脒鎓盐的制备及新型还原反应

Preparation and novel reduction reactions of vinamidinium salts.

作者信息

Davies I W, Taylor M, Marcoux J F, Wu J, Dormer P G, Hughes D, Reider P J

机构信息

Department of Process Research, Merck & Co., Inc., P.O. Box 2000, Rahway, New Jersey 07065, USA.

出版信息

J Org Chem. 2001 Jan 12;66(1):251-5. doi: 10.1021/jo005656p.

DOI:10.1021/jo005656p

PMID:11429907

Abstract

Substituted acetic acids and formamides react in the presence of phosphorus oxychloride to yield the vinamidinium hexafluorophosphate salts 5a-d, 6a-d, and 7 in moderate to good unoptimized recrystallized yields (40-67%) as easily handled nonhygroscopic solids. The 1,3-differentially substituted vinamidinium salts 8 was prepared by amine exchange in 81% yield as are the cyclic diazapinium salts 9 and 10 in > 76% yield. The symmetrical 2-chlorovinamidinium 11 was prepared by displacement of 3 in 71% yield. The 2-chlorovinamidinium salts are cleanly reduced to the parent vinamidinium salts 12-16 using HI or PPh3/pTSA in up to 99% assay yield.

摘要

取代乙酸和甲酰胺在三氯氧磷存在下反应，以中等至良好的未优化重结晶产率（40 - 67%）生成六氟磷酸亚氨盐5a - d、6a - d和7，这些产物为易于处理的非吸湿性固体。1,3 - 不同取代的亚氨盐8通过胺交换反应制备，产率为81%，环状二氮杂盐9和10的产率> 76%。对称的2 - 氯亚氨盐11通过取代反应制备，产率为71%。使用HI或PPh3/pTSA可将2 - 氯亚氨盐干净地还原为母体亚氨盐12 - 16，分析产率高达99%。