甲苯-2,4-二异氰酸酯与仲胺类化合物反应中的质子转移过程

引用本文: 王晓轩, 胡伟, 贵大勇, 池旭辉, 王明良, 田德余, 刘剑洪, 马新刚, 庞爱民. 甲苯-2,4-二异氰酸酯与仲胺类化合物反应中的质子转移过程[J]. 物理化学学报, 2014, 30(1): 34-42. doi: 10.3866/PKU.WHXB201311121 shu

Citation: WANG Xiao-Xuan, HU Wei, GUI Da-Yong, CHI Xu-Hui, WANG Ming-Liang, TIAN De-Yu, LIU Jian-Hong, MA Xin-Gang, PANG Ai-Min. Proton Transfer in Reaction between 2,4-Diisocyanatotoluene and Amine Compounds[J]. Acta Physico-Chimica Sinica, 2014, 30(1): 34-42. doi: 10.3866/PKU.WHXB201311121 shu

甲苯-2,4-二异氰酸酯与仲胺类化合物反应中的质子转移过程

王晓轩 ^1, ,
胡伟 ^2, ,
贵大勇 ^1, ,
池旭辉 ^2, ,
王明良 ^1, ,
田德余 ^1, ,
刘剑洪 ^1, ,
马新刚 ^2, ,
庞爱民 ^2,

基金项目:
国防973 (613142)，国家自然科学基金(20673073)，深圳市功能高分子重点实验室开放基金(FP20130007)资助项目 (613142)，国家自然科学基金(20673073)，深圳市功能高分子重点实验室开放基金(FP20130007)

摘要:

采用密度泛函理论B3LYP/6-31+G(d，p)方法研究了甲苯-2，4-二异氰酸酯(2，4-TDI)与仲胺类化合物反应过程中的质子转移效应. 研究发现甲醇分子对反应有显著的催化效应，可使反应能垒大幅降低，这表明含活泼氢的化合物会加速质子转移过程，从而加快反应速率. 2，4-TDI与甲基-N-甲基氨基甲酸酯的催化加成反应为一步反应，其反应过渡态呈六元环结构；而2，4-TDI与N-甲基对硝基苯胺、二苯胺、1，2-二氢-2，2，4-三甲基喹啉等芳香胺类化合物的催化加成反应经历了两步反应，其中第一步为速率控制步骤. 研究表明，在与2，4-TDI的反应中，芳胺化合物的活性高于甲基-N-甲基氨基甲酸酯的活性，计算的反应活性顺序与实验结果一致.

关键词:

English

Proton Transfer in Reaction between 2,4-Diisocyanatotoluene and Amine Compounds

1.
1 College of Chemistry and Chemical Engineering, Shenzhen University, Shenzhen 518060, Guangdong Province, P. R. China;
2 Hubei Institute of Aerospace Chemotechnology, Xiangfan 441003, Hubei Province, P. R. China
Received Date: 15 July 2013
Available Online: 01 January 2014
Fund Project:
国防973 (613142)，国家自然科学基金(20673073)，深圳市功能高分子重点实验室开放基金(FP20130007)资助项目

Abstract:

The effects of proton transfer on the reaction between 2,4-diisocyanatotoluene (2,4-TDI) and active-hydrogen-containing amine compounds were calculated using density functional theory (DFT) at the B3LYP/6-31+G(d, p) level. The energy barriers are significantly reduced when a methanol molecule serves as a proton transporter or a reactive catalyst, indicating that the labile hydrogen-containing compound plays a key role in accelerating the reaction rate and proton transfer. The catalytic addition of 2,4-TDI and methyl N-methylcarbamate follows a one-step mechanism, with a transition state characterized by a sixmembered ring. However, the catalytic additions of 2,4-TDI and aromatic amines such as N-methyl-p-nitroaniline, diphenylamine, and 1,2-dihydro-2,2,4-trimethylquinoline involve two steps, with the first step as the rate-limiting step. The reactions between 2,4-TDI and aromatic amines have lower energy barriers than that between 2,4-TDI and methyl N-methylcarbamate. The aromatic amines are more active than methyl N-methylcarbamate in the reaction with 2,4-TDI, which is in a od agreement with experimental results.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

甲苯-2,4-二异氰酸酯与仲胺类化合物反应中的质子转移过程

English

Proton Transfer in Reaction between 2,4-Diisocyanatotoluene and Amine Compounds

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CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

甲苯-2,4-二异氰酸酯与仲胺类化合物反应中的质子转移过程

English

Proton Transfer in Reaction between 2,4-Diisocyanatotoluene and Amine Compounds

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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