Synthesis of some 1-alkyl 3,5-bis(ω-haloalkyl) isocyanurates

Article abstract of DOI:10.1023/A:1013166023627

1-Methyl or 1-benzyl 3,5-bis(ω-bromoalkyl) isocyanurates with the alkyl chain comprising 3 through 6 methylene units were synthesized by the reaction of disodium methyl and benzyl isocyanurates with α,ω-dibromoalkanes. The reaction of disodium methyl and

Full text of DOI:10.1023/A:1013166023627

Russian Journal of General Chemistry, Vol. 71, No. 7, 2001, pp. 1091 1095. Translated from Zhurnal Obshchei Khimii, Vol. 71, No. 7, 2001,
pp. 1157 1161.
Original Russian Text Copyright
2001 by Fattakhov, Shulaeva, Reznik.
Synthesis of Some 1-Alkyl 3,5-Bis( -haloalkyl)
Isocyanurates
S. G. Fattakhov, M. M. Shulaeva, and V. S. Reznik
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received January 10, 2000
Abstract 1-Methyl or 1-benzyl 3,5-bis( -bromoalkyl) isocyanurates with the alkyl chain comprising 3
through 6 methylene units were synthesized by the reaction of disodium methyl and benzyl isocyanurates with
, -dibromoalkanes. The reaction of disodium methyl and benzyl isocyanurates with ethylene chlorohydrin
was used to obtain 1-methyl or 1-benzyl 3,5-bis(2-hydroxyethyl) isocyanurates whose treatment with PBr3 or
SOCl2 gave the corresponding 1-alkyl 3,5-bis(2-haloethyl) isocyanurates. 1-Methyl and 1-benzyl 3,5-bis-
(chloromethyl) isocyanurates were prepared by treatment with SOCl2 of 1-methyl or 1-benzyl 3,5-bis(hyd-
roxymethyl) isocyanurates obtained, in their turn, by condensation of methyl and benzyl isocyanurates with
formaldehyde.
The present work reports on the synthesis of
O
1-methyl and 1-benzyl 3,5-bis( -haloalkyl) isocyanu-
rates Ia If and IIa IIf, which are of interest as starting
materials for preparing a variety of compounds, in-
cluding practically valuable ones.
O
N(CH2)nBr
O
RN
N
RN
+ 2Br(CH2)nBr
N
O
O
N
O
(CH2)nBr
Ic If, IIc IIf
O
N(CH2)nHlg
O
RN
n = 3 6.
N
O
alkyl) isocyanurates, we always isolated oligomeric
products. The reaction of disodium methyl isocyanu-
rate with 1,2-dibromomethane under these conditions
results almost exclusively in oligomer formation, and
the yield of 1-methyl 3,5-bis(2-bromomethyl) iso-
cyanurate (Ib) is as low as 2%. This fact is nicely
consistent with the data on alkylation of disodium
salts of uracils with , -dibromoalkanes [11, 12] and
can be explained by increased activity of the bromine
atom in the N-alkyl chain of isocyanurate compared
with 1,2-dibromomethane, which results in preferen-
tial oligomer formation.
(CH2)nHlg
Ia If, IIa IIf
R = CH3 (I), C6H5CH2 (II); Hlg = Cl (Ia, IIa) or Br (Ib If,
IIb IIf); n = 1 (a), 2 (b), 3 (c), 4 (d), 5 (e), 6 (f).
No similar structures have yet been reported. As
follows from the available literature on related com-
pounds, such as 1,3-diallyl 5-( -haloalkyl) and 1,3,5-
tris( -haloalkyl) isocyanurates [1 10], as well as 1,3-
bis( -haloalkyl)uracils [11, 12], 1-alkyl 3,5-bis-
( -haloalkyl) isocyanurates are most expedient to
prepare by alkylation of disodium alkyl(aryl) iso-
cyanurates with , -dihaloalkanes. It was found that
these reactions are best performed with anhydrous
salts, in anhydrous DMF, and with a 5-fold molar
excess of , -dibromoalkane at 30 50 C. Under these
conditions we prepared 1-methyl and 1-benzyl 3,5-
bis( -bromoalkyl) isocyanurates Ic If and IIc IIf in
yields of 24 82% (Table 1).
