DFT Study of the Proton Transfer in the Urethane Formation between 2,4-Diisocyanatotoluene and Methanol
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<jats:title>Abstract</jats:title> <jats:p>The proton transfer effects on the urethane formation between 2,4-diisocyanatotoluene (2,4-TDI) and methanol was investigated by using density functional theory (DFT) calculations at the B3LYP/6-311G(d,p) level. The calculations show that the direct addition of methanol to 2,4-TDI follows a concerted path with an energy barrier of 31.71 kcal mol−1 and an activation free energy of 39.32 kcal mol−1. With the methanol, diphenylamine, and methyl N-methylcarbamate molecule serving as a proton transporter or a reactive catalyst, the energy barriers were significantly reduced to 12.28, 17.93, and 20.13 kcal mol−1 respectively, and the free energies of activation were lowered to 25.22, 32.54, and 36.86 kcal mol−1 correspondingly. The results indicate that the labile hydrogen-containing compounds play a key role in accelerating the reaction rate and the proton transfer. In the case of one extra methanol molecule serving as a proton transporter, the energy barrier was estimated to be 12.28 kcal mol−1, which is in good agreement with the experimental activation energy between 8.6 and 12.0 kcal mol−1. The urethane formation between 2,4-TDI and methanol is more likely a third-order reaction with respect to the initial reactants.</jats:p>
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- Bulletin of the Chemical Society of Japan
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Bulletin of the Chemical Society of Japan 86 (2), 255-265, 2013-02
Tokyo : Chemical Society of Japan
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詳細情報 詳細情報について
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- CRID
- 1520573331018775424
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- NII論文ID
- 10031155746
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- NII書誌ID
- AA00580132
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- ISSN
- 00092673
- 13480634
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- NDL書誌ID
- 024257851
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- 本文言語コード
- en
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- NDL 雑誌分類
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- ZP1(科学技術--化学・化学工業)
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- データソース種別
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- NDL
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