- Structures and conformations of trifluoromethanesulfonic anhydride, (CF3so2)2O, and bis(trifluoromethylsulfonyl)difluoromethane, (CF3so2)2CF2
-
The geometric structures and conformational properties of trifluoromethanesulfonic anhydride, (CF3SO2)2O, and bis(trifluoromethylsulfonyl)difluoromethane, (CF3SO2)2CF2 have been studied by gas electron diffraction (GED) and ab initio calculations (HF/3-21G*). The calculations predict for both systems two stable conformera with C2 symmetry and one with C1 symmetry. In both compounds structures with C2 symmetry and dihedral angles SOSC ≈ 100° ((CF3SO2)2O) and SCSC ≈ 150° ((CF3SO2)2CF2) are lowest in energy. According to the GED analyses the dominant conformer of (CF3SO2)2O possesses C2 symmetry with SOSC dihedral angles of 99.1(14)°. The presence of up to 30% of the two other conformers cannot be excluded; for (CF3SO2)2CF2 only one conformer with C2 symmetry and SCSC dihedral angles of 143(2)° is observed. A complete set of geometric parameters is given.
- Haist, Ralph,Mack, Hans-Georg,Waterfeld, Alfred,Gard, Gary L.,Oberhammer, Heinz
-
-
Read Online
- Dimethylaluminum methide complex Tf2CHAlMe2: an effective catalyst for Diels-Alder reaction of α,β-unsaturated lactone derivatives with cyclopentadiene
-
Lewis acid derived by mixing Tf2CH2 and Me3Al was found to be an effective catalyst system for the catalytic DA reaction of less reactive α,β-unsaturated lactone derivative with cyclopentadiene (CP). In this catalyst system, Tf2CHAlMe2 is an active species and an excess amount of Me3Al plays an important role to lower the catalyst loading. Substituent effect of the lactone framework on π-facial selectivity was also examined. In the reactions of both γ-substituted 5-membered lactone derivatives and γ- or δ-methylated 6-membered lactone derivatives with CP, selective attack on the anti face of γ- or δ-substituent was observed. On the other hand, in the cases of γ- or ε-methylated 7-membered lactone derivatives, CP favorably attacked on the syn face.
- Yanai, Hikaru,Takahashi, Arata,Taguchi, Takeo
-
p. 12149 - 12159
(2008/02/10)
-
- Sulfonates, polymers, resist compositions and patterning process
-
A sulfonate compound having formula (1) is novel wherein R1 to R3 are H, F or C1-20 alkyl or fluoroalkyl, at least one of R1 to R3 contains F. A polymer comprising units derived from the sulfonate compound is used as a base resin to formulate a resist composition which is sensitive to high-energy radiation, maintains high transparency at a wavelength of up to 200 nm, and has improved alkali dissolution contrast and plasma etching resistance
- -
-
-
- The addition of (CF3SO2)2CHBr to vinylidene fluoride
-
It has been found that a mixture of (CF3SO2)2CH2 and (CF3SO2)2CBr2 can be used instead of (CF3SO2)2CHBr in the radical addition to H2C{double bond, long}CF2; the 1:1 and 1:2 adducts have been isolated and characterized. An improved synthesis of (CF3SO2)2CBr2 is also reported.
- Winter, Rolf W.,Gard
-
p. 1324 - 1327
(2008/09/19)
-
- Pyrolysis of benzenediazonium bis(trifluoromethanesulfonyl)methide
-
The pyrolysis of benzenediazonium bis(trifluoromethanesulfonyl)methide in the absence of solvents did not give the carbon arylation product, PhCH(SO2CF3)2, but the oxygen phenylation product, PhO(CF3)S(O)=CHSO2CF3, in good yield. In contrast, the pyrolysis of the same compound in acetonitrile gave the acetonitrile-inserted compound, PhNH(Me)C=C(SO2CF3)2, quantitatively.
- Ishihara, Kazuaki,Hasegawa, Aiko,Yamamoto, Hisashi
-
p. 139 - 141
(2007/10/03)
-
- TRIBUTYLSTIBINE-INITIATED TRANSFORMATIONS OF DIBROMOBIS(TRIFLUOROMETHYL- AND TETRAFLUOROPROPOXYSULFONYL)METHANES
-
The reaction of dibromobis(trifluoromethyl- and tetrafluoropropoxysulfonyl)methanes with electron-deficient olefins in the presence of Bu3Sb results in formation of 1,1,2-trisubstituted electrophilic cyclopropanes in high yields.In the absence of olefins dibromobis(trifluoromethylsulfonyl)methane reacts with a threefold excess of tributylstibine, yielding the ylide Bu3Sb=C(SO2CF3)2.
- Pavlenko, N. V.,Yagupol'skii, Yu. L.
-
p. 1148 - 1151
(2007/10/02)
-
- Process for the preparation of sulfonylmethanes and derivatives thereof
-
The invention relates to a process for the synthesis of sulfonylmethanes and derivatives thereof of the formula M[(RSO2)2 CH]m (I), in which M represents H, an alkali metal or alkaline earth metal or NR'4, R' and R are monovalent organic radicals and m represents the valence of M. The process comprises reacting an ionic carbide with a sulfonyl halide, hydrolyzing the product obtained, adding a compound My Ym, in which Y represents an anion capable of reacting with the cation of the ionic carbide to the reaction medium before or after hydrolysis to give a compound which can be separated from compound (I), and y represents the valence of Y.
- -
-
-
- Bis(trifluoromethylchalcogenyl)ketenes (CF3E)2C=C=O (E = S, Se, SO2); Synthesis and Properties
-
Bis(trifluoromethylchalkogenyl)ketenes (1) are synthesized either by dehydrohalogenation of the corresponding acetyl chlorides or dehydratization of the corresponding acetic acids.In addition, treatment of trifluoromethylchalkogenyl chlorides with Ag2C=C=O provides 1a in low but 1b in good yields.Oxidation of bis(trifluoromethylsulfanyl)acetic acid with CrO3/H2SO4 gives some bis(trifluoromethylsulfonyl)ketene 1c.Starting materials for the preparation of the ketenes are mono- and bis(trifluoromethylchalkogenyl)-substituted orthoesters which are prepared from CH3C(OC2H5)3 and CF3ECl (E = S, Se).They are hydrolyzed to CH3-n(ECF3)nC(O)OH (4).For E = Se the acids 4b, d are converted by SOCl2 into CH3-n(seCF3)nC(O)Cl (7a,b).Mono- and disubstituted malonic esters 5, 6 are formed by treating diethyl malonate with sodium and then CF3ECl.Acidic hydrolysis with 62percent HBr converts 5 and 6 into the corresponding acetic acid derivatives 4.From CH3-n(SCF3)nC(O)Cl and (CH3)3SiN3 isocyanate CH3-n(SCF3)nNCO (n = 1, 2) are obtained in good yields.Hydrolysis of (CF3S)2C=C=O (1a) either in acidic or basic solution gives (CF3S)2CHC(O)OH (4c).Some chemical reactions of 1a are described.Key Words: Ketenes, bis(trifluoromethylchalkogenyl)- / Acetic acid derivatives, trifluoromethylselanyl- / Malonic acid ester, trifluoromethylselanyl- / Methane, trifluoromethylsulfanyl- / Ozonolysis / Cycloadditions
- Haas, Alois,Praas, Hans-Walter
-
p. 571 - 580
(2007/10/02)
-
