1-alkyl 3,5-diallyl isocyanurates as synthetic building blocks for sulfur-containing macroheterocycles

Article abstract of DOI:10.1007/s11176-005-0150-0

2-Sulfanylethanol was added to readily available 1-alkyl 3,5-diallyl isocyanurates to obtain 1-alkyl 3,5-bis[3-(2-hydroxyethylsulfanyl)propyl] isocyanurates. Treatment of the products with thionyl chloride gave 1-alkyl 3,5-bis[3-(2-chloroethylsulfanyl)pro

Full text of DOI:10.1007/s11176-005-0150-0

Russian Journal of General Chemistry, Vol. 74, No. 8, 2004, pp. 1267 1276. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 8, 2004,
pp. 1368 1376.
Original Russian Text Copyright
Reznik.
2004 by Fattakhov, Shulaeva, Saifina, Efremov, Rizvanov, Solov’eva, Nafikova, Azancheev, Gubaidullin, Litvinov,
1-Alkyl 3,5-Diallyl Isocyanurates As Synthetic Building Blocks
for Sulfur-containing Macroheterocycles
S. G. Fattakhov, M. M. Shulaeva, L. F. Saifina, Yu. Ya. Efremov,
I. Kh. Rizvanov, S. E. Solov’eva, A. A. Nafikova, N. M. Azancheev,
A. T. Gubaidullin, I. A. Litvinov, and V. S. Reznik
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received July 25, 2002
Abstract 2-Sulfanylethanol was added to readily available 1-alkyl 3,5-diallyl isocyanurates to obtain
1-alkyl 3,5-bis[3-(2-hydroxyethylsulfanyl)propyl] isocyanurates. Treatment of the products with thionyl chlo-
ide gave 1-alkyl 3,5-bis[3-(2-chloroethylsulfanyl)propyl] isocyanurates whose reaction with thiourea followed
by hydrolysis resulted in preparation 1-alkyl 3,5-bis[3-(2-sulfanylethylsulfanyl)propyl] isocyanurates. Oxi-
ative cyclization of the latter gave macrocyclic disulfides in 56 75% yields. The composition and structure of
1
the macrocyclic disulfides were established on the basis of the elemental and X-ray diffraction analyses, H
and 13C NMR and IR spectra, as well as MALDI TOF and electron impact mass spectra.
Organic sulfur compounds (cystine, cysteine,
glutathione, coenzyme A, lipoic acid, sulfur-contain-
ing proteins, etc.) play an exceptionally important role
in biochemical processes. Therewith, sulfur atoms
incorporated in various functional groups act as active
centers of biological molecules. Chemically, of par-
ticular interest are biological molecules containing SH
groups. A distinctive feature of SH groups is their
ability to undergo reversible oxidative in mild condi-
tions to form S S bonds. It is along this pathway that
glutathione functions in biological processes to
maintain, via oxidation reduction, a definite cell
medium and the reduced state of protein SH groups
[1]. Dithiol disulfide transformations (such as
cysteine cysteine) play a vitally important regulatory
role in metabolic processes in the cell [2].
Sulfur-containing podands and crown ethers
occupy a prominent place on supramolecular che-
mistry in view of their ability to selectively bind
transition and heavy metal ions. Moreover, such com-
pounds hold promise as active components of the
membranes of ion-selective electrodes and molecular
receptors [3, 4]. Crown ethers with disulfide bridges
are potential redox and electrochemically switched
systems [5 7]. Earlier we reported on the synthesis of
macrocyclic disulfides with an isocyanurate fragment
and ester groups in the rim [8]. In the present work
we have synthesized new compounds of this series,
containing in the macroring rim an isocyanurate
fragment, sulfur atoms, and a redox switched disufide
function. To prepare isocyanurates with sulfide groups
in the N-alkyl chain, we developed a procedure for
addition of 2-sulfanylethanol to readily available
1-alkyl 3,5-diallyl isocyanurates. The reaction was
performed in an anhydrous solvent in the presence of
an initiator of free-radical reactions in an inert at-
mosphere. Thus, refluxing diallyl cyanurates with
Disulfide groups incorporated in the active centers
of certain oxidizing enzymes take part in electron and
proton transfer from substrates to receptors, under-
going reversible conversion into dithiols [1].
