Polyphenyl Synthesis by Means of the Kharash-type Grignard Cross-coupling Reaction
Polyphenyl Synthesis by Means of the Kharash-type Grignard Cross-coupling Reaction
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DOI：
10.1248/cpb.30.2369
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发表时间：
1982-07
影响因子：
1.7
通讯作者：
E. Ibuki;S. Ozasa;Y. Fujioka;M. Okada;Y. Yanagihara
中科院分区：
文献类型：
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作者：
E. Ibuki;S. Ozasa;Y. Fujioka;M. Okada;Y. Yanagihara
以芳基格氏试剂与二碘化芳烯为原料，在双（乙酰丙酮）镍（II）存在下，通过交叉偶联反应合成了27个多苯基，包括四苯基到六苯基。在温度低于60°C的温和条件下，在几小时内，在乙醚-苯溶液中以相当好的收率（50-95%）获得了其中的20种。然而，对于其余7种多苯基，由于反应物的空间拥挤几何结构，较低的产率（1-34%）是不可避免的。因此，kharash型Grignard交叉偶联反应被证明是合成各种多苯基的一种有效和方便的方法，除非反应物具有非常拥挤的几何形状。介绍并讨论了3-（2-联苯基）-邻季苯基、6'-（3-联苯基）-间季苯基和3,4 '-二（2-联苯基）联苯等3个新化合物的红外、紫外和质子磁共振光谱性质。
A series of twenty-seven polyphenyls, including quater-to sexiphenyls, was synthesized by the cross-coupling reaction of aryl Grignard reagents with arylene diiodides in the presence of bis (acetylacetonato) nickel (II). Twenty of them were obtained in fairly good yields (50-95%) under mild conditions at temperatures below ca. 60°C in ether-benzene solution within a few hours. In the cases of the remaining seven polyphenyls, however, lower yields (1-34%) were inevitable owing to the sterically crowded geometry of the reactant (s). Thus, the Kharash-type Grignard cross-coupling reaction was proved to be an efficient and convenient method for synthesizing a variety of polyphenyls, except in the cases of reactants with remarkably crowded geometry. The infrared, ultraviolet, and proton magnetic resonance spectral properties of several polyphenyls including three new compounds, 3-(2-biphenylyl)-o-quaterphenyl, 6'-(3-biphenylyl)-m-quaterphenyl, and 3, 4'-di (2-biphenylyl) biphenyl, are presented and discussed.