PHOSPHOMACROCYCLIC SYSTEMS
925
off 2 days later, and the residue was subjected to
column chromatography eluating products with the
system benzene–dioxane (7: 1). The obtained sub-
stances were dried in the vacuum for 2 h (1 mm Hg,
70ºC).
yield 15%, oily substance, Rf 0.75 (B). 31P NMR
spectrum, δ, ppm (1,4-dioxane): 66.2; 67.1.
Oxidation (general procedure). To 1 mmol of
compound XIV, XV in 5 ml of anhydrous methylene
chloride was added 2 mmol of (NH2)2CO·H2O2, and
the mixture was left for 1 day. Then solution was
filtered, the solvent was distilled off to a minimum
quantity, and 12 ml of hexane was added. After 1 h
from the solution above the precipitate was decanted
and the substance was twice washed with hexane and
dried in a vacuum for 2 h (1 mm Hg, 70ºC).
1,7-Dithiono-1,7-diethylamido-11,11-dihydro-
3,4,5-benzo-9,10;12,13-di(1,2-naphtho)-2,6,8,14-
tetraoxy-1,7-diphosphacyclotetradecane (XXVIII),
1
yield 30%, oily substance, Rƒ 0.61 (C). H NMR
3
spectrum, δ, ppm (CDCl3): 1.09 br. t (9H, CH3, JHH
3
7.2 Hz), 3.40 m (8H, CH2, JPH 14.2 Hz), 4.49 d [1H,
CH2 (bridge), 2JHH 16.2 Hz], 4.95 d [1H, CH2 (bridge),
2JHH 16.2 Hz], 6.66 d [2H, CH (resorcynol)], 6.76 s
(1H, CH (resorcynol)], 7.05 d (2H, CH), 7.14–7.86 m
1,7-Dioxo-1,7-diethylamido-11,11-dihydro-3,4,5-
benzo-9,10;12,13-di(1,2-naphtho)-2,6,8,14-tetraoxy-
1,7-diphosphacyclotetradecane (XXXII), yield 79%,
3
(8H, CH), 8.29 d (2H, CH, JHH 7.7 Hz). 31P NMR
1
mp 89–91ºC, Rƒ 0.63 (A). H NMR spectrum, δ, ppm
spectrum, δ, ppm (CH2Cl2): 66.8. Found, %: C 62.14;
H 5.64; N 4.11; P 9.18. C35H38N2O4P2S2. Calculated,
%: C 62.12; H 5.66; N 4.14; P 9.15.
3
(CDCl3): 1.03 br. t (9H, CH3), 1.30 t (3H, CH3, JHH
3
7.3 Hz), 3.18 br.m (6H, CH2, JPH 12.4 Hz), 3.33 m
3
(2H, CH2, JPH 12.8 Hz), 4.93 d [1H, CH2 (bridge),
1,9-Diethylamido-1,9-dithiono-13,13-dihydro-
3,4,5,6,7-naphtho-11,12;14,15-di(1,2-naphtho)-
2,8,10,16-tetraoxy-1,9-diphosphacyclodecahexane
(XXIX), yield 34%, oily substance, Rf 0.75 (A), 0.65
2JHH 16.2 Hz], 5.16 d [1H, CH2 (bridge), 2JHH 16.2 Hz],
3
6.58 d [2H, CH (resorcynol), JHH 7.7 Hz], 6.9 s [1H,
CH (resorcynol)], 7.05 br.t [1H, CH (resorcynol)], 7.21
3
3
d (2H, CH, JHH 8.5 Hz), 7.43 t (2H, CH, JHH 6.8 Hz,
1
3
3
(B). H NMR spectrum, δ, ppm (CDCl3): 1.30 t (12H,
3JHH 8.1 Hz), 7.54 t (2H, CH, JHH 7.7 Hz, JHH
3
CH3), 3.38 m (8H, CH2, JPH 12.8 Hz), 4.45 d [1H,
7.7 Hz), 7.73 d (2H, CH, 3JHH 8.9 Hz), 7.82 d (2H, CH,
CH2 (bridge), 2JHH 16.1 Hz], 5.32 d [1H, CH2 (bridge),
3JHH 9.1 Hz), 8.28 d (2H, CH, JHH 8.5 Hz). P NMR
spectrum, δ, ppm (CH2Cl2): 0.9. Found: M (MALDI–
TOF), m/z: 645 [M + H]+. Calculated: M 644.
