通过苯并硫代吡喃的快速真空热解形成芳基-芳基键。

Aryl-aryl bond formation by flash vacuum pyrolysis of benzannulated thiopyrans.

作者信息

Amick Aaron W, Wakamiya Atsushi, Scott Lawrence T

机构信息

Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467-3860, USA.

出版信息

J Org Chem. 2008 Jul 4;73(13):5119-22. doi: 10.1021/jo800379x. Epub 2008 May 30.

DOI:10.1021/jo800379x

PMID:18510364

Abstract

In contrast to fully unsaturated 7-membered ring sulfur heterocycles (thiepines), some of which extrude sulfur and give the ring-contracted hydrocarbon even at room temperature in solution, benzannulated thiopyrans (6-membered sulfur heterocycles) require flash vacuum pyrolysis (FVP) conditions in the gas phase at temperatures in the range of 1000-1200 degrees C to promote the corresponding reaction. Thus, FVP of benzo[kl]thioxanthene (1) gives fluoranthene, and naphtho[2,1,8,7-klmn]thioxanthene (6) gives benzo[ghi]fluoranthene (7). FVP of thioxanthone (9) gives fluorenone (10), together with lesser amounts of dibenzo[b,d]thiophene (11), from competing decarbonylation.

摘要

与完全不饱和的七元环硫杂环（硫杂环庚三烯）不同，其中一些即使在室温下于溶液中也会挤出硫并生成环收缩的烃，而苯并稠合的硫代吡喃（六元硫杂环）在气相中需要1000 - 1200摄氏度范围内的闪蒸真空热解（FVP）条件来促进相应反应。因此，苯并[k,l]噻吨（1）的FVP生成荧蒽，萘并[2,1,8,7 - k,l,m,n]噻吨（6）生成苯并[g,h,i]荧蒽（7）。噻吨酮（9）的FVP生成芴酮（10），同时由于竞争脱羰基反应会生成少量的二苯并[b,d]噻吩（11）。