1095-04-1Relevant articles and documents
Isotope Effects on 31P Nuclear Shielding in Thiophosphites
Demarcq, Michel C.,Gleut, Louis Le,Hemelryck, Bruno G. Van
, p. 231 - 237 (1991)
The 34S isotope effect on the chemical shift of PIII nuclei in P(SR)3 esters is close to 20.6 ppb per PIII-34S bond, i.e. 3-4 times larger than for thiolo sulphur atoms in S=P(SR)3.A similar behaviour is noted for the P(-S-)3 sites in P4S9 and P4S3 and for the downfield triplet of P4S8, which, accordingly, is assigned to the tri-coordinate P atoms of this sulphide. 13C isotope effects are also reported for trialkyl(aryl) phosphorotrithioites and S,S,S-phosphorotrithioates.
Synthesis of bis(trithio)phosphines by oxidative transfer of phosphorus(i)
Kosnik, Stephanie C.,Nascimento, Maxemilian C.,Rawson, Jeremy M.,Macdonald, Charles L. B.
, p. 9769 - 9776 (2017)
The synthesis of novel bis(trithio)phosphines is achieved by oxidative addition of tetrathiocins to the phosphorus(i) reagent [PIdppe][Br] in good yields under ambient conditions. These bis(trithio)phosphines and the related intermediate diphosphine species are characterized by X-ray diffraction and multinuclear NMR and a mechanism is proposed for the formation of these molecules. In contrast, the related reaction with diphenyldisulfide produces a mononuclear tris(phenylthio)phosphine.
Synthesis, structure, and reactivity of a stabilized phosphiranylium salt
Jansen, Helen,Laeng, Florian B.,Slootweg,Ehlers, Andreas W.,Lutz, Martin,Lammertsma, Koop,Gruetzmacher, Hansjoerg
supporting information; experimental part, p. 5485 - 5488 (2010/09/15)
Chargedl Combining MeBABAR-Phos and methyl triflate affords an amino-stabilized phosphiranylium ion (see picture; C. gray, N blue, P orange), which undergoes various nucleophilic addition reactions to give P-substituted phosphiranes and an N-heterocyclic carbene stabilized phosphiranylium cation. (Figure Presented)
REACTION OF 2-DIETHYLAMINO-3-DIETHYLAMINOMETHYL-1,3,2-BENZOXAZAPHOSPHOLINE WITH THIOLS
Pudovik, M. A.,Terent'eva, S. A.,Litvinov, I. A.,Kataeva, O. N.,Naumov, V. A.,Pudovik, A. N.
, p. 1900 - 1903 (2007/10/02)
The reaction of 2-diethylamino-3-diethylaminomethyl-1,3,2-benzoxazaphospholine with an equimolar amount of benzenethiol occurs with rupture of the N-CH2 bond and formation of 2-diethylamino-1,3,2-benzoxazaphospholine. With excess of benzenethiol more deep transformations occur, up to formation of triphenyl phosphorotrithioite. A method for preparation of diethylammonium diphenyl tetrathiophosphate was found. Reactions of 2-diethylamino-3-diethylaminomethyl-1,3,2-benzoxazaphospholine with ethyl mercaptoacetate and mercaptoacetic anilide were examined.
Syntheses und NMR-Spektren phosphororganischer Antioxidantien und verwandter Verbindungen
Koenig, T.,Habicher, W.D.,Haehner, U.,Pionteck, J.,Rueger, C.,Schwetlick, K.
, p. 333 - 349 (2007/10/02)
The syntheses of various aliphatic, aromatic, sterically hindered, and cyclic organophosphorus compounds (phosphorous acid esters, esters chlorides and ester amides, hydrogen phosphites, phosphinates and phosphates) are reported, and general procedures for preparation are given.The compounds synthesized were investigated by means of 31P-, 1H- and 13C-n.m.r. spectroscopy, and the chemical shifts measured are listed.
Organophosphorus Antioxidants. X. The Hydroperoxide Decomposing Action of Phosphites, Phosphonites and Thiophosphites
Koenig, T.,Habicher, W. D.,Schwetlick, K.
