Trifluoromethyl chloride, reaction

With the exception of the reactions of trifluoromethyl radicals with sulfur vapor, which is really a separate class of reactions, if the power supplied to the load coil surrounding the reactor (see Fig. 2) was maintained at, or near, the minimum amount needed to support the discharge, in only two cases were compounds found that clearly resulted from reactions other than replacement of halogen by trifluoromethyl. The reaction of tellurium tetrabromide (or the chloride) gave, in addition to the products just reported, very small proportions of such species as BrCF2TeCF2Br and (C2F5)2Te, which were isolated in yields of... 

TRIFLUOROMETHYL CHLORIDE (75-72-9) Violent reaction with aluminum. Reacts with magnesium, zinc, and their alloys. Reacts, possibly violently, with barium, sodium, and potassium. Undergoes thermal decomposition when exposed to red-hot surfaces or fire, forming chlorine, hydrogen fluoride or chloride, phosgene, and carbonyl fluoride. 

The direct insertion of indium C-X bond of bromoallqrlphosphonates (584) in the presence of CuCl afforded phosphorylated allq lindium reagents (585). A practical application of (585) has been evaluated in the synthesis of arylallg l phosphonates (586) via a Pd-catalysed crosscoupling reaction (Scheme 170). A wide range of functional groups, including ester, ketone, aldehyde, nitrile, nitro, trifluoromethyl, chloride, methojq, hydroxy, and amino, have been tolerable in this reactions. ... 

Reactions Involving the Trifluoromethyl Group. Aluminum chloride effects chlorinolysis of ben2otrifluoride to give ben2otrichloride (307). High yields of volatile acid fluorides are formed from ben2otrifluoride and perfluorocarboxyUc acids (308). 

Codeposition of silver vapor with perfluoroalkyl iodides at -196 °C provides an alternative route to nonsolvated primary perfluoroalkylsilvers [272] Phosphine complexes of trifluaromethylsilver are formed from the reaction of trimethyl-phosphme, silver acetate, and bis(trifluoromethyl)cadmium glyme [755] The per-fluoroalkylsilver compounds react with halogens [270], carbon dioxide [274], allyl halides [270, 274], mineral acids and water [275], and nitrosyl chloride [276] to give the expected products Oxidation with dioxygen gives ketones [270] or acyl halides [270] Sulfur reacts via insertion of sulfur into the carbon-silver bond [270] (equation 188)... 

The reactions of mercuric iodide, mercuric bromide, and mercuric chloride with the excited species produced in the hexafluoroethane plasma were examined first, as the expected products were known to be stable and had been well characterized 13). Thus, these reactions constituted a "calibration of the system. Bis(trifluoromethyl)mercury was obtained from the reaction of all of the mercuric halides, but the highest yield (95%, based on the amount of metal halide consumed) was obtained with mercuric iodide. The mole ratios of bis(trifluoro-methyDmercury to (trifluoromethyl)mercuric halides formed by the respective halides is presented in Table I, along with the weight in grams of the trifluoromethyl mercurials recovered from a typical, five-hour run. 

A novel synthesis of a germanimine involves the reaction between germane and CF3NO.36 The N-trifluoromethylgermanimine was subsequently treated with (CF3)2NO to give the mono- and the bis[bis(trifluoromethyl) nitroxy]-substituted derivatives. These derivatives were subsequently treated with hydrogen chloride to give the mono- or the dichloro derivatives, respectively. 

The triethylamine-induced reaction of benzohydroximinoyl chlorides, precursors of nitrile oxides, with P-trifluoromethyl-substituted acetylenic esters gives rise to three products 5-trifluoromethyl-4-isoxazolecarboxylates, 213 (R1 =CF3,... 

