Chloroacetic acid drying

Phenylglycine-o-carboxylic acid. In a 750 ml. round-bottomed flask, fitted with a reflux condenser, place 14 g. of anthranilic acid (Section IV,170), 10 g. of chloroacetic acid, 20 g. of anhydrous sodium carbonate and 200 ml. of water. Reflux the mixture for. 3 hours, then pour into a beaker, cool, render shghtly acid with concentrated hy dro-chloric acid, and allow to stand overnight. Filter off the crude acid and wash it with water. Recrystalhse from hot water with the aid of a little decolourising carbon, and dry the acid at 100°. The yield of phenyl-glycine-o-carboxyhc acid, m.p. 208°, is 12 g. 

Sodium Chloroacetate Sodium chloroacetate [3926-62-3] mol wt 116.5, C2H2C102Na, is produced by reaction of chloroacetic acid with sodium hydroxide or sodium carbonate. In many appHcations chloroacetic acid or the sodium salt can be used interchangeably. As an industrial intermediate, sodium chloroacetate may be purchased or formed in situ from free acid. The sodium salt is quite stable in dry soHd form, but is hydrolyzed to glycoHc acid in aqueous solutions. The hydrolysis rate is a function of pH and temperature (29). 

Cellulose. The principal stmctural component of plant ceU waUs is ceUulose (qv). The most widely used ceUulose derivative is the sodium salt of carboxymethylceUulose (CMC). It is made by treating ceUulose with sodium hydroxide—chloroacetic acid. CMC is widely used in the food industry in products such as baked goods, icings, symps, gla2es, fro2en dairy products, and dry drink mixes (89). 

Chloroacetic acid [79-11-8] M 94.5, m 62.8 , b 189 , pK 2.87. Crystd from CHCI3, CCI4, benzene or water. Dried over P2O5 or cone H2SO4 in a vacuum desiccator. Further purification by distn from MgS04, and by fractional crystn from the melt. Stored under vac or under dry N2. [Bemasconi et al. J Am Chem Soc 107 3621 1985.]... 

Scheme 1 Synthetic steps for compounds 1 and 2.1 2-chloroacetic acid, 2 M aq. Na2C03, 80 °C, 20h, yield 51% 11 acetic anhydride, anhydrous sodiiun acetate, 60 °C, 5h, yield 65% 111 sodium sulfite, H2O, 90 °C, 4h, yield 82% IV toluene/piperidines, reflux 4h, yield 61% V tert-butyl acrylate, tri-(0-tolyl)phosphine, Pd(OAc)2, EtsN, DMF, reflux, yield 70-91% VI H2, 10% Pd/C, rt, yield 96-100% Vll TFA, DCM, rt, yield 75-100% Vlll (a) isobutylchloroformate, EtsN, dry DCM, 0°C, (b) R2NH, DCM, rt, 62-70% IX UAIH4, dry THF, yield 24-44% [11]...

Bromoacetic acid has been prepared by direct bromination of acetic acid at elevated temperatures and pressures,2-3-4 or with dry hydrogen chloride as a catalyst 6 and with red phosphorus as a catalyst with the formation of bromoacetyl bromide.6-7-8-9-19 Bromoacetic acid has also been prepared from chloroacetic acid and hydrogen bromide at elevated temperatures 6 by oxidation of ethylene bromide with fuming nitric acid 7 by oxidation of an alcoholic solution of bromoacetylene by air 8 and from ethyl a,/3-dibromovinyl ether by hydrolysis.9 Acetic acid has been converted into bromoacetyl bromide by action of bromine in the presence of red phosphorus, and ethyl bromoacetate has been... 

The commercial grade (m.p. 61-63°) of monochloroacetic acid should be ground and thoroughly dried over concentrated sulfuric acid in a vacuum desiccator for two days. The yield was lowered by about 10 per cent when the chloroacetic acid was used without previous drying. 

After the reaction mixture has been refluxed for fifteen hours, the stirrer is stopped, the reaction mixture is allowed to cool, and the excess sodium (Note 3) is carefully removed. The apparatus is then assembled as before (Note 1), but with a 1-1. separatory funnel fitted into the third neck of the flask (Note 4). The temperature of the oil bath is raised to 85-90°, and with continued stirring, a solution of 95 g. (1.01 moles) of monochloroacetic acid (Note 5) in 800 cc. of warm dry toluene is added from the separatory funnel at such a rate that refluxing is not too vigorous. A heavy precipitate of sodium chloroacetate forms immediately. After all the chloroacetic acid has been added, the mixture is refluxed and stirred for forty-eight hours. During this period, the stirring must be as thorough as possible it is necessary to add 1-1.51. of dry toluene, and the stirrer must be stopped at frequent intervals while the solid material is removed from the side of the flask. 

