Comparative Studies on the Reactions of Carbamyl and Thiocarbamyl Halides with NH3 in the Gas Phase and in Aqueous Solution: A Theoretical Study

被引：4

作者：

Kim, Chang Kon ^{[1
]}

Han, In Suk ^{[1
]}

Sohn, Chang Kook ^{[2
]}

Yu, Yu Hee ^{[2
]}

Su, Zhishan ^{[1
]}

Kim, Chan Kyung ^{[1
]}

机构：

[1] Inha Univ, Dept Chem, Inchon 402751, South Korea

[2] Chonnam Natl Univ, Dept Chem Educ, Kwangju 500757, South Korea

来源：

BULLETIN OF THE KOREAN CHEMICAL SOCIETY | 2012年 / 33卷 / 06期

关键词：

Aminolyses of carbamyl and thiocarbamyl halides; Stability of tetrahedral structures; Deformation energy; Double bond strength; ADDITION-ELIMINATION REACTIONS; PHENOLATE ION NUCLEOPHILES; POTENTIAL-ENERGY SURFACES; SINGLE TRANSITION-STATE; ACETYL GROUP-TRANSFER; ACYL GROUP-TRANSFER; BENZOYL CHLORIDES; S(N)2 MECHANISM; CARBON; DISPLACEMENT;

D O I：

10.5012/bkcs.2012.33.6.1955

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

In this work, the reactions of carbamyl and thiocarbamyl halides with NH3 were studied in the gas phase at the MP2(FC)/6-31+G(d) level of theory. Single point calculations were performed at the QCISD/6-311+G(3df,2p) to refine the energetics. The reaction mechanisms were also studied in aqueous solution. The structures were fully optimized at the CPCM-MP2(FC)/6-31+G(d) and refined by a single point CPCM-QCISD/6-311+G(3df,2p) calculations. The reaction mechanisms for the title compounds were compared with those for the acetyl and thioacetyl halides. The lower reactivity of carbamyl (and thiocarbamyl) groups was explained by comparing the C=O and C=S pi-bond strengths as well as resonance contributions in the ground state.

引用

页码：1955 / 1961

页数：7

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