18-crown-6-ether or more conveniently using lead thiocyanate. The phosphonium salt 8 and phosphoranes 9 were employed as convenient novelreagents for convertinghydroxygroups into thiocyanate and isothiocyanatefunctions with high stereoselectivity under very mild conditions. The efficient synthesis of acylisothiocyanales RCONCS, R2P(O)NCS and R2P(S)NCS via addition of thiocyanogen to mixed anhydrides is
已通过31 P NMR光谱研究了硫氰酸盐在三苯基膦中的氧化加成反应,表明形成了异硫氰酸根合salt盐8。硫氰酸根与烷基邻亚苯基亚磷酸酯7之间的类似反应导致生成二异硫氰酸根合膦酸酯9。在18-冠-6-醚的存在下,或更优选地使用硫氰酸铅,通过硫氰酸钾的作用,通过相应的氯salt盐12和烷基二氯-邻亚苯基亚膦酸酯13的配体取代,制备了相同的产物。salt盐8和膦烷9在非常温和的条件下,将其用作方便的新颖试剂,用于将羟基基团转化为具有高立体选择性的硫氰酸酯和异硫氰酸酯官能团。通过将硫氰酸根加到混合酸酐中来有效合成酰基异硫氰酸酯RCONCS,R 2 P(O)NCS和R 2 P(S)NCS。
Novel synthesis of isothiocyanatophosphoranes and isothiocyanatophosphonium salts via ligand substitution. Versatile reagents for converting hydroxy groups into thiocyanate and isothiocyanate functions
Alkoxy- or acyloxy-isothiocyanatophosphoranes (7) and phosphoniumsalts (12), prepared under mild conditions by stepwise ligand substitution from (5) and (11), respectively, decompose in excellent yield into the corresponding thiocyanato (9) and isothiocyanato (10) derivatives, thus providing a new method of synthesis of (9) and (10).
phosphororganische Antioxidantien. XII. Synthesen und NMR-Spektren phosphororganischer Antioxidantien und verwandter Verbindungen
作者:T. K�nig、W. D. Habicher、U. H�hner、J. Pionteck、C. R�ger、K. Schwetlick
DOI:10.1002/prac.19923340407
日期:——
The syntheses of various aliphatic, aromatic, sterically hindered, and cyclic organophosphorus compounds (phosphorous acid esters, ester chlorides and ester amides, hydrogen phosphites, phosphonates and phosphates) are reported, and general procedures for preparation are given.The compounds synthesized were investigated by means of P-31-, H-1- and C-13-n.m.r. spectroscopy, and the chemical shifts measured are listed.
Koenig, T.; Habicher, W. D.; Schwetlick, K., Journal fur praktische Chemie (Leipzig 1954), 1989, vol. 331, # 6, p. 913 - 922