Phenylglycine.1—Chloroacetic acid (19 g.) is exactly neutralised in the cold with 100 c.c. of 2 A-sodium hydroxide solution, 18-6 g. of aniline are added, and the mixture is boiled for a short time under reflux until the aniline has reacted and dissolved. On cooling, the phenylglycine separates as an oil which soon crystallises when rubbed. The crystalline material is kept cool in ice for some time, collected at the pump, and washed with a little ice-cold water. Yield 22-24 g. of dry substance. 

Bromine (dry gas) Bromine (liquid) Bromobenzene Butanol Butyl acetate Butylamine Butylchloride Butyric acid Calcium chloride Carbon tetrachloride Castor oil Cellosolve Cellosolve acetate Chlorine (dry gas) Chlorine water Chloroacetic acid Chlorobenzene Chloroform Chlorosulfonic acid Chromic acid Citric acid Colza oil Copper sulfate Cyclohexane Cyclohexanol Cyclohexanone... 

Nitromethane. 103 cc of 40% sodium hydroxide solution is added, slowly with stirring, to a mixture of 100 g of chloroacetic acid and 100 g of crushed ice until the mixture is just barely alkaline to phenolphthalein. Keep the temp between 10-20° during this addition. 73 g of sodium nitrite in 100 cc of water is added and the whole is heated in a 500 cc flask, rigged to a distillation apparatus that has the thermometer immersed in the liquid. Distillation of nitromethane starts at about 87° and continues to come over to 108-110°, which is where the temp is maintained for 30 min. Nitromethane is separated from the aqueous layer of the distillate in a separation funnel and is distilled three more times, being separated from the aqueous layer after each distillation. The nitro is then dried over calcium chloride and distilled again, collecting the fraction boiling at 98-101°. Yield 27 g. 

To a solution of 2,3-O-isopropyIidene-D-glyceraldehyde (12.6 g, 97 mmol) in furan (20 mL), chloroacetic acid (5.7 g, 60 mmol) dissolved in furan (20 mL) was added and the mixture was refluxed for 8 h. After 12 h at room temperature saturated aqueous NaHCOj solution (50 mL) was added and the product was extracted with ether (3 x 100 mL). Combined ether extracts were dried (MgS04), concentrated to dryness, and the residue was chromatographed on a silica gel column with light petroleum-ether-methanol (6 4 0.5) to yield If ,2ft- and lS,2ft-l-C-(2-furyl)-2,3-0-isopropylidene-glycerols 1 (95 5, 7.0 g, 36.5%). 

A. o-Formylphenoxyacetic acid. A solution of 80.0 g. (2 moles) of sodium hydroxide pellets in 200 ml. of distilled water is added to a mixture of 106 ml. (122 g., 1 mole) of salicylaldehyde (Note 1), 94.5 g. (1 mole) of chloroacetic acid (Notes 1 and 2), and 800 ml. of water. The mixture is stirred slowly and heated to boiling. The resulting black solution (Note 3) is heated under reflux for 3 hours (Note 4). The solution is acidified with 190 ml. of concentrated hydrochloric acid (sp. gr. 1.19) and is steam-distilled to remove unchanged salicylaldehyde (40.0-40.5 g.) (Note 5). The residual acidic mixture is cooled to 20°, and the precipitated product is collected on a Buchner funnel and rinsed with water. The light tan solid when dry weighs 99-100 g. (82-83% based on recovered salicylaldehyde), m.p. 130.5-133.0° (Note 6). 

A 100-mL sample aliquot adjusted to pH 11.5 sample extracted with methyl tert-butyl ether (MTBE) chloroacetic acid partitions into aqueous phase basic and neutral compounds in MTBE phase discarded the aqueous phase now adjusted to pH 0.5 and extracted again with MTBE the MTBE extract dried and concentrated chloroacetic acid in the MTBE extract esterified with diazomethane the methyl ester determined by capillary GC on an ECD (U.S. EPA Method 552, 1990). 

Naphthol (100 g., 0.70 mole) is dissolved in an aqueous solution containing 360 g. (6.3 moles) of potassium hydroxide. To this solution is added an aqueous solution of 95 g. (1.0 mole) of chloroacetic acid. Water is added to the mixture until a total volume of 2 1. is reached, and the resulting solution is stirred and heated on a water bath for 4 hours. The reaction mixture is treated with 100 ml. of concentrated hydrochloric acid and cooled the precipitated solid is filtered off, washed with water, and dried. There is obtained a 95 yield of crude product melting at 145-150 . The crude acid is treated with excess aqueous ammonium carbonate solution, and the resulting mixture is extracted with ether to remove the unreacted /8-naphthol. Acidification of the aqueous solution precipitates the yj-naphthoxy-acetic acid, which is collected by filtration and recrystallized from hot water to give white prisms melting at 156°. 

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