NMR study of reactions of organyltrichlorophosphonium hexachlorophosphorates with triethylamine
作者:L. I. Larina、T. N. Komarova、V. G. Rozinov
DOI:10.1007/s11172-015-0927-1
日期:2015.3
The reactions of trichloro(2-ethoxyethenyl)phosphonium and trichloro(styryl)phosphonium hexachlorophosphorates with triethylamine were studied by 1H, 13C, and 31P NMR spectroscopy. It was shown that phosphonyl chlorides are the primary products of the reactions. The presence of the alkoxy group in hexachlorophosphorate results in the oxidation of the PCl2 group to form phosphonyl chlorides. Diphosphorylated oxaphosphinines were synthesized.
A process for the preparation of a phosphorus complex corresponding to the following general formula:
wherein R represents optionally substituted aryl, wherein the substitution may comprise at least one selected from nitro, chloro, fluoro, alkyl, fluoro-alkyl and alkoxy, or optionally substituted alkyl; characterised in that it comprises reacting phosphorus pentachloride and a phosphonic dichloride corresponding to the following general formula:
RPOCl₂
wherein R is as defined above; in the presence of an inert solvent boiling at a temperature of from 120 to 150°C, which is capable of co-distilling a phosphorus oxychloride reaction product, and co-distilling a phosphorus oxychloride reaction product, the molar ratio of phosphorus pentachloride:phosphonic dichloride being from 0.1:1 to 10:1 is disclosed.
There is further disclosed a process for chlorinating compounds containing a carbon atom bonded to a hetero-atom selected from oxygen, nitrogen and sulfur which comprises contacting the carbon hetero-atom containing compound with a chloro phosphorus complex corresponding to the following general formula:
wherein R represents optionally substituted aryl or optionally substituted alkyl, so that the hetero-atom is replaced by at least one chlorine atom; the reaction may be extended to compounds containing the carbon to chlorine bond alpha to a carbon atom having at least one hydrogen atom, it may be further dehydrochlorinated by either heating to a temperature of from 50 to 300°C or by reaction with a selected base.
一种制备通式如下的磷络合物的工艺:
其中 R 代表任选取代的芳基,其中取代基可包括至少一个选自硝基、氯基、氟基、烷基、氟代烷基和烷氧基或任选取代的烷基的取代基;其特征在于,该工艺包括使五氯化磷与对应于下式通式的膦酰二氯反应:
RPOCl₂
其中 R 如上定义;在沸腾温度为 120 至 150°C 的惰性溶剂存在下,该溶剂能够共同蒸馏出氧氯化磷反应产物,并共同蒸馏出氧氯化磷反应产物,五氯化磷与膦酰二氯的摩尔比为 0.1:1 至 10:1。
还进一步公开了一种对含有与选自氧、氮和硫的杂原子成键的碳原子的化合物进行氯化的工艺,该工艺包括将含碳杂原子的化合物与对应于下通式的氯磷络合物接触:
其中 R 代表任选取代的芳基或任选取代的烷基,这样杂原子就被至少一个氯原子取代;该反应可扩展到含有碳-氯键α-至少有一个氢原子的碳原子的化合物,它可通过加热到 50 至 300°C 的温度或通过与选定的碱反应进一步脱氢氯化。
Nurtdinov, S. Kh.; Khairullina, S. V.; Khairullin, V. K., Journal of general chemistry of the USSR, 1983, vol. 53, # 4, p. 685 - 690
作者:Nurtdinov, S. Kh.、Khairullina, S. V.、Khairullin, V. K.、Shagidullin, R. R.、Chernov, A. N.
DOI:——
日期:——
KRYLOV L. V.; KORMACHEV V. V.; KUXTIN V. A., XIMIYA I PRAKTICH. PRIMENENIE KREMNIJ-I FOSFORORGANICH. OSEDIN. L., 1979,+
作者:KRYLOV L. V.、 KORMACHEV V. V.、 KUXTIN V. A.
DOI:——
日期:——
TIMOXIN, B. V.;KAZANTSEVA, M. V.;DONSKIX, V. I.;RATOVSKIJ, G. V.;CHUVASHE+, ZH. OBSHCH. XIMII, 60,(1990) N, S. 1019-1024
作者:TIMOXIN, B. V.、KAZANTSEVA, M. V.、DONSKIX, V. I.、RATOVSKIJ, G. V.、CHUVASHE+