Bis trifluoromethyl

FLUORINECOMPOUNDS,ORGANIC - FLUORINATED AROMATICCOMPOUNDS] (Volll) p-Fluoro-a,a-bis(trifluoromethyl)benzyl alcohol [2402-74-6]... 

Inorganic analytical appHcations for ben2otrifluoride derivatives include sodiumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate (Kobayashi s reagent) (345), and 4-(2,6-dinitro-4-trifluoromethylphenyl)aminoben2o-15-crown-5 (modified Takagi reagent (346). 

Commercial trifluoromethylquiaoline-based products are mefloquiae [53230-10-7], an antimalarial, and floctafenine [23779-99-9], an analgesic. The cycli2ation step to constmct the 2,8-bis(trifluoromethyl)quiaoiine nucleus ia mefloquiae employs 2-amiaobea2otrifluoride [88-17-5] and ethyl 4,4,4-trifluoroacetoacetate [372-31-6] (448). 

StericaHy hindered or very electrophilic substituted ketenes, such as diphenylketene, di-Z rZ-butylketene [19824-34-17, and bis(trifluoromethyl)ketene, are quite stable as monomers. Ketenimines tend to polymerize. The dimerization of thioketenes results in 1,3-dithiacyclobutanones (6) (45), a type of dimer not observed with ketenes. 

Methylarsine, trifluoromethylarsine, and bis(trifluoromethyl)arsine [371-74-4] C2HAsF, are gases at room temperature all other primary and secondary arsines are liquids or solids. These compounds are extremely sensitive to oxygen, and ia some cases are spontaneously inflammable ia air (45). They readily undergo addition reactions with alkenes (51), alkynes (52), aldehydes (qv) (53), ketones (qv) (54), isocyanates (55), and a2o compounds (56). They also react with diborane (43) and a variety of other Lewis acids. Alkyl haUdes react with primary and secondary arsiaes to yield quaternary arsenic compounds (57). 

Diene moieties, reactive in [2 + 4] additions, can be formed from benzazetines by ring opening to azaxylylenes (Section 5.09.4.2.3). 3,4-Bis(trifluoromethyl)-l,2-dithietene is in equilibrium with hexafluorobutane-2,3-dithione, which adds alkenes to form 2,3-bis-(trifluoromethyl)-l,4-dithiins (Scheme 17 Section 5.15.2.4.6). Systems with more than two conjugated double bonds can react by [6ir + 2ir] processes, which in azepines can compete with the [47t + 27t] reaction (Scheme 18 Section 5.16.3.8.1). Oxepins prefer to react as 47t components, through their oxanorcaradiene isomer, in which the 47r-system is nearly planar (Section 5.17.2.2.5). Thiepins behave similarly (Section 5.17.2.4.4). Nonaromatic heteronins also react in orbital symmetry-controlled [4 + 2] and [8 + 2] cycloadditions (Scheme 19 Section 5.20.3.2.2). 

A few special syntheses of thiirane derivatives from four-membered sulfur heterocycles are known. Methylenethiiranes are derived by thermolysis of the tosylhydrazones of thietan-3-ones (Scheme 143) (81TL4815), and 2,2,3,3-tetrakis(trifluoromethyl)thiirane is obtained by thermolysis of 2,2,4,4-tetrakis(trifluoromethyl)-l,3-dithietane 1,1-dioxide with loss of sulfur dioxide. 2,2,3,3-Tetrakis(trifluoromethyl)thiirane 1,1-dioxide is obtained in low yield by heating a mixture of 3,3-bis(trifluoromethyl)-l,2,4-oxadithietane 2,2,4,4-tetroxide and bis(trifluoromethyl)ketene. The mono-episulfide of norbornadiene is obtained from thietane derivative (65 Scheme 144) (73JOC649). 

Pyrazole, 1 -bis(dimethylamino)phosphino- H NMR, 5, 185 (B-73NMR165, B-75MI40402) Pyrazole, 3,5-bis(trifluoromethyl)-1 -trimethylsilyl-5, 213 <71JOM(27)185)... 

