Mendeleev Commun., 2009, 19, 279–280
5a (Figure 1) is very similar to that in its analogue with 5,7-di-
O(2W)
N(6)
methyl-3-thioxoperhydroimidazo[4,5-e]-1,2,4-triazin-6-ones.5
The conformation of the imidazole cycle is twist; the N(1) and
N(2) atoms deviate from the plane of the three carbons by
0.37(1) and –0.32(1) Å, respectively. The conformation of
the triazine moiety can also be described as twist. The angle
between mean planes formed by N(3), N(4), N(5) and one of
the carbon atoms is 21.4(1)°. Note that two hydrogen atoms
belonging to the N(4)H and N(5)H groups of the triazine frag-
ment are in the equatorial plane with the H(3N) atom which is
an axial one. The sum of the CNC and CNH angles is 339.0(1)°
for N(3) atom, 353.3(1) and 351.1(1)° for N(4) and N(5), respec-
tively. The mutual disposition of the phenyl substituents is a
cisoid one with the torsion angle C(7)C(1)C(3)C(13) of 30.0(1)°.
Cl(1)
O(1W)
O(1)
C(6)
N(2)
C(2)
N(4)
N(3)
C(4)
C(3)
C(5)
N(5)
N(1)
C(1)
C(18)
C(13)
C(14)
C(15)
C(7)
C(12)
C(8)
C(11)
C(9)
C(10)
‡
The 1H and 13C NMR spectra were recorded on a Bruker AM-300 spectro-
Figure 1 General view of compound 5a in representation of atoms via
thermal ellipsoids at 50% probability level.
meter (300.13 MHz for 1H and 75.47 MHz for 13C). Chemical shifts were
measured with reference to the residual protons of a [2H6]DMSO solvent
(d 2.50 ppm). Melting points were determined with a Gallenkamp instrument
(Sanyo). Commercially available compound 3b from ACROS and dihydrate
of hydrochloride of aminoguanidine 3a synthesized at the Institute of
Reagents were used. The solvents were used without preliminary purifica-
tion. Starting DHI 4 was synthesized similarly to the described procedure.10
Synthesis of 3-imino-5,7-dimethyl-4a,7a-diphenylperhydroimidazo-
[4,5-e]-1,2,4-triazin-6-one 5a. A solution of DHI 4 (0.03 mol) and
aminoguanidine hydrochloride dihydrate 3a (0.03 mol) in 150 ml MeOH
with ten drops of concentrated HCl was heated at 40–45 °C for 1 h and
concentrated in vacuo. After cooling the oily residue was triturated with
50 ml Et2O. White precipitate of 5a was filtered off. Yield 93–95%,
mp 224–226 °C (MeOH). 1H NMR ([2H6]DMSO) d: 2.63 (s, 3H, MeN),
2.68 (s, 3H, MeN), 6.85–7.12 (m, 11H, 2Ph + HN), 7.99 (s, 2H, H2NCl),
9.75 (s, 1H, HN), 10.11 (s, 1H, HN). 13C{1H} NMR ([2H6]DMSO) d:
25.9 (MeN), 26.2 (MeN), 80.7 (CH), 84.2 (CH), 126.2 (CPh), 127.7 (CPh),
127.8 (CPh), 127.9 (CPh), 128.0 (CPh), 128.2 (CPh), 128.4 (CPh), 133.9
(CPh), 134.7 (CPh), 157.8 (C=O), 158.1 (C=N). Found (%): C, 52.88;
H, 6.14; Cl, 8.69; N, 20.50. Calc. for C18H25ClN6O3 (%): C, 52.87;
H, 6.16; Cl, 8.67; N, 20.55.
Salt 5a crystallizes with two solvate water molecules per
molecule of the product and this governs the supramolecular
organization in the crystal. Cations of 5a are assembled into
double chains via N(6)–H(6NA)···O(1) bonds [N···O 2.873(3) Å;
NHO 152(1)°]. These associates are additionally stabilized by
hydrogen bonds with H2O(2W) water molecule [N···O 2.919(4)–
2.955(4) Å; NHO 159(1)–165(1)°] serving as both the donor
and acceptor of proton. The cationic species also participate in
the formation of the H-bond with the second water molecule,
namely, N(4)–H(4N)···O(1W) one with the N···O distance and
NHO angle of 2.771(3) Å and 159°, respectively. The interionic
H-bonds [N···Cl 3.238(3) Å; NHCl 172(1)°] and those between
the water molecules and chloride anions [O···Cl 3.206(3)–
3.248(3) Å; OHCl 143(1)–173(1)°] interlink the above water-
cationic chains leading to the formation of the 3D framework.
Thus, the research on the condensation of 1,3-dimethyl-
4,5-dihydroxy-4,5-diphenylimidazolidin-2-one with amino-
guanidine and semicarbazide (as hydrochlorides) allowed us to
synthesize 3-imino-5,7-dimethyl-4a,7a-diphenylperhydroimidazo-
[4,5-e]-1,2,4-triazin-6-one and 5,7-dimethyl-4a,7a-diphenyl-
perhydroimidazo[4,5-e]-1,2,4-triazine-3,6-dione. Their structures
were analyzed by XRD and a new conglomerate 5a was found.
