Reactions of dispiro[2.0.2.2]oct-7-ene. Electrophilic and free radical additions
作者:A.T. Bottini、L.J. Cabral
DOI:10.1016/0040-4020(78)87016-1
日期:1978.1
trans-7,8-dichlorodispiro[2.0.2.2]octane 3b with magnesium. Stepwise electrophilic additions to 1 of HBr, HI, Br2 and Cl2 were studied. The major products (and yields) from these reactions were: 7-bromodispiro[2.0.2.2]octane 2a (43%), 4-iodo-4,5-ethanospiro[2,3]hexane 4b (ca. 50%); trans-3a (40%); and cis-3b (20%). Free-radical addition of hydrogen bromide to 1 gave an 80% yield of 7-bromodispiro[2.0.2
二螺[2.0.2.2]辛-7-烯1用的debrominatioa合成顺式-和反式-7,8- dibromodispiro [2.0.2.2]辛烷3A用LAH通过脱氯顺-和反式-7,8- dichlorodispiro [2.0.2.2]辛烷3b与镁。研究了对1 HBr,HI,Br 2和Cl 2的逐步亲电子加成。这些反应的主要产物(和产率)为:7-溴二螺[2.0.2.2]辛烷2a(43%),4-碘-4,5-乙螺[2,3]己烷4b(约50%);和4-碘-2-5,5-乙螺[2,3]己烷4b。反式- 3A(40%);与顺式-图3b(20%)。将溴化氢自由基加成到1中可得到80%的7-溴二螺并[2.0.2.2]辛烷2a。在-10°下,发现硼氢化氧化为1,主要在大约20℃下得到7-羟基二螺并[2.0.2.2]辛烷2a。90%的产率;在25°下,获得接近等量的2c和4-(2-羟乙基)螺[2.3]己-4-烯14。