THE ACTION OF SODIUM ON ORTHO-XYLYLENE DIBROMIDE
THE ACTION OF SODIUM ON ORTHO-XYLYLENE DIBROMIDE
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DOI：
10.1039/jr9450000027
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发表时间：
1945-01-01
期刊：
影响因子：
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通讯作者：
MANN, FG
中科院分区：
文献类型：
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作者：
BAKER, W;BANKS, R;MANN, FG
钠与邻二甲苯二溴在沸腾的二恶烷中反应，生成产率 6% 的 s-二苯并环十二烯 (I)，以及产率低得多的二邻甲苯乙烷和 s-三苯并环十二碳二烯 (11)。在沸腾的乙醚中，不发生明显的反应，除非加入少量的乙酸乙酯，然后加入邻二甲苯（5%）、二邻甲苯乙烷（6%）、十二碳三烯（11）。以及可以是3:4:7:8-二苯并*的产物。形成4环-As：7-壬二烯(111)，同时高产率地形成具有与(111)相同组成的无定形产物。讨论了烃类(I)和(11)的立体化学；建立了理论上可以以两种异构体形式存在的(I)的结构。当邻苯二甲撑二溴在干燥二恶烷中的溶液在过量的“粉状”钠存在下回流时，发生缓慢但自发的反应，在搅拌15-20小时后完成。从产物中分离出s-苯并环辛二烯(I)，m，p。 108-5O，约。 6% 的收率，并且对二邻甲苯基乙烷、C、H、Me-CH、-CH、-C、H、Me、m 的量少得多。 p。 65'。和s-tvibenz环十二碳烯
Sodium reacts with o-xylylene dibromide in boiling dioxan to give a 6% yield of s-dibewcycloocfdzene (I) and much smaller yields of di-o-tolylethane and s-tribenzcyclododecafriene (11). In boiling ether no apparent reaction occurs unless a small quantity of ethyl acetate is added, whereupon o-xylene (5%), di-o-tolylethane (6%), the dodecatriene (11). and a product which may be 3: 4: 7: 8-dibenzo*. 4cyclo-As: 7-nonadiene (111) are formed, together with a high yield of an amorphous product having a composition identical witft that of (111). The stereochemistry of the hydrocarbons (I) and (11) is discussed; the structure of (I), which can theoretically exist in two isomeric forms, is established.WHEN a solution of o-xylylene dibromide in dry dioxan was refluxed in the presence of an excess of" powdered" sodium, a slow but spontaneous reaction occurred, which was complete after 15-20 hours' bolhng. From the product there have been isolated s-dzbenzcyclooctadiene (I), m, p. 108-5O, in ca. 6% yield, and much smaller quantities of ap-di-o-tolylethane, C, H, Me-CH,-CH,-C, H, Me, m. p. 65'. and s-tvibenzcyclododecafriene