Gary L. Gard

5-(1,2,3-Triazol-1-yl)tetrazole derivatives of an azidotetrazole via click chemistry.

N-C bonded (non-bridged) 5-(1,2,3-triazol-1-yl)tetrazoles were synthesized by the Cu(I)-catalyzed 1,3-dipolar azide-alkyne cycloaddition click reaction using 5-azido-N-(propan-2-ylidene)-1H-tetrazole (1). For example, the click reaction of 1 in the presence of CuSO(4)5 H(2)O and Na ascorbate at 65-70 degrees C for 48 h in CH(3)CN/H(2)O co-solvent was found to be limited to only terminal alkynes that have electron-withdrawing groups, CF(3)C[triple chemical bond]CH (2 a) and SF(5)C[triple chemical bond]CH (2 b), giving rise to isopropylidene-[5-(4-trifluoromethyl-1,2,3-triazol-1-yl)tetrazol-1-yl]amine (3 a) and isopropylidene-[5-(4-pentafluorosulfanyl-1,2,3-triazol-1-yl)tetrazol-1-yl]amine (3 b) in 47 % and 66 % yields, respectively. When carried out under conditions using CuI and 2,6-lutidine as catalysts at 0 degrees C for 13 h in CHCl(3), the click reaction was versatile toward alkynes even those having electron-donating groups. Properties of new products were determined and compared with those of 1. Heats of formation, detonation pressures, detonation velocities and impact sensitivities are reported for these new 5-(1,2,3-triazol-1-yl)tetrazoles.

Electrochemical properties of perfluoroalkane disulfonic [HSO[sub 3](CF2)[sub n]SO[sub 3]H] acids relevant to fuel cell technology

The electrochemical properties of a homologous series of perfluoroalkane‐α, ω‐disulfonic acids were measured. These acids are high molecular weight analogs of trifluoromethane sulfonic acid, having the general molecular formula. Properties measured included the solubility and conductivity of aqueous solutions, the extent of anion specific adsorption on platinum, and oxygen reduction kinetics on platinum, for acids having . The following trends in properties with variation in were observed: solubility in water and the conductivity of aqueous solutions decreased dramatically with increasing ; an increase in the extent of anion specific adsorption with increasing ; at constant pH, rate of oxygen reduction on Pt decreased with increasing ; for a given acid (value of ), the rate of oxygen reduction decreased exponentially with increasing acid concentration. These trends in physical properties can be explained in a straightforward manner if it is assumed that there is successively weaker hydration of the anions with increasing ,i.e., size of the anion. Of the acids in this homologous series, the acid appears to have the best combination of properties for a fuel cell electrolyte.

Specific heat and critical fields of the organic superconductor β″–(BEDT-TTF)2SF5CH2CF2SO3

We report on specific-heat, magnetization, and ac-susceptibility measurements of {beta}{sup {double_prime}}-(BEDT-TTF){sub 2}SF{sub 5}CH{sub 2}CF{sub 2}SO{sub 3}, an organic superconductor with T{sub c}=4.5 K, where BEDT-TTF stands for bis(ethylenedithio)-tetrathiafulvalene. The jump of the specific heat C at T{sub c} and the exact form of the specific-heat difference between C in the superconducting (B=0 T) and in the normal (B=3.5 T) state can be well described by BCS theory with strong coupling. We estimate an electron-phonon coupling parameter {lambda}{approx}1.1. From measurements of C in magnetic fields we extract the upper critical field B{sub c2}(T). Low-field dc-magnetization measurements were used to determine the temperature dependence of the lower critical field B{sub c1}. From T{sub c} down to {approximately}3 K the characteristic suppression of B{sub c1}{sup {perpendicular}}(T) below the sensitivity limit is observed. {copyright} {ital 1998} {ital The American Physical Society}

Use of controlled oxidation to increase the surface area of coal: Application to a bituminous and a semi-anthracite coal

