Chloracetic acid reactions

Caffeine, 131 ( arbamide, 126 Carbamine reaction, 71 Carbolic acid, 179 Carbon, qualitative analysis t Carbon, quantitative analysis 4 Carlus method, 22, 28 Chaiitiway s Xi QX o 174 Chloracetic acid, S7 Chloral, 99 Chloral hydrade, 99 ( hlorbydrin, tii / Chlorobenzoic acid, 166 < hlorofonTi, 70 / Chlorutulueiie, 16 ... 

Similarly, the position of the acyl group in derivatives formed by the reaction with acetic hydride or benzoyl chloride and the position of the carboxymethyl group in the derivative formed by the reaction with chloracetic acid are not established. ... 

To a solution of 4 g of sodium in 200 ml of n-propanol is added 39 g of homovanillic acid-n-propyl ester (boiling point 160°C to 162°C/4 mm Hg) and the mixture is concentrated by evaporation under vacuum. After dissolving the residue in 200 ml of dimethylformamide and the addition of 0.5 gof sodium iodide, 26.2 g of chloracetic acid-N,N-diethylamide are added drop-wise with stirring at an internal temperature of 130°C, and the mixture is further heated at 130°C for three hours. From the cooled reaction mixture the precipitated salts are removed by filtering off with suction. After driving off the dimethylformamide under vacuum, the product is fractionated under vacuum, and 44.3 g of 3-methoxy-4-N,N-diethylcarbamido-methoxy phenyl acetic acid-n-propyl ester are obtained as a yellowish oil of boiling point 210°C to 212°C/0,7 mm Hg,... 

Bifunctional catalysis in nucleophilic aromatic substitution was first observed by Bitter and Zollinger34, who studied the reaction of cyanuric chloride with aniline in benzene. This reaction was not accelerated by phenols or y-pyridone but was catalyzed by triethylamine and pyridine and by bifunctional catalysts such as a-pyridone and carboxylic acids. The carboxylic acids did not function as purely electrophilic reagents, since there was no relationship between catalytic efficiency and acid strength, acetic acid being more effective than chloracetic acid, which in turn was a more efficient catalyst than trichloroacetic acid. For catalysis by the carboxylic acids Bitter and Zollinger proposed the transition state depicted by H. 

An alternative general process involves coextraction of palladium and platinum, followed by selective stripping (see Fig. 11.12). A novel amino acid extractant, made by the reaction between chloracetic acid and Amberlite LA-2, a secondary amine, is used to extract the two elements from the leach liquor. However, in the given flow sheet, no selective stripping is employed, both elements being stripped by hydrochloric acid. The resulting chloroanions are then separated by using di- -hexylsulfide to extract PdCll. ... 

The third way for the synthesis emanates from 2-methylamino-5-chlorobenzophenone (5.1.5), which is acylated by chloracetic acid chloride, forming 2-chloracetylmethylamido-5-chlorbenzophenone (5.1.6). Reaction of this product with hexamethylenetetramine replaces the chlorine atom in the chloracetyl part of the molecule, giving a hexamethyl-enetetramino derivative of 2-aminoacetyhnethylamido-5-chlorbenzophenone, which upon hydrolysis in an hydrochloric acid ethanol solution undergoes cyclocondensation and gives diazepam (5.1.2) [6,7]. 

At a time when the only practicable methods for the preparation of nitromethane were the interaction of methyl iodide with silver nitrite and the Kolbe reaction from chloracetic acid, the explosive was far too expensive to merit consideration. The present cheap and large scale production of nitromethane by the vapor-phase nitration of methane and of ethane has altered the situation profoundly. Trimethylolnitromethane trinitrate is an explosive which can now be produced from coke, air, and natural gas. Nitromethane too has other interest for the manufacturer of explosives. It may be used as a component of liquid explosives, and it yields on reduction methylamine which is needed for the preparation of tetryl. 

Substituted thiazolidin-4-ones (449) are easily prepared by the reaction between chloracetic acid, or its derivatives (447), and a thiourea, a thiosemicarbazide, or a mono-or di-thiocarbamate (448 Scheme 255). The same a-chloro acid derivatives react with metallic thiocyanates yielding an intermediate (450), the cyclization of which gives a 2-iminothiazolidin-4-one (451). In these reactions a -chloracetic acid may be replaced by... 

