THE ADDITION OF HYDROGEN CHLORIDE TO ALIPHATIC ALLENIC HYDROCARBONS
THE ADDITION OF HYDROGEN CHLORIDE TO ALIPHATIC ALLENIC HYDROCARBONS
复制标题
DOI：
10.1021/ja01509a050
复制
发表时间：
1960-01-01
影响因子：
15
通讯作者：
JOHNSON, RN
中科院分区：
文献类型：
--
作者：
JACOBS, TL;JOHNSON, RN
氯化氢与异丙烯和1，2-丁二烯在-78℃的加成涉及对烯系的末端亚甲基的攻击。异戊烯需要三氯化铋等催化剂，生成2-氯丙烯和2，2-二氯丙烷的混合物。在加成过程中发生轻微的丙炔重排。1，2-丁二烯以87/13的比例生成反式和顺式-2-氯-2-丁烯的混合物；在此条件下也生成2-丁炔，但不加氯化氢。当体系的一端被双取代时，氯化氢加成到烯系中的方向颠倒了；进攻发生在中间碳。在-78位3-甲基-L，2-丁二烯生成3-氯-3-甲基-丁烯和L-氯-3-甲基-2-丁烯的混合物，比例为/36，也发生重排生成异戊二烯。结果表明，这些烯丙基氯化物在所用条件下不会重排。在相同的条件下，氯化氢与异戊二烯加成的速度更快，得到相同的产物，但比例为83/17。这表明，并不是所有的异戊二烯加成都是通过异戊二烯进行的，经典的碳正离子在两种情况下都应该是相同的，不可能是两种情况下的中间体。在这些氯化氢加成中，没有其他可能的加成产物；如果它们存在到0.1%的程度，就可以被检测到。2，4-二硝基苯磺酰氯与异丙烯加成的主要产物为2-(2，4-二硝基苯硫基)-3-氯-L-丙烯，与氯化氢的取向相反。这种试剂与1，2-丁二烯和3-甲基-L、2-丁二烯的混合物；纯加成产物并不是孤立的。不对称试剂HA对烯烃体系的离子加成还没有被广泛研究，甚至这种反应中的取向仍然存在一些不确定因素。在第一篇关于化合物2和脂肪族单取代烯烃的第一篇权威论文中，证明了在硫酸存在下，异烯本身水合生成丙酮。
The addition of hydrogen chloride to aliene and 1, 2-butadiene at—78 involves attack at a terminal methylene group of the allenic system. Aliene requires a catalyst such as bismuth trichloride and yields a mixture of 2-chloropropene and 2, 2-dichloropropane. Slight rearrangement to propyne occurs during the addition. 1, 2-Butadiene yields a mixture of transand cis-2-chloro-2-butene in the ratio 87/13; 2-butyne is also formed but does not add hydrogen chloride under the conditions. The orientation of addition of hydrogen chloride to the allenic system is reversed when one end of the system is disubstituted; attack occurs at the middle carbon. At—78 3-methyl-l, 2-butadiene gives a mixture of 3-chloro-3-methyl-lbutene and l-chloro-3-methyl-2-butene in the ratio 64/36; rearrangement to isoprene also occurs. It was shown that these allylic chlorides do not rearrange under the conditions employed. Hydrogen chloride addsto isoprene more rapidly under the same conditions to give the same products but the ratio is 83/17. This shows that not all of the addition to the aliene occurs through isopreneand that the classical carbonium ion, which should be the same from both hydrocarbons, cannot be the intermediate in both instances. In these hydrogen chlorideadditions other possible addition products were absent; they could have been detected if present to the extent of 0.1%. The principal product of the addition of 2, 4-dinitrobenzenesulfenyl chloride to aliene is 2-(2, 4-dinitrobenzenethio)-3-chloro-l-propene which represents the opposite orientation to that observed with hydrogen chloride. This reagent gives mixtures with 1, 2-butadiene and 3-methyl-l, 2-butadiene; pure addition products were not isolated.The ionic addition of unsymmetrical reagents HA to allenic systems has not been studied extensively and some uncertainty remains about even the orientation in such reactions. Hydration of aliene itself in the presence of sulfuric acid was shown to yield acetone in the first definitive paper on this compound2 and aliphatic monosubstituted allenes