醌類脫氫反應之立體化學　第一報　模型基體－順式萘駢乙烷1,2二氘之合成

Stereochemistry of Quinone Dehydrogenation I. Synthesis of Model Substrate-Cis-Acenaphthene-1, 2-d_2

許鍾瑤(Chung-Yao Hsu)

《化學》 55年1期 (1966/03) Pp. 1-8

https://doi.org/10.6623/chem.1966001

摘要

萘駢乙烷醌以氘化鋁鋰(LiAlD_4)還原，可得萘駢乙烷1, 2二氘1, 2二醇，產率為71.8%。此二醇與氯化甲磺醯起反應後，再以碘化鈉還原，可變為萘駢乙烯1,2 二氘，其產率為50.4%，同位素純度為D_2 98.1%，D_1 1.9%，D_0＜0.1%。萘駢乙烯1,2 二氘經氫硼化反應及加酸分解後，得順式萘駢乙烷1, 2二氘，產率為57.4%，同位素純度為D_2 97.8%，D_1 2.1%，D_0 0.1%，其主要副產物為3-醯基萘駢乙烷及1-萘駢乙烷醇。順式萘駢乙烷1,2二氘可用為研究醌類脫氫反應立體化學過程之模型基體。

並列摘要

Reduction of acenaphthenequinone with lithium aluminum deuteride gave acenaphthene-1, 2-d_r-1, 2-diol on a yield of 71.8%. The diol was converted to acenaphthylene-1,2-d_2 by mesylation with methanesulfonyl chloride and reduction with sodium iodide. The yield was 50.496, and the isotope purity of the product was D_2 98.1%, D_1.9%, D_0＜0.1%. Brown's hydroboration and protonolysis of acenaphthylene1,2- d_2 afforded cls-acenaphthene-1, 2-d_2, on a yield of 57.4% and isotope purity of D_2 97.8%. D_1 2.1%, and D_0 0.1%. The major by-products were characterized as 3-acylacenaphthene and 1-acenahthenol. The final labeled product, cis-acenaphthene-1, 2-d_2, is to be used as a model substrate for investigating the stereochemical course of quinone dehydrogenation.