The composition of the products was proved by
elemental analysis (Table 1). 1-Methyl and 1-benzyl
3,5-bis( -bromoalkyl) isocyanurates Ic If and IIc IIf
are transparent thick oils readily soluble in benzene
and acetone. In agreement with the proposed structure,
the IR spectra of compounds Ic If and IIc IIf
(Table 2) contain characteristic bands of the isocyanu-
rate ring at 750 760, 1440 1460, and 1670
1
1
1720 cm [ (C=O)] [13]. In the 3200 3400 cm
Along with the target 1-alkyl 3,5-bis( -bromo-
region, no (NH) absorption is observed.
1070-3632/01/7107-1091$25.00 2001 MAIK Nauka/Interperiodica

1092
FATTAKHOV et al.
Table 1. Yields, Rf values, melting points, and elemental analyses of 1-alkyl 3,5-bis( -haloalkyl) isocyanurates
Ia If and IIa IIf
Rf (diethyl
ether hexane,
1: 1)
Found, %
Br (Cl)
Calculated, %
Br (Cl)
Comp. Yielda,
mp,
C
Formula
no.
%
C
H
N
C
H
N
Ia
Ib
Ic
Id
Ie
If
34
20
24
53
63
40
33
29
79
41
82
76
47
0.24
0.33
0.28b
0.33
0.53c
0.41
0.46
0.66
0.52
0.36
0.34
0.47
0.52
128
125
29.87 2.60 (29.14) 17.63 C6H7Cl2N3O3
26.69 3.28 44.70 11.81 C8H11Br2N3O3
31.34 4.31 40.80 10.97 C10H15Br2N3O3 31.18 3.92 41.50 10.91
35.38 4.49 39.61 10.16 C12H19Br2N3O3 34.88 4.63 39.68 10.17
30.02 2.94 (29.54) 17.51
26.91 3.11 44.77 11.77
38.02 5.25 37.42
41.33 6.28 34.12
9.64 C14H23Br2N3O3 38.09 5.26 37.24
9.21 C16H27Br2N3O3 40.93 5.80 34.08
9.51
8.95
IIa
174
77
81
45.06 3.67 (22.57) 13.07 C12H11Cl2N3O3 45.55 3.50 (22.41) 13.28
38.74 3.49 36.76 9.73 C14H15Br2N3O3 38.82 3.49 36.90 9.70
48.54 4.31 (20.03) 11.94 C14H15Cl2N3O3 48.85 4.39 (20.60) 12.21
IIb
IIb
IIc
IId
IIe
IIf
41.30 4.73 33.79
44.03 5.10 32.96
46.85 5.33 30.68
48.36 5.81 29.30
8.90 C16H19Br2N3O3 41.67 4.53 34.66
9.09 C18H23Br2N3O3 44.19 4.73 33.16
7.94 C20H27Br2N3O3 46.44 5.26 30.90
7.51 C22H31Br2N3O3 48.45 5.73 29.31
9.11
8.58
8.12
7.71
a
b
c
Per starting methyl or benzyl isocyanurate.
Diethyl ether pentane, 1:1.
Benzene ethyl acetate, 10:1.
Table 2. IR spectra and 1H NMR spectra of 1-alkyl 3,5-bis( -haloalkyl) isocyanurates Ia If and IIa IIf
IR spectruma, , cm
H NMR spectrum (CCl4) , , ppm
1
1
b
Comp.
no.
isocyanurate
ring
C=O
C Br
C6H5 C6H5CH2 CH3 NCH2 CH2Br
CH2
Ia
Ib
Ic
766 s
760 s
760 s, 1446 v.s
1686 v.s, 1720 v.s
1650 v.s, 1720 v.s
1686 v.s
3.40 s
3.35 s 4.29 t 3.55 t
5.67 s
650 w
650 w, 554 m
650 w, 554 m
650 w, 554 m
650 w, 567 m
3.25 s 3.95 t 3.35 t 2.15 m
3.29 s 3.88 t 3.43 t 1.88 m
3.28 s 3.81 t 3.40 t 1.68 m
3.22 s 3.78 t 3.35 t 1.45 m
5.62 s
Id 760 s, 1446 v.s
Ie
If
IIa
IIb 760 s, 1460 v.s 1686 v.s, 1700 v.s
IIb 760 s, 1460 v.s 1680 v.s, 1700 v.s
1686 v.s
1686 v.s
1690 v.s
1700 v.s
760 s, 1450 v.s
767 s, 1460 v.s
760 s
7.23 m 5.03 s
7.22 m 4.95 s
7.23 m 4.97 s
560 sl
4.20 t 3.47 t
4.19 t 3.67 t
IIc 760 s, 1446 v.s
IId 750 s, 1460 v.s
IIe 760 s, 1440 v.s
IIf 760 s, 1440 v.s
1686 v.s
1670 v.s
1670 v.s
1670 v.s
642 w, 560 m 7.23 m 4.95 s
644 w, 560 w 7.22 m 4.90 s
644 m, 560 m 7.27 m 4.90 s
634 m, 547 m 7.19 m 4.92 s
3.95 t 3.37 t 2.17 m
3.83 t 3.35 t 1.80 m
3.80 t 3.31 t 1.65 m
3.78 t 3.32 t 1.46 m
a
The IR spectra of compounds Ia, Ib, and IIa were obtained in Vaseline, and those of compounds Ic If and IIb IIf, in thin films.
