5-methyl-2-trichloromethyl

As has been mentioned in an earlier section, aqueous chlorination of sulphoxides leads to sulphones. If excess reagents are used, sulphonyl chlorides may be formed directly from sulphoxides in good yields (equation 75)89,90,193. In order for this reaction to be synthetically useful, the sulphoxide used should be symmetrical. The product is presumably formed in a stepwise manner via the sulphinyl chloride [RS(0)C1] and the sulphinic acid [RS(0)0H]. In the case of chloromethyl dichloromethyl sulphoxide, the only sulphonyl chloride formed is chloromethanesulphonyl chloride (equation 76) and this may be readily separated from the other products by distillation90,193. Similarly, oxidation of dichloromethyl methyl sulphoxide and methyl trichloromethyl sulphoxide with chlorine in aqueous acetic acid leads to the formation of methanesulphonyl chloride in 75% and 86% yields respectively. Other species are also produced but these are much more volatile and thus easily removed (equations 77 and 78). In the absence of acetic acid the yields are somewhat reduced. 

The reaction of chlorination does not stop at this stage, which forms, apart from methyl(chloromethyl)dichlorosilane, products of a deeper chlorination, i.e. methyl(dichloromethyl)dichlorosilane and methyl(trichloromethyl)dichlorosilane ... 

After partial separation of the unreacted dimethyldichlorosilane, the average composition of the chlorination products is the following 20-44% of dimethyldichlorosilane, 45-67% of methyl(chloromethyl)dichlorosilane and 11-13% of polychlorides (a mixture of methyl(dichloromethyl)- and methyl(trichloromethyl)dichlorosilanes). They are sent into boiler 15, which is a shell-and-tube heat exchanger, where the temperature of 115-120 °C is maintained with vapour (0.4 MPa). 

DSP710 CAS 71108-06-0 HR 3 5,5-DIMETHYL-2-((1-METHYLETHYL). IMINO)1,3-DITHiOLAN-4-ONE, o- (METHYL( TRICHLOROMETHYL)THI 0)AMINO)CARBONYL)OXIME mf CuHi6Cl3N302S3 mw 424.83 SAFETY PROFILE A poison by ingestion. When heated to decomposition it emits toxic vapors of NOx, SOx, and CL. 

METHYL((TRICHLOROMETHYL)THIO)AMINO)CAR BONYL)OXIME see DSP710 0,0-DIMETHYL-S-(N-xMETHYL-N-F0RMYL-CARBAMOYLMETHYL)-DITHIOPHOSPHAT see DRR200... 

METHYL((TRICHLOROMETHYL)THIO)AMINO)CAR BONYL)OXIME see MQC320... 

The reaction of methyl trichloromethyl ether with methyllithium, lithium iodide and cyclo-pentadiene gives anisole. It is formed by the rearrangement of the chloro(methoxy)carbene (or carbenoid) adduct... 

The reaction of chloromethylphosphonic dichloride with tetra-phosphorus decasulfide or with thiophosphoryl chloride are the only methods of preparation for this compound reported. The method is applicable more generally, and the syntheses of methyl-, trichloromethyl-, ethyl-, propyl-, cyclohexyl-, phenyl-, and -chlorophenylphosphonothioic dichloride from the corresponding phosphonic dichlorides have been reported. Phos-phinic chlorides of varying structures could also be converted to the corresponding thiono compounds by comparable procedures. The present method is preferable to the thiophosphoryl chloride procedure in that it does not require working under pressure. 

BenZotrichloride Method. The central carbon atom of the dye is supphed by the trichloromethyl group from iJ-chlorobenzotrichloride. Both symmetrical and unsymmetrical triphenyhnethane dyes suitable for acryhc fibers are prepared by this method. 4-Chlorobenzotrichloride is condensed with excess chlorobenzene in the presence of a Lewis acid such as aluminium chloride to produce the intermediate aluminium chloride complex of 4,4, 4"-trichlorotriphenylmethyl chloride (18). Stepwise nucleophihc substitution of the chlorine atoms of this intermediate is achieved by successive reactions with different arylamines to give both symmetrical (51) and unsymmetrical dyes (52), eg, N-(2-chlorophenyl)-4-[(4-chlorophenyl) [4-[(3-methylphenyl)imino]-2,5-cyclohexadien-l-yhdene]methyl]benzenaminemonohydrochloride [85356-86-1J (19) from. w-toluidine and o-chloroaniline. 

