4-CHLORO-3-METHYL-3-BUTENONITRILE AND RELATED COMPOUNDS
4-CHLORO-3-METHYL-3-BUTENONITRILE AND RELATED COMPOUNDS
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DOI：
10.1021/ja01209a025
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发表时间：
1946-01-01
影响因子：
15
通讯作者：
CLOKE, JB
中科院分区：
文献类型：
--
作者：
MOORADIAN, A;CLOKE, JB
几年前，该实验室的Stehr2发现氰化钠会与Eastman Kodak公司生产的1, 3-二氯异丁烷，8更好的名称1, 3-二氯-2-甲基丙烷，C1CH2CH(CH3) CH2C1(I)反应，得到γ-氯-d-甲基丁腈C1CH2CH(CH3) CH2CN和更高沸点的产物。他还发现氰化亚铜会与所谓的二氯异丁烷反应，生成三种意想不到的腈，即不同于γ-氯代-甲基丁腈的液体氯腈(A)、固体二氰化物(B)和液体二氰化物(C)。本文中描述的工作导致氯腈(A)被鉴定为4-氯-3-甲基-3-丁烯腈， C1CH= C-(CH3) CH2CN (VI)，不包括立体化学因素。现在很清楚，这种化合物 (VI) 源自氯化亚铜与 1, 3-二氯-2-甲基-1-丙烯 (C1CH= C (CH3) CH2Cl,(V)）的相互作用，后者是所使用的“1, 3-二氯异丁烷”的急剧沸腾馏分中的一种未怀疑的杂质。这些考虑导致了本文中描述的主要合成工作。1, 3-二氯-2-甲基-1-丙烯(V)。-化合物(V)由Pogorshelski首次描述。4最近，Rogers和Nelson6报道了通过热解l, 2, 制备由3-氯-2-氯甲基-1-丙烯、H2C= C (CH2Cl) 2 (XX), 6和(V)的顺式和反式异构体组成的混合物。 3-三氯-2-甲基丙烷(II) 也可通过异丁烯和甲基烯丙基氯7 的氯化以及1, 3-二氯-2-甲基-2-丙醇8 的脱水来制备。
Several years ago, Stehr2 working in this Labo-ratory found that sodium cyanide will react with Eastman Kodak Co. practical 1, 3-dichloroisobutane, 8 better named 1, 3-dichloro-2-methylpro-pane, C1CH2CH (CH3) CH2C1 (I) to give y-chloro-d-methylbutyromtrile C1CH2CH (CH3) CH2CN and a higher boiling product. He also found that cuprous cyanide will react with the so-called dichloroisobutane to give three unexpected nitriles, viz., a liquid chloronitrile (A) different from the y-chloro-fi-methylbutyronitrile, a solid dicyanide (B) and a liquid dicyanide (C).The work described in the present paper has led to the identification of the chloronitrile (A) as 4-chloro-3-methyl-3-butenonitrile, C1CH= C-(CH3) CH2CN (VI), exclusive of stereochemical considerations. It is now clear that this com-pound (VI) originated by the interaction of the cuprous chloride with l, 3-dichloro-2-methyl-l-propene, C1CH= C (CH3) CH2C1,(V), an unsus-pected impurity in the sharply boiling fraction of the ‘‘1, 3-dichloroisobutane” which was used. These considerations led to the mainsynthetic work described in this paper. 1, 3-Dichloro-2-methyl-1-propene (V).—Compound (V) was first described by Pogorshelski. 4 More recently, Rogers and Nelson6 reportedthe preparation of a mixture consisting of 3-chloro-2-chloromethyl-1-propene, H2C= C (CH2C1) 2 (XX), 6 and the cis and trans isomers of (V) by the pyrolysis of l, 2, 3-trichloro-2-methylpropane (II). The same product (V) has also been prepared by the chlorination of isobutylene and methallyl chloride7 and by the dehydration of 1, 3-dichloro-2-methyl-2-propanol. 8