Chloro acetate

To a suspension of 7.5 mol of sodamide (see Chapter 11, Exp. 11) in 4.5-5 1 of liquid ammonia were added 2.0 mol of the chloro acetal in 30 equal portions with intervals of 2 min. Twenty minutes after this addition the stirrer was removed,... 

Salicylaldehydc, reaction with chloro-acetic acid, 46,28... 

In a 5-I. round-bottomed flask, 500 g. (5.3 moles) of chloro-acetic acid (Note 1) is dissolved in 700 cc. of water. The solution is warmed to 50°, neutralized with 290 g. (2.7 moles) of anhydrous sodium carbonate, and again cooled to room temperature. Meanwhile, 294 g. (6.0 moles) of sodium cyanide (97 per cent) is dissolved in 750 cc. of water warmed to 55°, the solution is cooled to room temperature, and then added to the sodium chloroacetate solution, with rapid mixing of the two solutions and cooling under the water tap. When the solutions are completely mixed, the cooling is stopped and the temperature allowed to rise. When it reaches 95° the solution is cooled by adding 200 cc. of ice water, and this is repeated, if necessary, until the temperature no longer rises (Note 2). The solution is then heated on the steam bath for one hour to ensure completion of the reaction. 

In a 2-1. flask provided with a mechanical stirrer, separatory funnel, and thermometer, are placed 189 g. (2 moles) of chloro-acetic acid and 150 cc. of water. The flask is cooled in ice water, and a cold solution of 160 g. (4 moles) of sodium hydroxide in 500 cc. of water is added, with stirring, at such a rate that the temperature does not exceed 30° (Note 1). AfLer all the alkali has been added, the cooling bath is removed, and an aqueous solution (Note 2) containing 31 g. (1 mole) of methylamine is added slowly. The reaction is exothermic, and the temperature is kept below 50° by occasional immersion of the flask in ice water. After all the methylamine has been added, the solution is allowed to stand for two hours to complete the reaction. 

Answer Friedel-Crafts disconnection reveals 1,2-diX compound (21) easily made from thiol (22) and chloro-acetic acid. Thiol (22) can be made by the thiourea route (p T 37 ). 

B. Reactions.—(/) Halides. Whereas ylides are alkylated in the normal way on treatment with a-bromo- or a-iodo-esters, quite different reactions occur with a-fluoro- and a-chloro-acetates. When salt-free ylides were refluxed in benzene with ethyl fluoroacetate or trifluoroacetate normal Wittig olefin synthesis took place with the carbonyls of the ester groups to give vinyl ethers, e.g. (14). On the other hand, methyl chloroacetate with... 

The a-halogenated carboxylic adds, of which the simplest is chloro-acetic acid, are widely used in synthesis. Their conversion into hydroxy-acids (by hydrolytic elimination of the halogen) and into aminoacids (p. 275) may be mentioned here ... 

The ammonium -chlorophenyldithiocarbamate obtained is transferred immediately to a 1-1. beaker fitted with an efficient mechanical stirrer. Water (250 ml.) is added, and the temperature is raised to 30°. A solution of 28.4 g. (0.30 mole) of chloro-acetic acid in 30 ml. of water is neutralized with sodium carbonate [18.6 g. (0.15 mole) of Na2C03-H20 in 70 ml. of water] and is added to the weU-stirred dithiocarbamate suspension over a 10-minute period (Note 3). In the beginning the suspension gradually becomes less viscous, but at the end of the addition it rapidly turns into a creamy mass. Another 250 ml. of water is added to facilitate stirring, which is continued for 1 hour after the addition at about 30°. 

The lithiation of y-chloro acetal 175 with lithium and a catalytic amount of naphthalene (4%) allowed the preparation of the intermediate 176, which can be considered as a masked lithium homoenolate, and was used for the preparation of the hydroxy ketone 179 through the hydroxy acetal 177 and dithiane 178 using known chemistry (Scheme 62)" . 

The hthiation of the to-chloro acetal 230 using a catalytic amount of naphthalene (4%) in THF at —78°C gave the corresponding masked tu-lithio enolate 231, which reacted with different electrophiles at —78 °C to room temperature yielding, after hydrolysis with water, the expected functionalized acetals 232 (Scheme 78) . 

Cellulose Etherification with chloro-acetic acid (carboxymethylation) Carboxymethyl cellulose 5-6 HW 2042 K 1521... 

Carboxymethyl)-oximes are normally prepared in a single step from ketones, but the 11-oxo-group in 17j8-hydroxy-5a-androstane-3,ll-dione was too hindered to react with O-carboxymethylhydroxylamine. Instead the 11-oxime, obtained by selective cleavage of the 3,11-dioxime, was treated with alkaline sodium chloro-acetate to prepare the hapten (31) for linking to BSA via C-11. ... 

An example of anomalous behavior in closely related systems was reported some time ago during an investigation of the cychzation products derived from coumarin semicarbazones (Scheme 6.21). Thus, 78a reacted cleanly with chloro-acetic acid to yield 79a, which cyclized to the expected product 80a upon treatment with sodium acetate. On the other hand, 79b did not cyclize under the same reaction conditions. This was attributed to the absence of the enolizable hydrogen (Ph vs. H). The authors did not comment on the possibility of cyclization of 79b to 80b. The closely related urea analogue 81 did not react with chloroacetic acid thereby... 

Carboxymethyl starch (with mono chloro acetic acid)... 

A. Triethyl a-phtkalimidoethane-a,a, -tricarboxylate. Three hundred and twenty-seven grams (1.0 mole) of diethyl sodium phthalimidomalonate and 735 g. (6.0 moles) of ethyl chloro-acetate (b.p. 144-145°) are placed in a 2-1. Claisen flask fitted with a reflux condenser and rubber stoppers. The mixture is heated under reflux in an oil bath at 150-160° for 2.25 hours. The excess ethyl chloroacetate is removed by distillation at 30 mm. until the heating bath temperature reaches 150° and no more distillate is obtained (Note 1). The brown residual mass is... 

Ethyl /3,/3-pentamethyleneglycidate has been prepared in 65% yield by the condensation of cyclohexanone with ethyl chloro-acetate in the presence of sodium ethoxide,4 and in 50% yield in the presence of sodium in xylene.6 The present procedure employs potassium (erZ-butoxide as the condensing agent.3... 

Rcell. OCH2.COONa colorless, odorless and tasteless, non-toxic, hygroscopic substance, easily dispersible in hot or cold w, but insol in most organic solvents. Can be prepd by treating alkali cellulose with Na chloro-acetate ... 

Unsubstituted and mono substituted ammonium dithiocarbamates react with sodium chloro-acetate to produce different rhodanines, from which numerous metal complexes have been made.55... 

It is of interest to note that while chlorofonnic ester yields mostly the O-derivative, it is only the C-derivative that is obtained from chloro-acetic ester. 

Acetoxy-3-chloro-1 -butene 3-Buten-1-ol, 2-chloro-. acetate (96039-67-7), 67, 105 1-Acetoxy-4-chloro-2-cyclohexene, cis 2-Cydohexen-1-ol, 4-chloro-, acetate (82736-39-8), 69, 38... 

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