Bin Xu

Synthesis of 2-perfluoroalkyl-substituted acetals from the one-pot reaction of perfluoroalkyl iodides with vinyl ether and alcoholates

Abstract Treatment of perfluoroalkyl iodides, R f I (R f =C 4 F 9 , ClC 4 F 8 ), with alcoholales and vinyl ethyl ether gave 2-perfluoroalkyl acetals via perfluoroalkyl radical intermediates. Both R f and R f CH 2 CHOEt radicals were detected by ESR spectroscopy. A single-electron-transfer mechanism is proposed for this reaction.

Synthesis and reactions of N,N-dichloroperfluoroalkanesulfonylamides

Abstract Reactions of N , N -dichloroperfluoroalkanesulfonylamides with alkenes, benzene, dimethyl sulfide and dimethyl sulfoxide in the presence of zinc dust gave addition or insertion products via the fluoroalkanesulfonylnitrene intermediate. On heating R 1 SO 2 NCl 2 in the presence of alkene without zinc, 1:1 addition products were formed via a free-radical mechanism.

Preparation of N,N-dialkyl-N′-perfluoroalkanesulfonylformamidines RfSO2NCHNR2 via Vilsmeier reagents

Abstract Treatment of sodium perfluoroalkanesulfonylamides R f SO 2 NHNa with Vilsmeier reagents [YCHue605 + NR 2 ]Cl − (Y≡OP(O)Cl 2 , OS(O)Cl) give the title compounds R f SO 2 Nue605CHNR 2 in good yields. The molecular structure of I(CF 2 ) 2 O(CF 2 ) 2 SO 2 Nue605CHNMe 2 is presented.

SYNTHESIS OF NOVEL α-(N-PENTAFLUORO-PHENYLAMINO)BENZYLPHOSPHONATES AND PHOSPHONIC ACIDS

Abstract A series of novel α-(N-pentafluorophenylamino)benzyl phosphonic acids are prepared by hydrolysis of corresponding phosphonates, C6F5NHCH(Ar)P(O)(OR)2 which are synthesized from the addition of N-pentafluorophenyl aromatic aldimines with dialkyl phosphite. The X-ray diffraction of C6F5NHCH(4-CH3C6H4)P(O)(OCH3), is presented.

REACTIONS OF FLUORINE-CONTAINING N-SULFINYLAMIDES WITH CARBOXYLIC ACIDS AND ACID ANHYDRIDES

Abstract Heating N-sulfinylperfluoroalkane sulfonylamides, RtSO2NSO, or N-sulfinylpentafluoroaniline, C6F5NSO, with carboxylic acids in the presence of catalytic amounts of SOCl2 gave N-perfluoroalkane sulfonylamides, RtSO2NHCOR, or N-pentafluorophenylamides, C6F5NHCOR, respectively. Acid anhydrides reacted similarly with RtSO2NSO or C6F5NSO to form N-perfluoroalkane sulfonylimides or N-pentafluorophenylimides.

Synthesis of dialkyl N-alkyl-N-perfluoroalkanesulfonyl phosphoramidates

Abstract N-Halogenperfluoroalkanesulfonylamines RfSO2N(R)X (X = Br, Cl) which are obtained by treatment of the sodium or potassium salt of N-alkylperfluoroalkanesulfonylamides RfSO2N(R)M with bromine or chlorine react readily with triethyl phosphite P(OEt)3 giving the title compounds RfSO2N(R)P(O)-(OEt)2. The reaction mechanism is discussed. Hydrolysis of these compounds gives the N—P bond broken products.

Reactions of N-sulfinylfluoroalkanesulfonylamides with alkene oxides

Abstract Reactions of N -sulfinylfluoroalkanesulfonylamides, R f SO 2 NSO ( 1 ), with alkene oxides 2 at room temperature gave the cyclo condensation products 2-oxa-3-fluoroalkanesulfonyl-1,2,3-oxathiazolidines, R f SO 2 NCH(R)CH 2 OS(O) ( 3 ). When R was phenyl, the compound decomposed at 160 °C to give N -fluoroalkanesulfonylaziridine, R f SO 2 NCH 2 CH(C 6 H 5 ), with elimination of SO 2 . Acidic hydrolysis of 3c [R f =I(CF 2 ) 2 O(CF 2 ) 2 , R = Ph] gave R f SO 2 NHCH(Ph)CH 2 OH ( 5 ) which was identified by X-ray diffraction analysis.

A convenient synthesis of N-perfluoroalkanesulfonylphosphoramidates

Abstract N-Perfluoroalkanesulfonylphosphoramidates, R f SO 2 N(R)P(O)(OR′) 2 , have been prepared by a one-step reaction of perfluoroalkanesul-fonylphosphoramidates R f SO 2 NHR with dialkyl phosphites and KOH in carbon tetrachloride in the presence of a catalytic amount of a tetraalkylphosphonium bromide.

A convenient synthetic method for N-perfluoroalkanesulfonyl sulfilimines and sulfoximides

Abstract Reaction of perfluoroalkanesulfonyl amides with dialkyl sulfides or sulfoxides in the presence of stoichiometric amounts of lead tetra-acetate gave N -perfluoroalkanesulfonyl sulfilimines or N -perfluoroalkanesulfonyl sulfoximides, respectively, in moderate to good yield.

A convenient route to N-perfluoroalkanesulfonyl, N′-phenyldiazene N′-oxide RfSO2N=N+(O)−Ph

Abstract A synthesis of N -perfluoroalkanesulfonyl- N′ -phenyldiazene, N′ -oxides in fair to good yields is described by condensation of nitrosobenzene and N,N -dichloroperfluoroalkanesulfonyl amide without promoters.