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1.在苯甲酰过氧化物存在下,2,3-二甲基丁烯-2容易与N-溴代丁二酰亚胺起反应,主要形成取代产物。当烯烴与溴化剂的用量为1:1克分子比例时,反应产物为1-溴代-2,3-二甲基丁烯-2(Ⅰ)(58％),2,3-二溴代-2,3-二甲基丁烷(Ⅱ)(2％)及順式-与反式-1,4-二溴代-2,3-二甲基丁烯-2(Ⅲ)的混合物(23％)。当烯烴与溴化剂的用量为1:2克分子比例时,反应产物为Ⅰ(1％),Ⅲ(66％)及一“三溴化物”,可能为1,4-二溴代-2-甲基-3-溴甲基丁烯-2(Ⅸ)(23％)。 2.Ⅲ在与溴作用时,除形成1,2,3,4-四溴代-2,3-二甲基丁烷(Ⅵ)外,还导致形成一个新的“四溴化物”,可能为四溴甲基乙烯(Ⅴ)。Ⅴ为一个新的化合物,它与三甲胺,吡啶,硫脲作用所形成的衍生物(Ⅵ),(Ⅶ),(Ⅷ)亦經制备。 3.2.3-二甲基丁烯-2与四倍克分子N-溴代丁二酰亚胺在苯甲酰过氧化物存在下作用时可直接得到Ⅴ,产率47％。Ⅲ(反式異构体)与二倍克分子N-溴代丁二酰亚胺在同样条件下作用时亦得到Ⅴ,产率70％。在上述的溴化反应中,都没有观察到有双键的移位作用发生。 4.从苯甲酰过氧化物引发的溴化反应产物中,曾經分离出苯甲酸,苯甲酰过氧化物在2,3-二甲基丁烯-2中分解时,亦有苯甲酸形成。根据这些結果,作者提出由C_6H_5COO·夺取烯烴分子中∝-甲基上的氫原子所引发的溴化反应的鏈式历程。本文中所报告的臭氧分解实驗系在中国科学院应用化学研究所进行的,作者謹表謝意。碳氫分析及一部分氮、溴的分析系請中国科学院有机化学研究所代做,一部分氮、溴的分析系由本系赵尊同志所做,均此致謝。
1. In the presence of benzoyl peroxide, 2,3-dimethylbutene-2 readily reacts with N-bromosuccinimide to form primarily the substitution product. The reaction product was 1-bromo-2,3-dimethylbutene-2 (I) (58%) when 2,3-dibromo-2-butene was used in the molar ratio of 1: 2,3-dimethylbutane (II) (2%) and a mixture of cis- and trans-1,4-dibromo-2,3-dimethylbutene-2 (twenty three%). The reaction products were Ⅰ (1%), Ⅲ (66%) and a “tribromide” when the amount of alkene and brominating agent was 1: 2 mole ratio, probably 1,4-dibromo- Methyl-3-bromomethylbutene-2 (IX) (23%). In addition to the formation of 1,2,3,4-tetrabromo-2,3-dimethylbutane (VI), III causes a new “tetrabromide” formation when it is reacted with bromine, possibly Is tetrabromomethyl ethylene (V). V is a new compound. The derivatives (VI), (VII) and (VIII) formed by the interaction with trimethylamine, pyridine and thiourea are also prepared. 3.2.3-dimethyl butene-2 and four times the molecular weight of N-bromosuccinimide benzoyl peroxide in the presence of the role can be directly obtained Ⅴ, the yield of 47%. Ⅲ (trans isomer) and double the molecular N-bromosuccinimide also under the same conditions V, the yield of 70%. In the above bromination reaction, no double bond shift was observed. 4. From benzoyl peroxide induced bromination reaction products, once isolated benzoic acid, benzoyl peroxide decomposition in 2,3-dimethylbutene-2, but also benzoic acid . Based on these results, the authors propose a chain reaction of the bromination reaction initiated by C 6 H 5 COO · to sequester the hydrogen atoms of α-methyl groups in alkene molecules. The ozone decomposition experiments reported in this article were conducted at the Institute of Applied Chemistry, Chinese Academy of Sciences, and the authors would like to thank them. Hydrocarbon analysis and part of the analysis of nitrogen and bromine Department of Organic Chemistry, Chinese Academy of Sciences, please do, some of the analysis of nitrogen, bromine by the Department of Comrade Zhao Zun do, are grateful.