Benzenes fluoromethyl

REACTION OF SULFOXIDES WITH DIETHYLAMINOSULFUR TRIFLUORIDE PREPARATION OF FLUOROMETHYL PHENYL SULFONE, A REAGENT FOR THE SYNTHESIS OF FLUOROALKENES (Benzene, [(fluoromethyl)sulfonyl]-)... 

Diethylaminosulfur trifluoride Sulfur, (diethylaminato)trifluoro- (9) (38078-09-0) Fluoromethyl phenyl sulfide Benzene, [(fluoromethyl)thio]- (9) (60839-94-3)... 

How do the charges on the ring carbons of toluene and (tri fluoromethyl)benzene relate to the regioselectivity of nitration" ... 

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... 

Alkynes substituted with one or two trifluoromethyl groups are also highly reactive dienophiles [9] Indeed, hexafluoro-2-butyne is used increasingly as a definitive acetylenic dienophile in "difficult Diels-Alder reactions. It was used, for example, to prepare novel inside-outside bicycloalkanes via its reaction with cir,trnns -l,3-undecadiene [74] (equation 67) and to do a tandem Diels-Alder reaction with a l,l-bis(pyrrole)methane [75] (equation 68) Indeed, its reactions with pyrrole derivatives and furan have been used in the syntheses of 3,4-bis(tri-fluoromethyl)pyrrole [76, 77] (equation 69) and ],4-bis(trifluoromethyl)benzene-2,3-oxide [78] (equation 70), respectively. 

A mixture of 2.0 g (0.064 mol) of 2-fluoromethyl-3-(o-tolyl)-6-nitro-4(3H)-qulnazolinone, Oi g of 5% palladium-carbon and 100 ml of acetic acid is shaken for 30 minutes in hydrogen gas. The initial pressure of hydrogen gas is adjusted to 46 lb and the mixture is heated with an infrared lamp during the reaction. After 30 minutes of this reaction, the pressure of hydrogen gas decreases to 6 lb. After the mixture is cooled, the mixture is filtered to remove the catalyst. The filtrate is evaporated to remove acetic acid, and the residue is dissolved in chloroform. The chloroform solution is washed with 5% aqueous sodium hydroxide and water, successively. Then, the solution is dried and evaporated to remove solvent. The oily residue thus obtained is dissolved in 2 ml of chloroform, and the chloroform solution is passed through a column of 200 g of silica gel. The silica gel column is eluted with ethyl acetate-benzene (1 1). Then, the eluate is evaporated to remove solvent. The crude crystal obtained is washed with isopropylether and recrystallized from isopropanol. 0.95 g of 2-fluoromethyl-3-(o-tolyl)-6-amino-4(3H)-quinazolinone Is obtained. Yield 52.5% MP 195°-196°C. 

Dediazoniation of three o-substituted benzenediazonium salts in pyridinium poly(hydrogen fluoride) yields different products depending on the substituent, as Olah and Welch (1975) have found. The 2-methyl derivative gives 2-fluoro-toluene. With the 2-nitrobenzenediazonium ion the main product is 3-nitrofluoro-benzene, the 2-isomer being formed only in small quantities. Finally, the 2-tri-fluoromethyl derivative yields all three isomeric trifluoromethylfluorobenzenes. 

Aniline, 2-chloro- [Benzenamine 2-chloro-], p-bromination of, 55, 23 Aniline, 3 chloro- [Benzenamine, 3-chloro-], p bjomination of, 55, 23 Aniline, //.A -diethyl- [Benzenamine, N,N-diethyl-], p-bromination of, 55, 23 Aniline,TV,//-dimethyl- [Benzenamine, N,N-dimethyl-], p-brommation of, 55, 23 Aniline, 2,3-dimethyl- [Benzenamine, 2,3-dimethyl-], p-bromination of, 55, 23 Aniline, 2,5-dimethyl- [Benzenamine, 2,5-dimethyl-], p-biomination of, 55,23 Aniline, 3,5-dimethyl [Benzenamine, 3,5-dimethyl ], p bromination of, 55,23 Aniline, Ar,iV-dimethyl-3-(trifluoromethyl) [Benzenamine, At,Ar-dimethyl-3-tn-fluoromethyl-], 55,21 Aniline, 3-methoxy- [Benzenamine, 3-methoxy-], p-bromination of, 55, 23 Aniline, TV-methyl- [Benzenamine, //-methyl-], p-biomination of, 55, 23 Aniline, 2-methyl-//,JV-dimethyl- [Benzen-amme, 2/V,/V-tnmethyl-], p-bromina-tion of, 55, 23... 

