Trichloro-acetal

Successful results have been obtained (Renfrew and Chaney, 1946) with ethyl formate methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl and iso-amyl acetat ethyleneglycol diacetate ethyl monochloro- and trichloro-acetates methyl, n-propyl, n-octyl and n-dodecyl propionates ethyl butyrate n-butyl and n-amyl valerates ethyl laurate ethyl lactate ethyl acetoacetate diethyl carbonate dimethyl and diethyl oxalates diethyl malonate diethyl adipate di-n-butyl tartrate ethyl phenylacetate methyl and ethyl benzoates methyl and ethyl salicylates diethyl and di-n-butyl phthalates. The method fails for vinyl acetate, ieri.-butyl acetate, n-octadecyl propionate, ethyl and >i-butyl stearate, phenyl, benzyl- and guaicol-acetate, methyl and ethyl cinnamate, diethyl sulphate and ethyl p-aminobenzoate. 

Trichloroacetaldehyde (chloral) reacts with glucose in the presence of sulfuric acid to form two monoacetals and four diacetals. The trichloro acetal is cleaved by reduction (H2, Raney Ni, 50% NaOH, EtOH, 15 min). The trichloro acetal can probably be cleaved with Zn/AcOH [cf. ROCH(R )OCH2CCl3 cleaved by Zn/ AcOH, AcONa, 20°, 3 h, 90% yield ]. 

Trichloroacetic acid behaves somewhat similarly in that protonation of the enamine occurs l7J7d). Subsequent decarboxylation of the trichloro-acetate gives trichloromethyl anion, which adds to the iminium cation to give the trichloromethyl amine derivative. Thus the enamine (113) undergoes reaction with trichloroacetic acid to give N-[l-(trichloromethyl)cyclo-hexyl]-morpholine (8). The latter compound undergoes rearrangement on... 

M. St. C. Flett and P. H. Plesch, J, Chem. Soc., 1952 3355, found evidence for the presence of the trisubstituted ethylene end group and also for trichloro-acetate end groups in low molecular weight polyisobutylenes prepared at 0°C using TiCh and CI3COOH as catalyst and co-catalyst, respectively. For results on the similar polymerization of styrene with TiCh, see P. H. Plesch, J. Chem. Soc., 1963, 1653, 1659, 1662. 

Oxidation of benzene to phenol. This was attempted in the former U.S.S.R. and Japan on a pilot-plant scale. High yields were reported, but full-scale operation apparently was discontinued because of destruction of product by irradiation and the possibility of explosion in the reaction vessel. The latter danger can be controlled in the oxidation of halo-genated hydrocarbons such as trichloro- or tetrachloroethylenes, where a chain reaction leads to the formation of dichloro- or trichloro-acetic acid chlorides through the respective oxides. 

In a more complex type of reaction, propene reacts with methyl trichloro-acetate under the catalytic influence of cyclopentadienylmolybdenum tricarbonyl or cyclopentadienyliron dicarbonyl dimers to give 4-methyl-2,2 -... 

These considerations lead, for example, to the assignment of a predominantly outer sphere character to Cl, Br, F, CIO3, NO3, sulfonate, and trichloro-acetate complexes and an inner sphere character to F", IO3, SO, and acetate complexes of trivalent actinides and lanthanides. The variation in AH° and AS° of complexation of related ligands indicates that those whose pA), values are <2 form predominantly outer sphere complexes, while those for whom > 2 form predominantly inner sphere complexes with the trivalent lanthanides and actinides. As the pK increases above 2, increasing predominance of inner sphere complexation is expected for these metals. 

In a closely related investigation, designed to generate vinyl alcohol in solution, divinyl hemiorthoformate [68] was detected as an intermediate in the hydrolyses of divinyloxymethyl dichloro- and trichloro-acetate [67] (Capon et al., 1981b). It is interesting that methyl vinyl hemiorthoformate could not be detected in the hydrolysis of methoxyvinyloxymethyl acetate and chloroacetate under similar conditions. So dimethyl and divinyl hemiorthoformate appear to be more stable than methyl vinyl hemiorthoformate. 

The generation of dichlorocarbene for addition to olefins has been realized by the use of chloroform and alkali metal alk-oxides4 6 (preferably potassium feri-butoxide), sodium trichloro-acetate,6 butyllithium and bromotrichloromethane,7 and the reaction of an ester of trichloracetic acid with an alkali metal alkoxide.2,8 The latter method, which is here illustrated by the preparation of 2-oxa-7,7-dichloronorcarane, generally gives higher yields of adducts. 

With the V0(0 ter-C Hj)j—Al2(C2Hj)3Clj catalytic system and with ethyl tri-chloroacetate acting as a promoter , polyethylene with very narrow MWD was obtained (Q = 2.1 to 2.6 values from fractionation data). Similar behaviour was observed for a modified Carrick-like catalytic system prepared from a soluble vanadium compound, Sn(CgH5)4 and AlBrj, in the presence of methyl trichloro-acetate as promoter . 

CARBENES, GENERATION Benzyltrieth-ylammonium chloride. Dehydro-N,N, N -tricyclohexylguanidinohexacarbonyldi-iron(O). Ethylene oxide. Ethyl trichloro-acetate. Phenyl(l-bromo-l-chloro-2,2,2-trifluoroethyI)mercury. Phenyl(trihalo-methyl)mercury. Trimethyl-silyldiazo-methane. 

Schweizer and O Neill, unsuccessful in an attempt to follow the Reutov-Eovtsova procedure using commercial potassium l-butoxide, developed a convenient synthesis of phenyl(trichloromethyl)mercury in which phenylmercuric bromide is treated with trichloroacetate anion generated in large excess from ethyl trichloro-acetate and commercial sodium methoxide. A mixture of 200 ml. of benzene, 0.18 mole of ethyl trichloroacetate, and 0.37 mole of pulverized phenylmercuric bromide is stirred for 1.5 mln< In an ice hath and 0.154 mole of sodium methoxide is added all... 

Fig. 9.20 pH-depcndence of the degradation of trichloro-acetate (+) and chloroethy-lammonium (A) during illumination of Ti02 suspensions. (After ref. [86])... 

Tetraphenylbismuthonium nitrate, perchlorate, tetraphenylborate, cyanate, thiocyanate, perchlorate, tetrafluoroborate, hexafluorophosphate and trichloro-acetate have been prepared by this metathesis method [52LA(578)136, 73JCS(D)1394]. Unsymmetrical tetraarylbismuth(V) compounds can be prepared similarly [68LA(720)198]. 

The main advantages of this procedure are simplicity of apparatus and technique, availability of reactants, ease of product isolation in good yield, and purity of product. The submitter has also used this method successfully for the preparation of trichloromethylmercuric chloride (from mercuric chloride), bis-(trichloromethyl) mercury (from a 2 1 ratio of sodium trichloro-acetate to mercuric chloride or mercuric acetate), and trichloromethylmercuric bromide (from mercuric bromide). 

Reaction of trichloro-acetic anhydride with 11 led to the isolation of [2]C1 (R = CC13) in unspecified yield [88ZAC(562)31]. 

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