- The effect of fluorination in trimethylamine: gas-phase structures of CF3N(CH3)2 and (CF3)2NCH3
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The molecular structures of CF3N(CH3)2 and (CF3)2NCH3 have been determined by gas electron diffraction.The following skeletal parameters (ra distances and H=148.1(10) pm, N-CF=138.3(16) pm, CHNCH=113.0(27) o, CHNCF=111.9(9) o; (CF3)2NCH3:C-F=133.3(3) pm, N-CH=147.8(13) pm, N-CF=142.0(8) pm, CHNCF=116.8(13) o, CFNCF=117.8(11) o.CH and CF are the methyl and trifluoromethyl carbon atoms, respectively.Experimental uncertainties are 3? values and include possible systematic errors.The most surprising result is the large difference between the N-CH and N-CF bond lengths of about 10 and 6 pm in these compounds.All nitrogen bond angles increase concomitantly with increasing number of CF3 groups.An attempt is made to rationalize the observed structural trends.
- Jin, Anding,Zhu, Xiao-Lei,Kirchmeier, Robert L.,Shreeve, Jean'ne M.,Patel, Nimesh R.,Oberhammer, Heinz
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- Die Desulfonierung-Fluorierung von Thiuramdisulfiden, [R2NC(S)S]2 und Silberdithiocarbamaten, Ag[SC(S)NR2] (R = CH3, CH3CH2, C6H5CH2), mit Silber(I)fluorid, AgF - ein einfacher Zugang zu Diorgano(trifluormethyl)aminen, R2NCF3, und Thiocarbamoylfluoriden, R2NC(S)F
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AgF and [R2NC(S)S]2 (R = CH3, CH3CH2, C6H5CH2), selectively react at room temperature in the stoichiometric ratio of 1:1 to give the corresponding N,N-diorganothiocarbamoyl fluorides, R2NC(S)F, AgSC(S)NR2 and elemental sulfur. Under comparable conditions in a ratio >3:1 both reactants selectively yield diorgano(trifluoromethyl)amines, R2NCF3, AgSC(S)NR2, Ag2S and elemental sulfur. At stoichiometry 6:1, R2NCF3, Ag2S besides elemental sulfur are formed. By analogy, thiocarbamoyl fluorides and silver dithiocarbamates react with AgF yielding selectively the corresponding trifluoromethylamines.
- Tyrra, Wieland
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p. 189 - 194
(2007/10/03)
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- REACTION OF TETRAKIS(DIMETHYLAMINO)ETHYLENE WITH CF2Br2 IN THE PRESENCE OF SECONDARY AMINES, FORMATION OF N-TRIFLUOROMETHYL-DIALKYLAMINES
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N-trifluoromethylamines of the general formula R2NCF3 (R= Me (I), Et (II), i-Pr (III), i-Bu (IV); 2R = (CH3)2C-(CH2)3-C(CH3)2 (V) and (CH2)6 (VI)) have been obtained from the corresponding secondary amines R2NH with the reagent combination tetrakis(dimethylamino)ethylene/CF2Br2/(CH2)4SO2 in moderate yields.The new N-trifluoromethylamines have been characterized by elemental analyses, multinuclear NMR and vibrational spectra and the mechanism of formation is discussed.
- Pawelke, G.
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p. 229 - 234
(2007/10/02)
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- REACTIONS OF TERTIARY FORMAMIDES WITH SULPHUR TETRAFLUORIDE. DIRECT SYNTHESIS OF (TRIFLUOROMETHYL)AMINES
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Treatment of dimethylformamide 1a, diethylformamide 1b, 1-formylpiperidine 3a, 4-formylmorpholine 3b, and ethyl-phenylformamide 5 with sulphur tetrafluoride in the presence of potassium fluoride resulted in a direct conversion of the formyl group to the t
- Dmowski, Wojciech,Kaminski, Maciej
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p. 207 - 218
(2007/10/02)
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- QUATERNARY AMMONIUM SALTS WITH PERFLUOROALKYL GROUPS AT THE NITROGEN ATOM
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Quaternary salts of aliphatic, aromatic, and heterocyclic amines with perfluoroalkyl groups at the nitrogen atom were obtained for the first time.A method is proposed for the synthesis of N,N,N',N'-tetraalkylperfluoroalkylenediamines.Diquaternary ammonium
- Yagupol'skii, L. M.,Kondratenko, N. V.,Timofeeva, G. N.,Dronkina, M. I.,Yagupol'skii, Yu. L.
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p. 2139 - 2143
(2007/10/02)
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