b
1
The H NMR spectra of compounds Ia, Ib, and IIa were obtained in CDCl .
3
In addition, the IR spectra of 1-benzyl 3,5-bis( -
(2-haloethyl) isocyanurates (IIa, IIb, IIb ) were ob-
tained by halogenation of the corresponding hydroxy
derivatives III VI.
bromoalkyl)isocyanurates contain characteristic ab-
sorption bands of the benzene ring [14]. In the 550
1
650 cm region, there are two medium or weak bands
assignable to (C Br) [14].
The previously unknown 1-methyl and 1-benzyl
3,5-bis(2-hydroxyethyl) isocyanurates (III, IV) were
prepared by the reactions of disodium methyl and di-
sodium benzyl isocyanurates with a small excess of
1-Methyl and 1-benzyl 3,5-bis(chloromethyl) iso-
cyanurates (Ia, Ib) and 1-methyl and 1-benzyl 3,5-bis-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 7 2001

SYNTHESIS OF SOME 1-ALKYL 3,5-BIS( -HALOALKYL) ISOCYANURATES
1093
O
O
O
N
PBr3,
SOCl2
N(CH2)2Hlg
O
RN
N
N(CH2)2OH
O
RN
RN
+ 2ClCH2CH2OH
N
O
O
N
O
O
(CH2)2Hlg
Ib, IIb, IIb
(CH2)2OH
(CH2)2OH
III, IV
O
N
O
N
O
NCH2OH
O
NCH2Cl
O
RN
RN
O
NH
RN
SOCl2
+ 2CH2O
O
N
H
O
O
CH2OH
CH2Cl
VII, VIII
V, VI
Ia, IIa
R = CH3 (I, III, V, VII), C6H5CH2 (II, IV, VI, VIII); Hlg = Br (Ib, IIb), Cl (IIb ).
ethylene chlorohydrin in DMF at 90 100 C. Com-
pounds III and IV are transparent resin-like solids
soluble in methanol. Their IR spectra contain all
characteristic bands of the isocyanurate ring, as well
By treatment of compounds V and VI with thionyl
chloride we obtained respectively 1-methyl and
1-benzyl 3,5-bis(chloromethyl) isocyanurates (Ia, IIa)
whose composition and structure were confirmed by
1
1
as a strong broad band near 3400 cm , assignable
the elemental analyses and the H NMR and IR spec-
to (OH).
tra (Tables 1 and 2).
Treatment of compounds III and IV with phos-
Methyl and benzyl isocyanurates (VII, VIII) were
phorus tribromide gave respectively 1-methyl and obtained by the known procedure [15] by conden-
1-benzyl 3,5-bis(2-bromomethyl) isocyanurates (Ib,
IIb). Treatment of compound IV with thionyl chloride
gave 1-benzyl 3,5-bis(2-chloroethyl) isocyanurate
(IIb ). The structure and composition of the products
were confirmed by the elemental analyses and the H
NMR and IR spectra (Tables 1 and 2).
sation of N-substituted biurets with diethyl carbonate.
It is known that N-substituted biurets are prepared by
reactions of nitrobiuret with primary amines, but for a
reasonable (50%) yield of N-methylbiuret (IX) the
reaction should be performed at 100 C in a sealed
ampule [16]. We propose a more convenient synthetic
procedure for this compound (see Experimental).
1
1-Methyl and 1-benzyl 3,5-bis(hydroxymethyl)
isocyanurates (V, VI) were synthesized by the reac-
tions of respectively methyl and benzyl isocyanurates
(VII, VIII) with formaldehyde [7]. Methyl isocyanu-
rate (VII) was dissolved in 34% formaldehyde on
heating at 60 C. Unreacted methyl isocyanurate was
then filtered off, and the solvent was removed to leave
a transparent glassy product whose elemental analysis
and IR spectrum corresponded to 1-methyl 3,5-bis-
(hydroxymethyl)isocyanurate (V).
