Phosphine difluoro

Rhodium, iodotetrakis(difluoro(diethylamino)-phosphine)-, 4, 924 Rhodium, pentaamminethiocyanato-base hydrolysis, 1, 504 Rhodium, pentaammincurea-linkage isomerism, 4, 961 Rhodium, pentaammine(urea)-decomposition, 1,186... 

Species 5 (Scheme 8), commonly known as dialkylaminodifluorophosphines, are readily synthesized via the selective cleavage of the phosphorus-carbon bond of difluoro(trichloromethylphosphane) by the action of secondary amines [65,66]. Compounds 5 show selective F/H exchange with LiAlH4/HN(Tr)2 to give the respective PH2 (P-unsubstituted) phosphinous amides [13]. 

Bis(trimethylsilyl)phosphines 1681, whose chemistry has been reviewed [5], condense with DMF and eliminate HMDSO 7 to give, e.g., the phosphaalkene 1682 [6]. Bis(trimethylsilyl)phosphines 1681 react with bis(dialkylamino)difluoro-methanes 1683 with elimination of Me3SiF 71 to give the phosphaalkenes 1684 [7, 8], whereas acid chlorides such as Me3CCOCl afford, with elimination of TCS 14, the O-trimethylsilylphosphaalkenes 1685 [9]. Bis(trimethylsilyl)phosphines 1681 condense with CO2 to the phosphacarbamates 1686 [10] whereas CS2 furnishes the methylenephosphanes 1687 [11, 12] (Scheme 11.1). 

Notable examples of general synthetic procedures in Volume 47 include the synthesis of aromatic aldehydes (from dichloro-methyl methyl ether), aliphatic aldehydes (from alkyl halides and trimethylamine oxide and by oxidation of alcohols using dimethyl sulfoxide, dicyclohexylcarbodiimide, and pyridinum trifluoro-acetate the latter method is particularly useful since the conditions are so mild), carbethoxycycloalkanones (from sodium hydride, diethyl carbonate, and the cycloalkanone), m-dialkylbenzenes (from the />-isomer by isomerization with hydrogen fluoride and boron trifluoride), and the deamination of amines (by conversion to the nitrosoamide and thermolysis to the ester). Other general methods are represented by the synthesis of 1,1-difluoro olefins (from sodium chlorodifluoroacetate, triphenyl phosphine, and an aldehyde or ketone), the nitration of aromatic rings (with ni-tronium tetrafluoroborate), the reductive methylation of aromatic nitro compounds (with formaldehyde and hydrogen), the synthesis of dialkyl ketones (from carboxylic acids and iron powder), and the preparation of 1-substituted cyclopropanols (from the condensation of a l,3-dichloro-2-propanol derivative and ethyl-... 

First, dibromodifluoromethane and hexamethylphosporous amide form a phosphonium salt. The intermediate thus formed reacts with tris(dimethyl-amino)phosphine to give dibromotris(dimethylamino)phosphorane and an ylide with difluoromethylene group attached to phosphorus, difluoro-methylenetris(dimethylamino)phosphorane. 

Tri-n-butyldifluorophosphorane was first obtained upon interaction between tri-re-butylphosphine and hexafluoro-thioacetone dimer.The method described here involves the reaction of tri-n-butylphosphine sulfide with antimony-(III) fluoride. The method is more generally apphcable in the synthesis of difluorophosphoranes from tertiary phosphine sulfides. The only previously reported difluoro-phosphorane, triphenyldifluorophosphorane, was obtained by the reaction of triphenylphosphine or triphenylphos-phine oxide with sulfur(IV) fluoride under autogenous pressure. ... 

Dihalomethylenephosphoranes are easily available from tetrahalomethanes and tertiary phosphines, especially triphenylphosphine (equation 2). From mixed tetrahalomethanes preferably difluoro- and di-chloro-methenylenephosphoranes are formed. The primarily resulting dihalomethylenephosphorane may undergo subsequent reaction giving rise to the formation of a semi-ylide salt (equation 3). ... 

The formation of C-P bonds by the radical addition of phosphines to exocyclic carbohydrate alkenes was originally reported by Whistler [109], who demonstrated that irradiation of alkene 171 in the presence of phenylphosphine afforded the phosphine oxide 172 (Scheme 29). Sinay [110] prepared the gem-difluoro-C-galactofuranoside 173 by phosphonyl radical addition to gem-difluoroalkene 174 during studies related to the preparation of potential inhibitors of the enzyme UDP-galactofuranose mutase. 

Band Assignments.—The Fourier transform infrared spectrum of C-difluoro-phosphaethane has been analysed and the P=C band assigned. The Vps, band assignments for silylphosphines have been discussed. The positions of and Vp isNH are reported and used to characterize isomeric phosphine-iminium salts. The vpo (sym) bands of barium dialkyl phosphates have been compared in liquid crystal and aqueous media. ... 

Rhodium. iodoletrakis( difluoro(diethylamino)-phosphine)-. 924 Rhodium, pentaammineurea-linkage isomerism, 961 Rhodium, pentakjs(trialkyl phosphite), 929 Rhodium, tctrakis(acctato)di-antitumor properties, 936 (tzonization. 9.51... 

Strong evidence for intramolecular fluorine exchange in PhaPFg has been obtained from and P n.m.r. spectra in the temperature range 32— 170 °C. Silyl esters of bis(trifluoromet%l)- and difluoro-phosphinic acids and their thio-analogues result from reactions of the type ° ... 

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