Synthesis of 1-alkyl 3,5-bis(ω-mercaptoacetoalkyl) isocyanurates and macrocyclic disulfides derived thereof

Article abstract of DOI:10.1023/B:RUGC.0000007661.56422.a7

1-Alkyl 3,5-bis(ω-hydroxyalkyl) isocyanurates were reacted with mercaptoacetic acid to obtain 3,5-bis(ω-mercaptoacetoxyalkyl) isocyanurates whose oxidation gives rise to macrocyclic disulfides.

Full text of DOI:10.1023/B:RUGC.0000007661.56422.a7

Russian Journal of General Chemistry, Vol. 73, No. 8, 2003, pp. 1297 1302. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 8, 2003,
pp. 1371 1376.
Original Russian Text Copyright
2003 by Fattakhov, Shulaeva, Gubaidullin, Litvinov, Nafikova, Latypov, Reznik.
Synthesis of 1-Alkyl 3,5-Bis( -mercaptoacetoalkyl)
Isocyanurates and Macrocyclic Disulfides Derived Thereof
S. G. Fattakhov, M. M. Shulaeva, A. T. Gubaidullin,
I. A. Litvinov, A. A. Nafikova, Sh. K. Latypov, and V. S. Reznik
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received July 28, 2001
Abstract 1-Alkyl 3,5-bis( -hydroxyalkyl) isocyanurates were reacted with mercaptoacetic acid to obtain
3,5-bis( -mercaptoacetoxyalkyl) isocyanurates whose oxidation gives rise to macrocyclic disulfides.
Earlier [1, 2] we reported on the synthesis of
O
1-alkyl 3,5-bis( -mercaptoalkyl) isocyanurates by re-
RN
N(CH2)nOH
O
action of 1-alkyl 3,5-bis( -haloalkyl) isocyanurates
with thiourea followed by hydrolysis of the resulting
isothiuronium salts. The present work deals with the
synthesis of new podands on the basis of 1-alkyl
isocyanurates containing in the N-alkyl chain a
mercaptoacetyl group whose oxidation gives rise to
macrocyclic disulfides.
+ 2HSCH2COOH
O
N
(CH2)nOH
I V
O
N
O
H+
RN
N(CH2)nOCCH2SH
O
O
The interest in such structures is motivated, first,
by their potential biological activity. It is known that
thiols and their derivatives (cystine, cysteine, gluta-
thione, lipoic acid, etc.) play an exceptionally im-
portant role in biochemical processes. Such processes
as energy accumulation, electron transport, acyl and
alkyl transfer, structure stabilization, and detoxication
all involve CH groups [3]. The proposed structures
can be used as building blocks for designing sulfur-
containing macrocycles with azine fragments (pyrim-
dine, 1,3,5-triazine-2,4,6(1H,3H,5H-trione), which
makes possible modeling biological systems and
processes involving SH groups.
(CH2)nOCCH2SH
O
VI X
R = CH3, n = 2 (I, VI), 3 (II, VII); R = C6H5CH2, n = 2
(II, VIII), 3 (IV, IX); R = o-CH3OC6H4O(CH2)2, n = 2
(V, X).
The starting isocyanurates II, IV, and V were pre-
pared by alkylation of disodium salts of the corres-
ponding isocyanurates with 3-chloropropanol and
ethylene chlorohydrin similarly to the synthesis of
1-alkyl 3,5-bis(3-hydroxyethyl) isocyanurates I and
III, described in [2]. The synthesis of compounds
XVI and XVII used as starting materials for preparing
compound V is described in Experimental.
On the other hand, sulfur-containing podands and
crown ethers occupy an important place in supramole-
cular chemistry, since they are capable of selectively
binding transition and heavy metal ions. Moreover,
such compounds hold promise as active components
of membranes of ion-selective electrodes and mole-
cular receptors [4, 5], as well as potential redox-
switched and electrochemically switched systems
[6 8].
Thiols VI X are transparent thick oily substances
with a characteristic odor. They are spontaneously
oxidized on handling, forming oligomeric disulfides.
The IR spectra of compounds VI X contain a medium-
intensity (SH) band at 2560 cm , which is no longer
observed in the spectra of oligomeric oxidation
products.
