Sodium chloroacetate

CgHjClaOj. M.p. 155°C. Used as a selective herbicide. It is made from 2,4,5-trichloro-pheno) and sodium chloroacetate. Ester sprays and combined ester sprays with 2,4-D are available. 2,4,5-T products are of particular value in that they control many woody species, and eradicate perennial weeds such as nettles in pastures. 

Halogen, Chloral hydrate, sodium chloroacetate, chlorobenzene, />-chlorophenol, dichlorhydrin, bromobenzene, iodobenzene. 

Conduct the preparation in the fume cupboard. Dissolve 250 g. of redistilled chloroacetic acid (Section 111,125) in 350 ml. of water contained in a 2 -5 litre round-bottomed flask. Warm the solution to about 50°, neutralise it by the cautious addition of 145 g. of anhydrous sodium carbonate in small portions cool the resulting solution to the laboratory temperature. Dissolve 150 g. of sodium cyanide powder (97-98 per cent. NaCN) in 375 ml. of water at 50-55°, cool to room temperature and add it to the sodium chloroacetate solution mix the solutions rapidly and cool in running water to prevent an appreciable rise in temperature. When all the sodium cyanide solution has been introduced, allow the temperature to rise when it reaches 95°, add 100 ml. of ice water and repeat the addition, if necessary, until the temperature no longer rises (1). Heat the solution on a water bath for an hour in order to complete the reaction. Cool the solution again to room temperature and slowly dis solve 120 g. of solid sodium hydroxide in it. Heat the solution on a water bath for 4 hours. Evolution of ammonia commences at 60-70° and becomes more vigorous as the temperature rises (2). Slowly add a solution of 300 g. of anhydrous calcium chloride in 900 ml. of water at 40° to the hot sodium malonate solution mix the solutions well after each addition. Allow the mixture to stand for 24 hours in order to convert the initial cheese-Uke precipitate of calcium malonate into a coarsely crystalline form. Decant the supernatant solution and wash the solid by decantation four times with 250 ml. portions of cold water. Filter at the pump. 

Chloroacetic acid can be esterified and aminated to provide useful chemical intermediates. Amphoteric agents suitable as shampoos have been synthesized by reaction of sodium chloroacetate with fatty amines (4,5). Reactions with amines (6) such as ammonia, methylamine, and trimethylamine yield glycine [66-40-6J, sarcosine [107-97-17, and carhoxymethyltrimethylammonium chloride, respectively. Reaction with aniline forms /V-phenylglycine [103-01 -5] a starting point for the synthesis of indigo (7). 

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). 

Carboxymethylcellulose Sodium. Carboxymethyl ether of cellulose sodium salt (Citmcel) (8) is a white granular substance soluble in water depending on the degree of substitution. It is equally soluble in cold and hot water and may be prepared by treating alkaU cellulose with sodium chloroacetate. 

A solution of sodium cyanide [143-33-9] (ca 25%) in water is heated to 65—70°C in a stainless steel reaction vessel. An aqueous solution of sodium chloroacetate [3926-62-3] is then added slowly with stirring. The temperature must not exceed 90°C. Stirring is maintained at this temperature for one hour. Particular care must be taken to ensure that the hydrogen cyanide, which is formed continuously in small amounts, is trapped and neutrali2ed. The solution of sodium cyanoacetate [1071 -36-9] is concentrated by evaporation under vacuum and then transferred to a glass-lined reaction vessel for hydrolysis of the cyano group and esterification. The alcohol and mineral acid (weight ratio 1 2 to 1 3) are introduced in such a manner that the temperature does not rise above 60—80°C. For each mole of ester, ca 1.2 moles of alcohol are added. 

