1070-4272/03/7609-1530$25.00C2003 MAIK [Nauka/Interperiodica]
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.
Synthesis of Monochloroacetic Acid from Ethylene Chlorohydrin
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
production of polymers, pesticides, pharmaceuticals,
etc. The main industrial and laboratory procedures for
MCAA synthesis, and also its properties and applica-
tion fields are described in . The main industrial
process for MCAA synthesis, chlorination of acetic
acid, has a number of drawbacks; in particular, di- and
trichloroacetic acids are formed as by-products, and
their separation involves certain problems.
MCAA can be prepared by oxidation of ethylene
chlorohydrin (ECH) with CrO
, but this procedure
is of little promise for industrial use because of toxic-
ity and high cost of the oxidant.
In this work, we prepared MCAA by oxidation of
ECH with nitric acid, a readily available and relatively
cheap oxidant used in industry for preparing carboxyl-
ic acids (e.g., oxalic, adipic) . Oxidation of ECH
was performed with 60380% HNO
; ECH was added
at 20325oC. The reaction was accompanied by slight
warming-up and release of nitrogen oxides coloring
the reaction mixture. After that, the temperature in-
creased to 60370oC, with vigorous evolution of ni-
ECH is oxidized with nitric acid to MCAA more
difficultly compared to unsubstituted alcohols .
Presumably, oxidation of ECH with concentrated
involves intermediate formation of ECH ni-
trates and nitrites [4, 5], which are relatively stable in
an electrophilic medium. When kept in an acid solu-
tion, these ECH esters decompose to MCAA.
The IR spectrum of MCAA in Vaseline oil was re-
corded on a UR-20 spectometer. The
H NMR spec-
trum of MCAA was taken in acetone-d
on a Tesla-
497 spectrometer (working frequency 100 MHz) at
room temperature against internal HMDS.
ECH was of pure grade; technical-grade 97%
was diluted to the required concentration with
To prepare monochloroacetic acid, ECH (17 g,
0.2 mol) was added with stirring at 20325oC to 80%
(63 g as calculated on 100% HNO
, 1 mol).
In the process, the temperature rose by 233oC, and
nitrogen oxides (which were not analyzed) were re-
leased. After stirring for 0.5 h, the mixture became
colorless owing to removal of nitrogen oxides. Then
the stirring was stopped, and the temperature of the
reaction mixture was controlled, so as to prevent self-
heating above 60370oC. After reaction completion,
the mixture was stirred at 20oC to remove nitrogen
oxides; unchanged HNO
O were distilled off
in a water-jet-pump vacuum. The bottom residue was
transferred into a beaker, in which it crystallized with-
in 20330 min. The crystalline precipitate was filtered
off and dried in air; yield of MCAA 16.5 g (85%), mp
62oC [from chloroform; published data : mp 63oC
(a-modification)]. IR spectrum, n,cm
: 1716, 21003
H NMR spectrum, d, ppm: 4.0 s (2H,
Cl), 10.0 s (1H, COOH).
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