1
1-Alkyl 3,5-bis( -mercaptoacetoxyalkyl) isocyanu-
rates VI X were obtained by esterification of 1-alkyl
3,5-bis( -hydroxyalkyl) isocyanurates I V with
mercaptoacetic acid.
Oxidative cyclization of thiols VI X in the condi-
tions described in [9] gave macrocyclic compounds
XI XV.
1070-3632/03/7308-1297$25.00 2003 MAIK Nauka/Interperiodica

1298
FATTAKHOV et al.
macrocyclic moiety are soluble in ethyl acetate,
O
N
O
S
acetone, and methanol. The composition and structure
of macrocycles XI XV were proved by X-ray diffrac-
tion, elemental analysis, and NMR and IR spectro-
scopy. The yields of macrocycles XI, XIII, and XV
with two methylene groups (Figs. 1a, 1b, and 2) are
50 60%, whereas the yields of macrocycles XII and
XIV with three methylene groups (Figs. 3a and 3b)
are much lower (10 12%). It should be noted that
thiols VI X were oxidized into disulfides XI XV in
air, and, therefore, oxidation into oligomeric disul-
fides is highly probable, especially in the case of
relatively unstable thiols VII and IX.
RN
N(CH2)n
O
I2
S
VI X
O
O
O
(CH2)n
O
XI XV
R = CH3, n = 2 (XI), 3 (XII); R = C6H5CH2, n = 2 (XIII),
3 (XIV); R = o-CH3OC6H4O(CH2)2, n = 2 (XV).
Compounds XI XV are colorless crystalline sub-
stances readily soluble in chloroform. Compounds
XII and XIV that have three methylene groups in the
As seen from the figures, the conformation of the
macrocycle radically changes both in going from
compounds containing two methylene groups in the
chain to compounds containing three methylene
groups and with change of 1-substituent. It should be
noted that in crystals of the compounds we observe
differences in the type of intermolecular contacts and
in molecular packing, which, too, may affect macro-
ring conformation. The X-ray diffraction results for
these compounds will be considered in more detail in
a separate publication.
(a)
O6
C18
C6
C19
O16
N5
N1
C4
C17
C2
C14
C15
S13
O4
O2
N3
It should be noted that similar dilactone structures
derived from pyridine have been prepared in yields of
15 80% by template condensation with bis(triphenyl-
stannyloxymethyl)pyridine of dicarboxylic acid di-
fluorides containing sulfide and disulfide bridges [10],
and their ability to complexation with Eu(fod)3 has
been studied [11]. Compounds containing two uracil
moieties and a disulfide bridge incorporated in the
macrocycle, 3,4-dithia[6.6](1,3)- and 3,4-dithia[6.1]-
(1,5)-pyrimidinophanes, have also been described
[12, 13].
O15
C7
O10
O9
S12
C8
C10
C11
(b)
C17
C18
C16
N5
O4
O6
EXPERIMENTAL
C15
O15
C4
N3
C14
C6
The IR spectra were obtained on a Specord IR-75
instrument in thin films or suspensions in Vaseline.
N1
1
The H NMR spectra of compounds II, IV X, XVI,
S13
O10
and XVII were obtained on a Varian T-60 spectro-
C19
1
meter at 60 MHz, and the H and 13C NMR spectra
C7 C8
C2
of compounds X XV were obtained on a WM-250
instrument at 250 MHz, internal reference TMS. Thin-
layer chromatography was performed on Silufol,
developer iodine vapor. Single-crystal X-ray diffrac-
tion analysis was performed on an Enraf Nonius
CAD-4 automatic four-circle diffractometer.
C10
S12
O9
O2
C21
C20 C25
C24
C11
C23
C22
1-Benzyl-3,5-bis(3-hydroxypropyl)-1,3,5-tri-
azine-2,4,6(1H,3H,5H)-trione (IV). Benzyl iso-
cyanurate, 6.6 g, was added with stirring to sodium
butylate obtained from 1.4 g of sodium in 100 ml of
Fig. 1. Molecular geometry of compounds (a) XI and
(b) XIII in crystals. For compound XIII, hydrogen atoms
are not shown.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 8 2003

SYNTHESIS OF 1-ALKYL 3,5-BIS( -MERCAPTOACETOALKYL)
1299
(a)
O14
C18
C23
O9
S1
O11
C19
C17
C16
N10
C25
O8
S2
O6
O7
O4 O10
N5
C26
S2
O4
C22
C13
N13
O6
N12
O9
N7
C21
O12
C20
O3
S1
O8
O3
N11
C14
C24
C15
(b)
S13A
O5
N5B
O6B
N1B
S14A
O16A
O4B
O17B
N3B
Fig. 2. Molecular geometry of compound XV in crystal
(hydrogen atoms are not shown).
