DMITRIEVA et al.
1112
CH2OAr), 6.39 d (1H, 6-H, J = 9.0 Hz), 7.53 d (1H,
3-H, J = 2.4 Hz), 7.77 d.d (1H, 5-H, J = 9.0, 2.4 Hz).
13C NMR spectrum, δC, ppm: 22.07 (Me), 42.38
(CH2Cl), 43.52 (CHN), 68.35 (CH2O), 68.97 (CH2O),
70.10 (CH2O), 70.17 (4C, CH2O), 70.27 (CH2O),
70.89 (CH2O), 106.66 (C3, C6), 119.94 (C5), 135.86
(C4), 143.64 and 143.69 (C1, C2). Mass spectrum, m/z
(Irel, %): 436 (16) [M]+ (37Cl), 434 (35) [M]+ (35Cl), 419
(16), 207 (16), 196 (15), 181 (20), 151 (19), 109 (21),
107 (65), 65 (34), 63 (100). Found: m/z 434.1825 [M]+.
C19H31ClN2O7. Calculated: M 434.1820 (35Cl).
13C NMR spectrum, δC, ppm: 3.28 (CH2I), 11.69 (Me),
21.41 (CH2), 44.84 (CH2N), 68.81 (CH2O), 69.54
(CH2O), 70.2 (CH2O), 70.71 (CH2O), 70.81 (CH2O),
72.03 (CH2O), 106.78, 106.89 (C3, C6), 120.52 (C5),
136.48 (C4), 144.24 and 145.21 (C1, C2). Mass spec-
trum, m/z (Irel, %): 526 (48) [M]+, 284 (10), 253 (9),
199 (18), 196 (15), 195 (11), 193 (16), 167 (15), 155
(100), 119 (9). Found: m/z 526. 1168 [M]+.
C19H31IN2O7. Calculated: M 526.1176.
N-Benzyl-2-(14-iodo-3,6,9,12-tetraoxatetradecyl-
oxy)-4-nitroaniline (VId). Yield 95%. IR spectrum, ν,
1
cm–1: 3412 (NH), 1496 (NO2). H NMR spectrum, δ,
Iodides VIb–VIe (general procedure). A solution
of 1.6 mmol of compound Vb–Ve and 4.8 g (32 mmol)
of sodium iodide in 50 ml of anhydrous acetone was
heated for 100 h under reflux with stirring. The mix-
ture was evaporated under reduced pressure, and the
residue was treated with 50 ml of water and extracted
with benzene. The combined extracts were evaporated
under reduced pressure, and the residue was subjected
to chromatography on silica gel using benzene–ethyl
acetate (5:1) as eluent. Compounds VIb–VIe were
isolated as yellow oily substances.
ppm: 3.17 t (2H, CH2I, J = 6.7 Hz), 3.56 s (4H, CH2O),
3.58 s (4H, CH2O), 3.61 m (2H, CH2O), 3.65 m (4H,
CH2CH2I, CH2O), 3.85 m (2H, CH2CH2OAr), 4.18 m
(2H, CH2OAr), 4.44 d (2H, CH2Ph, J = 4.2 Hz),
6.03 br.t (1H, NH), 6.37 d (1H, 6-H, J = 9.2 Hz),
7.24 m (1H, 4′-H), 7.25–7.31 m (4H, 2′-H, 3′-H, 5′-H,
6′-H), 7.60 d (1H, 3-H, J = 1.8 Hz), 7.75 br.d (1H, 5-H,
J = 9.2 Hz). 13C NMR spectrum, δC, ppm: 3.42 (CH2I),
47.04 (CH2Ph), 68.84 (CH2O), 69.54 (CH2O), 70.27
(CH2O), 70.71 (4C, CH2O), 70.81 (CH2O), 72.02
(CH2O), 106.96 (C3), 107.61 (C6), 120.43 (C5), 127.21
(C2′, C6′), 127.69 (C4′), 128.99 (C3′, C5′), 137.03 and
138.05 (C1′, C4), 144.54 and 144.92 (C1, C2). Mass
spectrum, m/z (Irel, %): 574 (22) [M]+, 558 (7), 557
(28), 332 (6), 288 (5), 199 (8), 155 (62), 92 (11), 91
(100), 64 (6). Found: m/z 574.1175 [M]+. C23H31IN2O7.
Calculated: M 574.1176.
