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

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: 12 November 2013
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 (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)

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.
- Density functional theory,
- Proton transfer,
- 2,4-Diisocyanatotoluene,
- Urethane formation
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