Preparation of o-Vinylbenzyl d-sec-Butyl Sulfide.1An Attempted Asymmetric Polymer Synthesis
Preparation of o-Vinylbenzyl d-sec-Butyl Sulfide.1An Attempted Asymmetric Polymer Synthesis
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邻乙烯基苄基 d-仲丁基硫醚的制备 1 一种尝试的不对称聚合物合成
DOI：
10.1021/ja01584a039
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发表时间：
1956
期刊：
影响因子：
--
通讯作者：
L. C. Palmer
中科院分区：
文献类型：
--
作者：
C. Overberger;L. C. Palmer
介绍了邻乙烯基苄基仲丁基硫化物的制备方法。这种光学活性单体在自由基催化剂的作用下聚合和共聚，试图实现不对称聚合物的合成。在用Raney镍氢解定量除去硫和光学活性基团后，得到的聚合物和共聚物在光学上是不活性的，拉伸的聚合物膜的X射线图表明它是无取向的。一些非晶态聚合物，如聚苯乙烯和聚甲基丙烯酸甲酯，在链的主干上含有不对称的碳原子。有人认为，d-构型和？-构型的聚合物链中随机分布的不对称碳原子的存在使每个链都是外消旋混合物或介观形式，这阻碍了链段的适当取向以形成晶体。含有过量d构型或？构型的聚合物将有兴趣测试这一假设的有效性。
The preparation of o-vinylbenzyl¿-sec-butyl sulfide is described. This optically active monomer was polymerized and copolymerized with a free radicalcatalyst in an attempt to effect an asymmetric polymer synthesis. After quantitatively removing the sulfur and the optically active group by hydrogenolysis with Raney nickel, the resulting polymer and copolymer were found to be optically inactiveand an X-ray diagram of a stretched polymer film showed it to be non-oriented.A number of amorphous polymers such as polystyrene and polymethyl methacrylates contain asymmetric carbon atoms in the backbone of the chain. It has been suggested that the presence of asymmetric carbon atoms randomly distributed in the polymer chain of both the d-and¿-configura-tions makes each chain a racemic mixture or meso form which prevents proper orientation of chain segments for crystal formation. A polymer con-taining an excess of either the d or¿-configuration would be of interest to test the validity of this postulate.