Sodium trichloroacetate

Sodium trichloroacetate [650-51-17, C2Cl202Na, is used as a herbicide for various grasses and cattails (2). The free acid has been used as an astringent, antiseptic, and polymerisation catalyst. The esters have antimicrobial activity. The oral toxicity of sodium trichloroacetate is quite low (LD q rats, 5.0 g/kg). Although very corrosive to skin, trichloroacetic acid does not have the skin absorption toxicity found with chloroacetic acid (28). 

Similarly, a-trichloromethylamines (522) were obtained by decomposition of trichloroacetic acid in morpholine enamines, but an amide ester was formed from sodium trichloroacetate and the imonium salt of pyrrolidino-cyclohexene (523). The product is presumably derived from opening of an intermediate dichloroaziridinium salt. 

In a similar manner, metapyridophanes 18 can be prepared by reaction of sodium trichloroacetate with pyrrole 17 (Scheme 8.3.5). The transformation can also be achieved with phenyl(bromodichloromethyl)mercury, albeit in lower yield. 

The Ciamician-Dennstedt reaction is currently the only way to date to make calix[4]pyridine 20.(Scheme 8.3.6) Four sequential treatments of calix[4]pyrrole 19 with sodium trichloroacetate results in all four possible geometric isomers of 20 (all four... 

I. Zinc-copper couple (Chapter 13, Section I) Alpha Inorganics Potassium /-butoxide MCB cM-Cyclooctcne A, MCB Sodium trichloroacetate EK... 

Dichlorocarbene can be generated by heating sodium trichloroacetate. Propose a mechanism for the reaction, and use curved arrows to indicate the movement of electrons in each step. What relationship does your mechanism bear to the base-induced elimination of HC1 from chloroform ... 

Sodium trichloroacetate, thermal decomposition in presence of phe-nylmercuric chloride to give phenyltnchloromethy lmercury, 46,95... 

A commercially branded product believed to be sodium trichloroacetate this is added at a concentration of 5% to the dyebath 20 minutes before the end of dyeing. Sodium carbonate is formed by hydrolysis of the trichloroacetate (Scheme 12.5), accompanied by a change of pH from 5.0-6.0 to 6.7-6.9 [2]. This reaction also releases the volatile AOX-generating chloroform, however. 

Treatment of benzo[c][l,5]naphthyridine with dichlorocarbene, formed from the thermal decomposition of sodium trichloroacetate, gives the corresponding iV-dichloromethylide, 1,3-dipolar cycloaddition of which with DMAD, with loss of HC1, gives the corresponding pyrrolonaphthyridine 284 (Equation 98) <1995M227>. In the [1,6]- and [1,7]-naphthyridine series, compounds 285 and 286 are obtained by the same route and in the [l,8]naphthyridine series compound 287 is obtained from the parent naphthyridine, dichlorocarbene, and dimethyl maleate followed by oxidation (Equation 99) <1998RJ0712>. 

Chloromethyltriphenyllead compounds, Ph3PbR (R = CC13 or CHC12), have been proposed as products of the decomposition of the triphenyllead chloroacetates in refluxing pyridine on the basis of equivocal spectroscopic data (37). Trichloromethyltriphenyllead was isolated for use as a source of dichlorocarbene from the reaction of triphenyllead chloride and sodium trichloroacetate in dme at 85° C (35) [Eq. (33)]. 

Sodium trichloroacetate, 1 141 Sodium trichlorometaphosphimate, 4 54 Sodium trimetaphosphate (STMP), 18 844, 847-848... 

Potassium peroxodisulfate, 4668 f 2-Propen-l-ol, 1223 f Propylene oxide, 1225 Pyridine N--oxide, 1849 Sodium azide, 4758 Sodium chloroacetate, 0694 Sodium methoxide, 0464 Sodium 3-nitrobenzenesulfonate, 2184 Sodium peroxodisulfate, 4809 Sodium trichloroacetate, 0608 Styrene, 2945 Sucrose, 3558... 

Alternative procedures for the generation of dichlorocarbene and dibromocarbene under phase-transfer catalysed conditions are also available. Where the reactive substrate is labile under basic conditions, the thermal decomposition of solid sodium trichloroacetate or bromoacetate under neutral conditions in an organic solvent is a valuable procedure [10-12], The decarboxylation is aided by the addition of a quaternary ammonium salt, which not only promotes dissolution of the trihaloacetate anion in the organic solvent, but also stabilizes the trihalomethyl anion. Under optimum reaction conditions, only a catalytic amount of the quaternary ammonium salt is required, as a large amount of the catalyst causes the rapid generation of the dichlorocarbene with resultant side reactions. 

Phase-transfer catalysed reaction of dichlorocarbene generated from sodium trichloroacetate... 

Figure 3—Applying sodium trichloroacetate at edges of cane and along ditches to control malojillo or para grass (Paspalum purpurascens Raddi). For spot sprays of this type, TCA is mixed at 0.5 pound per gallon of water.

Dehydrochlorination of pentachlorocyclopropane, formed from trichloroethylene and sodium trichloroacetate as a source of dichlorocarbene, yields tetrachloro-cyclopropene [150], a particularly versatile reagent for various applications. It is a reasonably reactive dienophile [151], a reagent applicable to heterocyclic synthesis [152], and an electrophile for aromatic substitutions [153] and additions to alkenes [154] in the presence of Lewis acids. 

For example, methyl 3-phenylbicyclofl.l.0]butane-l-carboxylate (11, R1 = Ph R2 = C02Me) was converted to methyl 2,2-dichloro-3-phenylbicyclo[l.l.l]pentane-l-carboxylate (12, R1 = Ph R2 = C02Me) in 46% yield on reaction with dichlorocarbene generated by thermolysis of sodium trichloroacetate. 3,14... 

The dichloromethyl derivative 20 is isolated (10%) from 3,4,5-trimethyI-pyrazole and chloroform in the presence of sodium ethoxide generation of dichlorocarbene by thermolysis of sodium trichloroacetate does not give any 4/Z-pyrazole.30 The same product is formed, in lower yield, using chloroform and base with a phase-transfer catalyst.31... 

Sodium trichloroacetate may be purchased from the Dow Chemical Company (96.4% pure by Cl analysis) or prepared by neutralizing trichloroacetic acid (Matheson Coleman and Bell) with aqueous sodium hydroxide to the phenolphthalein end point. The product is dried under vacuum for 12 hours, sieved, then dried an additional 12 hours under vacuum, all at room temperature. The salt prepared by this method and used in this preparation was 98.5% pure, based on chlorine analysis, and can be stored indefinitely without decomposition. The submitter has obtained nearly identical yields of phenyltrichloromethyl-mercury from the commercial and from the prepared salts. 

Yields as high as 77% have been obtained by this procedure. It is difficult to recover all the product from the mother liquor. The use of a 1 1 ratio of sodium trichloroacetate and phenyl-mercuric chloride gave yields of 39-45%, while a 1.25 1 ratio gave a 61% yield of product. 

Tetrachlorocyclopropene was prepared from sodium trichloroacetate and trichloroethylene.2 3 It is also available from the Aldrich Chemical Company, Inc., Eastman Organic Chemicals, and the Merck-Schuchardt Company (in Europe). 

The reaction of dihydrobenzothiazepines (1) with dichlorocarbene, generated in situ from chloroform using a phase-transfer catalyst or by thermal decomposition of sodium trichloroacetate, afforded compounds 2 in low yields (18-24%) (Scheme 1). The structure of 2 was postulated on the basis of analytical and spectroscopic data and confirmed by X-ray diffraction (92MI1). 

---