O
N
O
O
RN
RN
N(CH2)3S(CH2)2OH
O
N(CH2)3S(CH2)2OH
O
RN
NCH2CH=CH2
O
+ 2HSCH2CH2OH
+
O
O
N
O
N
(CH2)3S(CH2)2OH
I IV
CH2CH=CH2
V VIII
CH2CH=CH2
R = CH3 (I, V), C6H5CH2 (II, VI), CH3OC(O)CH2 (III, VII), CNCH2 (IV, VIII).
1070-3632/04/7408-1267 2004 MAIK Nauka/Interperiodica

1268
FATTAKHOV et al.
Table 1. Yields, Rf values, and elemental analyses of compounds I VIII
Found, %
Calculated, %
Reaction
Rf (solvent)
Formula
time, ha
C
H
N
S
C
H
N
S
I
V
II
66
22
71
14
14
15
0.32 (ethyl acetate) 44.06 6.72 10.42 17.52 C14H25N3O5S2
0.62 (ethyl acetate) 48.14 6.11 14.07 9.65 C12H19N3O4S
0.27 (benzene ethyl 52.57 6.16 9.01 14.48 C20H29N3O5S2
acetate, 1:1)
0.68 (benzene ethyl 57.06 6.02 11.10 8.33 C18H23N3O4S
acetate, 1:1)
0.30 (ethyl acetate 43.88 6.39 9.45 14.98 C16H27N3O7S2
benzene, 5:2)
0.66 (ethyl acetate 46.57 6.06 11.16 9.05 C14H21N3O6S
benzene, 5:2)
43.61 6.64 11.07 16.90
47.83 6.35 13.94 10.64
52.73 6.42
57.28 5.78 11.13 8.49
43.92 6.22 9.60 14.16
9.22 14.07
VI
III
11
65
15
12
12
VII 20
IV 55
46.77 5.89 11.69 8.92
26
26
0.36 (ethyl acetate) 44.14 5.62 13.78 15.24 C15H24N4O5S2
0.77 (ethyl acetate) 47.97 5.31 17.29 9.79 C13H18N4O4S
44.54 5.98 13.85 15.85
47.84 5.56 17.17 9.82
VIII 27
a
Boiling in dioxane.
1
2-sulfanylethanol in dioxane in the presence of ca-
talytic amounts of 2,2 -azobisisobutyronitrile under
argon gave 55 70% of 1-alkyl 3,5-bis[3-(2-hydroxy-
ethylsulfanyl)propyl] isocyanurates I IV (Table 1). In
addition, from the reaction mixture we isolated com-
pounds V VIII formed by addition 2-sulfanylethanol
by one allyl group of the starting isocyanurate.
[ (CO)], and 3400 cm [ (OH)]. In addition, the IR
spectra of compounds V VIII contain bands at 990
and 930 cm , characteristic of the allyl group.
1
Treatment of 1-alkyl 3,5-bis[3-(2-hydroxyethylsul-
fanyl)propyl] isocyanurates with thionyl chloride
gives rise to 1-alkyl 3,5-bis[3-(2-chloroethylsulfanyl)-
propyl] isocyanurates IX XII. Reaction of the latter
with thiourea followed by hydrolysis afforded 1-alkyl
3,5-bis[3-(2-sulfanylethylsulfanyl)propyl] isocyanu-
rates XIII XVI. The composition and structure of the
resulting compounds were proved by the elemental
The ratio of mono- and bis-addition products
depends on the reaction temperature and time. The
reaction of 1,3-diallyl 5-methyl isocyanurate with
2-sulfanylethanol in THF (80 C, 1 h) resulted in isola-
tion of 3-allyl 1-[3-(2-hydroxyethylsulfanyl)propyl]
5-methyl isocyanurate (V) and 1,3-bis[3-(2-hydroxy-
ethylsulfanyl)propyl] 5-methyl isocyanurate (I) in a
7:3 molar ratio. Increased reaction temperature and
time increase the yield of the bis-addition product.
With the above reagents in dioxane under reflux
(100 C, 14 h), the ratio of the mono- and bis-addition
products was 1:3.
1
analyses (Tables 1 and 2) and H and IR spectra
(Tables 3 and 4). Compounds IX XVI are yellowish
transparent oily liquids. Thiols XIII XVI have a
characteristic odor. The IR spectra of compounds
IX XVI contain bands characteristic of the isocyanu-
rate ring. In the spectra of compounds IX XII, there
is a medium-intensity band at 865 860 cm , that
probably belongs to the C Cl bond. The spectra of
compounds XIII XVI display a weak band at
2560 cm , characteristic of thiols. On standing thiols
XIII XVI are oxidized into oligomeric disulfides.