Synthesis of 5,7-dimethyl-4a,7a-diphenylperhydroimidazo[4,5-e]-1,2,4-
triazine-3,6-dione 5b. A solution of DHI 4 (0.07 mol) and semicarbazide
hydrochloride 3b (0.07 mol) in 300 ml MeOH was heated at 40–45 °C
for 1 h. After cooling white precipitate of 5b was filtered off. Yield
1
49–52%, mp 275–276 °C (MeOH). H NMR ([2H6]DMSO) d: 2.58 (s,
3H, MeN), 2.59 (s, 3H, MeN), 6.41 (s, 1H, HN), 6.99 (br. s, 10H, 2Ph),
7.62 [s, 1H, HN(4)], 8.17 [s, 1H, HN(2)]. 13C{1H} NMR ([2H6]DMSO)
d: 25.7 (MeN), 26.1 (MeN), 83.3 (CH), 84.5 (CH), 126.4 (CPh), 126.5
(CPh), 127.3 (CPh), 127.4 (CPh), 127.5 (CPh), 128.0 (CPh), 135.8 (CPh),
137.2 (CPh), 158.9 (C=O), 160.0 (C=O). Found (%): C, 64.05; H, 5.69;
N, 20.79. Calc. for C18H19N5O2 (%): C, 64.08; H, 5.68; N, 20.76.
References
1
M. D. Mashkovskii, Lekarstvennye Sredstva (Medicines), Novaya Volna,
Moscow, 2005, vol. 1, pp. 439, 562, 563; vol. 2, pp. 88, 230, 290, 299,
313, 335, 336 (in Russian).
2
E. Jagiello-Wojtowicz, I. Zebrowska-Lupina, M. Wielosz, M. Stelmasiak,
G. Szurska, A. Porowska and Z. Kleinrok, Acta Polon. Pharm., 1984,
41, 495.
§
Crystallographic data. Crystals of 5a (C18H25ClN6O3, M = 408.89)
are monoclinic, space group P21, at 120 K: a = 8.2145(6), b = 9.8678(6)
and c = 12.5084(8) Å, b = 96.929(5)°, V = 1006.51(12) Å3, Z = 2 (Z' = 1),
dcalc = 1.349 g cm–3, m(MoKα) = 2.22 cm–1, F(000) = 432. Intensities of
8322 reflections were measured with a Bruker SMART 1000 CCD
diffractometer [l(MoKα) = 0.71072 Å, w-scans, 2q < 56°] and 4680
independent reflections [Rint = 0.0272] were used in further refinement.
The structure was solved by a direct method and refined by the full-
matrix least-squares technique against F2 in the anisotropic–isotropic
approximation. The hydrogen atoms of NH groups and those of water
molecules were located from the Fourier density synthesis and refined in
isotropic approximation. The H(C) atom positions were calculated. All
hydrogen atoms were refined in the isotropic approximation in riding
model with the Uiso(H) parameters equal to 1.2Ueq(Ci), for methyl
groups equal to 1.5Ueq(Cii), where U(Ci) and U(Cii) are respectively the
equivalent thermal parameters of the carbon atoms to which corresponding
H atoms are bonded. For 5a the refinement converged to wR2 = 0.1203
and GOF = 1.008 for all independent reflections [R1 = 0.0489 was cal-
culated against F for 3846 observed reflections with I > 2s(I)]. All
calculations were performed using SHELXTL PLUS 5.0.11
3
4
W. J. Brouillette, V. P. Jestkov, M. L. Brown and M. S. Akhar, J. Med.
Chem., 1994, 37, 3289.
N. N. Mel’nikov, K. V. Novozhilov and S. R. Belan, Spravochnik
‘Pestitsidy i regulyatory rosta’ (Handbook ‘Pesticides and Growth
Regulators’), Khimiya, Moscow, p. 81 (in Russian).
5
6
A. S. Sigachev, A. N. Kravchenko, K. A. Lyssenko, P. A. Belyakov,
O. V. Lebedev and N. N. Makhova, Mendeleev Commun., 2003, 190.
A. S. Sigachev, A. N. Kravchenko, K. A. Lyssenko, P. A. Belyakov,
O. V. Lebedev and N. N. Makhova, Izv. Akad. Nauk, Ser. Khim., 2006,
836 (Russ. Chem. Bull., Int. Ed., 2006, 55, 865).
7
8
9
A. N. Kravchenko, G. K. Kadorkina, A. S. Sigachev, E. Yu. Maksareva,
K. A. Lyssenko, P. A. Belyakov, O. V. Lebedev, O. N. Kharybin, N. N.
Makhova and R. G. Kostyanovsky, Mendeleev Commun., 2003, 114.
Yu. V. Nelyubina, K. A. Lyssenko, A. S. Sigachev, M. Yu. Antipin and
A. N. Kravchenko, Izv. Akad. Nauk, Ser. Khim., 2006, 387 (Russ.
Chem. Bull., Int. Ed., 2006, 55, 399).
H. Pauly and H. Sauter, Ber. Dtsch. Chem. Ges., 1930, 63, 2063.
10 R. G. Neville, J. Org. Chem., 1958, 23, 1588.
11 G. M. Sheldrick, SHELXTL v. 5.10, Structure Determination Software
CCDC 745851 contains the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The Cambridge
For details, see ‘Notice to Authors’, Mendeleev Commun., Issue 1, 2009.
Suit, Bruker AXS, Madison, Wisconsin, USA.
Received: 27th March 2009; Com. 09/3308
– 280 –