Hydrochloric acid [7647-01-0], which is formed as by-product from unreacted chloroacetic acid, is fed into an absorption column. After the addition of acid and alcohol is complete, the mixture is heated at reflux for 6—8 h, whereby the intermediate malonic acid ester monoamide is hydroly2ed to a dialkyl malonate. The pure ester is obtained from the mixture of cmde esters by extraction with ben2ene [71-43-2], toluene [108-88-3], or xylene [1330-20-7]. The organic phase is washed with dilute sodium hydroxide [1310-73-2] to remove small amounts of the monoester. The diester is then separated from solvent by distillation at atmospheric pressure, and the malonic ester obtained by redistillation under vacuum as a colorless Hquid with a minimum assay of 99%. The aqueous phase contains considerable amounts of mineral acid and salts and must be treated before being fed to the waste treatment plant. The process is suitable for both the dimethyl and diethyl esters. The yield based on sodium chloroacetate is 75—85%. Various low molecular mass hydrocarbons, some of them partially chlorinated, are formed as by-products. Although a relatively simple plant is sufficient for the reaction itself, a si2eable investment is required for treatment of the wastewater and exhaust gas. 

Manufacture. Cyanoacetic acid and cyanoacetates are iadustrially produced by the same route as the malonates starting from a sodium chloroacetate solution via a sodium cyanoacetate solution. Cyanoacetic acid is obtained by acidification of the sodium cyanoacetate solution followed by organic solvent extraction and evaporation. Cyanoacetates are obtained by acidification of the sodium cyanoacetate solution and subsequent esterification with the water formed being distilled off. Other processes reported ia the Hterature iavolve the oxidation of partially oxidized propionittile [107-12-0] (59). Higher esters of cyanoacetic acid are usually made through transesterification of methyl cyanoacetate ia the presence of alumiaiumisopropoxide [555-31-7] as a catalyst (60). 

Polyalkoxycarboxylates. These surfactants ate produced either by the reaction of sodium chloroacetate with an alcohol ethoxylate ... 

Imidazolinium Derivatives. Amphoteric imida2olinium derivatives are prepared from the 2-aLkyl-l-(2-hydroxyethyl)-2-imida2olines and from sodium chloroacetate. The most likely stmcture of the reaction product is as follows (109) ... 

Unlike the 2-aLkyl-2-imida2olines, this stmcture is stable and resistant to hydrolysis. After ring cleavage, reaction with sodium chloroacetate yields linear products ... 

Manufacture. Common to all manufacturing processes for CMC is the reaction of sodium chloroacetate [3926-62-3] with alkaU cellulose complex represented here as OH NaOH ... 

Many of the surfactants made from ethyleneamines contain the imidazoline stmcture or are prepared through an imidazoline intermediate. Various 2-alkyl-imidazolines and their salts prepared mainly from EDA or monoethoxylated EDA are reported to have good foaming properties (292—295). Ethyleneamine-based imida zolines are also important intermediates for surfactants used in shampoos by virtue of their mildness and good foaming characteristics. 2- Alkyl imidazolines made from DETA or monoethoxylated EDA and fatty acids or their methyl esters are the principal commercial intermediates (296—298). They are converted into shampoo surfactants commonly by reaction with one or two moles of sodium chloroacetate to yield amphoteric surfactants (299—301). The ease with which the imidazoline intermediates are hydrolyzed leads to arnidoamine-type stmctures when these derivatives are prepared under aqueous alkaline conditions. However, reaction of the imidazoline under anhydrous conditions with acryflc acid [79-10-7] to make salt-free, amphoteric products, leaves the imidazoline stmcture essentially intact. Certain polyamine derivatives also function as water-in-oil or od-in-water emulsifiers. These include the products of a reaction between DETA, TETA, or TEPA and fatty acids (302) or oxidized hydrocarbon wax (303). The amidoamine made from lauric acid [143-07-7] and DETA mono- and bis(2-ethylhexyl) phosphate is a very effective water-in-od emulsifier (304). 

SODIUM CHLORITE SODIUM CHLOROACETATE SODIUM CHROMATE SODIUM CUPROCYANIDE SOLID SODIUM CUPROCYANIDE SOLUTION... 

The use of acid chlorides instead of acid anhydrides has also been described. Wittig and coworkers converted propiophenone 31 to chromone 32 in 50% yield with chloroacetyl chloride in the presence of sodium chloroacetate at 190 C. Despite the acid chloride s increased reactivity, a high temperature was still required. 