Abstract This Paper supplements previous work on the use of controlled oxidation to increase the surface area of coal by examining the effects of different temperatures of treatment and different ranks of coal. The work on an hvA bituminous coal showed no increase in the area by nitrogen when the oxidation was carried out at 375 °C, but at least a 72-fold increase at 400 °C. The increase in surface area measured by nitrogen adsorption for two other coals (a semi-anthracite and an hvC bituminous coal) similarly oxidized, varied from 3 to 20-fold, depending on whether comparison is made with the values for the raw coal or with values obtained after heating to 400 °C in nitrogen. Measurements made on the stability of the increased surface as a function of time showed that the newly created surface disappeared at rates as high as 30% per month.

Crystal structure, physical properties and electronic structure of a new organic conductor β″-(BEDT-TTF)2SF5CHFCF2SO3

John A. Schlueter,* Brian H. Ward, Urs Geiser, Hau H. Wang, Aravinda M. Kini, James Parakka, Emilio Morales, H.-J. Koo, M.-H. Whangbo, R. W. Winter, J. Mohtasham and Gary L. Gard Materials Science Division, Argonne National Laboratory, Argonne IL 60439. E-mail: JASchlueter@anl.gov Department of Chemistry, North Carolina State University, Raleigh, USA NC 27695-8204 Department of Chemistry, Portland State University, Portland, USA OR 97207-0751

New pentafluorothio (SF5) esters

Abstract The addition of either SF5Br or SF5Cl to a number of unsaturated esters is discussed. The new SF5 esters, SF5CH2CHBr(OAc), SF5CH2CHBrC(O)OC2H5, SF5CH(C(O)OC2H5)CHBr(OAc) and SF5CH2CHClCH2OAc, were prepared from vinyl acetate, ethyl acrylate, β-acetoxyethyl acrylate and allyl acetate, respectively (OAcCH3C(O)O). The ester SF5CH2C(O)OCH3 was prepared by peracid oxidation of the acetal SF5CH2CH(OCH3)2. Base treatment of SF5CH2CHClCH2OAc did not give an epoxide but, unexpectedly, produced the novel SF5CHCHCH2OH. This alcohol is the first example of an SF5-containing ene-ol.

Iodofluoroalkylsulfonyl fluorides - synthesis and conversion to new derivatives

Abstract The thermal reaction of I(CF2)2O(CF2)2SO2F 1 with unsaturated alkenes and alkynes, in the presence of benzoyl peroxide, was studied as a means for preparing reactive iodofluoroalkylsulfonyl fluorides. The following compounds have been prepared and characterized: R(CF2)2O(CF2)2SO2F where R = I (CH2)2, I(CH2)4, CH3CH2, -(CH23-, ClCH2CHICH2, ICHCH (cis and trans), CF3CHCH (E and Z). The Alcohol, HO (CH2)2(CF2)2O(CF2)2SO2F, and olefin, H2CCH(CF2)2O(CF2)2SO2F, have been also synthesized from the corresponding iodoalkane. Infrared, mass and NMR spectra data are presented in order to support the assigned structures.

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 polyfluoroalkoxysulfonyl fluorides (II)

Abstract The reaction of CF 2 CF 2 OS O 2 with haloalkanes (RX, X = I, Br) in the presence of metal fluorides, MF (M = Cs + , Ag + ) was studied as a means for preparing novel reactive polyfluoroalkoxysulfonyl fluorides. The following compounds have been prepared and characterized: ROCF 2 CF 2 SO 2 F where R = OCH 2 C HCH 2 , (CH 3 ) 3 SiCH 2 , (CF 3 ) 2 CFCH 2 CH 2 , HCCCH 2 , BrCH=CHCH 2 ( cis and trans ), CH 2 =CBrCH 2 , (CH 3 CH 2 O) 2 P(O)CH 2 CH 2 , CH 3 CH 2 OPF(O)CH 2 CH 2 . Infrared, mass and nmr spectra are presented in order to support the assigned structures.

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.