R2=MeC>2C, R3 = d-F CC F ), regioisomeric 4-trifluoromethyl-5-isoxazole-carboxylates, 213 (R1 =Me02C, R2 =CF3, R3 = 4-F3CC6H4) and unexpectedly oximinoyl chloride 214, resulted by 1,4-addition. Product distribution is rationalized in terms of two competing reactions, either 1,4-addition of the oximate anion to the acetylenic ester or formation of the nitrile oxide followed by 1,3-dipolar cycloaddition. Anionic 1,4-addition of the oximinoyl chloride to the acetylenic ester is favoured at low temperatures, while nitrile oxide formation, followed by cycloaddition, occur at temperatures above 0 ° (371). 

Smooth conversion of ( )-(—)-neocarazostatin B (268) to carquinostatin A (278) was achieved by oxidation using ceiium(IV) ammonium nitrate (CAN). The identity of the absolute configuration of both alkaloids, and also the enantiopurity of neocarazostatin B (>99% ee), has been additionally confirmed by the transformation of carquinostatin A (278) to the (l ,l )-]VIosher ester 822 by reaction with (S)-(+)-a-methoxy-a-(trifluoromethyl)phenylacetyl (MTPA) chloride (613) (Scheme 5.97). 

There are several different routes to carboxamides. In most of these reactions, a carboxylic acid is converted to a more reactive intermediate, e.g. the acid chloride, which is then allowed to react with an amine. For practical reasons, it is preferable to form the reactive intermediate in situ. Arylboronic acids with electron-withdrawing groups such as (3,4,5-trifluorophenyl)boronic acid act as highly efficient catalysts in the amidation between carboxylic acids and amines. (3-Nitrophenyl)boronic acid and [3,5-bis(trifluoromethyl)phenyl]boronic acid are also effective eimidation catalysts and commercially available. 

To date, however, only few reactions between phosphine and a non-metal halide, in which a chemical bond is formed between phosphorus and a non-metal by HCl condensation, are known. To these, apart from the above-mentioned reactions, belongs also the reaction with CF3SCI which, depending upon the chosen proportions of the reactants, in a sealed tube at -95 °C leads to the formation of (CF3S)2PH or (CF3S)3P Both compounds are not very stable thermally and decompose at 40-50 °C. Tris(trifluoromethylthio)-phosphine forms an unstable adduct with chlorine, which decomposes at 0 °C to give a mixture of PCI3, bis(trifluoromethyl)-disulphide and trifluoromethyl-sulphenyl chloride. 

A recent report on trifluoromethylsulfenylation of (3-keto acids and derivatives describes isolation of 29 in good yield from reaction of 27 with trifluoromethyl-sulfenyl chloride (Scheme 6.10). Mechanistically, this was rationalized via electrophilic attack of trifluoromethylsulfenyl chloride on the enamine tautomer 27a to generate 28 followed by intramolecular cyclization through the imide oxygen with concomitant loss of CF3SH to produce 29. The product was characterized spectroscopically. 

Phase-transfer catalysis was found <1996CHEC-II(7)1> to be successful for N-substitution of the furo[3,2-/ ]pyrrole system. The reaction of 81a with methyl iodide or benzyl chloride gave 81b and 81c derivatives. Methyl 4-acetyl-2-[3-(trifluoromethyl)phenyl]furo[3,2-3]pyrrole-5-carboxylate 82 was obtained by reacting 81a in boiling acetic anhydride (Scheme 6) <2005CEC311>. 

To make the transformation even more useful, different carbon electrophiles should be connected sequentially in a stepwise manner. For this purpose, a transition-metal-catalyzed cross-coupling reaction opened the way. As shown in Scheme 22, cinnamyl chloride is treated with bis(iodozincio)methane (3) in the presence of palladium catalyst with various phosphine ligands. Phosphine ligands, having an electron-withdrawing group, such as tris[3,5-bis(trifluoromethyl)phenyl]phosphine and tris(2-furanyl)phosphine, show excellent results47. 

This reaction has been carried out in DMAC for the trifluoromethylation of activated aryl chlorides such as 2,4-dinitro-l-chlorobenzene [95-97]. Similar trifluoromethylation can be accomplished with trifluoromethylcopper generated from trifluoromethanesulfonyl chloride and copper powder in DMAC [98] (Scheme 33). 

---