From Monochloroacetic Acid

COCH2CI - Preparation by Fries rearrangement of 2,4-dichlo-rophenyl chloroacetate with aluminium chloride without solvent at 135-145° [4412,4540], (56%) [4540]. 

Also obtained by reaction of chloroacetonitrile on 4-chlorophenol with aluminium chloride and boron trichloride mixture in ethylene dichloride [4549,4550], (18%) [4549], 

COCH2CI Preparation from 5-amino-2-hydroxy-4-nitro-a-chloro-acetophenone [4555] (see above). 

Preparation by reaction of hexachloro-2,4-cyclohexadienone on 2-hydroxyace-tophenone in refluxing ethanol (66%) [4559], 

Also obtained by reaction of chloroacetyl chloride on bromomagnesium pheno-late in toluene at r.t. (17%) [4564]. 

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Beryllium, calcium, boron, and aluminum act in a similar manner. Malonic acid is made from monochloroacetic acid by reaction with potassium cyanide followed by hydrolysis. The acid and the intermediate cyanoacetic acid are used for the synthesis of polymethine dyes, synthetic caffeine, and for the manufacture of diethyl malonate, which is used in the synthesis of barbiturates. Most metals dissolve in aqueous potassium cyanide solutions in the presence of oxygen to form complex cyanides (see Coordination compounds). 

Carboxymethyl (CM) cellulose is synthesised from monochloroacetic acid and cellulose and has weak cation exchange capability ... 

The cyanoacetic acid obtained from monochloroacetic acid and sodium cyanide, is treated with hydrochloric acid and ethanol to yield the diethyl ester of malonic acid. The ester, in absolute ethanol, is reacted with the stoichiometric proportion of metallic sodium so as to replace only one active hydrogen of the methylene (CH2) group. Thereupon, a slight excess of the calculated amount of allyl bromide is added. The second replaceable hydrogen is abstracted with 1-methyl butyl bormide and the resulting product is made to react with a theoretical amount of thiourea to yield thiamylal. The free acid thus obtained is conveniently transformed into the official sodium salt by neutralization with a stoichiometric proportion of sodium hydroxide (1 1). 

Y 85%. - The deactivating effect of the nitro group prevents intramolecular ring closure (s. Synth. Meth. 6, 854). F. e. s. S. K. Datta, Soc. Perkin 11972, 62 ketones from monochloroacetic acid s. Synth. Commun. 1972, 97. 

Nitroethane may be similarly obtained from sodium a chloropropionate. This is a general reaction for a chloro carboxylic acids, but in practice only monochloroacetic acid and a chloropropionic acid are readily available. 

Transfer the reaction product to a 500 ml. Claisen flask and distil over a wire gauze or from an air bath. Some acetyl chloride and acetic acid passes over first, the temperature then rises, and the fraction, b.p. 150-200°, is collected separately run out the water from the condenser when the temperature reaches 150°. The fraction, b.p. 150-200°, solidifies on cooling. Drain off any hquid from the crystals as rapidly as possible, and redistil the solid using an air condenser. CoUect the fraction b.p. 182-192° this sets to a sohd mass on cooling and melts at 63°. The yield of monochloroacetic acid is 150-175 g. 

Devrinol, 2-(l-naphthoxy)-Al,A/-diethylpropionamide/7 i25 5 -5 5 -7/ (napropamide) (23), which is prepared from 1-naphthol, is used as a herbicide (61). Another agricultural chemical, 1-naphthoxyacetic 2Lcid[2976-75-2] (24), is prepared by stirring 1-naphthol with monochloroacetic acid and sodium hydroxide in water at 100—110°C for several minutes. After treatment with concentrated HCl about 94% of the product is obtained (62). 

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. 