Benzimidazole, l-methyl-2-trichloromethyl-substitution reactions, 5, 432 Benzimidazole, naphthoyl-, 1, 327 Benzimidazole, 5-nitro-alkylation, 5, 390 Benzimidazole, 6-nitro-1-oxide... 

This topic has been reviewed [2, pp 94, 100-111, 130-134] All of the standard approaches to the synthesis of a compound like methyl 2-fluorostearate from methyl 2-bromostearate result mall yield of the 2-fluoro ester and the unsaturated esters. Although silver fluoride is not a new reagent, its use moist in wet acetonitrile to convert methyl 2-bromostearate to its fluoro ester is a departure from the traditional set of anhydrous conditions (Procedure 6, p 194) [71] In contrast, silver tetrafluoroborate converts a-chloroketones to their respective fluoroketones under anhydrous conditions. The displacement of less activated halogen groups by silver tetrafluoroborate to form their respective fluorides is novel Although silver tetrafluoroborate could not be used to convert an aliphatic terminal dichloromethyl or trichloromethyl group to its corresponding fluoro derivative, it is an effective fluorine source in other situations [72] (Table 8)... 

First examine the geometry of methyl radical. Is it planar or puckered Examine the geometries of 2-methy 1-2-propyl radical, trifluoromethyl radical, trichloromethyl radical and tricyanomethyl radical. Classify each of the substituents (methyl, fluoro, chloro and cyano) as a n-electron donor or as a Tt-electron acceptor (relative to hydrogen). Does replacement of the hydrogens by 7t-donor groups make the radical center more or less puckered Does replacement by Jt-acceptor groups make the radical center more or less puckered Justify your observations. 

Dichloro-s-triazine and its 6-alkyl analogs are as easily hydrolyzed by water as trichloro-s-triazine and, on suspension in aqueous ammonia (25°, 16 hr), the first is diaminated in good yield. 2,4-Bistrichloromethyl-6-methyl- and -6-phenyl-s-triazines (321) require a special procedure for mono-alkoxylation (0-20°, 16 hr, alcoholic triethylamine) disubstitution occurs at reflux temperature (8 hr). Aqueous triethylamine (100°, 3 hr) causes complete hydroxy-lation of 2,4,6-tris-trichloromethyl-s-triazine which can be mono-substituted with ammonia, methylamine, or phenoxide ion at 20°. 

On the basis of the reaction of alkyl radicals with a number of polycyclic aromatics, Szwarc and Binks calculated the relative selectivities of several radicals methyl, 1 (by definition) ethyl, 1.0 n-propyl, 1.0 trichloromethyl, 1.8. The relative reactivities of the three alkyl radicals toward aromatics therefore appears to be the same. On the other hand, quinoline (the only heterocyclic compound so far examined in reactions with alkyl radicals other than methyl) shows a steady increase in its reactivity toward methyl, ethyl, and n-propyl radicals. This would suggest that the nucleophilic character of the alkyl radicals increases in the order Me < Et < n-Pr, and that the selectivity of the radical as defined by Szwarc is not necessarily a measure of its polar character. 

Relative rate constants for reaction of methyl, trifluoromethyl, trichloromethyl,13 and t-butoxy radicals22,23 with the fluoro-olcfins arc summarized in Table 1.2. Note the following points ... 

The overall trend of reactivities for t-butoxy radicals with the fluoro-olcfins more closely parallels that for methyl radicals than that for the electrophilic trifluoromethyl or trichloromethyl radicals. 

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