677-74-7Relevant academic research and scientific papers
A convenient one-pot synthesis of Di-t-butylphosphinic chloride
Brayton, Daniel F.,Goldberg, Karen I.,Kaminsky, Werner,Heinekey, D. Michael
, p. 2534 - 2540 (2008)
A convenient one-pot synthesis of (t-Bu)2P(O)Cl (1) from m-chloroperbenzoic acid and (t-Bu)2PCl is described. The byproduct m-chlorobenzoic acid is neutralized by addition of Et3N. Complex 1 crystallizes in the monoclinic space group P21/c (No. 14), with a = 5.9637(2) , b = 11.4734(4) , c = 16.2400(5) and = 107.7160(14).
Cleavage and Formation of P-C Bonds during an Unusual Kinnear-Perren Reaction
Plack, Volker,Goerlich, Jens R.,Schmutzler, Reinhard
, p. 1265 - 1266 (1998)
Treatment of triphenylmethyldichlorophosphine 1 with aluminium trichloride in the presence of tert-butyl chloride leads, after hydrolysis, with high selectivity to di-tert-butylphosphinic chloride 5. The reaction is suggested to proceed via a chlorophosphinidene intermediate which is trapped by the alkyl chloride.
Synthesis and characterisation of severely hindered P-OR compounds
Williams, D. Bradley G.,Netshiozwi, Takelani E.
experimental part, p. 9973 - 9982 (2010/02/27)
P-Cl substrates were converted into their P-OR analogues from hindered alcohols using an amine base. Where the system was severely hindered, more forcing conditions were required that necessitated the presence of a metal alkoxide nucleophile before succes
POLYSULFONYLAMINE: TEIL LXXI. EIN MOLEKUEL MIT EINER LANGEN Si(sp3)-O-BINDUNG: SYNTHESE, STRUKTUR UND REAKTIVITAET VON N,N-DIMESYLAMIDOSCHWEFELSAEURETRIMETHYLSILYLESTER
Hiemisch, Oliver,Blaschette, Armand,Jones, Peter G.
, p. 161 - 172 (2007/10/03)
The title compound (MeSO2)2N-SO2-O-SiMe3 (2; m.p. 57 deg C) is obtained by treating (MeSO2)2N-SiMe3 (3) with one equivalent of sulfur trioxide in CH2Cl2 at -20 deg C.The crystal structure of 2 (triclinic, space group P) was established by low-temperature X-ray diffraction.The most interesting feature of the molecular structure is the geometry of the S-O-Si sequence, displaying a very long Si(sp3)-O bond, a short S(sp3)-O bond and a large angle at oxygen (mean values for two independent molecules: Si-O 174.1, S-O 151.1 pm, S-O-Si 134.3 deg).The coordination at nitrogen is trigonal-planar (S-N-S 118.5-121.0 deg, S-N 170.5-173.1 pm). 2 is instantaneously hydrolyzed by excess water to form (MeSO2)2NH, sulfuric acid and (Me3Si)2O.In vacuo at 60 deg C, molten 2 will readily dissociate into its precursors 3 and SO3.It is shown that 2 may react either as an SO3 donor or as a sulfosilylating reagent.Reaction with Lewis bases such as Me3N, pyridine or R2PCl (R = tBu, Ph) proceeds with the formation of the corresponding complexes B*SO3; thermolysis of the isolable phosphane complexes affords the respective phosphane oxides R2(Cl)PO.Sulfosilylation of phenol, cyclohexene or 2,3-dimethyl-2-butene with 2 in CH2Cl2 gives the trimethylsilyl esters of 4-hydroxybenzenesulfonic, cyclohexene-3-sulfonic, or 2,3-dimethyl-1-butene-3-sulfonic acids, respectively.Key words: Trimethylsilyl N,N-dimesylamidosulfonate, synthesis, X-ray structure, long Si(sp3)-O bond, SO3 transfer, sulfosilylation.
SOLVOLYSIS OF CHLORODIALKYL- AND DIARYLPHOSPHINES, DIALKYL PHOSPHOROCHLORIDITES AND DIALKYL PHOSPHINYL CHLORIDES
Halmann, M.
, p. 251 - 262 (2007/10/02)
The kinetics of solvolysis of chlorodiethylphosphine, chloro(di-n-propyl)phosphine and chlorodiphenylphosphine was studied by conductometry in pure ethanol and in various mixed solvents, and was compared with that of dialkyl phosphorochloridites and of dialkyl and diaryl phosphinyl chlorides.The rate of ethanolysis of chloro(di-n-propyl)phosphine was found to be larger at higher initial concentrations.Addition of sulfuric or perchloric acid enhanced the rate of solvolysis, while sodium perchlorate and lithium chloride had no influence.In ethanol containing water, the rate of solvolysis of chloro(di-n-propyl)phosphine is approximately proportional to the concentration of water.In formic acid, the solvolysis of chloro(di-n-propyl)phosphine is slower than in ethanol.Addition of acetone to ethanol increases the rate of solvolysis of chloro(di-n-propyl)phosphine - possibly due to a condensation reaction producing a 1-chloroalkyl dialkylphosphine oxide.The rate of ethanolysis of chloro(di-n-propyl)phosphine is considerably enhanced in the presence of isobutylamine, di-n-butylamine and triethylamine.The solvolysis of di-t-butylphosphinyl chloride in absolute ethanol is very much slower than that of dimethyl and diethyl phosphinyl chloride.Key words: Solvolysis; chlorodialkylphosphines; chlorodiphenylphosphine; dialkyl phosphorochloridite; dialkylphosphinyl chlorides; acid catalysis.
Photochemical Rearrangement of Dialkylphosphinic Azides in Methanol and Other Protic Solvents
Harger, Martin J. P.,Stephen, Michael A.
, p. 736 - 740 (2007/10/02)
On photolysis in methanol di-t-butylphosphinic azide (4; R=But) rearranges with loss of nitrogen to give methyl NP-di-t-butylphosphonamidate (6; R=But, X=OMe) (71percent), presumably by way of a monomeric metaphosphonimidate (5; R=But) which is trapped by the solvent.Analogous rearrangements occur in other alkohols and in t-butylamine, althogh di-t-butylphosphinic amide is also a substantial product in ethanol and the major product in isopropyl alcohol.Di-isopropylphosphinic azide (4; R=Pri) behaves in a similar way, but in methanol the less hindered diethylphosphinic azide (4; R=Et) suffers extensive solvolysis to methyl diethylphosphinate.
