Chloracetic anhydride

Imino-4-thiazolines are far more basic than their isomeric 2-aminothiazoles (see Table VI-1). They react with most electrophDic centers through the exocyclic nitrogen and are easily acylated (37, 477, 706) and sulfonated (652). The reaction of 2-imino-3-methyi-4-thiazoline (378) with a-chloracetic anhydride yields 379 (Scheme 217) (707). This exclusive reactivity of the exocyclic nitrogen precludes the direct synthesis of endocyclic quaternary salts of 2-imino-4-thiazolines. although this class of compounds was prepared recently according to Scheme 218 (493). 

Chloracetic anhydride (CH2CIC0)20 Useful for electron capture detection of lower... 

Chloracetic acid, alkylation with, 33 dialkvlation with. 37 Chloracetic anhydride. 124 Chloracetic ester, alkylation with. 33 Chloracetvl chloride, with aminothiazoles, 49... 

Ketene passed 15-20 min, into stirred chloracetic acid, the resulting liquid containing the intermediate acetic chloracetic anhydride added to the calculated amount of aniline, then 1-2 ml. water added chloracetanilide. Y 78%. F. e., also isolation of the intermediate, s. Y. V. Svetkin and G. Kretsu, 28, 1864 (1958) G. A. 53, 1112d. 

Aminothiazole, with acetaldehyde, 42 to 2-mercaptothiazoie, 370 4-Aminothiazole-2,5-diphenyl, to 2,5 di-phenyl-A-2-thiazoline-4-one, 421 Ammothiazoie-A -oxide, 118 2-Aminothiazoles. 12 acidity of, 90 and acrylophenone, 42 acylations of, with acetic acid. 53 with acetic anhydride, 52 with acyl halides, 48 with chloracetyl chloride, 49 with-y-chlorobutyrylchloride, 50 with 0-chloropropionylchloride, 50 with esters, 53 with ethy acrylate, 54 with indoiyl derivatives, 48 with malonic esters, 55 with malonyl chloride, 49 with oxalyl chloride, 50 with sodium acetate, 52 with unsaturated acyl chloride, 49 additions to double bonds, 40 with aldehydes, 98 alkylations, with alcohols, 38 with benzyhydryl chloride, 34 with benzyl chloride, 80 with chloracetic acid, 33 with chloracetic esters, 33 with 2-chloropropionic acid, 32 with dialkylaminoalkyl halides, 33 with dimethylaminoethylchloride, 35 with ethylene oxide, 34, 38... 

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-... 

The bis-a-haloamides, resulting from the reaction of 1,3-diazaadamantanes with a-halo derivatives of acetic anhydrid or chloracetic acid (95, 96), are useful agents for cyclization reactions (35, 97-99), following known cyclization methods (100), to yield the macrocyclic compounds 71-74 (see Chart 8). Other interesting macrocyclic bispidine compounds with crown ether fragments were also described (101). 

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). ... 

Stearic acid shaken 30 min. at 25° with excess trifluoroacetic anhydride, then chloramphenicol added portionwise, the resulting soln. allowed to stand 45 min. at 25°, warmed 5 min. at 50°, poured into ice and neutralized with NaHCOg after a few min.crude d(—)-fhreo-l-(p-nitrophenyl)-l-stearoyl-2-dichloracet-amido-1,3-propanediol. Y 82.5%.—This method cannot he used for the acylation with strong acids such as formic, chloracetic, or dichloracetic acids. F. e. s. L. Almirante and G. Tosolini, J. Org. Chem. 26, 111 (1961). 

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