Russian Journal of Applied Chemistry, Vol. 77, No. 10, 2004, pp. 1667 1669. Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 10, 2004,
pp. 1681 1683.
Original Russian Text Copyright
2004 by Magerramov, Abdinbekova, Kurbanova, Zamanova, Allakhverdiev.
ORGANIC SYNTHESIS
AND INDUSTRIAL ORGANIC CHEMISTRY
Synthesis of Substituted Ureas from Urea and Halohydrins
A. M. Magerramov, R. T. Abdinbekova, M. M. Kurbanova,
A. V. Zamanova, and M. A. Allakhverdiev
Baku State University, Baku, Azerbaijan
Received April 15, 2004; in final form, July 23, 2004
Abstract Substituted ureas were prepared by reactions of 1,2-halohydrins with urea and were tested as
antimicrobial additives to motor oils.
Substituted ureas attract researchers’ attention
thanks to a set of valuable properties allowing their
use in industry, agriculture, and medicine. Substituted
ureas are used as insecticides, as plant growth regu-
lators, as effective additives of various purposes to
hydrocarbon fuels, oils, and polymeric materials, as
drugs, and as dyes [1].
R
RCHCH Cl + NH CNH
2
CHNHCNH2 ,
CH Cl
2
2
OH
O
2
O
I V
where R H (I), CH OCH (II), C H OCH (III),
3
2
2
5
2
C H OCH (IV), C H CH OCH (V).
4
9
2
6
5
2
2
Classical synthetic routes to substituted ureas are
mostly based on reactions of amines with urea or with
isocyanic acid derivatives, or on carbonylation of
amino and nitro compounds [1]. These routes are
diverse, but many procedures have certain drawbacks
restricting their applicability. Development of new
procedures is interesting from both scientific and
practical viewpoints. In particular, synthesis of substi-
tuted ureas by direct reaction of aliphatic and aromatic
alcohols with urea has been reported [2, 3]. However,
there are no data on reactions of urea with alkoxy-sub-
stituted 1,2-halohydrins. These reactions are examined
in our study.
By reactions of I with HCHO and (C H ) N, we
prepared N-hydroxymethyl-N -chloroethylurea VI and
cyclic urea VII (see table):
2
5 3
HCHO
ClCH CH NHCNHCH OH
2
2
2
O
VI
I
(C H ) N
2
5 3
HN NH
VII
O
The compounds prepared were tested as antimicro-
bial additives to MS-11 lubricating oil [GOSTs (State
Previously, we have studied the reactions of alk- Standards) 9.052 75 and 9.085 75]. The compounds
oxy- and alkylthio-substituted 1,2-chlorohydrins with showed a pronounced antimicrobial effect when pres-
thiourea in the presence of various acids [4 6]. Pro- ent in low concentrations (0.5 1.0%); they are readily
ceeding with analysis of the reactivity of ureas and soluble in MS-11 oil and do not stimulate corrosion.
thioureas [7], we prepared in this study N-substituted Compounds VI and VII are more effective than the
ureas by reactions of 1,2-halohydrins with urea in the commercial antimicrobial additive, 8-quinolinol. With
presence of a mixture of H SO and CH COOH.
VI, the width of the suppression zone is 0.6 1.4 cm
for bacteria and 1.0 1.9 cm for fungi. With 8-quino-
linol, these parameters are 0.4 0.9 and 0.7 0.9 cm,
respectively.
2
4
3
The starting 1,2-halohydrins were prepared by reac-
tions of appropriate alcohols with epichlorohydrin in
the presence of ZnCl at 65 C [8].
2
The yield of N-substituted ureas containing various
functional groups (see table) can be optimized by
varying the temperature (from 60 to 115 C), amount
of H SO (1 5 ml), and reaction time (4 8 h).
EXPERIMENTAL
1
The H NMR spectra were recorded on a Bruker
spectrometer (300 MHz, internal reference TMS). The
2
4
1
070-4272/04/7710-1667 2004 MAIK Nauka/Interperiodica