Chun-yuan Hou, Xiao-fang Chen, Jian-yong Liu, Wei-peng Lai, Bo-zhou Wang. DFT Study of Benzofuroxan Synthesis Mechanism from 2-Nitroaniline via Sodium Hypochlorite[J]. Chinese Journal of Chemical Physics , 2010, 23(4): 387-392. doi: 10.1088/1674-0068/23/04/387-392
Citation: Chun-yuan Hou, Xiao-fang Chen, Jian-yong Liu, Wei-peng Lai, Bo-zhou Wang. DFT Study of Benzofuroxan Synthesis Mechanism from 2-Nitroaniline via Sodium Hypochlorite[J]. Chinese Journal of Chemical Physics , 2010, 23(4): 387-392. doi: 10.1088/1674-0068/23/04/387-392

DFT Study of Benzofuroxan Synthesis Mechanism from 2-Nitroaniline via Sodium Hypochlorite

doi: 10.1088/1674-0068/23/04/387-392
  • Received Date: 2010-01-01
  • The oxidative cyclization reaction of 2-nitroaniline via sodium hypochlorite to yield benzo-furoxan is investigated by the hybrid density functional theory B3LYP/6-31G(d,p) method. Solvent effects are estimated with the polarizable continuum model to optimize structures. The title reaction is predicted to undergo two pathways, each of which is a stepwise process.Path A includes four steps, namely oxidization, H-attack, hydrolysis, and cyclization. Path B involves the nucleophilic attack of OH- to the H atom of the N-H bond and the proton transfer to the N atom of amino group leading to the cleavage of the N-H single bond in the amino group. The calculated results indicate that path A is favored mechanism for the title reaction. Furthermore, it is rational for one water molecule serving as a bridge to assist in the hydrolysis step of Path A and our calculations exhibit that this process is the rate-determining step.
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DFT Study of Benzofuroxan Synthesis Mechanism from 2-Nitroaniline via Sodium Hypochlorite

doi: 10.1088/1674-0068/23/04/387-392

Abstract: The oxidative cyclization reaction of 2-nitroaniline via sodium hypochlorite to yield benzo-furoxan is investigated by the hybrid density functional theory B3LYP/6-31G(d,p) method. Solvent effects are estimated with the polarizable continuum model to optimize structures. The title reaction is predicted to undergo two pathways, each of which is a stepwise process.Path A includes four steps, namely oxidization, H-attack, hydrolysis, and cyclization. Path B involves the nucleophilic attack of OH- to the H atom of the N-H bond and the proton transfer to the N atom of amino group leading to the cleavage of the N-H single bond in the amino group. The calculated results indicate that path A is favored mechanism for the title reaction. Furthermore, it is rational for one water molecule serving as a bridge to assist in the hydrolysis step of Path A and our calculations exhibit that this process is the rate-determining step.

Chun-yuan Hou, Xiao-fang Chen, Jian-yong Liu, Wei-peng Lai, Bo-zhou Wang. DFT Study of Benzofuroxan Synthesis Mechanism from 2-Nitroaniline via Sodium Hypochlorite[J]. Chinese Journal of Chemical Physics , 2010, 23(4): 387-392. doi: 10.1088/1674-0068/23/04/387-392
Citation: Chun-yuan Hou, Xiao-fang Chen, Jian-yong Liu, Wei-peng Lai, Bo-zhou Wang. DFT Study of Benzofuroxan Synthesis Mechanism from 2-Nitroaniline via Sodium Hypochlorite[J]. Chinese Journal of Chemical Physics , 2010, 23(4): 387-392. doi: 10.1088/1674-0068/23/04/387-392

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