Synthesis of Monochloroacetic Acid from Ethylene Chlorohydrin

Synthesis of Monochloroacetic Acid from Ethylene Chlorohydrin Russian Journal of Applied Chemistry, Vol. 76, No. 9, 2003, p. 1530. Translated from Zhurnal Prikladnoi Khimii, Vol. 76, No. 9, 2003, pp. 1569. Original Russian Text Copyright 2003 by Svetlakov, Nikitin, Nikolaeva. BRIEF COMMUNICATIONS N. V. Svetlakov, V. G. Nikitin, and E. A. Nikolaeva Kazan State Technological University, Kazan, Tatarstan, Russia Received May 22, 2003 Abstract The possibility of preparing monochloroacetic acid by oxidation of ethylene chlorohydrin with nitric acid was examined. Monochloroacetic acid (MCAA) is widely used in distilled water. production of polymers, pesticides, pharmaceuticals, To prepare monochloroacetic acid, ECH (17 g, etc. The main industrial and laboratory procedures for 0.2 mol) was added with stirring at 20 25 C to 80% MCAA synthesis, and also its properties and applica- HNO (63 g as calculated on 100% HNO , 1 mol). 3 3 tion fields are described in [1]. The main industrial In the process, the temperature rose by 2 3 C, and process for MCAA synthesis, chlorination of acetic nitrogen oxides (which were not analyzed) were re- acid, has a number of drawbacks; in particular, di- and leased. After stirring for 0.5 h, the mixture became trichloroacetic acids are formed as by-products, and colorless owing to removal of nitrogen oxides. Then their separation involves certain problems. the stirring was stopped, and the temperature of the MCAA can be prepared by oxidation of ethylene reaction mixture was controlled, so as to prevent self- chlorohydrin (ECH) with CrO [2], but this procedure heating above 60 70 C. After reaction completion, is of little promise for industrial use because of toxic- the mixture was stirred at 20 C to remove nitrogen ity and high cost of the oxidant. oxides; unchanged HNO and H O were distilled off 3 2 in a water-jet-pump vacuum. The bottom residue was In this work, we prepared MCAA by oxidation of transferred into a beaker, in which it crystallized with- ECH with nitric acid, a readily available and relatively in 20 30 min. The crystalline precipitate was filtered cheap oxidant used in industry for preparing carboxyl- off and dried in air; yield of MCAA 16.5 g (85%), mp ic acids (e.g., oxalic, adipic) [3]. Oxidation of ECH 62 C [from chloroform; published data [1]: mp 63 C was performed with 60 80% HNO ; ECH was added ( -modification)]. IR spectrum, ,cm : 1716, 2100 at 20 25 C. The reaction was accompanied by slight 3250 (COOH). H NMR spectrum, , ppm: 4.0 s (2H, warming-up and release of nitrogen oxides coloring CH Cl), 10.0 s (1H, COOH). the reaction mixture. After that, the temperature in- creased to 60 70 C, with vigorous evolution of ni- REFERENCES trogen oxides. 1. Zanaveskin, L.N., Aver’yanov, V.A., Kunitsyn, D.G., ECH is oxidized with nitric acid to MCAA more and Bulanov, V.N., Khim. Prom st., 2001, no. 5, difficultly compared to unsubstituted alcohols [3]. pp. 28 45. Presumably, oxidation of ECH with concentrated 2. Dictionary of Organic Compounds, Heilborn, I. and HNO involves intermediate formation of ECH ni- Banbury, H.M., Eds., London: Eyre and Spottiswoode, trates and nitrites [4, 5], which are relatively stable in 1946, vol. 2. Translated under the title Slovar’ organi- an electrophilic medium. When kept in an acid solu- cheskikh soedinenii, Moscow: Inostrannaya Literatura, tion, these ECH esters decompose to MCAA. 1949, vol. 2, p. 29. 3. Freidlin, G.N., Alifaticheskie dikarbonovye kisloty (Ali- EXPERIMENTAL phatic Dicarboxylic Acids), Moscow: Khimiya, 1978. 4. Orlova, E.Yu., Khimiya i tekhnologiya brizantnykh The IR spectrum of MCAA in Vaseline oil was re- vzryvchatykh veshchestv (Chemistry and Technology of corded on a UR-20 spectometer. The H NMR spec- High Explosives), Moscow: Oborongiz, 1960, pp. 301 trum of MCAA was taken in acetone-d on a Tesla- 497 spectrometer (working frequency 100 MHz) at 5. Comprehensive Organic Chemistry. The Synthesis and room temperature against internal HMDS. Reactions of Organic Compounds, Barton, D. and Ol- ECH was of pure grade; technical-grade 97% lis, W.D., Eds., vol. 2: Nitrogen Compounds, Oxford: HNO was diluted to the required concentration with Pergamon, 1979. 1070-4272/03/7609-1530$25.00 2003 MAIK Nauka/Interperiodica Russian Journal of Applied Chemistry Springer Journals

Synthesis of Monochloroacetic Acid from Ethylene Chlorohydrin

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Kluwer Academic Publishers-Plenum Publishers
Copyright © 2003 by MAIK “Nauka/Interperiodica”
Chemistry; Chemistry/Food Science, general
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