This work was useful in establishing that the low quantum yield in the photolysis of pure methyl iodide was due to back reactions and that the initial decomposition into a methyl radical and iodine atom occurred with approximately 100% efficiency. In 1942, Blaedel et al.22 showed that the quantum yield for the decomposition of methyl iodide was, in fact, somewhat less than unity in the presence of oxygen because Bates and Spence11 had used an incorrect value for the quantum yield of the chloracetic acid actinometer. They suggested the reactions... 

Let us take here also the customary equation to the reaction, e. g. for solution of chloracetic acid ... 

This reaction seems to be of general application, and has been carried out using ethyl and isoamyl iodides, also benzyl chloride. In the presence of alkali, phenylarsenoxide reacts with chloracetic acid to give arsinophenylacetic acid, which melts with decomposition at 145° C. p-Chlorophenylarsenoxide, Cl.CgH4.AsO, crystallises from benzene in white needles, M.pt. 198° C. 

A considerable amount of work has been done on condensations between aminoarylarsinic adds and chloracetic acid and its derivatives. The reaction, which produces glycine derivatives, may be represented as follows ... 

There is thus obtained, besides the molecule of chloracetic acid, the molecule of acetyl chloride, first formed in reaction 2, which is utilised repeatedly by its regeneration in accordance with reactions 3, 4, and 5. 

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). 

CHLORACETIC ACID or a-CHLORACETIC ACID (79-11-8) Combustible solid (flash point 258°F/126°C). Aqueous solution is a strong acid violent reaction with strong... 

The hydrogen-ion catalysed hydrolysis of dimethyl acetal is a particularly suitable reaction to use because of the small primary kinetic salt effect. The assumption is made, however, that because the salt effect is negligible in perchloric acid solution within the range of concentration studied, this is also true in chloracetic acid. 

Dumas announced the discovery of trichloracetic acid on 27 August 1838, and in April 1839 he detailed account of its reactions and of its salts and esters, saying that he had begun to study the action of chlorine on acetic acid about 1830. Laurent claimed that he had predicted the existence of a chloracetic acid. Dumas obtained crystals of trichloracetic acid, which he analysed, by the action of i litre of dry chlorine gas on 0-9 gm. of glacial acetic acid in a flask exposed to direct sunlight, and he represented the reaction as (C=6) ... 

Berzelius, who gave a long summary of Dumas and other work on the theory of substitution, doubted the close similarity between acetic and chloracetic acids, whereupon Dumas drew attention to their decomposition reactions on heating with caustic potash, giving methane and chloroform, respectively ... 

To a mixture of 50 g 2-[4-[(4-chlorophenyl)phenylmethyl]-l-piperazinyl]-ethanol and 225 ml of tert-butanol at 45°C under a nitrogen was added 21 g tert-BuOK. The temperature was raised to 75-80°C and the mixture was kept at this temperature. After 45 min was added 11 g sodium chloracetate after 1.5 hour was added 5.2 g tert-BuOK after 2 hours was added 5.64 g sodium chloracetate after 2.5 hours was added 1.9 g tert-BuOK after 3 hours was added 1.9 g sodium chloracetate after 3.5 hours was added 0.8 g tert-BuOK and after 4 hours was added 1.13 g sodium chloracetate. Then about 150 ml tert-butanol was distilled of, 190 ml of water was added and the distillation of tert-butanol was continued until the temperature of the vapour reaches 100°C. To the reaction mixture was added 60 ml of water and 8 ml concentrated hydrochloric acid to pH 8. Unreacted 2-[4-[(4-chlorophenyl) phenylmethyl]-l-piperazinyl]-ethanol was extracted with diethyl ether. The aqueous phase was acidified to pH 5 by addition of hydrochloric acid and extracted with dichloromethane (200 ml x 3). The extract was dried over MgS04, filtered and concentrated in a rotary evaporator. An obtained oil was allowed to crystallize by addition of 150 ml of 2-butanone, yields of 2-[4-[(4-chlorophenyl)phenylmethyl]-l-piperazinyl]-ethoxy]acetic acid 55.5%, M.P. 146-148°C. 

---