Therewith, the thiol absorption band disappears from
the IR spectra.
1
1
Compounds I VIII are transparent thick oily
liquids readily soluble in methanol. The IR spectra of
these compounds contain absorption bands at 1700
1680 [ (C=O)], 760 750 (isocyanurate ring), 1040
O
O
RN
N(CH2)3S(CH2)2SH
O
RN
SOCl2
N(CH2)3S(CH2)2Cl
O
SC(NH2)2, OH
I IV
O
O
N
N
(CH2)3S(CH2)2SH
XIII XVI
(CH2)3S(CH2)2Cl
IX XII
R = CH3 (IX, XIII), C6H5CH2 (X, XIV), CH3OC(O)CH2 (XI, XV), CNCH2 (XII, XVI).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 8 2004

1-ALKYL 3,5-DIALLYL ISOCYANURATES AS SYNTHETIC BUILDING BLOCKS
1269
Table 2. Yields, Rf values, and elemental analyses of compounds IX XVI
Found, %
Cl
Calculated, %
Cl
Rf (solvent)
Formula
C
H
N
S
C
H
N
S
IX 48 0.60 (benzene ethyl 40.81 5.13 17.08 10.34 15.74 C14H23Cl2N3O3S2 40.38 5.57 17.03 10.09 15.40
acetate, 10:1)
X
58 0.57 (benzene ethyl 49.11 6.02 14.13 8.21 13.35 C20H27Cl2N3O3S2 48.78 5.53 14.40 8.53 13.02
acetate, 20:1)
XI 38a 0.60 (benzene ethyl 40.36 5.24 14.52 8.56 13.99 C16H25Cl2N3O5S2 40.50 5.30 14.90 8.86 13.52
acetate, 5:1)
XII 51 0.42(benzene ethyl 40.74 4.95 15.96 12.21 14.38 C15H22Cl2N4O3S2 40.82 5.02 16.06 12.69 14.53
acetate, 10:1)
XIII 30 0.43(benzene ethyl 40.72 5.95
acetate, 10:1)
XIV 63 0.70(benzene ethyl 49.11 5.87
acetate, 10:1)
XV 58 0.71(benzene ethyl 40.81 5.34
acetate, 5:1)
XVI 40 0.56(benzene ethyl 41.12 5.21
acetate, 5:1)
10.08 30.94 C14H25Cl2N3O3S4 40.86 6.12
8.54 26.12 C20H29Cl2N3O3S4 49.26 5.99
8.63 27.41 C16H27Cl2N3O5S4 40.92 5.80
12.74 29.18 C15H24Cl2N4O3S4 41.26 5.54
10.21 31.15
8.62 26.29
8.95 27.30
12.83 29.37
a
Yield per taken 1,3-diallyl 5-methoxycarbonylmethyl isocyanurate.
Table 3. 1H NMR spectra of compounds I VIII, , ppm (3JHH, Hz); CDCl3
Allyl
=CH
>NC1H2C2H2C3H2SC4H2C5H2OH
R
NCH2
=CH2
C1H2
C2H2
C3H2
C4H2
C5H2
I
3.32 s (3H,
CH3)
5.03 s (2H,
3.98 t
(7.0)
4.00 t
(7.0)
1.82
2.15 m
1.83
2.48 2.97 m
3.72 t
(6.0)
3.70 t
(5.5)
II
2.50 2.83 m
2.50 2.83 m
CH2),
2.20 m
7.33 m (5H,
C6H5)
III
3.76 s (3H,
CH3),
4.00 t 1.82
2.48 2.75
3.71 t
(6.0)
(7.0)
2.18 m
4.62 s (2H,
CH2)
4.82 s (2H,
IVa
V
4.02 t 1.82
2.61 t (6.5) 2.71 t (5.7) 3.71 t
(6.0)
CH2)
(7.0)
2.15 m
3.33 s (3H, 4.28 d (6.0) 5.73 6.10 m 5.19 d (cis, 9.0), 3.98 t
CH3) (7.5)
1.82
2.17 m
2.47 2.80 m
3.70 t
(6.5)
5.22 d
(trans, 18.0)
VI
5.02 s (2H, 4.45 d (6.0) 5.72 6.10 m 5.22 d (cis, 9.0), 4.00 t
1.82
2.18 m
2.50 2.80 m
3.70 t
(6.0)
CH2),
7.33
(7.2)
m
5.25 d
(5H, C6H5)
(trans, 18.0)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 8 2004

1270
FATTAKHOV et al.