N-Ethyl-2-(14-iodo-3,6,9,12-tetraoxatetradecyl-
oxy)-4-nitroaniline (VIb). Yield 94%. IR spectrum, ν,
1
cm–1: 3413 (NH), 1495 (NO2). H NMR spectrum, δ,
ppm: 1.23 t (3H, Me, J = 7.1 Hz), 3.17 t (2H, CH2I, J =
6.9 Hz), 3.20 q (2H, CH2N, J = 7.1 Hz), 3.57 s (4H,
CH2O), 3.58 s (4H, CH2O), 3.62 m (4H, CH2O), 3.65 t
(2 H , C H 2 C H 2 I , J = 6 . 9 H z ) , 3 . 8 1 m ( 2 H,
CH2CH2OAr), 4.14 m (2H, CH2OAr), 6.40 d (1H,
6-H, J = 8.9 Hz), 7.54 d (1H, 3-H, J = 2.3 Hz),
7.79 d.d (1H, 5-H, J = 8.9, 2.3 Hz). 13C NMR spectrum
(CDCl3), δC, ppm: 2.75 (CH2I), 13.09 (Me), 37.23
(CH2N), 68.26 (CH2O), 69.04 (CH2O), 69.80 (CH2O),
70.21 (5C, CH2O), 71.55 (CH2O), 106.35 and 106.28
(C3, C6), 120.06 (C5), 136.09 (C4), 143.76 and 144.55
(C1, C2). Mass spectrum, m/z (Irel, %): 512 (29) [M]+,
270 (9), 199 (14), 182 (18), 181 (8), 167 (7), 155
(100), 135 (9), 128 (5), 78 (6). Found: m/z 512.1028
[M]+. C18H29IN2O7. Calculated: M 512.1020.
2-(14-Iodo-3,6,9,12-tetraoxatetradecyloxy)-N-
isopropyl-4-nitroaniline (VIe). Yield 89%. IR spec-
1
trum, ν, cm–1: 3411 (NH), 1496 (NO2). H NMR spec-
trum, δ, ppm: 1.25 d (6H, Me, J = 6.4 Hz), 3.22 t (2H,
CH2I, J = 6.8 Hz), 3.62 s (4H, CH2O), 3.63 s (4H,
CH2O), 3.67 m (4H, CH2O), 3.69 m (1H, CHN),
3.71 t (2H, CH2CH2I, J = 6.8 Hz), 3.86 m (2H,
CH2CH2OAr), 4.20 m (2H, CH2OAr), 6.48 d (1H,
6-H, J = 9.0 Hz), 7.62 d (1H, 3-H, J = 2.4 Hz),
7.86 d.d (1H, 5-H, J = 9.0, 2.4 Hz). 13C NMR spec-
trum, δC, ppm: 2.81 (CH2I), 22.38 (Me), 43.83 (CHN),
68.57 (CH2O), 69.27 (CH2O), 70.04 (CH2O), 70.48
(4C, CH2O), 70.56 (CH2O), 71.77 (CH2O), 106.89 and
107.04 (C3, C6), 120.23 (C5), 136.28 (C4), 143.69 and
143.93 (C1, C2). Mass spectrum, m/z (Irel, %): 526 (47)
[M]+, 511 (12), 284 (8), 240 (6), 207 (10), 199 (18),
196 (12), 181 (14), 165 (6), 155 (100). Found: m/z
526.1168 [M]+. C19H31IN2O7. Calculated: M 526.1176.
2-(14-Iodo-3,6,9,12-tetraoxatetradecyloxy)-4-
nitro-N-propylaniline (VIc). Yield 89%. IR spectrum,
ν, cm–1: 3411 (NH), 1496 (NO2). 1H NMR spectrum, δ,
ppm: 0.91 t (3H, Me, J = 7.7 Hz), 1.60 m (2H, CH2),
3.10 t (2H, CH2N, J = 7.4 Hz), 3.15 t (2H, CH2I, J =
6.9 Hz), 3.55 m (8H, CH2O), 3.60 m (4H, CH2O),
3.64 t (2H, CH2CH2I, J = 6.9 Hz), 3.79 m (4H,
CH2CH2OAr), 4.12 m (2H, CH2OAr), 5.34 br.s (1H,
NH), 6.38 d (1H, 6-H, J = 8.9 Hz), 7.52 d (1H, 3-H,
J = 2.3 Hz), 7.77 d.d (1H, 5-H, J = 8.9, 2.3 Hz).
16-Methyl-19-nitro-2,3,5,6,8,9,11,12,15,16-deca-
hydro-14H-1,4,7,10,13,16-benzopentaoxazacyclo-
octadecine (Ia) was synthesized according to the
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 7 2011