3
31
3
2JHH 16.1 Hz], 7.17 d (2H, CH), 7.22 d (2H, CH, JHH
9.1 Hz), 7.40–7.68 m (10H, CH), 7.82 d (2H, CH, 3JHH
3
8.2 Hz), 8.38 d.d (2H, CH, JHH 8.4 Hz). 31P NMR
1,9-Diethylamido-1,9-dioxo-13,13-dihydro-3,4,5,6,7-
naphtho-11,12;14,15-di(1,2-naphtho)-2,8,10,16-
tetraoxy-1,9-diphosphacyclodecahexane (XXXIII),
spectrum, δ, ppm (1,4-dioxane): 66.6. 1,7-dithiono-
1,7-diethylamido-11,11-dihydro-3,4,5-naphtho-9,10;
12,13-di(1,2-naphtho)-2,6,8,14-tetraoxy-1,7-[diphos-
phacyclotetradecane] (XXX), yield 25%, oily sub-
1
yield 85%, mp 149–150ºC, Rf 0.56 (A). H NMR
3
1
spectrum, δ, ppm (CDCl3): 1.31 t (12H, CH3, JHH
stance, Rf 0.70 (B), 0.58 (D). H NMR spectrum, δ,
3
3
7.0 Hz), 3.33 m (8H, CH2, JPH 12.8 Hz), 4.94 d [1H,
ppm (CDCl3): 1.17 t (12H, CH3, JHH 6.9 Hz), 3.26 m
CH2 (bridge), 2JHH 16.2 Hz], 5.16 d [1H, CH2 (bridge),
3
(8H, CH2, JPH 12.4 Hz), 4.81 d [1H, CH2 (bridge),
3
2JHH 16.2 Hz], 7.21 d (2H, CH, JHH 9.2 Hz), 7.31 d
2JHH 16.1 Hz], 5.26 d [1H, CH2 (bridge), 2JHH 15.4 Hz],
3
3
3
(2H, CH), 7.39 s (2H, CH), 7.44 m (2H, CH, JHH
7.04 d (1H, CH, JHH 8.7 Hz), 7.13 d.d (1H, CH, JHH
4
3
4
7.9 Hz, JHH 1.2 Hz), 7.54 m (2H, CH, JHH 7.6 Hz,
4JHH 1.2 Hz), 7.67 d (2H, the CH), 7.73 d (2H, CH,
3JHH 8.9 Hz), 7.82 d (2H, CH, 3JHH 7.6 Hz), 8.30 d (2H,
8.8 Hz, JHH 1.1 Hz), 7.22 d (2H, CH), 7.35 m (1H,
CH), 7.43 m (1H, CH, 4JHH 3.3 Hz), 7.48 m (2H, CH),
3
4
7.59 m (2H, CH), 7.67 d.d (1H, CH, JHH 8.8 Hz, JHH
3.3 Hz), 7.74 d (2H, CH, 3JHH 8.8 Hz), 7.83 d (2H, CH,
3JHH 8.4 Hz), 8.12 d (1H, CH, 3JHH 8.0 Hz), 8.20 d (2H,
3
CH, JHH 8.2 Hz). 13C NMR spectrum, δС, ppm
3
(CDCl3): 13.9 d (4C, CH3, JPC 20.7 Hz), 23.9 s [1C,
2
CH, JHH 8.4 Hz). 31P NMR spectrum, δ, ppm (1,4-
3
CH2 (bridge)], 39.9 d (4C, CH2, JPC 24.2 Hz), 109.9 s
(2C, CH), 116.1 s (2C, CH), 119.7 s (2C, CH), 120.0 d
dioxane): 66.4; 67.0. Found, %: C 64.34; H 5.74; N
3.89; P 8.48. C39H40N2O4P2S2. Calculated, %: C 64.45;
H 5.55; N 3.85; P 8.52.
3
(2C, CH, JPC 5.2 Hz), 123.3 s (2C, CH), 124.8 s (2C,
CH), 127.0 s (2C, CH), 127.9 s (1C, C), 128.7 s (4C,
CH), 129.2 s (2C, C), 129.5 s (2C, CH), 132.6 s (2C,
C), 134.5 s (1C, C), 149.1 d (2C, CO), 149.6 d (2C,
3JPC 9.5 Hz). 31P NMR spectrum, δ, ppm (CH2Cl2): 1.1.
Found, %: C 67.34; H 5.74; N 4.05; P 8.22.
1,8-Dithiono-1,8-diethylamido-12,12-dihydro-
3,4,5,6-naphtho-10,11;13,14-di(1,2-naphtho)-2,7,9,15-
tetraoxy-1,8-diphosphacyclopentadecane (XXXI),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 5 2010