GOLOBOKOVA et al.
(1C, 5′-CH2, JCH = 137 Hz), 55.2 t (1C, CH2Ph, JCH
136
=
a similar way from 5.7 g (0.043 mol) of pentaerythritol
and 10 g (0.18 mol) of acrylonitrile. Yield 27.4 g
(84%), mp 43°C. 13C NMR spectrum, δC, ppm: 20.7 t
(4C, CH2CN, JCH = 143 Hz), 48.8 s [C(CH2)4], 61.3 t
140 Hz), 63.2 t (1C, 4-CH2, JCH = 139 Hz), 65.0 t
(1C, OCH2, JCH = 145 Hz), 69.1 t (1C, CH2O, JCH
149 Hz), 126.5 d (1C, C5, JCH = 192 Hz), 133.8 s (1C,
=
Ci); 128.4, 129.3, 129.1 d (5C, Co, Cm, Cp, JCH
=
(4C, CH2O, JCH = 146 Hz), 71.9 t (4C, CH2O, JCH =
160 Hz), 145.9 s (1C, C4), 161.1 s (1C, C5′). Found, %:
C 54.21; H 5.92; N 34.47. C13H15N7O. Calculated, %:
C 54.73; H 5.30; N 34.37.
144 Hz), 118.1 s (4C, C≡N). Found, %: C 59.40;
H 6.81; N 15.88. C17H24N4O4. Calculated, %: C 58.61;
H 6.94; N 16.08.
b. As described above for compound VIII, from
3.4 g (0.052 mol) of NaN3, 2.6 g (0.05 mol) of NH4Cl,
and 9.6 g (0.04 mol) of XVa in 25 ml of DMF we
obtained 4.6 g (41%) of XVIIa with mp 143°C. The
product showed no depression of the melting point on
mixing with a sample prepared as described in a.
1,2,3,4,5,6-Hexakis[2-(1H-tetrazol-5-yl)ethoxy]-
hexane (XX). A suspension of 7.5 g (0.12 mol) of
NaN3 and 5 g (0.09 mol) of NH4Cl in 30 ml of DMF
was added at room temperature to a solution of 5 g
(0.001 mol) of compound XVIII in 25 ml of DMF, and
the mixture was stirred for 24 h at 105°C. The mixture
was cooled to 20–25°C, the solvent was distilled off
under reduced pressure, and 50 ml of 0.1 N aqueous
HCl was added to the residue until pH 2. The precip-
itate was filtered off, repeatedly washed with water
until neutral washings, and dried in air. Yield 7.2 g
(97%), mp 150°C. 13C NMR spectrum, δC, ppm: 21.9 t
5-(2-{[1-(1H-1,2,4-triazol-3-yl)-1H-1,2,3-triazol-
4-yl]methoxy}ethyl)-1H-tetrazole (XVIIb) was syn-
thesized as described above for compound VIII from
2.5 g (0.011 mol) of XVb, 1.4 g (0.022 mol) of NaN3,
and 1.2 g (0.022 mol) of NH4Cl in 15 ml of DMF.
Yield 2.4 g (84%), mp 158–158°C. IR spectrum, ν,
cm–1: 1465–1440 (Ht), 1245–1110 (C–O–C). 13C NMR
spectrum, δC, ppm: 24.7 t (5′-CH2, JCH = 139 Hz),
(4C, 5-CH2, JCH = 137 Hz), 22.3 t (2C, 5-CH2, JCH
=
137 Hz), 63.8 t (4C, OCH2, JCH = 147 Hz), 64.7 t (2C,
OCH2, JCH = 147 Hz), 68.7 t (2C, CH2), 76.5–77.8
(overlapping signals, 4C, CH), 152.5–152.8 br.s (C5).
Found, %: C 38.10; H 5.01; N 43.38. C24H38N24O6.
Calculated, %: C 37.99; N 5.05; N 44.31.
63.0 t (4-CH2, JCH = 135 Hz), 65.1 t (OCH2, JCH
=
147 Hz), 126.8 d (C5, JCH = 191 Hz), 143.0 s (C4),
148.1 d (C5″, JCH = 220 Hz), 149.7 s (C3″), 161.3 s
(C5′). Found, %: C 36.89; H 3.48; N 53.95. C8H10N10O.
Calculated, %: C 36.64; H 3.84; N 53.41.
1,3-Bis[2-(1H-tetrazol-5-yl)ethoxymethyl]-2,2-
bis[2-(1H-tetrazol-5-yl)ethoxymethyl]propane
(XXI) was synthesized in a similar way from 5 g of
(0.014 mol) tetranitrile XIX, 7.5 g (0.12 mol) of NaN3,
and 5 g (0.09 mol) of NH4Cl in 25 ml of DMF. Yield
6.1 g (84%), mp 143°C. 13C NMR spectrum, δC, ppm:
20.7 (5-CH2, JCH = 135 Hz), 48.5 s [C(CH2)4], 63.1 t
(OCH2, JCH = 144 Hz), 71.6 t (OCH2, JCH = 143 Hz),
152.5 s (C5). Found, %: C 38.10; H 5.01; N 42.51.
C17H28N16O4. Calculated, %: C 39.23; N 5.42; N 43.06.
1,2,3,4,5,6-Hexakis(2-cyanoethoxy)hexane
(XVIII). A solution of 0.3 g of sodium hydroxide in
1 ml of water was added under stirring over a period of
10 min to a solution of 5 g (0.027 mol) of sorbitol and
10 g (0.18 mol) of acrylonitrile in 5 ml of water, and
the mixture was stirred for 5 h at 60°C. The mixture
was cooled to room temperature, poured into 25 ml of
water under stirring, and neutralized with 0.1 N aque-
ous HCl. The solvent was distilled off under reduced
pressure, the residue was extracted with ethyl acetate
(4×20 ml), the extracts were combined and dried over
calcined MgSO4, the solvent was removed on a rotary
evaporator, and the viscous oily residue was dried
under reduced pressure. Yield 8.5 g (90%). 13C NMR
spectrum, δC, ppm: 21.0 t (4C, CH2CN, JCH = 137 Hz),
21.9 t (2C, CH2CN, JCH = 137 Hz), 61.8 t (4C, OCH2,
This study was performed under financial support
by the Ministry of Education and Science of the
Russian Federation.
REFERENCES
1. Verkhozina, O.N., Kizhnyaev, V.N., Vereshchagin, L.I.,
Rokhin, A.V., and Smirnov, A.I., Russ. J. Org. Chem.,
2003, vol. 39, p. 1792.
2. Vereshchagin, L.I., Petrov, A.V., Proidakov, A.G.,
Pokatilov, F.A., Smirnov, A.I., and Kizhnyaev, V.N., Russ.
J. Org. Chem., 2006, vol. 42, p. 912.
3. Vereshchagin, L.I., Petrov, A.V., Kizhnyaev, V.N.,
Pokatilov, F.A., and Smirnov, A.I., Russ. J. Org. Chem.,
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JCH = 148 Hz), 62.6 t (2C, OCH2, JCH = 148 Hz), 68.8 t
(2C, CH2, JCH = 148 Hz), 76.6–77.9 (overlapping
signals, 4C, CH), 119.1 br.s (6C, C≡N). Found, %:
C 57.88; H 7.31; N 16.10. C24H32N6O6. Calculated, %:
C 57.59; H 6.44; N 16.79.
1,3-Bis[(2-cyanoethoxy)methyl]-2,2-bis[(2-cyano-
ethoxy)methyl]propane (XIX) was synthesized in
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 1 2013