Polymerization of aromatic nuclei. XII. Oligomerization of halobenzenes by aluminum chloride‐cupric chloride
Polymerization of aromatic nuclei. XII. Oligomerization of halobenzenes by aluminum chloride‐cupric chloride
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DOI：
10.1002/pol.1967.150050501
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发表时间：
1967-05
期刊：
影响因子：
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通讯作者：
P. Kovacic;J. Uchic;L. Hsu
中科院分区：
文献类型：
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作者：
P. Kovacic;J. Uchic;L. Hsu
氯化铝-氯化铜聚合氯苯和氟苯产生高度着色的低聚物。氯苯在芳香族/催化剂/氧化剂的摩尔比为6/1/0.5的标准条件下，在60℃下反应1小时。，以14%的收率获得红色固体。有关结构的证据来自元素分析、红外和紫外光谱、脱氯、氧化、溶解度、分子量和颜色。数据表明，主链由无多苯基结构组成，氯原子位于4位。多核区可能是结构的一部分。分子量数据表明，每条链平均有10-12个单位。氟苯偶联产物在大多数方面与氯苯低聚物非常相似。与氯苯的情况相反，有证据表明，在某种程度上，通过对氟的正极攻击发生了繁殖。溴苯显然是通过歧化反应生成溴化对多苯，然后苯作为单体发挥作用。提出了核耦合的氧化阳离子机制（σ聚合）。
Polymerization of chloro‐ and fluorobenzene by aluminum chloride‐cupric chloride produced highly colored oligomers. Chlorobenzene reacted under the standard conditions, i.e., 6/1/0.5 (molar ratio) of aromatic/catalyst/oxidant at 60°C. for 1 hr., to give a red solid in 14% yield. Evidence concerning the structure was obtained from elemental analyses, infrared and ultraviolet spectra, dechlorination, oxidation, solubility, molecular weight, and color. The data indicate that the backbone chain consists of ano‐polyphenyl structure with chlorine atoms situated at the 4‐positions. Polynuclear regions presumably comprise part of the structure. Molecular weight data pointed to an average of 10–12 units per chain. The coupled product from fluorobenzene was very similar to the chlorobenzene oligomer in most respects. In contrast to the chlorobenzene case, there was evidence of propagation occurring to some extent by attackorthoto the fluorine. Bromobenzene produced brominatedp‐polyphenyl apparently by disproportionation to benzene which then functioned as the monomer. An oxidative cationic mechanism (σ polymerization) is proposed for the nuclear coupling.