O11A
O17A
O16B
O2B
O10A
O10B
S13B
absolute methanol, and the mixture was heated under
reflux for 6 h. Butanol was distilled off in a vacuum,
the residual butanol was removed by azeotropic di-
stillation with toluene, and the residual toluene was
distilled off in a vacuum. Absolute DMF, 200 ml, and
6.3 g of 3-chloropropanol were added, and the mixture
was heated at 80 90 C for 4 6 h (to pH 7). After
cooling, the precipitate was filtered off, and DMF was
distilled off in a vacuum. The residue was subjected
to column chromatography on silica gel in benzene
methanol (20:1) to isolate 8.4 g (84%) of compound
IV as a transparent thick oily substance. Rf 0.435
(benzene methanol, 10:1). IR spectrum (thin film),
N1A
S14B
N5A
O6A
O2A
4A O3A
O11B
N
Fig. 3. Conformations of macrocycles with three me-
thylene groups in the chain. (a) Compound XII and
(b) compound XIV. The crystal of compound XIV
contains two independent molecules A and B (hydrogen
atoms are not shown).
spectrum (CD3OD), , ppm (3JHH, Hz): 1.88 m (4H,
CH2), 3.34 s (3H, CH3), 3.67 m (4H, CH2O, 6.0),
4.03 m (4H, CH2N, 7.0). Found, %: C 46.62; H 6.27;
N 16.33. C10H17N3O5. Calculated, %: C 46.33; H 6.61;
N 16.21.
1
cm : 3400 v.s (OH), 3080 3025 m (several bands,
C6H5), 1670 v.s (C=O), 1045 s (C O), 755 s (iso-
1
cyanurate ring), 690, 673 m (C6H5). H NMR spec-
trum (CD3OD), , ppm (3JHH, Hz): 1.82 m (4H, CH2),
3.57 m (4H, CH2O, 5.8), 3.97 m (4H, CH2N, 6.4),
4.97 s (2H, CH2Ph), 7.28 m (5H, C6H5). Found, %: C
57.14; H 6.48; N 12.58. C16H21N3O5. Calculated, %:
C 57.30; H 6.31; N 12.53.
3,5-Bis(2-hydroxyethyl)-1-[2-(o-methoxyphen-
oxy)ethyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione
(V) was prepared by alkylation of 1,3-disodium 5-[2-
(o-methoxyphenoxy)ethyl isocyanurate (XVI) with
2-chloroethanol. Yield 84%, thick transparent oily
substance, crystallizes on standing. Rf 0.43 (ethyl
acetate methanol, 10:1). IR spectrum (thin film),
Compounds II and V were prepared in a similar
way.
3,5-Bis(3-hydroxypropyl)-1-methyl-1,3,5-tri-
azine-2,4,6(1H,3H,5H)-trione (II). Yield 61%, thick
1
cm : 3500 3300 v.s (OH), 1710, 1670 v.s (C=O),
nontransparent oily substance, crystallizes on standing. 1590 m (C6H4), 1245, 1212 s (Carom O), 1120, 1020 s
Rf 0.46 (ethyl acetate methanol, 10:1). IR spectrum
(Calif O), 1045 s (C O alc.), 755 s (isocyanurate ring),
740 s (C6H4). H NMR spectrum (CD3OD), , ppm:
3.75 m (4H, CH2O), 3.80 s (3H, CH3O), 3.99 m (2H,
1
1
(thin film), cm : 3450 v.s (OH), 1670 v.s (C=O),
1
1045 s (C O), 755 s (isocyanurate ring). H NMR
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 8 2003

1300
FATTAKHOV et al.
OCH2), 4.25 m (6H, CH2N), 6.87 m (4H, C6H4).
Found, %: C 52.15; H 5.71; N 11.44. C16H21N3O7.
Calculated, %: C 52.31; H 5.76; N 11.44.
