Formation and thermal cleavage reactions of the cycloadduct of 9,10-dimethylanthracene and nitrosyl cyanide
作者:Peter Horsewood、Gordon W. Kirby、Ram Prakash Sharma、James G. Sweeny
DOI:10.1039/p19810001802
日期:——
capture of nitrosyl cyanide by thebaine. A similar first-order rate, k= 6.8 × 10–5s–1, was observed for the reaction of the adduct (1) and triphenylphosphine (2 mol equiv.) under the same conditions, the products being DMA, triphenylphosphine oxide, and triphenylphosphine N-cyanoimide (5). The reactions of nitrosyl cyanide, generated thermally from the adduct (1), were studied with a range of dienes. The
亚硝基氰化物和9,10-二甲基蒽(DMA)(2)在–25°C下反应形成结晶环加合物9,10-二氢-9,10- (N-氰基环氧亚氨基)-9,10-二甲基蒽(1) 。加合物(1)在共轭二烯蒂巴因(3)的存在下分解,形成DMA(2)以及亚硝酰基氰化物和蒂巴因的加合物(4)。在40°C时,观察到一级动力学(k = 6.9×10 –5 s –1)对于DMA在苯中的释放,这与加合物(1)的缓慢解离,然后由蒂巴因快速捕获亚硝酰氰相一致。类似的一阶速率,k = 6.8×10 –5 s –1观察到在相同条件下加合物(1)和三苯基膦(2摩尔当量)的反应,产物为DMA,三苯基膦氧化物和三苯基膦N-氰酰亚胺(5)。用一系列二烯研究了由加合物(1)热生成的亚硝酰基氰化物的反应。共轭二烯,N-氰甲基-N-鸟氨酸(3; NCH 2 CN代替NMe),反式,反式-1,4-二苯基丁-1,3-二烯(6; R = H)和乙酸麦