Trichloromethyl benzene

The common names of (di chloromethyl)benzene and (trichloromethyl)benzene are benzal chloride and benzo trichloride respectively... 

SULFURIC AND SULFUROUS ESTERS] (Vol 23) l-Pichloromethyl)-2-(trichloromethyl)benzene... 

Dichloromethyl)benzene and (trichloromethyl)benzene arise by further side-chain chlorination of benzyl chloride. 

Heating the bis(trichloromethyl)benzene with potassium nitrate, selenium dioxide or sodium chlorate to effect conversion to the bisfacyl chloride) led to eruptions at higher temperatures, and was too dangerous to pursue. 

Trichloromethane, cl45 (Trichloromethyl)benzene, t251 Tricyclophenylsilane, pi 59 3,3,3-Trichloropropylene oxide, el 8... 

At the beginning of the 20th century, arenes carrying fluorinated side chains were made from (trichloromethyl)benzene (benzotrichloride, 12). Unexpectedly perhaps, this was a facile exchange. Proceeding stepwise, it went to completion, and full fluorination could be achieved even using antimony(III) fluoride alone. 

Kinetically controlled conditions favor the formation of mixed fluorinated compounds if per-halo derivatives are fluorinated with hydrogen fluoride. Therefore, catalysts or coreagents are used to overcome this problem. Thus, selective fluorination of l,3-bis(trichloromethyl)benzene cannot be achieved by hydrogen fluoride using variations in temperature, pressure or time.247 However, if antimony(V) fluoride is added to hydrogen fluoride the reaction produces l-(tri-chloromethyl)-3-(trifluoromethyl)benzene. Selective fluorination can also be performed in compounds with different substitution patterns.247,251 253... 

Aluminum trichloride and boron trifluoride as additives have a similar effect on the fluorination of (trichloromethyl)benzene by antimony(III) fluoride. With the additives, the reaction starts even at O C but no exchange is observed in the absence of the catalysts.12 The relative exchange reactivity order of the antimony halides is as follows antimony(III) fluoride < anti-mony(III) fluoride + antimony/V) chloride < antimony(V) dichlorotrifluoride, antimony/V) di-bromotrifluoride < antimony/V) fluoride.3... 

Chlorine atoms in (trichloromethyl)benzenes which have fluoro, chloro, dichloromethyl, chloroformyl, cyano, isocyanato, jV-phthalimino or methyl substituents in the ring are substituted by fluorine using antimony(III) fluoride (Swarts reaction).3 4 2-(Trifluoromethyl)phen-yl isocyanate, 4-chloro-2-(trifluoromethyl)phenyl isocyanate, 2,4- and 2,5-bis(trifluoro-methyl)phenyl isocyanate, and 2,4-bis(trifluoromethyl)-l,5-phenylenc diisocyanate can be obtained in this way.5... 

Exhaustive exchange of chlorine atoms for fluorine can take place in l-(dichloromethyl)-2-(trichloromethyl)benzene treated with antimony(III) fluoride, while under the action of hydrogen fluoride the exchange occurs only in the trichloromethyl group.13... 

Trichloromethyl)benzene and its derivatives are easily fluorinated with antimony(III) fluoride however, with a trifluorosilyl group in the 2-position, the use of antimony(V) chloride catalyst is required. Trifluoro[2-(trifiuoromethyl)phenyl]silane (6) can be prepared by this procedure in 87% yield.80... 

Other catalysts used in fluorinations with antimony(III) fluoride are boron trifluoride and aluminum trichloride. The reaction of (trichloromethyl)benzene with antimony(III) fluoride and catalytic amounts of aluminum trichloride at 0 X gives mainly (dichlorofluoromethyl)ben-zene and a little (chlorodifluoromethyl)benzene. With greater amounts of aluminum trichloride, the major product is (chlorodifluoromethyl)benzene, bp 142 C.81... 

The relative fluorination activity of the aromatic antimony(V) fluorides can be judged by comparing the products of their reaction with (trichloromethyl)benzene conducted in l-2mL of dichloromethane for 2 hours at a fluorinating agcnl/substrate ratio of 1 -1.2 1 (Table 4).104... 

As can be seen, trifluorodi(phenyl)-/t5-stibane is less reactive than tctrafluoro(phenyl)-/l5-stibane. Even at 100 C the former converts (trichloromethyl)benzene into (trifluoromethyl)ben-zene in only 50%. However, the lower reactivity of trifluorodi(phenyl)-/5-stibane can be used for partial fluorination. Thus, the reaction of (trichloromethyl)benzene with trifluorodi(phenyl)-25-stibane (at the molar ratio of 1 1.1) in dichloromethane for 2 hours at 50-55 C gives (chlorodifluoromethyl)benzene in 65% yield and only 4% (trifluoromethyl)benzene.104... 

To ice-cold PhSbF4 (2 2.75 g, 10 mmol) in a quartz flask was added a solution of (trichloromethyl)benzene (1.95 g, 10 mmol) in anhyd CH2C12 (8 mL) and the mixture was heated for 2h at 50-55 C. (Tri-(luoromelhyl)benzene and the solvent were distilled in vacuo (1 Torr) into a trap cooled with liquid N2. The product was separated by fractional distillation yield 1.31 g (90%) bp 101-102 C nD2(l 1.4147. 

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... 

Lead(II) fluoride is a toxic, commercially available solid which melts at 822 °C. Lead(II) fluoride converts (trichloromethyl)benzene into (trifluoromethyl)benzene in 45 % yield in the gas-liquid phase at 225°C.17... 

Chem. Abstr. Name. (Trichloromethyl)benzene lUPAC Systematic Name. a.a.a-Trichlorotoluene... 

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