Table 3. (Contd.)
Allyl
=CH
VII 3.76 s (3H, 4.50 d (6.0) 5.70 6.10 m 5.21 d (cis, 9.0), 4.00 t
>NC1H2C2H2C3H2SC4H2C5H2OH
R
NCH2
=CH2
C1H2
C2H2
C3H2
C4H2
C5H2
1.82
2.48 2.75 m
3.71 t
(6.0)
CH3,
(7.0)
2.17 m
4.62 s (2H,
5.24 d
CH2)
(trans, 18.0)
VIIIa 4.76 s (2H, 4.48 d (6.1) 5.78 5.93 m 5.28d(cis, 10.3), 4.02 t
1.82
2.16 m
2.60 t (7.0) 2.71 t (6.1) 3.70 t
(5.9)
CH2)
(7.0)
5.35 d
(trans, 17.2)
a
The spectra of compounds IV and VIII were recorded on a WM-250 instrument (250 MHz), and the spectra of the other compounds,
on a T-60 instrument (60 MHz).
Table 4. 1H NMR spectra of compounds IX XVI, , ppm (3JHH, Hz); CDCl3
>NC1H2C2H2C3H2SC4H2C5H2X
R
C1H2
C2H2
C3H2
C4H2
C5H2
SH(X)
IXa
X
3.32 s (3H, CH3)
5.00 s (2H, CH2), 7.23 m 3.97 t (6.5) 1.80 2.10 m
(5H, C6H5)
3.78 s (3H, CH3), 4.52 s 3.83 4.13 m 1.89 2.10 m
(2H, CH2)
4.78 s (2H, CH2)
3.99 t (6.0) 1.82 2.15 m 2.61 t (6.8) 2.83 t (7.7) 3.59 t (7.7)
2.48 2.90 m
2.47 3.00 m
2.62 2.89 m
3.57 t (8.0)
3.40 3.78 m
3.63 t (8.0)
XI
XIIa
4.02 t (7.0) 1.94 2.06 m
XIIIa 3.33 s (3H, CH3)
XIVa 5.02 s (2H, CH2), 7.15
7.33 m (5H, C6H5)
3.90 4.00 m 1.90 1.98 m
3.98 t (6.6) 1.90 1.98 m 2.56 t (7.0)
2.50 2.73 m
2.67 2.70 m
1.68 t (7.4)
1.67 t (7.4)
XVa
3.78 s (3H, CH3), 4.63 s 1.94 4.07 m 1.92 1.97 m 2.58 t (7.0)
(2H, CH2)
2.70 2.80 m
2.69 2.84 m
1.70 1.77 m
1.69 t (7.5)
XVIa 4.76 s (2H, CH2)
4.00 t (6.9) 1.93 1.99 m 2.60 t (6.9)
a
The spectra of compounds IX and XII XVI were recorded on a WM-250 instrument (250 MHz), and the spectra of compounds X
and XI, on a T-60 instrument (60 MHz).
Oxidative cyclization of thiols XIII XV [8] gave
O
macrocyclic disulfides XVII XIX in 56 75% yields.
Compounds XVII XIX were purified by column
chromatography. They are colorless transparent oily
liquids crystallizing on standing, soluble in chloro-
form and methylene chloride, and insoluble in water
and alcohols. The composition and structure of the
products were established by the elemental analyses
R
N
S
S
I2
N
XIII XV
CH2Cl2
O
O
S
N
S
1
and H and 13C NMR and IR spectra (Tables 5 and
XVII XIX
6), as well as MALDI TOF and electron impact mass
spectra.
R = CH3 (XVII), C6H5CH2 (XVIII), CH3OC(O)CH2 (XIX).
The structure of compound XVIII was proved by
X-ray diffraction analysis (Fig. 1, Tables 7 and 8).