EXPERIMENTAL
The IR spectra were recorded on a Specord IR-75
instrument in thin films or in suspensions in Vaseline
1
oil. The H NMR spectra were obtained on a Varian
T-60 spectrometer (60 MHz), internal reference TMS.
1,3-Bis( -bromoalkyl)-1-methyl- and 1-benzyl-
3,5-bis( -bromoalkyl)-1,3,5-triazin-2(1H),4(3H),
6(5H)-triones Ic If and IIc IIf. Methyl or benzyl
isocyanurate (VII, VIII), 0.05 mol, was added with
stirring to sodium butylate prepared from 0.1 mol of
sodium in 300 ml of absolute butanol, and the mixture
was stirred for 8 h, after which the butanol was re-
moved by vacuum azeotropic distillation with toluene.
Excess toluene was removed by vacuum distillation.
The residual anhydrous disodium salt was treated with
300 ml of absolute DMF and 0.5 mol (5-fold excess)
of corresponding , -dibromoalkane. The mixture
was stirred at 35 45 C for 2 5 h (to pH 7), the pre-
The yield of 1-benzyl 3,5-bis(hydroxymethyl) iso-
cyanurate (VI) in the similar reaction was as low as
20%. This compound proved to be thermally unstable:
It decomposed above 55 C with evolution of formal-
dehyde. To improve the yield of 1-benzyl 3,5-bis(hy-
droxymethyl) isocyanurate, the reaction was performed
at 40 C in the presence of pyridine. After removal of
the solvent, a white amorphous substance remained,
whose elemental analysis and IR spectrum corres-
ponded to 1-benzyl 3,5-bis(hydroxymethyl) iso-
cyanurate (VI).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 7 2001

1094
FATTAKHOV et al.
cipitate was filtered off, and the DMF and , -di-
bromoalkane were distilled off in a vacuum. The re-
sidue was treated with toluene, the mixture was fil-
tered, and the filtrate was evaporated in a vacuum.
The product was purified by column chromatography
on silica gel, eluents benzene ethyl acetate, 20:1
(Ic Ie, IIc), benzene acetone, 100:1 (IId, IIe), or
benzene dioxane, 100:1 (If, IIf). Compounds Ic If
and IIc IIf are colorless or yellowish thick oils; com-
pound IIc crystallizes on standing, mp 61 63 C.
of ice water. The layers were separated, and the
aqueous layer was extracted with 25 ml of 1,2-di-
chloroethane. The combined organic layers were
washed with 10% Na2CO3 and water, and dried with
MgSO4. The solvent was removed, and the solid
residue was treated with diethyl ether and recrystal-
lized from acetone hexane. Yield 3.5 g (33%).
1-Benzyl-3,5-bis(2-bromomethyl)-1,3,5-triazine-
2(1H),4(3H),6(5H)-trione (IIb) was prepared in a
similar way from compound IV and purified by
column chromatography on silica gel, eluent benzene.
The eluate was evaporated to leave a transparent oily
substance which quickly crystallized. Yield 36%.
1,3-Bis(2-hydroxyethyl)-5-methyl-1,3,5-triazine-
2(1H),4(3H),6(5H)-trione (III). Methyl isocyanurate,
7.15 g, was added with stirring to sodium butylate
obtained from 2.3 g of sodium in 200 ml of absolute
butanol, and the mixture was refluxed for 8 h. The
butanol was distilled off in a vacuum and completely
removed by azeotropic distillation with toluene.
Excess toluene was removed, the residue was treated
with 200 ml of absolute DMF, heated to 90 C, and
8.9 g of ethylene chlorohydrin was added dropwise to
the solution. The reaction mixture was stirred at 95
100 C for 3 h (to pH 7), cooled, the precipitate was
filtered off, the DMF and ethylene chlorohydrin were
distilled off in a vacuum, and the residue was sub-
jected to column chromatography on silica gel, eluents
benzene methanol, 10:1, to obtain 7.1 g (62%) of
compound III. Rf 0.13 (benzene methanol, 10:1). IR
1-Benzyl-3,5-bis(2-chloroethyl)-1,3,5-triazine-
2(1H),4(3H),6(5H)-trione (IIb ). Thionyl chloride,
42.5 g (5-fold excess), was added dropwise at 20 C
to a solution of 11 g of compound IV in 80 ml of
absolute 1,2-dichloroethane. The reaction mixture was
slowly heated to boiling and then boiled for 2 h. After
cooling, the mixture was treated with 80 ml of water,
the organic layer was separated, washed with two
portions of water, and dried with MgSO4. The re-
sidue was subjected to column chromatography on
silica gel, eluent benzene methanol, 20:1. Yield
10.3 g (84%), transparent oily substance crystallizing
on handling.
