Unexpected dealkylation of Bischler-Napieralski cyclization of 2-(3,4-dimethoxy-2- nitro-phenyl)-N-[2-(3,4-dimethoxyphenyl) ethyl]-N-[(S)-1-phenyl-ethyl] acetamide 3 was reported. The electronic effect of the substitu...Unexpected dealkylation of Bischler-Napieralski cyclization of 2-(3,4-dimethoxy-2- nitro-phenyl)-N-[2-(3,4-dimethoxyphenyl) ethyl]-N-[(S)-1-phenyl-ethyl] acetamide 3 was reported. The electronic effect of the substituent at 2-position of C ring was also discussed.展开更多
Reactions of C60 with Si(CH_3)_nCl_(4-n) (n=2,3)in the ion source of the mass spectrometer have been studied.The corresponding adduct ions[C60Si(CH_3)_mCl3_(-m)]^+(m=1,2,3),[C60SiCl]^+ and[C60CH_3]^+ were observed and...Reactions of C60 with Si(CH_3)_nCl_(4-n) (n=2,3)in the ion source of the mass spectrometer have been studied.The corresponding adduct ions[C60Si(CH_3)_mCl3_(-m)]^+(m=1,2,3),[C60SiCl]^+ and[C60CH_3]^+ were observed and their possible structures were discussed.The results indicated that C60 is very reactive to electrophiles in the gas phase.展开更多
The reaction mechanisms between formaldehyde and MoOx(x = 1, 2, 3) have been studied thoroughly in this paper. Five reaction pathways were found in three reactions(reactions Ⅰ to Ⅲ) through studying the mechanisms o...The reaction mechanisms between formaldehyde and MoOx(x = 1, 2, 3) have been studied thoroughly in this paper. Five reaction pathways were found in three reactions(reactions Ⅰ to Ⅲ) through studying the mechanisms of MoOx(x = 1, 2, 3) catalyzing formaldehyde. Different products were obtained from three reactions. Of all three reactions, the barrier energy of Route ⅡA is the lowest(4.70 kcal/mol), which means in MoOx(x = 1, 2, 3), MoO2 has the best catalytic effect. Compared with other similar non-toxic treatments of formaldehyde, our barrier energy is the lowest. In this research, there was no good leaving group of the compound, so the mechanisms are addition reaction. We speculate that there must be an addition reaction to the more complex reactions to molybdenum oxides and aldehydes. As a chemical reagent for removing formaldehyde, it only absorbs formaldehyde and does not emit other toxic substances outward. Molybdenum oxides retain its original structures of the final products, which means it has excellent stability in the reaction of MoOx(x = 1, 2, 3) + HCHO. The mechanisms of all three reactions are addition reactions, but they are entirely different. As the number of oxygen atoms increases, the reaction mechanisms become simpler.展开更多
The α-hydroxy-acid gas-phase elimination process has been studied theoretically by HF/3-21G.The calculated results can be summed up as follows:(1) The elimination process is a stepwise reaction.In the first step,a 3-...The α-hydroxy-acid gas-phase elimination process has been studied theoretically by HF/3-21G.The calculated results can be summed up as follows:(1) The elimination process is a stepwise reaction.In the first step,a 3-membered ring intermediate is formed via a 5-membered ring transition state;while the product is formed in the second step via a 3-membered ring transition state.(2) The obtained results of the substituent effect show that the increase of electronic donation of the alkyl groups is favorable for the reaction.Other substituents which show the electron-withdrawing inductive effect (e.g.-Cl,-CN,-CF3) are unfavorable for this process.展开更多
The reaction of HFe_2Co(CO)_9(μ_3-S)with(η~5-C_5H_4CH_3)Mo(CO)_3CI has been carried out in refluxing tetrahydrofuran(THF)to give out heterometallic trinuclear clusters(η~5-C_5H_4CH_3)MoFeCo- (CO)_8(μ_3-S)and(η~5-...The reaction of HFe_2Co(CO)_9(μ_3-S)with(η~5-C_5H_4CH_3)Mo(CO)_3CI has been carried out in refluxing tetrahydrofuran(THF)to give out heterometallic trinuclear clusters(η~5-C_5H_4CH_3)MoFeCo- (CO)_8(μ_3-S)and(η~5-C_5H_4CH_3)_2Mo_2Fe(CO)_7(μ_3-S)by electrophilic addition-elimination reaction.Howev- er,(η~5-C_5H_4CH_3)Fe(CO)_2Cl reacted with HFe_2Co(CO)_9(μ_3-S)at room temperature to yield a tetranuclear cluster(η~5-C_5H_4CH_3)Fe_3Co(CO)_(11)(μ_4-S).The μ_4-S cluster could be used as an intermediate in confirmation of the mechanism of the electrophilic addition-elimination reaction.The syntheses,characterizations and X-ray crystal structures of these clusters are reported herein as well as the discussion on the reaction mecha- nism.展开更多
文摘Unexpected dealkylation of Bischler-Napieralski cyclization of 2-(3,4-dimethoxy-2- nitro-phenyl)-N-[2-(3,4-dimethoxyphenyl) ethyl]-N-[(S)-1-phenyl-ethyl] acetamide 3 was reported. The electronic effect of the substituent at 2-position of C ring was also discussed.