The compound crystallizes in a monoclinic cell with
one independent molecule in the asymmetric part.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 8 2004

1-ALKYL 3,5-DIALLYL ISOCYANURATES AS SYNTHETIC BUILDING BLOCKS
1271
Table 5. 1H NMR spectra of compounds XVII XIX, , ppm (3JHH); CDCl3
>NC1H2C2H2C3H2SC4H2C5H2S
C2H2 C3H2 C4H2
4.08 t (6.4) 1.97 2.02 m 2.60 2.67 m 2.80 2.94 m
R
C1H2
C5H2
XVII 3.36 s (CH3)
XVIII 5.05 s (CH2), 7.26 7.49 m (C6H5) 4.07 t (6.4) 1.94 2.05 m
XIX 3.80 s (CH3), 4.65 s (CH2) 4.09 t (6.6) 1.95 2.06 m
2.62 t (7.0)
2.64 t (7.0)
2.75 2.92 m
2.80 2.91 m
Table 6. 13C NMR spectra of compounds XVII XIX, , ppm; CDCl3
>NC1H2C2H2C3H2SC4H2C5H2S
Isocyanurate
R
ring
C1
C2
C3
C4
C5
XVII
CH3: 29.39
CH2: 46.16
q
(142.2)
149.25 (2C),
149.41 (1C)
42.08 t
(142.4)
27.47 t
(130.0)
29.70 t
(138.3)
39.50 t
(143.4)
31.43 t
(140.4)
XVIII
t
(142.43);
Ph: 128.14 d.t Cn (160.5; 7.9), 149.14 (2C),
128.61 d.d Co (159.4; 7.9), 149.30 (1C)
129.07 d.t Cm (159.4; 5.6;
42.14 t
(143.5)
27.40 t
(130.0)
29.64 t
(139.0)
39.31 t
(142.4)
31.31 t
(140.2)
4.0), 135.84 t Ci
XIX
CH2: 43.27 t (144.6)
CH3: 52.64 q (147.7)
148.86 (2C),
149.18 (1C)
42.28 t
(143.3)
27.48 t
(130.0)
29.58 t
(138.7)
39.45 t
(142.6)
31.42 t
(140.6)
a
2
3
The methylene proton signals were assigned by the sum of substituent increments for alkanes and the J
and J
constants.
CCCH
CCH
C24
O20
C12
C23
C22
C13
C25
C26
C10
S11
C14
N15
C21
C10
C18
C9
C27
S8
N19
O16
C16
N17
O20
S7
C2
C6
C1
C5
C3
S4
Fig. 1. Molecular geometry of compound XVIII in crystal. Dashed lines show intramolecular hydrogen bonds.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 8 2004

1272
FATTAKHOV et al.
Table 7. Coordinates ( 104) of non-hydrogen atoms and
Table 8. Selected bond lengths (d, ) and bond angles
( , deg) in compound XVIII
equivalent isotropic thermal parameters Uiso ( 103)
3
U = 1/3
3(aiaj)U(i, j) ( 2) in compound XVIII
Bond
d
Bond
d
i=1 j=1
S4 C3
1.70(3)
1.92(3)
1.79(3)
1.980(10)
1.80(2)
1.76(2)
1.85(2)
1.18(2)
1.23(2)
1.21(3)
1.37(2)
1.41(3)
1.46(2)
N17 C16
N17 C1
N19 C20
N19 C18
N19 C21
C1 C2
1.37(2)
1.49(2)
1.37(3)
1.40(2)
1.44(2)
1.56(2)
1.44(2)
1.40(3)
1.37(2)
1.56(2)
1.50(2)
1.54(2)
1.38(2)
Atom
x
y
z
U
S4 C5
S7 C6
S4
S7
S8
S11
O16
O18
O20
N15
N17
3062(10) 5071(9)
135(5)
1572(5)
146(4)
126(3)
S7 S8
5499(6)
4750(6)
5097(5)
3071(9)
1597(7)
3447(8)
S8 C9
1936(4)
4236(4)
113(3)
94(2)
61(5)
81(6)
84(6)
45(5)
55(6)
S11 C12
S11 C10
O16 C16
O18 C18
O20 C20
N15 C20
N15 C16
N15 C14
C2 C3
3180(11) 5173(13) 2380(7)
211(12) 7217(14) 1467(8)
1317(10) 6285(16) 4077(10)
2262(14) 5670(15) 3242(10)
1680(16) 6138(18) 1904(12)
C5 C6
C9 C10
C12 C13
C13 C14
C21 C22
N17 C18
N19
766(16) 6815(19) 2803(13)
1860(16) 6126(21) 1099(14)
1698(14) 4698(23)
1923(24) 4551(26)
4005(20) 3777(24)
67(6)
74(7)
76(6)
140(13)
113(11)
139(14)
128(11)
103(10)
86(8)
76(6)
49(6)
54(4)
54(4)
C1
Angle
Angle
C2
716(13)
35(13)
428(17)
C3
C3S4C5
105.9(12)
107.2(9)
C13C12S11
C14C13C12
N15C14C13
O16C16N17
O16C16N15
N17C16N15
O18C18N17
O18C18N19
N17C18N19
O20C20N15
O20C20N19
N15C20N19
N19C21C22
C23C22C21
C27C22C21
C10C9S8
117.3(14)
109.2(18)
111.4(19)
124.1(31)
120.3(29)
115.6(24)
119.8(27)
125.0(26)
114.8(22)
122.6(27)
121.3(26)
116.0(31)
114.5(17)
121.1(20)
118.8(20)
113.7(20)
118.2(19)
C5
