ALUMINUM CHLORIDE-CATALYZED FORMATION OF 2,5-DICHLORO-2,5-DIMETHYLHEXANE FROM TERT-BUTYL CHLORIDE
ALUMINUM CHLORIDE-CATALYZED FORMATION OF 2,5-DICHLORO-2,5-DIMETHYLHEXANE FROM TERT-BUTYL CHLORIDE
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DOI：
10.1021/jo01113a011
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发表时间：
1956-01-01
影响因子：
3.6
通讯作者：
CONDON, FE
中科院分区：
文献类型：
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作者：
CONDON, FE
在1953年的工作中，Schlubach和Fran-zen1得到了2，5-二氯-2，5-二甲基己烷，这是一种结晶固体，约熔化，是氯化铁和乙炔在三氯化铝存在下在三氯化铝存在下反应的副产物，并试图将其从氯化铝和三氯化铁单独的室温反应中分离出来。几年前，在一项卤化铝催化的卤代烷和饱和烃之间的卤素和氢的交换的研究中，2有少量具有2，5-二氯-2，2，5-二氯-2的组成和性质的固体5-二甲基己烷是由氯化铝和丁基氯化铁在0附近反应得到的。3这项早期的工作现在已被重复，通过混合物熔点的方法，固体已被鉴定为2，5-二氯-2，5-二甲基己烷。产率约为转化后丁基氯化铁的1%。在氢氟酸存在的情况下，这种二氯化物与10-17%的丁基氯化亚铁一起由氯化戊铁生成。4由氯化亚铁和氯化铝生成的2，5-二氯-2，5-二甲基己烷，从巴克莱和贝茨最近的工作中获得了重要的意义，6他们表明，从氯化铝催化的苯、6 1，4-二铁丁基苯、6·7或1，3，5-三氟丁基苯6与丁基铁的烷基化反应中得到的高熔点碳氢化合物与L，L，4，4，5，5，8，8-八甲基-L，2，3，4，5，-6，7，7，8-八甲基-L相同氯化铝催化苯烷基化制备8-八氢菲(I)
In work described in 1953, Schlubach and Fran-zen1 obtained 2, 5-dichloro-2, 5-dimethylhexane, a crystalline solid melting about 64, as a by-product of the reaction of ferf-butyl chloride and acetylene in the presence of aluminum chloride and made an un-successful attempt to isolate it from a room temperature reaction of aluminum chloride with ferf-butyl chloride alone.Several years ago, during a study of the aluminum halide-catalyzed exchange of halogen and hydrogen between alkyl halides and saturated hydrocarbons, 2 a small amount of a solid having the composition and properties of 2, 5-dichIoro-2, 5-dimethylhexane was obtained from a reaction of aluminum chloride with ferf-butylchloride near 0. 3 This early work has now been repeated and the solid has been identified as 2, 5-dichloro-2, 5-dimethylhexane by means of a mixture melting point. The yield was about 1% of the ferf-butyl chloride con-verted. This dichloride is also produced, along with 10-17% of ferf-butyl chloride, from ferf-amyl chlo-ride in the presence of hydrofluoric acid. 4 The formation of even so little as 1% of 2, 5-diehloro-2, 5-dimethylhexane from ferf-butyl chloride and aluminum chloride gains significance from re-cent work of Barclay and Betts, 6 who showed that a high-melting hydrocarbon obtained in quantity from the aluminum chloride-catalyzed alkylation of benzene, 6 1, 4-di-ferf-butylbenzene, 6· 7 or 1, 3, 5-tri-ferf-butylbenzene6 with ferf-butylchloride is identical with l, l, 4, 4, 5, 5, 8, 8-octamethyl-l, 2, 3, 4, 5,-6, 7, 8-octahydroanthracene (I) prepared by the aluminum chloride-catalyzed alkylation of benzene