Glufosinate-ammonium is a highly efficient, non-selective herbicide. The former synthesis schemes of glufosinate-ammonium were introduced and analyzed, the main of which are Arbuzov synthesis method, method under cata...Glufosinate-ammonium is a highly efficient, non-selective herbicide. The former synthesis schemes of glufosinate-ammonium were introduced and analyzed, the main of which are Arbuzov synthesis method, method under catalyzer and high pressure, targeted method under low temperature, Gabriel synthesis method, Zelinsky-Strecher synthetic method, synthetic method with chiral-synthon, and several special methods such as with enzyme or stereochemistry. Based on the structure and synthesis characteristic of glufosinate-ammonium as well as Arbuzov reaction and Michael reaction, a novel and reasonable scheme, which was named Arbuzov-Michael method, was put forward as the more economical one with simpler raw reagents and less waste.展开更多
The mechanisms of gold（I）-catalyzed cycloaddition of 1-（1-alkynyl） cyclopropyl ketones with nucleophiles have been investi- gated using density functional theory calculations at the B3LYP/6-31G （d, p） level of t...The mechanisms of gold（I）-catalyzed cycloaddition of 1-（1-alkynyl） cyclopropyl ketones with nucleophiles have been investi- gated using density functional theory calculations at the B3LYP/6-31G （d, p） level of theory. A polarizable continuum model （PCM） has been established in order to evaluate the effects of solvents on the reactions. The results of the calculations indicate that the first step of the catalytic cycle is the cyclization of the carbonyl oxygen onto the triple bond which forms a new and stable resonance structure of an oxonium ion and a carbocation intermediate. The subsequent ring expansion step results in the formation of the final product and regeneration of the catalyst. Furthermore, the regioselectivity and effect of substituents has been discussed, including an analysis of energy, bond length, and natural bond orbital （NBO） charge distributions in the rate-determining step. Our computational results are consistent with earlier experimental observations.展开更多
文摘Glufosinate-ammonium is a highly efficient, non-selective herbicide. The former synthesis schemes of glufosinate-ammonium were introduced and analyzed, the main of which are Arbuzov synthesis method, method under catalyzer and high pressure, targeted method under low temperature, Gabriel synthesis method, Zelinsky-Strecher synthetic method, synthetic method with chiral-synthon, and several special methods such as with enzyme or stereochemistry. Based on the structure and synthesis characteristic of glufosinate-ammonium as well as Arbuzov reaction and Michael reaction, a novel and reasonable scheme, which was named Arbuzov-Michael method, was put forward as the more economical one with simpler raw reagents and less waste.
基金supported by the Natural Science Foundation of Gansu Province (10710RJZA114)
文摘The mechanisms of gold（I）-catalyzed cycloaddition of 1-（1-alkynyl） cyclopropyl ketones with nucleophiles have been investi- gated using density functional theory calculations at the B3LYP/6-31G （d, p） level of theory. A polarizable continuum model （PCM） has been established in order to evaluate the effects of solvents on the reactions. The results of the calculations indicate that the first step of the catalytic cycle is the cyclization of the carbonyl oxygen onto the triple bond which forms a new and stable resonance structure of an oxonium ion and a carbocation intermediate. The subsequent ring expansion step results in the formation of the final product and regeneration of the catalyst. Furthermore, the regioselectivity and effect of substituents has been discussed, including an analysis of energy, bond length, and natural bond orbital （NBO） charge distributions in the rate-determining step. Our computational results are consistent with earlier experimental observations.