C6S7S8
C6
4609(23) 4314(25) 1115(18)
4388(19) 2293(27) 2775(15)
5119(16) 2213(24) 3454(15)
3972(13) 3095(21) 4498(11)
2991(15) 3638(24) 3944(12)
3064(13) 5144(22) 3870(12)
2428(20) 5625(24) 2484(19)
814(17) 6718(26) 2021(17)
1435(18) 6234(25) 3416(20)
56(17) 7567(21) 2959(13)
949(11) 6692(14) 3047(14)
1127(12) 6433(16) 3778(10)
1971(16) 5716(17) 3839(10)
2638(11) 5259(14) 3168(16)
2460(14) 5518(17) 2437(11)
C9S8S7
104.5(10)
103.7(10)
123.8(27)
119.9(22)
116.2(21)
124.7(23)
119.1(22)
116.1(22)
124.5(24)
118.9(24)
116.6(23)
112.2(17)
116.7(20)
118.1(20)
112.6(21)
109.5(20)
C9
C12S11C10
C20N15C16
C20N15C14
C16N15C14
C18N17C16
C18N17C1
C16N17C1
C20N19C18
C20N19C21
C18N19C21
N17C1C2
C3C2C1
C10
C12
C13
C14
C16
C18
C20
C21
C22
C23
C24
C25
C26
C27
54(4)
74(7)
60(7)
72(8)
85(9)
103(11)
95(11)
81(9)
C2C3S4
C6C5S4
C9C10S11
1616(18) 6234(17)
2376(9)
C5C6S7
The dihedral angle between the isocyanurate and
benzene rings is 58.63(2) . Comparison of the crystal
structure of compound XVIII with those of previously
studied compounds of the same series [8] shows that
the macroring conformation changes essentially in
going from molecules with two methylene groups to
molecules with four methylene groups and depending
on the nature of the substituent in the isocyanurate
fragment. It should also be noted that the crystals
studied differ in the type of intermolecular contacts
and packing.
absence of classical hydrogen bonds. This system
includes both intra- and intermolecular C H O and
C H S contacts, as well as
and C H
inter-
actions. The totality of intramolecular contacts
appears to stabilize the molecular conformation in
crystal and determines the macroring geometry
(Fig. 1). The donor acceptor distances span the range
2.32 2.89 , and most short contacts are many-center.
The crystal packing is probably determined by
interactions between the benzene and isocyanurate
rings. The mutual arrangement of molecules is so that
the benzene and isocyanurate rings of one molecule
interact with the same rings of neighboring molecules
related to the initial one by the glide reflection plane
The system of hydrogen bonds in the crystal of
compound XVIII is rich and diverse in spite of the
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 8 2004

1-ALKYL 3,5-DIALLYL ISOCYANURATES AS SYNTHETIC BUILDING BLOCKS
1273
H21A
H12A
Fig. 2. Zigzag chain of C H O- and
-bonded molecules XVIII in crystal. Shown are only hydrogen atoms involved in
hydrogen bonding (dashed lines).
(a)
(b)
0 a
c
b
0
b
a
Fig. 3. Packing of molecules XVIII in crystal. Hydrogen atoms are not shown, except for those involved in hydrogen bonding.
View along the (a) 0x and (b) 0y axes, hydrogen bonds are shown by dashed lines.
and shifted along the 0x axis by 1/2 and +1/2. The
interaction parameters are the same: the interplanar
dihedral angle is 6.0 and the distance between the
aromatic ring centers is 3.569 . As a result, a zigzag
chain of molecules, running along the 0a axis is
formed (Fig. 2). Therewith, the arrangement of the
aromatic rings proves favorable for intermolecular
hydrogen bonding between the carbonyl O16 atom
and the methylene H21A proton of neighboring mole-
cules of the same chain [O16 H21A distance
2.62(2) , C16 O16 H21A angle 118 ; Fig. 2].
