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The Reaction of Diethylthiophosphinyl Iodide, Et 2 P(S)I, with Nucleophiles
Author(s) -
Tsivgoulis Gerasimos M.,
Kordopati Golfo G.,
Vachliotis Dimitris G.,
Ioannou Panayiotis V.
Publication year - 2017
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201700143
Subject(s) - chemistry , nucleophile , iodide , iodine , reactivity (psychology) , medicinal chemistry , methyl iodide , ethyl iodide , moiety , organic chemistry , catalysis , medicine , alternative medicine , pathology
The compound Me 2 AsSI can exist in two different forms, either as dimethylarsinosulfenyl iodide [or (iodothio)dimethylarsane)], Me 2 As–S–I ( A ), or as dimethylthioarsinyl iodide (or dimethylarsinothioic iodide), Me 2 As(S)–I ( B ). To confirm that the structure of the product of the reaction between Bunsen's cacodyl disulfide Me 2 As(S)–S–AsMe 2 and iodine is A and not B , the known diethylthiophosphinyl iodide (or diethylphosphinothioic iodide), Et 2 P(S)–I ( 2 ) was prepared and its hydrolytic stability and reactivity towards a variety of nitrogen, phosphorus(III), arsenic(III), oxygen, and sulfur(II) nucleophiles were studied. The results indicated that only a few reactions of 2 resembled those of A , thus strengthening the proposal that the reaction of Bunsen's cacodyl disulfide with iodine produced A and not B . A series of 31 P NMR chemical shifts of diethylthiophosphinyl moiety is also reported. Et 2 P(S)–DMAP, synthesized and isolated during the presented study, is the ethyl analogue of Me 2 P(S)–DMAP, previously described as an important molecule. In our case, Et 2 P(S)–DMAP was found to be a good intermediate for the synthesis of phosphoryl or thiophosphoryl derivatives since it was more reactive than 2 towards nucleophiles.