• 제목/요약/키워드: aminolysis

검색결과 98건 처리시간 0.034초

Curing Behavior of Epoxy Resins Using Aminolysis Products of Waste Polyurethanes as Hardeners

  • Lee, Dai-Soo;Hyun, Song-Won;Seo, Seung-Wook;Kim, Kyoung-Jong
    • 대한전자공학회:학술대회논문집
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    • 대한전자공학회 2001년도 The 6th International Symposium of East Asian Resources Recycling Technology
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    • pp.738-741
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    • 2001
  • We carried out aminolyses of various rigid polyurethane foams (PUFs) using diethylene triamine and studied application of the aminolysis products as hardners of epoxy resins. Diglycidyl ether of bisphenol A was used for the study on the curing behavior of epoxy resin with the aminolysis product employing differential scanning calorimeter. Curing reaction of the epoxy resin is generally known to be autocatalytic second order reaction. We found that the curing reaction of the epoxy resin with the aminolysis product of rigid PUF did not show autocatalytic characteristics but followed the n-th order kinetics. The activation energy of the curing reaction of the epoxy resin with the aminolysis product of rigid PUF made from sugar based polyol was slightly lower than that of the epoxy resin with aminolysis product of rigid with made from amine based polyol.

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Kinetics and Mechanism of the Aminolysis of Phenacyl Bromides in Acetonitrile. A Stepwise Mechanism with Bridged Transition State

  • Lee, Ik-Choon;Lee, Hai-Whang;Yu, Young-Kab
    • Bulletin of the Korean Chemical Society
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    • 제24권7호
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    • pp.993-998
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    • 2003
  • In the aminolysis of phenacyl bromides ($YC_6H_4COCH_2Br$) with benzylamines ($XC_6H_4CH_2NH_2$) in acetonitrile, the Bronsted βx (βnuc) values observed are rather low ( βX = 0.69-0.73). These values are similar to those (βx $^~_=$ 0.7) for other aminolysis reactions of phenacyl compounds with anilines and pyridines, but are much smaller than those ( βx = 1.1-2.5) for the aminolysis of esters with benzylamines which are believed to proceed stepwise with rate-limiting expulsion of the leaving group. The relative constancy of the βx values (βx $^~_=$ 0.7) irrespective of the amine, leaving group and solvent can be accounted for by a bridged type transition state in the rate-limiting expulsion of the leaving group. Thus the aminolysis of phenacyl derivatives are proposed to proceed stepwise through a zwitterionic tetrahedral intermediate ($T^{\pm}$), with rate-limiting expulsion of the leaving group from $T^{\pm}$. In the transition state, the amine is bridged between the carbonyl and α-carbons, which leads to negligible effect of amine on the leaving group expulsion rate.

3-Acyl-4(S)-isopropyl-1,3-Thiazolidine-2-Thione과 라세미아민의 입체선택적인 반응 (A Highly Stereoselective Reaction in Aminolysis of 3-Acyl-4-(S)-isopropyl-1,3-thiazolidine-2-thione with Racemic Amines)

  • 정태명;박기훈
    • 대한화학회지
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    • 제32권6호
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    • pp.588-592
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    • 1988
  • 키랄 보조제가 붙어있는 3-acyl-4(S)-isopropyl-1,3-thiazolidine-2-thione[4(S)-AITT]을 라세미 아민과 가아민 분해반응을 시켰을때 광학활성을 갖는 아미드(S-excess)와 아민(R-excess)이 얻어지는 입체 선택적인 반응이 관찰되었다. 이와같은 입체 선택적인 반응은 macrocyclic diamide, macrocylic sperimidine alkaloid, peptide 합성에 이용될 수 있다. 가아민 분해반응의 속도는 아민의 입체적인 영향을 많이 받았고 반응이 종료점은 노락색의 소실로 쉽게 관찰되었다. 4(S)-AITT는 4(S)-isopropyl-1,3-thiazolidine-2-thione과 carboxylic acid로부터 얻었다.

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Highly Efficient Microwave-assisted Aminolysis of Epoxides in Water

  • Zuo, Hua;Li, Zhu-Bo;Zhao, Bao-Xiang;Miao, Jun-Ying;Meng, Li-Juan;Jang, Ki-Wan;Ahn, Chul-Jin;Lee, Dong-Ha;Shin, Dong-Soo
    • Bulletin of the Korean Chemical Society
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    • 제32권spc8호
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    • pp.2965-2969
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    • 2011
  • Highly efficient and rapid aminolysis of epoxides with various amines in water under microwave irradiation in the absence of catalyst was developed. Chiral ${\beta}$-amino alcohols were formed in a short time with excellent yields.

Aminolysis of Aryl Thiol-2-furoates and Thiol-2-thiophenates in Acetonitrile

  • 오혁근;이준용;이익춘
    • Bulletin of the Korean Chemical Society
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    • 제19권11호
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    • pp.1198-1202
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    • 1998
  • Aminolysis of aryl thiol-2-furoates and thiol-2-thiophenates with benzylainines are investigated in acetonitrile at 50.0 ℃. Relatively large selectivity parameters, ρx(βx), ρz(βx) and ρxz (> 0) together with the valid reactivity-selectivity principle are consistent with a stepwise acyl transfer mechanism with rate-limiting expulsion of the leaving group, thiophenolate anion, from the tetrahedral intermediate, T±. The first-order kinetics with respect to the benzylamine concentration and the relatively large secondary kinetic isotope effect involving deuterated benzylamine nucleophiles suggest a four-center type transition state in which concurrent leaving group departure and proton transfer are involved.