These chains of C H O- and
-bonded mole-
cules (the top view of these chains is shown in
Fig. 3a) are not directly involved in short contacts
with neighboring chains running along the 0y axis.
However, there is one more C H O interaction
between the carbonyl O20 atoms and methylene H12A
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 8 2004

1274
FATTAKHOV et al.
100
80
60
40
20
91
485.1
210.1
425.1
400
0
50
100
150
200
250
300
350
450
500
550
Fig. 4. Electron impact mass spectrum of compound XVIII.
1
protons in molecules related to each other by the 21
oil. The H NMR spectra were taken on a WM-250
instrument at 250 MHz, internal reference TMS. The
13C NMR spectra were obtained on an MSL-400
instrument at 100 MHz. Thin-layer chromatography
was performed on Silufol plates, development in
iodine vapor.
screw axis along the 0y direction (O20 H16A
distance 2.67 , C20 O20 H16A angle 164 ). This
interaction combines antiparallel molecular chains into
a zigzag bilayer.
Together the above contacts form 2D bilayer supra-
molecular structures (Fig. 3b). Therewith, molecular
fragments containing donor acceptor groups are
arranged in the inner part of the bilayers, whereas the
more hydrophobic sulfur-containing fragments of the
macrorings, between them, i.e. here, too, we observe
localization of predominantly hydrophilic and pre-
dominantly hydrophobic fields. In whole the crystal
packing represents similar bilayer supramolecular
structures packed in parallel along the 0z axis; there-
with, a fairly tight crystal packing is attained (packing
coefficient 0.67). Such structure may cause an ap-
preciable anisotropy in the properties of these crystals.
The MALDI TOF spectra were obtained on a
Finnigan Maldi TOF-Dynamo mass spectrometer for
5
3
10 10 M solutions in CH2Cl, matrix 1,8,9-tri-
hydroxyanthracene. The electron impact mass spec-
trum was obtained on a Finnigan MAT-212 mass spec-
trometer with direct inlet (130 C), ionizing voltage
60 V, emission current 0.5 mA. Data treatment was
performed using the Maspec II32 software. The mass
spectra were obtained at a resolution (R) of 1000, and
the exact masses were obtained at R 10000.
X-ray diffraction analysis of compound
XVIII was performed on an Enraf-Nonius CAD-4
automated four-circle diffractometer. Crystals of com-
pound XVIII, C20H27O3N3S4, monoclinic. At 20 C,
The mass spectrum of compound XVIII (Fig. 4)
has a strong molecular ion peak M 485.09456 (calcu-
lated M 485.09351 for the molecular formula C20H27
N3O3S4). The mass spectrum also contains a C18H23
N3O3S3 ion peak, m/z 425 (calculated 425.09015,
found 425.09088), formed from the molecular ion by
expulsion of a C2H4S molecule. The strong peak at
m/z 210 belongs to a C9H12N3O3 ion (calculated
210.08786, found 210.08792). The ion peak at m/z
91 is formed by a C7H+7 ion that is expected by the
structure of the compound.
a 13.810(4), b 9.890(3), c 17.60(1)
,
103.67(3) ,
3
V 2335.5(4) 3, Z 4, dcalc 1.38 g cm , space group
Þ21/a. The unit cell parameters and the intensities of
1658 reflections, 514 of which had I
measured at 20 C ( MoK radiation, graphite mono-
chromator, /2 scanning, 19.9 ). No intensity
2 , were
decay of three control reflections was observed during
measurements. No corrections for absorption were
1
applied because of its negligibility ( Mo 4.3 cm ).
It should be noted that the MALDI TOF spectum
of compound XVIII contains two peaks separated by
60 amu, which corresponds to a C2H4S fragment. The
same pattern is observed with compounds XVII and
XIX.
The structure was solved by the direct method by the
SHELX [9], WingX [10], and SIR programs [11] and
refined by the SHELX program first isotropically and
then anisotropically. Hydrogen atoms were located
by difference synthesis and refined with fixed posi-
tional and isotropic thermal parameters. The structure
was refined to R 0.046 and RW 0.100 on 514 unique
EXPERIMENTAL
The IR spectra were recorded on a Specord IR-75
instrument for thin films or suspensions in mineral
reflections with F2
formed using the PLATON program [12].