1
1,3-Bis(hydroxymethyl)-5-methyl-1,3,5-triazine-
2(1H),4(3H),6(5H)-trione (V). Methyl isocyanurate
(VII), 2.86 g, was added to a solution of 5.5 ml of
34% formaldehyde in 30 ml of water. The mixture
was stirred at 55 60 C until the precipitate had dis-
solved completely (30 40 min), evaporated in a
vacuum at 50 60 C, the residue was dissolved in cold
methanol, and the methyl isocyanurate precipitate was
filtered off. The filtrate was evaporated in a vacuum
at 40 50 C. Yield 3.1 g (76%), transparent colorless
resin. Rf 0.45 (benzene methanol, 4:1). IR spectrum
spectrum (thin film), , cm : 3370 3200 s (OH),
1730 s, 1670 v.s (C=O), 1440 s, 760 m (triazine
1
ring), 1040 s (C O). H NMR spectrum (CDCl3), ,
ppm: 3.33 s (3H, CH3), 3.86 m (2H, CH2O), 4.06 t
(2H, NCH2). Found, %: C 41.10; H 5.40; N 18.43.
C8H13N3O5. Calculated, %: C 41.56; H 5.67; N 18.18.
1-Benzyl-3,5-bis(2-hydroxymethyl)-1,3,5-tri-
azine-2(1H),4(3H),6(5H)-trione (IV) was obtained
in a similar way and purified by column chromato-
graphy on silica gel, eluent benzene methanol, 20:1.
Yield 81%. Rf 0.26 (benzene methanol, 10:1). IR
1
(thin film), , cm : 3500 3400 s (OH), 1690 s,
1
spectrum (thin film), , cm : 3470 3330 s (OH),
1670 v.s (C=O), 1440 s, 766 m (triazine ring),
1
1700 s, 1680 v.s (C=O), 1440 s, 765 m (triazine
1060 s (C O). H NMR spectrum (acetone-d6),
,
1
ring), 1040 s (C O). H NMR spectrum (CDCl3), ,
ppm: 3.20 s (3H, CH3), 5.30 d (2H, NCH2O). Found,
%: C 35.56; H 4.32; N 20.41. C6H9N3O5. Calculated,
%: C 35.47; H 4.47; N 20.68.
ppm: 3.80 m (2H, CH2O), 3.98 t (2H, NCH2), 4.99 s
(2H, C6H5 CH2), 7.25 s (5H, C6H5). Found, %: C
55.35; H 5.37; N 10.58. C14H17N3O5. Calculated, %:
C 55.24; H 5.41; N 10.74.
1-Benzyl-3,5-bis(hydroxymethyl)-1,3,5-triazine-
2(1H),4(3H),6(5H)-trione (VI). Benzyl isocyanurate,
5.48 g, and 2 g of pyridine were added to a solution
of 5.5 ml of 34% of formaldehyde in 20 ml of water.
The mixture was stirred at 40 C for 1 h, after which
it was evaporated in a vacuum at 40 50 C, the residue
1,3-Bis(2-bromomethyl)-5-methyl-1,3,5-triazine-
2(1H),4(3H),6(5H)-trione (Ib). A solution of 8.08 g
of PBr3 in 5 ml of 1,2-dichloroethane was added
dropwise to a solution of 6.9 g of compound III in
50 ml of anhydrous 1,2-dichloroethane cooled to 3 C. was dissolved in cold methanol, and the residue was
The mixture was stirred for 30 min at 0 C, then for
8 10 h at 20 C, and, finally, for 2 h at 70 C. After
cooling, the reaction mixture was poured into 50 ml
filtered off. The filtrate was evaporated in a vacuum at
40 50 C. Yield 4.0 g (57%), white amorphous sub-
stance. Rf 0.30 (benzene methanol, 4:1). IR spec-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 7 2001

SYNTHESIS OF SOME 1-ALKYL 3,5-BIS( -HALOALKYL) ISOCYANURATES
1095
1
trum (thin film), , cm : 3500 3300 s (OH), 1720 s,
1690 v.s (C=O), 1440 s, 766 m (triazine ring),
and Kornev, K.A., in Sintez i fiziko-khimiya polimerov
(Synthesis and Physical Chemistry of Polymers),
Kiev: Naukova Dumka, 1972, no. 10, pp. 15 18.
