On the Probable Intermediacy of Thetrahedrane
On the Probable Intermediacy of Thetrahedrane
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关于四面体可能的中介作用
DOI：
10.1021/ja00705a614
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发表时间：
1970
影响因子：
15
通讯作者：
A. Wolf
中科院分区：
文献类型：
--
作者：
P. Shevlin;A. Wolf
然而，最近的质谱研究表明，取代的环己烯醇的碎片四面体对称的结构。2丙二酸经五氧化二磷脱水生成低碳氧化物，气相色谱纯化。使用前，用Closs和Krantz的方法从烯丙基氯制备的环丙烯，3在二甲基环丁砜柱上用气相色谱法在-40 ℃下纯化。将环丙烯（2.18 × 10-2 mmol）和低氧化碳（4.72 × 10-2 mmol）的混合物置于442-ml Pyrex光解烧瓶中。将该混合物在室温下用置于烧瓶中心的水冷浸没孔中的200-W Hanovia中压灯光解80分钟。用气相色谱法分析了在液氮中可冷凝的产物。产物为乙炔（24%）4和乙烯基乙炔（33%）。乙烯基乙炔是预期产物，因为低氧化碳与1，2-二甲基环丙烯的光解产生2-甲基-1-戊烯-3-炔作为主要产物。LD
However, recent mass spectral studies suggest structures of tetrahedral symmetry in the fragmentation of substituted cyclopentadienols. 2 Carbon suboxide was generated by dehydration of malonic acid with phosphorus pentoxide and purified by gas chromatography. The cyclopropene, prepared from allyl chloride by the method of Closs and Krantz, 3 was purified by gas chromatography on a dimethyl sulfolane column at—40 prior to use. A mixture of cyclopropene (2.18 X 10-2 mmol) and carbon suboxide (4.72 X 10-2 mmol) was placed in a 442-ml Pyrex photolysis flask. This mixture was photolyzed for 80 min at room temperature with a 200-W Hanovia medium-pressure lamp placed in a water-cooled immersion well in the center of the flask. The products condensable in liquid nitrogen were analyzed by gas chromatography. Acetylene (24%) 4 and vinylacetylene (33%) were the products. Vinylacetylene is an expected product, since the photolysis of carbon suboxide with 1, 2-dimethylcyclopropene gives 2-methyl-l-penten-3-yne as the major product. ld