Robin J. Terjeson

Pentafluoro-λ6-sulfanyl (SF5) fluoroalkyl iodides

Abstract Fluoroalkyl iodides are an important class of compounds used in the preparation of large numbers of fluoro-organo and fluoro-organometallic derivatives. We report the synthesis of several SF 5 -containing fluoroalkyl iodides derived from an improved synthesis of SF 5 CF 2 CF 2 I. They are: SF 5 CF 2 CF 2 CH 2 CH 2 I, SF 5 CF 2 CF 2 CF 2 CF 2 I, SF 5 CF 2 CF 2 (CH 2 CH 2 ) 2 I, SF 5 CF 2 CF 2 CH=CHI/isomer and SF 5 CF 2 CF 2 CHFCF 2 I/isomer. In addition, the higher homologs SF 5 (CF 2 ) 6 I, SF 5 CF 2 CF 2 (CHFCF 2 ) 2 I/isomer and SF 5 CF 2 CF 2 (CH 2 CH 2 ) 3 I have been identified.

New fluorosulfonyl-containing monomers/polymers

Abstract New fluorinated monomers and polymers containing the fluorosulfonyl group have been prepared and characterized via the reaction of β-fluorosultones ( CF 2 CF 2 OSO 2 , CF 3 CFCF 2 OSO 2 , SF 5 CFCF 2 OSO 2 , SF 5 CHCF 2 OSO 2 ) with polyvinyl and allyl alcohols.

AN IMPROVED AND FACILE PREPARATION OF SF5BR

Abstract A high yield and facile preparation of SF 5 Br is described. This preparation is carried out either at room temperature or with slight heating in a one-pot procedure.

A facile preparation of ICF2CF2I and its reaction with ethylene

Abstract A facile preparation of ICF2CF2I in high yield is carried out using a halogen lamp. In a similar manner, ICF2CF2I reacts with ethylene to give ICH2CH2CF2CF2CH2CH2I.

New pentafluorothio (SF5) fluoropolymers

Abstract New fluorinated polymers containing the pentafluorothio group have been prepared from SF 5 Br and the appropriate fluoroolefin under reaction temperatures of 90±5°C and autogeneous pressures of up to 90 atmosphere for periods of four days to two weeks. With ethylene, FCH 2 CH 2 Br and SF 5 CH 2 CH 2 Br were formed. A new monomer addition product, SF 5 CF 2 CF 2 Br, is also reported for the first time.

New fluoroalkenes and alcohol with pentafluoro-λ6-sulfanyl (SF5) terminal groupings

Abstract The synthesis of new compounds that contain both a terminal pentafluoro-λ 6 -sulfanyl (SF 5 ) group and an alkene or alcohol functional group is reported. Five new SF 5 containing alkenes and one new SF 5 containing alcohol were prepared: SF 5 CH 2 CHBrCH 2 CF CF 5 ( 1 ), SF 5 CF 2 CF 2 CH 2 CHICH 2 CF CF 2 ( 2 ), SF 5 CF 2 CF 2 CH 2 CH 2 CH 2 CF CF 2 ( 3 ), SF 5 CF 2 CF 2 CH CH 2 ( 4 ), SF 5 (CF 2 CF 2 ) 2 CH CH 2 ( 5 ) and SF 5 CF 2 CF 2 CH 2 CH 2 OH ( 6 ). These compounds are useful as monomers or as intermediates in the preparation of polymers, polymer surface coatings, and surfactants.

Silver (fluorosulfonyl)difluoroacetate - A new route to fluorosulfonyl esters

Abstract New fluorinated esters of the type FSO 2 CF 2 C(O)OR and (FSO 2 CF 2 C(O)O) 2 R′, (R = CH 3 , CH 3 CH 2 CH 2 , (CH 3 ) 3 Si, BrCH 2 CH 2 , CH 3 CH 2 OC(O)CH 2 , CH 2 = CHCH 2 ; R′ = CH 2 , CH 2 CH 2 , have been prepared and characterized via the reaction of silver difluoro(fluorosulfony)acetate with alkylbromides, alkyliodides, and trimethylsilyl iodide. All new compounds have been characterized by their respective IR/MS/NMR spectra.

New pentafluorothio (SF5)-containing alkyl dibromides

Abstract Preparation of two new SF 5 -containing compounds and one telomer was achieved by reaction of the olefins CH 2 =CHBr and CF 2 =CFBr with SF 5 Br to form SF 5 CH 2 CHBr 2 and SF 5 CF 2 CFBr 2 . In the reaction of SF 5 Br with CF 2 =CFBr, a waxy solid formed with an average formula of SF 5 (CF 2 CFBr) 10 Br.

Gas-phase structures of ethynyl- and vinyl pentafluorosulfur derivatives: an electron diffraction and microwave spectroscopy study

Abstract The gas-phase structures of ethynyl- and vinyl sulfur pentafluoride were determined by joint analyses of electron diffraction and microwave spectroscopic data. The following skeletal geometric parameters ( r z values with 3σ uncertainties) were obtained. SF 5 CCH: (SF) mean = 1.574 (1) A, ΔSF=(SF e SF a )=0.018 (14) A, SC=1.736 (6) A, CC=1.200 (7) A, F e SF a =88.9 (2)°; SF 5 CHCH 2 : (SF) mean 1.581 (1) A, ΔSF=0.020 (16) A, SC=1.787 (9) A, CC=1.337 (17) A, F e SF a =88.4 (3)° SCC=124.5 (15)°. In both compounds the equatorial SF bonds are longer than the axial ones, in accordance with the predicted “cis influence” in octahedral main group element compounds. The actual values for the bond length differences ΔSF, however, are poorly determined. The variation of the (SF) mean bond lengths between the ethynyl and vinyl derivatives can be rationalized by the different group electronegativities of these two substituents. The variation of the SC bond lengths reflects the different covalent radii of sp and sp 2 hybridized carbon atoms.

Monomeric sulfur trioxide — generation, handling and reactions with fluoroolefins

Abstract Sulfur trioxide (SO 3 ) is one of the most widely used chemicals in the world. Several convenient procedures for the generation and handling of monomeric SO 3 will be discussed here. Also, the reaction of monomeric SO 3 with CF 2 CF 2 and CF 2 CFH will be described.