Chloracetic acid preparation

A/-(4-Hydroxyphenyl)glycine can be prepared from 4-aminophenol and chloracetic acid (199,200) or by alkaline hydrolysis of the corresponding nitrile with subsequent elimination of ammonia (201). 

Figure 9.3b Conductivity/time curves (a) of cements, showing maxima. Prepared from ZnO ignited at 600 C with A-.-A dry eugenol 0...0 eugenol + 1% water O-.-O eugenol + 1% chloracetic acid ... eugenol+1% acetic acid ... eugenol+1% acetic acid+1% water. Cement powder/liquid ratio = 2-5 g cm (Crisp, Ambersley Wilson, 1980).

At a time when the only practicable methods for the preparation of nitromethane were the interaction of methyl iodide with silver nitrite and the Kolbe reaction from chloracetic acid, the explosive was far too expensive to merit consideration. The present cheap and large scale production of nitromethane by the vapor-phase nitration of methane and of ethane has altered the situation profoundly. Trimethylolnitromethane trinitrate is an explosive which can now be produced from coke, air, and natural gas. Nitromethane too has other interest for the manufacturer of explosives. It may be used as a component of liquid explosives, and it yields on reduction methylamine which is needed for the preparation of tetryl. 

Substituted thiazolidin-4-ones (449) are easily prepared by the reaction between chloracetic acid, or its derivatives (447), and a thiourea, a thiosemicarbazide, or a mono-or di-thiocarbamate (448 Scheme 255). The same a-chloro acid derivatives react with metallic thiocyanates yielding an intermediate (450), the cyclization of which gives a 2-iminothiazolidin-4-one (451). In these reactions a -chloracetic acid may be replaced by... 

Amino-6-mercaptouracil, easily prepared from 6-chloro-5-nitrouracil and sodium hydrosulfide, condenses with formic acid or acetic anhydride to furnish thiazolo[5,4-condensation with chloracetic acid and phenacyl halide gives 6-hydroxy- and 6-arylpyrim-... 

Among later syntheses of indigo was that from phenylglycine carboxylic acid by Heumann. This was first made from aniline, but its preparation from naphthalene made the process technically workable. The research was carried out for the Badische Co. by their chemist E. Sapper (1891-7) and depended on the oxidation of naphthalene to phthalic acid by heating with concentrated sulphuric acid in presence of mercury as a catalyst (said to have been discovered accidentally by the breaking of a thermometer bulb). Phthalic acid was converted into phthalic anhydride, phthalimide, and anthranilic acid, and phenylglycine carboxylic acid by condensation of this with chloracetic acid. On fusion with caustic potash, or better sodamide, this formed indoxylic acid, and indoxyl, which was easily oxidised to indigo. 

Alizarin blue was prepared from nitroalizarin, glycerol, and sulphuric acid by M. Prud homme, anthragallol (anthracene brown, i a 3-trihydroxy-anthraquinone) from pyrogallol and phthalic anhydride by C. Seuberlich, di- (or tetra-) azo dyes by Caro and Schraube, rhodamine from ammonium thiocyanate and chloracetic acid by M. Nencki, rocelline or echtrot (naphthalene sulphonic azonaphthol) by Roussin (1877) and Caro and Griess, and methylene blue by Caro (1877). ... 

Benzotrichloride added dropwise during 1-1.5 hrs. at ca. 60 under Ng to a mixture of KHS and KOH in abs. ethanol prepared from KOH and HgS, gently refluxed for 30 min., aq. chloracetic acid neutralized with NaHGOg added rapidly, the stirred mixture heated to boiling as rapidly as possible, refluxed 5 min., added to ice, stirred and slowly acidified with coned. HGl carboxy-methyl dithiobenzoate. Y 54-63%. F. Kurzer and A. Lawson, Org. Synth. 42, 100 (1962). 

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