Sodium tri chloroacetate

Phenylmercuric chloride, conversion to phenyltrichloromethylmercury by reaction with sodium tri-chloroacetate, 46, 98 2-Phenyl-2-oxazolin-5-one, 47, 101 2-Phenyl-5-oxazolone, 47,101... 

Under strongly basic conditions (generation of dichlorocarbene from chloroform and potassium hydroxide), electrophilic substitution of pyrrole by dichlorocarbene dominates, leading eventually to pyr-role-2-carbaldehyde. In a weakly basic medium (generation of dichlorocarbene by heating sodium tri-chloroacetate), the [2+1] cycloaddition prevails. The primary product eliminates hydrogen chloride to give 3-chloropyridine. 

Highly reactive free carbene species (i.e., the reaction under pyrolytic conditions of sodium tri-chloroacetate generates dichlorocarbene) can be considered as reactants for [1 + 2] cycloaddition to... 

Addition of dichlorocarbene, produced by treatment of ethyl tri-chloroacetate with sodium methoxide, to 3,4,6-tri-O-methyl-D-glucal gave, apparently, one product (gas-chromatographic analysis) in 82% yield. By stereochemical analogy with epoxidations, the product was considered to be l,5-anhydro-2-deoxy-l,2-C-(dichloromethylene)-3,4,6-tri-O-methyl-D-g/j/cero-D-ido-hexitol (21). Demethylation was brought about with boron trichloride at—70°, to give atriol from which a crystalline tribenzoate was obtained and reaction with lithium aluminum hydride caused reductive cleavage of the carbon-chlorine bonds.36 A similar addition was applied to 3,4-unsaturated furanosyl compound (see p. 247). 

Contrast the effect of heat on mercuric benzoate, when substitution of the aromatic ring ortho to the carboxyl group occurs. Mercuric tri-chloroacetate decar Wylates so rapidly that it has not yet been isolated. Bis(trichloromethyl)mercury was obtained in good yield by the reaction of sodium trichloroacetate and mercuric halides in ethyleneglycol-dimethyl ether ... 

Scheme 1 Synthetic steps for compounds 1 and 2.1 2-chloroacetic acid, 2 M aq. Na2C03, 80 °C, 20h, yield 51% 11 acetic anhydride, anhydrous sodiiun acetate, 60 °C, 5h, yield 65% 111 sodium sulfite, H2O, 90 °C, 4h, yield 82% IV toluene/piperidines, reflux 4h, yield 61% V tert-butyl acrylate, tri-(0-tolyl)phosphine, Pd(OAc)2, EtsN, DMF, reflux, yield 70-91% VI H2, 10% Pd/C, rt, yield 96-100% Vll TFA, DCM, rt, yield 75-100% Vlll (a) isobutylchloroformate, EtsN, dry DCM, 0°C, (b) R2NH, DCM, rt, 62-70% IX UAIH4, dry THF, yield 24-44% [11]...

Methyl fluoroacetate was first prepared by Swarts in small yield by the action of silver or mercurous fluoride on methyl iodoacetate. The method is impracticable for large-scale work and therefore the preparation was reinvestigated in detail. Methyl chloroacetate was used in place of the expensive iodoacetate, and a variety of fluorinating agents was tried. It was found that fluorination could be effected by heating methyl chloroacetate in a rotating autoclave with potassium fluoride at 220° for 4 hr. Sodium fluoride, on the other hand, was almost without action. 

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