H-Azepine, bis(trifluoromethyl)dihydro-synthesis, 7, 539 3H-Azepine, 2-butoxy-synthesis, 7, 536 3H-Azepine, 2-butylamino-synthesis, 7, 536 3H-Azepine, 2-dialkylamino-quaternization, 7, 511 synthesis, 7, 536... 

Benzimidazoline, 2,2-bis(trifluoromethyl)-synthesis, 5, 471 Benzimidazolines acidity, 5, 425 Benzimidazolinethiones Mannich reaction, 5, 390 synthesis, 5, 460 Benzimidazoline-2-thiones alkylation, 5, 444—445 S-alkylation, 5, 444 mercuration, 5, 445 reactions... 

Oxazolidin-5-one, bis(trifluoromethyl)-reactions, 6, 213 Oxazolidinones polymers, 1, 281-282 reactions, 6, 213 Oxazolidinones, imino-rearrangement, 5, 775 Oxazolidinones, vinyl-polymers, 1, 281 Oxazolidin-2-ones circular dichroism, 6, 185 H NMR, 6, 181 IR spectroscopy, 6, 183 PE spectroscopy, 6, 183 reactions, 6, 213... 

Thiirene, 2-acetyI-3-methyl-rearrangement, 7, 143 Thiirene, 2,3-bis(trifluoromethyl)-photolysis, 7, 142 Thiirene, 2,3-diaryl-... 

Steric factors would ordinarily be expected to induce a preference for the larger group to move outward and thus generate the -isomer. It was observed, however, that in the case of l,2,3,4-tetrafluoro-tran5-3,4-bis(trifluoromethyl)cyclobutene, ring opening occurred with an inward rotation of the trifluoromethyl groups. ... 

At 320 °C, cesium tetrafluorocobaltate converts benzotrifluoride to /n-fluo-robenzotrifluoride, 2f/-heptafluorotoluene, octafluorotoluene, pertluoro-l -meth-ylcyclohexene, and perfluoromethylcyclohexane [29] l,3-Bis(trifluoromethyl)-benzene is convened at 420 °C to 4,5,6-trifluoro-l,3-bis(trifluoroethyl)bcnzene, perfluoro-l,3-dimethylbenzene, and perfluoro-l,3-dimethylcyclohexane [29], p-Xylene gives at 350 °C l,4-bis(difluoromethyl)tetrafluorobenzene, 1-di-fluoromethyl-3-trifluoromethyltetrafluorobenzene, perfluoro-1,3-dimethyl-benzene, and perfluoro-1,3-dimethyloyclohexane... 

Methylmorpholine on treatment with cobalt trifluoride at 100 °C for 3 h yields 10 fluorinated morpholines and a small amount of bis(trifluoromethyl)-fluoromethylamine [/9] (equation 19)... 

The reaction of cyclohexane-cw-1,2-dicarboxylic acid with sulfur tetrafluoride affords the correspoding cyclic ether in a 70% yield with very limited formation of the bis(trifluoromethyl) derivative [2IJ] (equation 107)... 

Fluorination of thiophene-2,5-dicarboxylic acitl with a sulfur tetrafluoritie-hydrogen fluoride mixture provides 2,5-bis(trifluoromethyl)thiophene in a 69% yield no fluorine addition to the thiophene ring occurs [229J. Also, imidazole mono- and dicarboxylic acids yield only the respective trifluo-romethyliinidazoles [230],... 

Molybdenum hexafluoride, in the presence of boron trifluonde, reacts with acetic acid and haloacetic acids at 130-160 °C to give respectively, 1,1,1 tri fluoroethane and 1,1 1 trifluorohaloetlianes in 60-89% yields [2d0, 241] Prolonged treatment of pyridine mono and dicarboxylic acids with an excess of molybdenum hexafluoride at elevated temperatures provides the respective mono-and bis(trifluoromethyl)pyridines in good yields [241] (equation 127)... 

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