1
1080 s (C O). H NMR spectrum (CDCl3), , ppm:
4.93 s (2H, C6H5 CH2), 5.23 d (2H, NCH2O), 7.20 s
(5H, C6H5). Found, %: C 51.88; H 4.98; N 14.84.
C12H13N3O5. Calculated, %: C 51.61; H 4.69;
N 15.05.
3. Novikova, O.A., Samoilenko, M.I., and Shevlya-
kov, A.S., in Sintez i fiziko-khimiya polimerov (Syn-
thesis and Physical Chemistry of Polymers), Kiev:
Naukova Dumka, 1973, no. 11, pp. 123 126.
1,3-Bis(chloromethyl)-5-methyl- and 1-benzyl-
3,5-bis(chloromethyl)-1,3,5-triazine-2(1H),4(3H),
6(5H)-triones (Ia, IIa). A solution of 22 g (5-fold
excess) of thionyl chloride in 10 ml of 1,2-dichloro-
ethane was added dropwise at 10 12 C to a suspen-
sion of 0.018 mol of compound V or VI in 40 ml of
anhydrous 1,2-dichloroethane. The mixture was stirred
at 20 C for 1 h, after which it was heated to boiling
and boiled for 30 min. After cooling, it was treated
with caution with 40 ml of water, the organic layer
was separated, washed with water, and dried with
MgSO4. The filtrate was evaporated, and the residue
was subjected to column chromatography on silica
gel, eluent benzene. Compound Ia: yield 20%, white
crystals. Compound IIa: yield 43%, white crystals.
4. Esayan, G.T., Airapetyan, A.N., Isayan, G.A., Gaspa-
ryan, Zh.M., and Bagdasaryan, R.O., Arm. Khim. Zh.,
1974, vol. 27, no. 2, pp. 163 164.
5. Airapetyan, A.N., Esayan, G.T., and Babayan, A.A.,
Arm. Khim. Zh., 1982, vol. 35, no. 4, pp. 262 265.
6. Hofmann, A.W., Ber. B, 1886, vol. 19, pp. 2061
2098.
7. Pazenko, Z.N. and Chovnik, L.I., Ukr. Khim. Zh.,
1964, vol. 30, no. 2, pp. 195 198.
8. US Patent 4266055, Ref. Zh. Khim., 1982, 12N233P.
9. Vodop’yanov, V.G., Golov, V.G., Dvoeglazova, N.K.,
Ivanov, M.G., Mysin, N.I., and Gerega, V.F., Zh.
Obshch. Khim., 1981, vol. 51, no. 8, pp. 1885 1890.
N-Methylbiuret (IX). Nitrobiuret, 32.2 g, was
added with stirring to 120 ml of 25% methylamine
cooled to 17 C. The reaction mixture warmed up to
23 C. It was stirred for 2 h at 22 23 C, for 30 40 min
at 26 27 C, and for 30 40 min at 50 C. The water
and excess methylamine were distilled off in a
vacuum on a water bath (50 60 C), and the solid re-
sidue was recrystallized from isopropanol. Yield
16.5 g (67%), mp 168 168.5 C (published data [16]:
mp 166.5 167 C).
10. US Patent 4250309, Ref. Zh. Khim., 1981, 18N149P.
11. Reznik, V.S., Salikhov, I.Sh., Shvetsov, Yu.S., Shir-
shov, A.N., Bakulin, V.S., and Ivanov, B.E., Izv. Akad.
Nauk SSSR, Ser. Khim., 1977, no. 4, pp. 880 884.
12. Reznik, V.S., Salikhov, I.Sh., Shvetsov, Yu.S. and
Ivanov, B.E., Izv. Akad. Nauk SSSR, Ser. Khim., 1980,
no. 11, pp. 2568 2574.
13. Vorotyntseva, V.D., Kuz’mina, E.A., Roginskaya, I.N.,
Finkel’shtein, A.I., and Dergunov, Yu.I., Zh. Prikl.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 7 2001