2 . The drawing were per-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 8 2004

1-ALKYL 3,5-DIALLYL ISOCYANURATES AS SYNTHETIC BUILDING BLOCKS
1275
1-R-3,5-Bis[3-(2-hydroxyethylsulfanyl)propyl]-
1,3,5-triazine-2,4,6(1H,3H,5H)-triones I IV. 2-Sul-
fanylethanol, 0.066 mol, and 0.0006 mol of 2,2 -azo-
bisisobutyronitrile were added to a solution of
0.03 mol of 1-R 3,5-diallyl isocyanurate in 150 ml of
absolute dioxane. The reaction mixture was heated
under reflux under argon for 12 14 h (26 h at R =
CH2CN). The solvent was removed in a vacuum, and
the residue was subjected to column chromatography
on silica gel, eluents benzene (A) and benzene
methanol, 10:1 (B).
18-Methyl-1,16,18-triaza-5,8,9,12-tetrathiabi-
cyclo[14.3.1]eicosane-17,19,20-trione (XVII). Yield
75%, mp 112 117 C (triturated with ether). Rf 0.45
(benzene ethyl acetate, 10:1). MALDI TOF mass
spectrum: H 410 (M + H), calculated M 409; H 350
(M + H). Found, %: C 40.94; H 5.58;N 10.11; S
31.25. C14H23N3O3S4. Calculated, %: C 41.06; H 5.66;
N 10.56; S 31.30.
18-Benzyl-1,16,15-triaza-5,8,9,12-tetrathiabi-
cyclo[14.3.1]eicosan-17,19,20-trione (XVIII). Yield
56%, mp 102 104 C (CHCl3 CH3OH). Rf 0.63
(benzene ethyl acetate, 10:1). MALDI TOF mass
spectrum: H 486 (M + H), calculated M 485; H 426
(M + H). Found, %: C 49.30; H 5.73; N 8.47; S 26.36.
C20H27N3O3S4. Calculated, %: C 49.46; H 5.60; N
8.65; S 26.40.
1-R-3,5-Bis[3-(2-chloroethylsulfanyl)propyl]-
1,3,5-triazine-2,4,6(1H,3H,5H)-triones IX XII. A
solution of 0.057 mol of thionyl chloride in 10 ml of
absolute 1,2-dichloroethane was added to a solution of
0.025 mol of compound I IV in 100 ml of the same
solvent. The reaction mixture was left overnight, after
which is was first heated at 40 C for 4 h and then
refluxed for 1 h. Excess thionyl chloride was decom-
posed with water. The organic layer was washed with
water (2 50 ml) and dried with MgSO4. The solvent
was removed, and the residue was subjected to
column chromatography on silica gel, eluent benzene
ethyl acetate, 10:1.
Methyl 2-(17,19,20-trioxo-1,16,18-triaza-5,8,
9,12-tetrathiabicyclo[14.3.1]eicosan-18-yl)acetate
(XIX). Yield 62%, mp 112 113 C (CHCl3 CH3OH).
Rf 0.38 (benzene ethyl acetate, 10:1). MALDI TOF
mass spectrum: H 468 (M + H), calculated M 467; H
408 (M + H). Found, %: C 41.46; H 5.41; N 8.94; S
27.56. C16H25N3O3S4. Calculated, %: C 41.10; H 5.39;
N 8.99; S 27.20.
1-R-3,5-Bis[3-(2-sulfanylethylsulfanyl)propyl]-
1,3,5-triazine-2,4,6(1H,3H,5H)-triones XIII XVI.
Equimolar amounts of compound IX XII and thionyl
chloride was heated under reflux in absolute
2-propanol for 10 16 h. The solvent was removed in
a vacuum. The residue was diluted with water, and
aqueous K2CO3 was added to the mixture with stirring,
after which it was heated for 1h on a boiling water
bath. The reaction products were extracted with hot
benzene, and the extract was dried with MgSO4. The
solvent was removed, and the residue was subjected to
column chromatography on silica gel, eluent benzene
ethyl acetate, 10:1.
ACKNOWLEDGMENTS
The work was financially supported by the Russian
Foundation for Basic Research (project no. 02-03-
32280).
REFERENCES
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18-R-1,16,18-Triaza-5,8,9,12-tetrathiabicyclo-
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crystals of sodium thiosulfate added, 50 ml of 0.1 N
HCl, and water (2 50 ml), and dried with MgSO4.
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silica gel, eluent benzene and benzene ethyl acetate,
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