46%, colorless transparent oily substance. Rf 0.44
(benzene ethyl acetate, 5:1). IR spectrum (thin film),
1
cm : 3085 3030 w m (several bands, C6H5), 2570 m
(SH), 1745 v.s (ester C=O), 1680 v.s (isocyanurate
C=O), 1295 1270 s, 1150 s (C O), 760 s (isocyanu-
1-Benzyl-3,5-bis(2-mercaptoacetoxyethyl)-1,3,5-
triazine-2,4,6(1H,3H,5H)-trione (VIII). 1-Benzyl
3,5-bis(2-hydroxyethyl) isocyanurate (III) and 5 g of
mercaptoacetic acid were heated under reflux in ab-
solute toluene in the presence of 0.6 g of p-toluene-
sulfonic acid (or sulfosalicylic acid) with a Dean
Stark trap for 4 5 h. Toluene was removed by distilla-
tion, the residue was subjected to column chromato-
graphy on silica gel, eluent benzene ethyl acetate,
10:1. Yield 8.5 g (84%), colorless transparent oily
substance. Rf 0.50 (benzene ethyl acetate, 5:1). IR
1
rate ring), 685 702 s (C6H5). H NMR spectrum
(CDCl3), , ppm (3JHH, Hz): 1.92 t (2H, SH, 8.0),
2.02 m (4H, CH2), 3.14 d (4H, CH2S, 8.0), 4.00 m
(4H, CH2N), 4.15 m (4H, CH2O), 5.00 s (2H, CH2Ph),
7.33 m (5H, C6H5). Found, %: C 49.21; H 5.15; N
8.45; S 13.11. C20H25N3O7S2. Calculated, %: C 49.68;
H 5.21; N 8.69; S 13.26.
3,5-Bis(2-mercaptoacetoxyethyl)-1-[2-(o-meth-
oxyphenoxy)ethyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-
trione (X). Yield 37%, colorless transparent oily
substance). Rf 0.51 (benzene ethyl acetate, 2:1). IR
1
spectrum (thin film), cm : 3070 3015 m w (several
bonds, C6H5), 2560 w (SH), 1725 v.s (C=O ester),
1670 v.s (isocyanurate C=O), 1280 s, 1150 s (C O),
1
spectum (thin film), cm : 3040 3015 w (several
1
752 s (isocyanurate ring), 698 m (C6H5). H NMR
bands, C6H4), 2560 m (SH), 1730 s (ester C=O),
1690 v.s (isocyanurate C=O), 1585 m (C6H4), 1285,
1145 s (ester C O), 1245, 1215 s (Carom O), 1120,
1020 s (Calif O), 758 s (isocyanurate ring), 745 m
(shoulder, C6H4). 1H NMR spectrum (CDCl3), , ppm
(3JHH, Hz): 1.92 t (2H, SH, 8.0), 3.17 d (4H, CH2S,
8.0), 3.83 s (3H, OCH3), 4.17 4.46 m (12H, NCH2
CH2O), 6.92 m (4H, C6H4). Found, %: C 46.51; H
4.78; N 8.06; S 12.31. C20H25N3O9S2. Calculated, %:
C 46.59; H 4.89; N 8.15; S 12.44.
spectrum (CDCl3), , ppm (3JHH, Hz): 1.85 t (2H, SH,
8.0), 3.04 d (4H, CH2S, 8.0), 4.07 4.38 m (AA BB ,
8H, NCH2CH2O), 5.00 s (2H, CH2Ph), 7.32 m (5H,
C6H5). Found, %: C 47.28; H 4.32; N 9.08; S 13.93.
C18H21N3O7S2. Calculated, %: C 47.46; H 4.65; N
9.23; S 14.08.
Compounds VI, VII, and IX XI were prepared in
a similar way.