The chlorination proceeds considerably more rapidly, and also in the absence of light, if 1 5 g. of iodine, 7 g. of phosphorus pentachloride, and 3 g. of red phosphorus are added to the 150 g. of glacial acetic acid mentioned above.2 When the reaction is over, the hot mixture is decanted from the phosphorus, diluted with 40 c.c. of glacial acetic acid, and cooled. The monochloroacetic acid which crystallises is rapidly filtered and washed with a little glacial acetic acid. In this way a pale red product results, which is freed from adherent iodine by standing in a desiccator over potassium hydroxide. 

C. Ambient Air Analysb. Trace analysis of toxic gases in the environment is receiving more emphasis by many industries. Some of the more polar gases are very difficult to analyze by gas chromatography. One example is monochloroacetyl chloride. This gas can be collected from the atmosphere on Silica gel, extracted in dilute sodium bicarbonate, and then analyzed directly by IC as monochloroacetic acid (10). A... 

Electrochemical reduction in aqueous acid is useful in the treatment of waste liquors obtained from the formation of chloroacetic acid by chlorination of acetic acid. The liquors contain further chlorination products. These are reduced in an undivided cell at a magnetite cathode and a carbon anode to give excellent conversion to monochloroacetic acid [73]. 

Nitrilotriacetic acid N(CH2C02H)3 (nta) was first obtained by Heintz in 1862 from an ammon-iacal solution of monochloroacetic acid. Other products, i.e. glycolic, aminoacetic and iminodiacetic acids, were also formed. The next paper concerned with the preparation of aminopolycarboxylic acids appeared after 1930. A procedure similar to that given above, based on the treatment of ethylenediamine with monochloroacetic acid in presence of sodium hydroxide, was reported in 1935 by I.G.-Farbenindustrie.5 In a more recent version of the chloroacetic acid process, reaction (1) is carried out at 40-90 °C. For the preparation of edta, good yields of the tetrasodium salt can be obtained using appropriate conditions. The conversion to the insoluble free acid is achieved by acidification with a mineral acid. 

Instead of monochloroacetic acid, the condensation with a primary amine can be done using methyl bromoacetate. This procedure was used for the syntheses of /J-methoxyethyliminodiacetic acid /J-methoxyethylamine, methyl bromoacetate and potassium carbonate were reacted without solvent with formation of the corresponding ester (equation 6). This was separated, purified by distillation and hydrolyzed with a Ba(OH)2 solution. The separation of the acid from die solution was made after quantitative removal of barium ions with sulfuric acid.10... 

Oxygen can be supplied from an air separation plant, as well as from the cost-effective pressure swing adsorption (PSA) process. The Vinnolit oxychlorination process is also able to handle ethylene and/or anhydrous HCI containing vent streams from direct chlorination, acetaldehyde, monochloroacetic acid and other processes. 

Calculate the equilibrium molality m (in mol/kg of water) for each aliquot. If the results for the two aliquots from a given run are consistent, the average values of m and AT may be used in further calculations. For monochloroacetic acid, a weak electrolyte, calculate the effective total molality m from Eq. (10-20) using the appropriate constants in Table 10 I. Then calculate a and Tf for each of the two concentrations studied. 

Disposition in the Body. Rapidly absorbed from the lungs about 50 to 65% of an inhaled dose is retained. Absorbed from the gastro-intestinal tract and through the skin. It is highly soluble in lipid-rich tissues, from which it is slowly released. Chloral hydrate is a transient metabolite which is further metabolised by reduction to trichloroethanol and oxidation to trichloroacetic acid. Trichloroethanol is mainly excreted as its glucuronide conjugate (urochloralic acid). Monochloroacetic acid is a minor metabolite. About 45% of an absorbed dose is excreted as urochloralic acid and about 30% as trichloroacetic acid in the urine in 3 weeks small amounts are eliminated in the faeces. About 16% is excreted unchanged in expired air. 

Monochloroacetic acid, HC2H2C102, is a skin irritant that is used in chemical peels intended to remove the top layer of dead skin from the face and ultimately improve the complexion. The value of Ka for monochloroacetic acid is 1.35 X 10-3. Calculate the pH of a 0.10 M solution of monochloroacetic acid. 

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