R,7R)-7-[2-[2-(2-Chloroacetamido)-4-thiazolyl] -2-(methoxyimino) acetamido] -8-oxo-3-[ ((1,4,5,6-tetrahydro-4-methyl-5,6-dioxo-as-triazin-3-yl)thiol methyl 1 -5-thia-1 -azabicycio (4.2.01 oct-2-ene-2-carboxylic acid Ceftriaxone sodium Chloroacetic acid Carbocysteine Isobornyl thiocyanoacetate... 

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. 

The real Willamson synthesis with metallic sodium and sodium chloroacetate is only used for the preparation of pure ether carboxylates for analysis purposes or to obtain physicochemical measurements [229]. 

In comparison with other anionics, little has been published concerning methods of analysis of ether carboxylates. Gerhardt et al. [238] investigated the analytical determination of ether carboxylic acids in reaction mixtures obtained by reaction of nonylphenol ethoxylates with sodium chloroacetate as well as by cyanoethylation by different methods. Several methods, used for other surfactants as well [239], can be used for ether carboxylates. 

Treatment of alkali cellulose with sodium chloroacetate results in an ether with a free carboxyl group. This ether, in the form of its sodium salt, is water-soluble even when the degree of substitution is relatively low. Since the alkali-soluble modification of this substance is of much greater industrial importance it will be discussed in detail under that heading. 

By the action of relatively small quantities of sodium chloroacetate on alkali cellulose, carboxymethyl ethers are obtained which give smooth solution in dilute alkali but which can be regenerated to give threads or films of high tensile strength. These products are relatively hygroscopic. The substances are soluble in the form of their sodium salts and form insoluble salts with many metals.8... 

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. 

Sodium chloride-water system, phase diagram of, 22 801—802 Sodium chlorite, 6 133 Sodium chloroacetate, 1 139—140 Sodium AT-chlorobenzenesulfonamide (chloramine B), 4 54 Sodium AT-chloroimidodisulfonate, 4 54... 

Physical and chemical changes may often be induced by raising or lowering the temperature of a substance. Typical examples are phase transitions, such as fusion, or chemical reactions, such as the solid state polymerization of sodium chloroacetate, which has an onset at 471 K [227] ... 

Potassium peroxodisulfate, 4668 f 2-Propen-l-ol, 1223 f Propylene oxide, 1225 Pyridine N--oxide, 1849 Sodium azide, 4758 Sodium chloroacetate, 0694 Sodium methoxide, 0464 Sodium 3-nitrobenzenesulfonate, 2184 Sodium peroxodisulfate, 4809 Sodium trichloroacetate, 0608 Styrene, 2945 Sucrose, 3558... 

To 10.3 g, 0.075 mol aminobenzoic acid neutralized with 5 mol/L sodium hydroxide (or to 3-acetyl aniline in 250 mL of water), was added sodium chloroacetate (26.2 g, 0.225 mol). The solution was refluxed, and the pH was maintained between 10 and 12 by the addition of 5 M aqueous sodium hydroxide solution. After the pH ceased to fall, the solution was refluxed for an additional 1 h and then cooled and acidified with 0.5 mol/L HCl. The crystals were vacuum filtered and dried under high vacuum. The product was recrystallized from an acetone/water mixture. The yield of these aryliminodiacetic acids reaction varied from 3.1 g to 5.3 g. 

The synthesis and purification of C12BMG by the reaction of N-methyl-benzylamine with sodium chloroacetate followed by the quaternization of the resulting tertiary ammonioacetate with 1-bromododecane is described elsewhere (12). Purification of aqueous solutions of the surfactant for surface tension measurements and determination of the surface tension of the solutions by the Wilhelmy method using a sandblasted platinum blade were by techniques previously described (13). The concentration of C12BMG in aqueous solution was determined by measuring its absorbance at 263 nm (e = 350.5). 

Dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) dominated the herbicide market up to the late 1960s. These are sometimes called phenoxy herbicides. Phenol is the starting material for 2,4-D. Chlorination via electrophilic aromatic substitution (know the mechanism ) gives 2,4-dichlorophenol. The sodium salt of this compound can react with sodium chloroacetate (Sn2) and acidification gives 2,4-D. 

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