3,5-Bis(2-mercaptoacetoxyethyl)-1-methyl-1,3,5-
triazine-2,4,6(1H,3H,5H)-trione (VI). Yield 47%,
colorless transparent oily substance. Rf 0.31 (benzene
3,5-Bis(4,9-dioxo-3,10-dioxa-6,7-dithiadodeca-
1,12-diyl)-1-methyl-1,3,5-triazine-2,4,6(1H,3H,5H)-
trione (XI). Solutions of 1.8 g of thiol VI in 60 ml
of absolute dichloromethane and of 1.27 g of iodine
in 150 ml of absolute dichloromethane were added
dropwise with vigorous stirring (18 C) to a solution
of 1.1 g of triethylamine in 60 ml of absolute dichloro-
methane until the reaction mixture changed from
colorless to yellowish (7 ml of the iodine remained
unused). Stirring was continued for an additional 4 h,
after which the reaction mixture was washed with
50 ml of water with some crystals of sodium thio-
sulfate added, 50 ml of 0.1 N HCl, and water (2
50 ml), and dried with MgSO4. The solvent was dis-
tilled off, and the residue was subjected to column
chromatography on silica gel, eluent benzene followed
by benzene ethyl acetate, 10:1. Yield 1.1 g (61%),
crystallizes from the solvent as colorless needles. mp
151 152 C. Rf 0.38 (benzene ethyl acetate, 2:1). IR
1
ethyl acetate, 5:1). IR spectrum (thin film), cm :
2560 m (SH), 1730 v.s (C=O ef.), 1670 v.s (iso-
cyanurate C=O), 1285 1270 s, 1142 s (C O), 752 s
1
(isocyanurate ring). H NMR spectrum (CDCl3), ,
ppm (3JHH, Hz): 2.03 t (2H, SH, 8.0), 3.23 d (4H,
CH2S, 8.0), 3.33 s (3H, CH3), 4.08 4.43 m (AA BB ,
8H, NCH2CH2O). Found, %: C 37.67; H 4.38; N
10.94; S 16.53. C12H17N3O7S2. Calculated, %: C
37.99; H 4.52; N 11.08; S 16.53.
3,5-Bis(3-mercaptoacetoxypropyl)-1-methyl-
1,3,5-triazine-2,4,6(1H,3H,5H)-trione (VII). Yield
47%, colorless transparent oily substance. Rf 0.35
(benzene ethyl acetate, 3:1). IR spectrum (thin film),
1
cm : 2560 m (SH), 1740 v.s (ester C=O), 1670 v.s
(isocyanurate C=O), 1278 s, 1160 1145 s (C O),
760 s (isocyanurate ring). 1H NMR spectrum (CDCl3),
, ppm (3JHH, Hz): 2.05 t (2H, SH, 8.0), 3.26 d (4H,
CH2S, 8.0), 3.32 s (3H, CH3), 4.00 m (4H, CH2N),
4.18 m (4H, CH2O). Found, %: C 41.12; H 5.06; N
10.32; S 15.61. C14H21N3O7S2. Calculated, %: C
41.27; H 5.20; N 10.31; S 15.74.
1
spectum (Vaseline), cm : 1740, 1730 s (ester C=O),
1670 v.s (isocyanurate C=O), 1258 s, 1147 s (C O),
758 s (isocyanurate ring). 1H NMR spectrum (CDCl3),
, ppm (3JHH, Hz): 3.38 s (3H, CH3), 3.51 s (4H,
CH2S), 4.26 m (4H, CH2N, 4.6), 4.48 m (4H, CH2O,
4.6). 13C NMR spectrum (CDCl3), C, ppm (1JCH, Hz):
29.71 q (CH3, 142.7), 41.11 t (CH2S, 142.7), 41.75 t
(CH2N, 144.3), 61.81 t (CH2O, 150.9), 149.17 s (iso-
1-Benzyl-3,5-bis(3-mercaptoacetoxypropyl)-
1,3,5-triazine-2,4,6(1H,3H,5H)-trione (IX). Yield
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 8 2003

SYNTHESIS OF 1-ALKYL 3,5-BIS( -MERCAPTOACETOALKYL)
1301
cyanurate C=O, exocycl.), 149.26 s (isocyanurate
C=O, endocycl.), 169.73 s (O C=O). Found, %: C
38.13; H 4.00; N 11.13; S 16.96. C12H15N3O7S2.
Calculated, %: C 38.19; H 4.01; N 11.13; S 16.99.
CH2Ph); (C6H5): 7.31 m (3H, m and p), 7.47 m (2H,
o). 13C NMR spectrum (CDCl3), C, ppm (1JCH, Hz):
27.54 t (CH2, 128.8), 40.94 t (CH2N, 142.4), 41.53 t
(CH2S, 142.4), 46.44 t (PhCH2, 142.4), 63.71 t (CH2O,
149.2); (C6H5): 128.60 d.t (p, 159.4, 7.6); 129.03 d.d
(o, 161.1, 6.8), 129.65 d.t (m, 161.1, 3.0), 136.06 s
(C1), 149.49 s (isocyanurate C=O), 169.49 s (O C=O).