, p. 913 - 922 (2007/10/02)
The kinetics and mechanism of reactions of phosphites, phosphonites, thiophosphites and hydrogenphosphites with cumyl (CHP), t-butyl (TBHP) and α-tetralyl (THP) hydrogenperoxides has been studied by means of (31)P-n.m.r. spectroscopy, high performance liquid chromatography and iodometric titration.All three valent phosphorus compounds studied initially react with hydroperoxides stoichiometrically to give the corresponding P=O products and alcohol.Some species are able to decompose cumyl hydroperoxide catalytically to form phenol and aceton.Acyloin phosphites decompose CHP catalytically after a stoichiometric reaction as thiophosphites do.Tetramethylpiperidinyl phosphites ("HALS-phosphites") react with hydroperoxides only stoichiometrically but with high velocity.Phosphonites react with hydroperoxides in the same way as the corresponding phosphites.Their reactivity, however, is much higher.Hydrogenphosphites are less reactive than phosphites in the reaction with hydroperoxides.They are able to act catalytically.
The Reaction of Alkyl-substituted Thioanisoles with PCl3 and AlCl3: a Route to Benzothiadiphospholobenzothiadiphosphole Derivatives
Baccolini, Graziano,Mezzina, Elisabetta,Todesko, Paolo Edgardo
, p. 3281 - 3284 (2007/10/02)
The synthesis of benzothiadiphospholobenzothiadiphosphole derivatives starting from alkyl-substituted thioanisoles and PCl3-AlCl3 is reported.The reaction is carried out at reflux in the absence of solvent and the yields are dependent on the starting sulphide.These new heterocycles can be purified by simple filtration on a Florisil column and have been characterized by 1H-, 13C-, (1H)31P-n.m.r. and mass spectroscopy analyses.New unexpected findings are also described.
Reactions of Tetraphosphorus Trisulphide with Organic Disulphides under Ultraviolet Irradiation, and with Sulphuryl Chloride
Musa, Faleh H.,Tattershall, Bruce W.
, p. 1517 - 1520 (2007/10/02)
P4S3 under glass-filtered u.v. irradiation is rapidly cleaved by alkyl and aryl disulphides to give tetrathiophosphate esters, SP(SR)3, and trithiophosphite esters, P(SR)3 (R = Me or Ph), in quantitative yield, as measured in the product mixture by 31P and 1H n.m.r. spectroscopy.No sulphurisation of P4S3 was found.In a competition reaction, MeSSMe and PhSSPh reacted to a similar extent with P4S3 to give all eight possible products SxP(SPh)n(SMe)(3-n) (x = O or 1, n = 0-3) in relative quantities within each oxidation state approximating to a statistical distribution of ligands, but there was more MeS substitution of the phosphorus (V) produts and more PhS substitution of the phosphorus(III) products.Reaction of MeSSPh with P4S3 gave similar results.Redistribution of ligands took place when a mixture of P(SMe)3 and P(SPh)3 was photolysed, and photolysis of a mixture of P(SMe)3 and MeSSPh caused the PhS group to be distributed between the trithiophosphite and disulphide sites.P(SMe)3 and P(SPh)3 were not sulphurised by MeSSMe and PhSSPh respectively, but P(SMe)3 was sulphurised to SP(SMe)3 to a small extent by MeSSPh.P4S3 is similarly cleaved by sulphuryl chloride, but under thermal conditions, to give SPCl3 and PCl3, with no evidence for intermediates.
ATTEMPTED PREPARATIONS OF PHOSPHORANES CONTAINING PERFLUOROPHENYL GROUPS
Denney, Donald B.,Denney, Dorothy Z.,Liu, Lun-Tsu
, p. 1 - 8 (2007/10/02)
The reaction of perfluorophenol with phosphorus pentachloride in the presence of triethylamine or χ-collidine yielded perfluoropentaphenoxyphosphorane, 5, along with perfluorotriphenylphosphate, 6, and perfluorodiphenyl ether, 7.Attempts to prepare penta(perfluorobenzyloxy)phosphorane, 12, by a number of methods failed.Similarly attempts to prepare perfluorothiophenylphosphorane, 19, always resulted in perfluorothiophenyl phosphite, 20, and perfluorodiphenyl disulfide, 21.