A solution of 10.5 g. (0.046 mol) of freshly distilled bis(tri-fluoromethyl)-l,2-dithiete (Note 2) in 200 ml. of n-pentane is cooled to —10° in a 1-1. round-bottomed flask equipped with an efficient reflux condenser and protected from moist air by a dry nitrogen blanket. A solution of 3.0 ml. (0.023 mol) of nickel carbonyl dissolved in 100 ml. of w-pentane is added down the condenser in one portion to this solution. The mixture is swirled to mix. An intense blue-violet color develops in about 15 to 20 seconds and after 1 to 2 minutes, vigorous evolution of carbon monoxide occurs. This evolution subsides in 10 minutes and the deep violet solution is allowed to warm to 0° during 2 hours to ensure complete reaction. Most of the pentane is removed by distillation at atmospheric pressure, the remaining 50 to 60 ml. is removed in vacuo (0.1 mm.), and the resultant crystalline mass is evacuated (0.1 mm.) at 50° for 4 hours. The crude product consists of shiny black-purple needles and weighs 11.8 g. (98%). Recrystallization from dry benzene (Note 3) gives shiny black crystals, m.p. 134 to 135° (sealed tube). The complex is air-stable but should be kept out of contact with moist air. 

In contrast to linear unsaturated acids and anhydrides vide supra), 3,4,5,6-tetrahydrophthalic anhydride reacts with sulfur tetrafluoride to give mainly bicyclo products, lactone 31 and tetrafluoro ether 32, with the trifluoromethyl derivatives 33 and 34 as minor products. The ratio of products strongly depends on the reaction conditions at elevated temperature (> 150°C) cleavage of the C —O —C bond and dehydrogenation occur resulting in l,2-bis(tri-fluoromethyl)benzene (35) in high yield.252... 

Tetrabuty lammonium dihydrogen trifluoride (TB ADTF) fluorinates organic sulfides in the presence of l,3-dibromo-5,5-dimetbylhydantoin (DBH). l-Chloro-4-(methylsulfanyl)benzene (20) is fluorinated to l-chloro-4-[(fluoromethyl)sulfanyl]benzene (21) in 90% yield.216... 

Reaction of disodium hexafluorosilicate with (trichloromethyl)benzene at 221 C for 10 hours affords a mixture in which (chlorodifluoromethyl)benzene (35 %) predominates over (dichloro-fluoromethyl)benzene (15%) and (trifluoromethyl)benzene (0.5%).15 In contrast, addition of antimony(V) chloride to the reaction of l-chloro-4-(trichloromethyl)benzene with disodium hexafluorosilicate increases the yield of l-chloro-4-(trifluoromethyl)benzene.lb... 

Schlosser and co-workers have reported the shift of lithium in lithiated l-bromo-3-(tri-fluoromethyl)benzene 2,fa Quenching at — 100 C gives exclusively the product derived from 2, whereas after 2 hours at — 75 C, arene 2 is completely converted into less basic 3. A lithium-iodine exchange takes place in lithiated 2-chloro-3-iodo-6-(trifluoromethyl)pyridine 4, which at —85 C is totally converted into the less basic isomer 5.7 These rearrangements have been discussed in terms of a base-catalyzed halogen dance or halogen-shuffling mechanism. 

Substituted benzenes alkyl, fluoromethyl, chloro, iodo, hydroxy, nitro. 

A carbon-carbon double bond is cleaved in the reaction of hexakis(tri-fluoromethyl)benzene with Pt3(CNBu )6 to give 59 (374) (see Section V,E). 

Representative proton and carbon chemical shifts and coupling constants of benzyl fluorides and fluoromethyl naphthalenes are given in Scheme 3.78. Note that the proton chemical shifts for fluoromethyl naphthalenes are significantly larger than those of fluoromethyl benzenes. 

---