Found, %: C 50.05; H 5.12; N 8.55; S 13.34. C20H23
N3O7S2. Calculated, %: C 49.89; H 4.81; N 8.73;
S 13.32.
Compounds XII XV were obtained in a similar
way.
3,5-Bis(5,10-oxo-4,11-dioxa-7,8-dithiadodeca-
1,14-diyl)-1-methyl-1,3,5-triazine-2,4,6(1H,3H,5H)-
trione (XII). Yield 12%. Colorless crystals. mp
132 C. Rf 0.58 (benzene ethyl acetate, 1:1). IR spec-
3,5-Bis(4,9-dioxo-3,10-dioxa-6,7-dithiadodeca-
1,12-diyl)-1-[2-(o-methoxyphenoxy)ethyl]-1,3,5-tri-
azine-2,4,6(1H,3H,5H)-trione (XV). Yield 55%.
Colorless crystals. mp 129 131 C. Rf 0.47 (benzene
1
trum (Vaseline), cm : 1740, 1715 s (ester C=O),
1685 v.s (isocyanurate C=O), 1280, 1270 s, 1150 s
1
(C O), 752 s (isocyanurate ring). H NMR spectrum
(CDCl3), , ppm (3JHH, Hz): 2.07 m (4H, CH2), 3.34 s
(3H, CH3), 3.60 s (4H, CH2S), 4.07 m (4H, CH2N,
5.8), 4.20 m (4H, CH2O, 5.8). 13C NMR spectrum
(CDCl3), C, ppm (1JCH, Hz): 27.50 t (CH2, 128.2),
29.67 q (CH3, 143.0), 40.59 t (CH2N, 143.0), 41.92 t
(CH2S, 142.1), 63.38 t (CH2O, 150.0), 149.50 s
(isocyanurate C=O), 169.57 s (O C O). Found, %: C
41.40; H 4.50; N 10.14; S 15.77. C14H19N3O7S2.
Calculated, %: C 41.47; H 4.72; N 10.36; S 15.82.
1
ethyl acetate, 1:1). IR spectrum (Vaseline), cm :
1730 s (ester C=O), 1690 v.s (isocyanurate C=O),
1582, 1500 m (C6H4), 1262, 1290 m, 1245 s, 1210,
1175 m, 1140 s, 1120, 1022 m (C O C), 758 m
1
(isocyanurate ring), 742 s (C6H4). H NMR spectrum
(CDCl3), , ppm: 3.45 s (4H, CH2S), 3.83 s (3H, CH3),
4.27 m (6H, CH2N), 4.38 m (2H, CH2OPh), 4.47 m
(4H, CH2O), 6.86 6.97 m (4H, C6H4). 13C NMR spec-
trum (CDCl3), C, ppm (1JCH, Hz): 41.04 t (CH2S,
143.3), 41.80 t (endocycl. CH2N, 143.3), 42.09 t
(exocycl. CH2N, 144.1), 56.23 q (CH3O, 144.1),
1-Benzyl-3,5-bis(4,9-dioxo-3,10-dioxa-6,7-dithia-
dodeca-1,12-diyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-
trione (XIII). Yield 47%. Colorless thick-like crystals. 61.81 t (endocycl. CH2O, 150.9), 65.47 t (CH2OPh,
mp 176 178 C. Rf 0.37 (benzene ethyl acetate, 5:1).
IR spectum (Vaseline), cm : 1745, 1730 s (ester
C=O), 1690 v.s (isocyanurate C=O), 1268, 1252 s,
146.7); (C6H4): 112.43 and 114.18 d. d (o, o , 157.7,
6.8), 121.15 and 122.15 d.d (m, m , 161.9, 7.6),
148.04 and 149.22 s (C1, C1 ), 149.84 and 148.93 s
(isocyanurate C=O), 169.75 s (O C=O). Found, %: C
46.39; H 4.54; N 7.95; S 12.86. C20H23N3O9S2.
Calculated, %: C 46.78; H 4.50; N 8.18; S 12.49.
