特定双氘代十八烷酸酯和氧代十八烷酸酯的制备。
Preparation of specifically dideuterated octadecanoates and oxooctadecanoates.
作者信息
Tulloch A P
出版信息
Lipids. 1977 Jan;12(1):92-8. doi: 10.1007/BF02532978.
Sixteen methyl gem dideuterooctadecanoates with two deuterium atoms at positions 2- to 17- and seven oxo esters, 8-oxooctadecanoate-5,5-d(2), 8-oxooctadecanoate-11, 11-d(2), 11-oxooctadecanoate-8,8-d(2), 11-oxooctadecanoate-14,14-d(2), 12-oxooctadecanoate-9,9-d(2), 7-oxooctadecanoate-10,10-d(2) and 13-oxooctadecanoate-16,16-d(2) with two deuteriums on the carbon gamma to the oxo group, have been synthesized. Two prinicipal methods of introducing deuterium were used: preparation of 2,2-dideutero acids by exchange with deuterium oxide followed by chain extension giving dideuteroxooctadecanoates, which were then reduced, as tosylhydrazones, with sodium cyanoborohydride to dideuterooctadecanoates and stepwise introduction by reduction of oxooctadecanoates with sodium borodeuteride, formation of tosylate or mesylate, reduction with lithium aluminum deuteride to tetradeuterooctadecanol and oxidation to dideuterooctadecanoic acid.
合成了十六种在2至17位带有两个氘原子的甲基偕二氘代十八烷酸酯以及七种氧代酯，即8-氧代十八烷酸酯-5,5-d(2)、8-氧代十八烷酸酯-11,11-d(2)、11-氧代十八烷酸酯-8,8-d(2)、11-氧代十八烷酸酯-14,14-d(2)、12-氧代十八烷酸酯-9,9-d(2)、7-氧代十八烷酸酯-10,10-d(2)和13-氧代十八烷酸酯-16,16-d(2)，这些氧代酯在羰基的γ位碳上带有两个氘原子。使用了两种引入氘的主要方法：通过与氧化氘交换制备2,2-二氘代酸，然后进行链延长得到二氘代氧代十八烷酸酯，接着将其作为对甲苯磺酰腙用氰基硼氢化钠还原为二氘代十八烷酸酯；以及通过用硼氘化钠还原氧代十八烷酸酯、形成对甲苯磺酸酯或甲磺酸酯、用氘代氢化铝锂还原为四氘代十八烷醇并氧化为二氘代十八烷酸来逐步引入氘。
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