the ring-retained product 25 (66%) along with the ring-opened product 26 (33%). Apparently, an increasing number of spiro-annelated three-membered rings stabilizes a cyclopropyl cation against ring opening under solvolysis conditions. The rate of solvolysis, however, is only slightly affected by this spiroannelation, as the rate coefficient for the triflate 3 in sodium acetate-buffered methanol was determined
二螺[2.0.2.1]庚-1-基
三氟甲磺酸酯(3)、7-
溴-7-苯基二螺[2.0.2.1]
庚烷(4)和7-
氯-7-苯
硫基二螺[2.0.2.1]
庚烷(6)分别为分别以 50%、77% 和 90% 的总收率由双环亚丙基 (5) 制备。7-
溴-7-环丙基二螺[2.0.2.1]
庚烷(8)和7-
溴-7-甲基二螺[2.0.2.1]
庚烷(11)是通过7-环亚丙基-(7)和7-亚甲基二螺[2.0.2.1]
庚烷的氢
溴化得到的。 2.0.2.1]
庚烷 (10)(分别为 78% 和 95%)。triangulane 衍
生物 4、6 和 8 的
甲醇分解以及 6 的乙酰化都在保留二螺[2.0.2.1]
庚烷骨架的情况下进行,产生相应的 7-取代的 7-甲氧基二螺[2.0.2.1]
庚烷 15、21 和23 以及 7-乙酰氧基-7-苯基
硫基二螺[2.0.2.1]
庚烷 22 的产率分别为 90、100、100 和 88%。
1-溴-1-环丙基环丙烷