1
1145 s (C O), 770 s (isocyanurate ring), 720 s, 690 m
1
(C6H5). H NMR spectrum (CDCl3), , ppm (3JHH
,
Hz): 3.38s (4 H, CH2S), 4.27 m (4H, CH2N, 5.0),
4.46 m (4H, CH2O, 5.0), 5.08 s (2H, CH2Ph); (C6H5):
7.31 m (2H, m), 7.34 m (1H, p), 7.45 m (2H, o). 13C
NMR spectrum (CDCl3), C, ppm (1JCH, Hz): 40.88 t
(CH2S, 143.1), 41.69 t (CH2N, 144.1), 46.57 t (PhCH2,
143.3), 61.67 t (CH2O, 149.9); (C6H5): 128.52 d.t (p,
161.1, 6.8), 128.92 d.d (o, 161.1, 6.8), 129.19 d. t
(m, 157.7, 5.0), 135.82 m (C1), 149.14 s (isocyanurate
C=O), 169.71 s (O C=O). Found, %: C 47.77; H 4.20;
N 9.29; S 14.07. C18H19N3O7S2. Calculated, %: C
47.68; H 4.22; N 9.27; S 14.14.
1-[2-(o-Methoxyphenoxy)ethyl] isocyanurate
(XVI) was obtained by the procedure in [14] from
disodium salt of 2-(o-methoxyphenoxy)ethylbiuret
(XVII) and diethyl carbonate (refluxing in methanol,
10 h) and recrystallized from 2-propanol. Yield 85%.
1
mp 190 192 C. IR spectrum (Vaseline), cm : 3505,
3432, 3200, 3160, 3100 w m (NH), 1775, 1740 s,
1690 v.s (isocyanurate C=O), 1635 m (NH), 1590 m
(C6H4), 1242 s, 1210 m (Carom O), 1125, 1020 s
(Calif O), 760 s (isocyanurate ring), 740 s (C6H4).
Found, %: C 51.54; H 4.89; N 14.89. C12H13N3O5.
Calculated, %: C 51.61; H 4.69; N 15.05.
1-Benzyl-3,5-bis(5,10-dioxo-4,11-dioxa-7,8-di-
thiatetradeca-1,14-diyl)-1,3,5-triazine-2,4,6(1H,3H,
5H)-trione (XIV). After column chromatography, a
thick oily substance was isolated, which was crystal-
lized by trituration with ether. Yield 10%. mp 103
115 C. Rf 0.53 (benzene ethyl acetate, 3:1). IR spec-
2-(o-Methoxyphenoxy)ethylbiuret (XVII). Nitro-
biuret, 18 g, was added to a solution of 20.4 g of 2-(o-
methoxyphenoxy)ethylamine in a mixture of 200 ml
of water and 100 ml of 2-propanol. The mixture was
stirred for 2 h at 18 20 C and then heated under
1
trum (Vaseline), cm : 1730 1720 s (ester C=O),
1680 1670 v.s (isocyanurate C=O), 1270 s, 1145
1112 s (C O), 750 s (isocyanurate ring), 692 s (C6H5). reflux for 30 min. The precipitate was filtered off and
1H NMR spectrum (CDCl3), , ppm (3JHH, Hz):
2.06 m (4H, CH2), 3.34 s (4H, CH2S), 4.06 m (4H,
CH2N, 5.7), 4.18 m (4H, CH2O, 5.7), 5.02 s (2H,
recrystallized from 2-propanol. Yield 15 g (50%). mp
188 189 C. IR spectum (Vaseline), cm : 3430, 3365,
3305, 3200 m (NH), 1775, 1680 v.s ( amide-I ), 1590,
1
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1302
FATTAKHOV et al.
1500 m (C6H4), 1530 m ( amide-II ), 1248, 1220 s
(Carom O), 1120, 1020 m (Calif O), 740 m (C6H4).
Found, %: C 52.50; H 5.98; N 16.31. C11H15N3O4.
Calculated, %: C 52.17; H 5.97; N 16.59.
7. Raban, M., Greenblatt, J., and Kandil, F., Chem.
Commun., 1983, no. 23, p. 1409.
8. Reich, H.J., Yelm, K.E., and Reich, I.L., J. Org.
Chem., 1984, vol. 49, p. 3440.
9. Goodrow, M.H. and Musker, W.K., Synthesis, 1981,
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