西南师范大学学报（自然科学版）
西南師範大學學報（自然科學版）
서남사범대학학보（자연과학판）
JOURNAL OF SOUTHWEST CHINA NORMAL UNIVERSITY
2010年
2期
45-51
,共7页
胺类物质%炔酯类物质%CuBr催化剂%密度泛函理论
胺類物質%炔酯類物質%CuBr催化劑%密度汎函理論
알류물질%결지류물질%CuBr최화제%밀도범함이론
amine derivatives%alkynyl ester derivatives%CuBr-catalyst%density functional theory
采用密度泛函理论的B3LYP方法对CuBr(溴化亚铜)催化合成γ,δ-炔基-β-氨基酸衍生物的机理进行了理论计算,得到3条反应路线.对所有过渡态、中间体和产物做了频率分析.通过IRC扫描确认了重要过渡态的正确性.分析了反应中各物种的电荷分布、重要化学键的成键临界点和成环临界点的电荷密度.计算表明在气相和液相下,优势路线的决速步都是胺与炔酯的结合过程;建议的机理能合理解释所有实验现象.
採用密度汎函理論的B3LYP方法對CuBr(溴化亞銅)催化閤成γ,δ-炔基-β-氨基痠衍生物的機理進行瞭理論計算,得到3條反應路線.對所有過渡態、中間體和產物做瞭頻率分析.通過IRC掃描確認瞭重要過渡態的正確性.分析瞭反應中各物種的電荷分佈、重要化學鍵的成鍵臨界點和成環臨界點的電荷密度.計算錶明在氣相和液相下,優勢路線的決速步都是胺與炔酯的結閤過程;建議的機理能閤理解釋所有實驗現象.
채용밀도범함이론적B3LYP방법대CuBr(추화아동)최화합성γ,δ-결기-β-안기산연생물적궤리진행료이론계산,득도3조반응로선.대소유과도태、중간체화산물주료빈솔분석.통과IRC소묘학인료중요과도태적정학성.분석료반응중각물충적전하분포、중요화학건적성건림계점화성배림계점적전하밀도.계산표명재기상화액상하,우세로선적결속보도시알여결지적결합과정;건의적궤리능합리해석소유실험현상.
The mechanism of the synthesis of γ,δ - alkynyl -β - amino acid derivatives is investigated employing the density functional theory (the B3LYP functional is used), and three reaction pathways are suggested. The frequency analysis is performed for all the transition states, intermediates and products. The geometries of the important transition states are confirmed by the IRC scanning. In order to make clear the reaction mechanism, the charge distribution of all species and the electronic densities of the bond critical points (BCP) and the ring critical points (RCP) for the key bonds are calculated and discussed. The results indicate that in the gas phase and the liquid phase, the rate-determining steps of the dominant pathways are the reaction between amine and alkynyl ester. The suggested mechanism can explain reasonably all experimental observations.
