 1988-04-13 | Nippon Telegr & Teleph Corp <Ntt> | Data management system for japanese dictionary |
-
1985
- 1985-10-22 JP JP23446285A patent/JPS6296461A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6296461A (en) | 1987-05-02 |
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