文摘Reactions of C60 with Si(CH_3)_nCl_(4-n) (n=2,3)in the ion source of the mass spectrometer have been studied.The corresponding adduct ions[C60Si(CH_3)_mCl3_(-m)]^+(m=1,2,3),[C60SiCl]^+ and[C60CH_3]^+ were observed and their possible structures were discussed.The results indicated that C60 is very reactive to electrophiles in the gas phase.
基金supported by the school fund of Shanxi Institute of technology(201605001,20180010012)the 2016 annual major science and technology projects of Shanxi Province(MC2016-02/5)+2 种基金the Shanxi Advantageous and Characteristic Disciplines of “Project 1331”the National Natural Science Foundation of China(No.21373025)the major project of Tangshan Normal College(Nos.2017B01 and 2017B02)
文摘The reaction mechanisms between formaldehyde and MoOx(x = 1, 2, 3) have been studied thoroughly in this paper. Five reaction pathways were found in three reactions(reactions Ⅰ to Ⅲ) through studying the mechanisms of MoOx(x = 1, 2, 3) catalyzing formaldehyde. Different products were obtained from three reactions. Of all three reactions, the barrier energy of Route ⅡA is the lowest(4.70 kcal/mol), which means in MoOx(x = 1, 2, 3), MoO2 has the best catalytic effect. Compared with other similar non-toxic treatments of formaldehyde, our barrier energy is the lowest. In this research, there was no good leaving group of the compound, so the mechanisms are addition reaction. We speculate that there must be an addition reaction to the more complex reactions to molybdenum oxides and aldehydes. As a chemical reagent for removing formaldehyde, it only absorbs formaldehyde and does not emit other toxic substances outward. Molybdenum oxides retain its original structures of the final products, which means it has excellent stability in the reaction of MoOx(x = 1, 2, 3) + HCHO. The mechanisms of all three reactions are addition reactions, but they are entirely different. As the number of oxygen atoms increases, the reaction mechanisms become simpler.
文摘The α-hydroxy-acid gas-phase elimination process has been studied theoretically by HF/3-21G.The calculated results can be summed up as follows:(1) The elimination process is a stepwise reaction.In the first step,a 3-membered ring intermediate is formed via a 5-membered ring transition state;while the product is formed in the second step via a 3-membered ring transition state.(2) The obtained results of the substituent effect show that the increase of electronic donation of the alkyl groups is favorable for the reaction.Other substituents which show the electron-withdrawing inductive effect (e.g.-Cl,-CN,-CF3) are unfavorable for this process.
文摘The reaction of HFe_2Co(CO)_9(μ_3-S)with(η~5-C_5H_4CH_3)Mo(CO)_3CI has been carried out in refluxing tetrahydrofuran(THF)to give out heterometallic trinuclear clusters(η~5-C_5H_4CH_3)MoFeCo- (CO)_8(μ_3-S)and(η~5-C_5H_4CH_3)_2Mo_2Fe(CO)_7(μ_3-S)by electrophilic addition-elimination reaction.Howev- er,(η~5-C_5H_4CH_3)Fe(CO)_2Cl reacted with HFe_2Co(CO)_9(μ_3-S)at room temperature to yield a tetranuclear cluster(η~5-C_5H_4CH_3)Fe_3Co(CO)_(11)(μ_4-S).The μ_4-S cluster could be used as an intermediate in confirmation of the mechanism of the electrophilic addition-elimination reaction.The syntheses,characterizations and X-ray crystal structures of these clusters are reported herein as well as the discussion on the reaction mecha- nism.
