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炔键上的自由基加成反应,是合成许多重要不饱和的有机化合物的新方向,特别在綜合一系列碳杂原子键,如C-S键,C-Si,C-Ge,C-P,C-N,C-X键等方面,更具有独特的优越性。本文收集近年来散见于文献中的材料,系统讨论了在有机过氧化物,偶氮化合物、紫外光、X-射线、r-射线、等存在下,下述类型试剂,如:RSH(R为H,芳基、脂肪基等)Cl_3CX(X=Cl Br);X_3SiX’(X=X’=Cl,H;X=Cl、X=H;);Cl_3GeH;CH_3CHO;RR’PH(R=CNCH_2CH_2、R=R’=CNCH_2CH_2-);NH_2CHO;RSCl(Cl_3 C,C_6H_5);F_5SCl;(SCN)_2;N_2O_4;NO_2Cl;同炔键的加成反应。其中以硫醇研究得最广泛,而RR‘PH,X_3SiX’,NH_2COH,HGeCl_3、虽然只是开始研究,但在合成以及实际应用上更具有生命力。另外本文对炔键加成反应的一系列理论問题:立体化学、定位效应、加成反应活性、空间效应、等作了較多的討论、对于进一步认识自由基在加成反应中的规律性可能会有一点帮助。
The radical addition reaction on acetylenic bonds is a new direction for the synthesis of many important unsaturated organic compounds, especially in the synthesis of a series of carbon heteroatom bonds such as CS bond, C-Si, C-Ge, CP, CN, CX Keys, etc., but also has a unique superiority. This article collects materials that have been commonly found in the literature in recent years and systematically discuss the following types of agents in the presence of organic peroxides, azo compounds, UV light, X-rays, r-rays, etc., such as: RSH (R (X = X ’= Cl, H; X = Cl, X = H); Cl_3GeH; CH_3CHO; RR’PH (R = CNCH_2CH_2 , R = R ’= CNCH_2CH_2 -); NH_2CHO; RSCl (Cl_3C, C_6H_5); F_5SCl; (SCN) _2; N_2O_4; NO_2Cl; Thiols are the most widely studied among them, and RR’PH, X_3SiX ’, NH_2COH and HGeCl_3, though only just beginning to be studied, are more viable in synthesis and practical application. In addition, a series of theoretical problems of acetylenic addition reaction such as stereochemistry, orientation effect, addition reaction activity, space effect and so on are discussed in this paper. It is possible to further understand the regularity of free radical in addition reaction Will be a little help.