MINGALEEVA et al.
516
Found, %: C 71.98; H 10.73. C24H42O4. Calculated, %:
C 71.08; H 11.01. M 394.59.
28-H, 29-H), 2.09 s (2H, 18-H), 2.32 t (4H, J = 7.4 Hz,
13-H, 23-H), 2.40 t (4H, J = 6.7 Hz, 6-H, 30-H), 4.25 t
(4H, J = 4.3 Hz, 2-H, 3-H), 8.90 br.s (2H, NH).
13C NMR spectrum, δC, ppm: 15.02 q (14-CH3,
22-CH3), 24.73 t (C12, C24), 25.84 t (C7, C29); 29.12 t,
29.06 t, 28.94 t, 28.81 t (C8–C11, C25–C28); 33.98 t (C6,
C30), 38.89 t (C13, C23), 39.06 t (C18), 61.90 t (C2, C3),
158.30 s (C14, C22), 173.46 s (C5, C31), 175.55 s (C17,
C19). Mass spectrum, m/z (Irel, %): 523 (100) [M + H]+,
521 (29) [M – H]–. Found, %: C 63.04; H 9.87;
N 10.72. C27H46N4O6. Calculated, %: C 63.01; H 9.98;
N 10.02. M 522.68.
Ethane-1,2-diyl bis(10-oxoundecanoate) (4).
Oxygen was bubbled over a period of 20 h through
a mixture of PdCl2 (0.33 g, 1.9 mmol), CuCl (1.05 g,
10.6 mmol), and diester 3 (1.80 g, 4.57 mmol) in
a mixture of 70 mL of THF and 9 mL of water, heated
to 60°C. When the reaction was complete (TLC), the
mixture was diluted with 100 mL of diethyl ether,
washed with 5% aqueous HCl (3×5 mL) and brine
(3×5 mL), dried over MgSO4, and evaporated. The
residue was purified by chromatography on silica gel
(petroleum ether–diethyl ether, 10:1). Yield 1.63 g
(84%), Rf 0.64 (t-BuOMe). IR spectrum, ν, cm–1: 1710
14,24-Dimethyl-1,4-dioxa-15,16,22,21-tetraaza-
cyclotritriaconta-14,23-diene-5,17,21,33-tetraone
(6). Yield 0.49 g (84%), thick oil. IR spectrum, ν, cm–1:
1634 (C=N), 1668 (CONH), 1733 (O=CO), 3218
(NH). 1H NMR spectrum, δ, ppm: 1.30 s (6H, 14-CH3,
24-CH3), 1.45–1.56 m (8H, 9-H, 10-H, 28-H, 29-H),
1.58–1.68 m (8H, 8-H, 11-H, 27-H, 30-H), 1.79–
2.05 m (8H, 7-H, 12-H, 26-H, 31-H), 1.89–2.22 m
(2H, 19-H), 2.22 t (4H, J = 6.9 Hz, 18-H, 20-H), 2.32 t
(4H, J = 7.2 Hz, 13-H, 25-H), 2.40 t (4H, J = 6.4 Hz,
6-H, 32-H), 4.21 t (4H, J = 4.5 Hz, 2-H, 3-H), 8.80 br.s
(2H, NH). 13C NMR spectrum, δC, ppm: 15.00 q
(14-CH3, 24-CH3), 19.38 t (C19), 24.73 t (C12, C26),
26.09 t (C7, C31); 29.26 t, 29.09 t, 28.96 t, 28.81 t
(C8–C11, C27–C30); 32.07 (C18, C20), 33.97 t (C6, C32),
38.80 t (C13, C25), 61.90 t (C2, C3), 158.40 s (C14, C24),
173.46 s (C5, C33), 175.55 s (C17, C21). Mass spectrum:
m/z 551 (Irel 100%) [M + H]+. Found, %: C 64.25;
H 9.15; N 10.17. C29H50N4O6. Calculated, %: C 64.02;
H 9.80; N 10.02. M 550.73.
1
(C10=O), 1735 (C=O, ester). H NMR spectrum, δ,
ppm: 1.10–1.90 m (16H, 4-H, 5-H, 6-H, 7-H), 1.47–
1.53 m (4H, 3-H), 1.54–1.60 m (4H, 8-H), 2.08 s (6H,
11-H), 2.27 t (4H, J = 7.5 Hz, 9-H), 2.37 t (4H, J =
7.3 Hz, 2-H), 4.22 t (4H, J = 4.2 Hz, OCH2CH2O).
13C NMR spectrum, δC, ppm: 23.68 t (C8), 24.73 t (C3);
28.92, 28.97, 29.01, 29.11 t (C4–C7); 29.77 q (C11),
33.98 t (C2), 43.64 t (C9), 61.19 t (C1, C2), 173.44 s
(C1'), 209.19 s (C10'). Mass spectrum, m/z (Irel, %): 427
(78) [M + H]+, 444 (100) [M + H2O + H]+. Found, %:
C 68.57; H 9.92. C24H42O6. Calculated, %: C 69.01;
H 10.09. M 426.5867.
Macrocyclic compounds 5–8 (general procedure).
Malonic, glutaric, L-(+)-tartaric, or pyridine-2,6-dicar-
boxylic acid dihydrazide prepared as described in [5]
(1.06 mmol), was added with vigorous stirring to
a solution of diketone 4 (0.45 g, 1.06 mmol) in dioxane
(9.0 mL, 106.0 mmol) containing 0.02 mL
(1.06 mmol) of water. The mixture was stirred for 24 h
at room temperature, and the solvent was removed
under reduced pressure. The residue was diluted with
methylene chloride (50 mL), washed with water (3×
5 mL), dried over MgSO4, and evaporated. The residue
was treated with stirring in succession with anhydrous
methylene chloride (1 mL) and hexane (5 mL). The
mixture was allowed to settle down (it separated into
layers), and the upper layer was removed by decanting.
The bottom layer was washed with hexane (2 mL) and
evaporated under reduced pressure.
(18R,19R)-18,19-Dihydroxy-14,23-dimethyl-1,4-
dioxa-15,16,21,22-tetraazacyclodotriaconta-14,22-
diene-5,17,20,32-tetraone (7). Yield 0.37 g (61%),
thick oil, [α]D20 = +9.6° (c = 0.408, CH2Cl2). IR spec-
trum, ν, cm–1: 1627 (C=N), 1668 (CONH), 1733
1
(O=CO), 3218 (NH), 3310 (OH). H NMR spectrum,
δ, ppm: 1.20 s (6H, 14-CH3, 23-CH3), 1.40–1.60 m
(8H, 9-H, 10-H, 27-H, 28-H), 1.75–2.10 m (16H, 7-H,
8-H, 11-H, 12-H, 25-H, 26-H, 29-H, 30-H), 2.22 t (4H,
J = 6.7 Hz, 13-H, 24-H), 2.30 t (4H, J = 6.4 Hz, 6-H,
31-H), 4.20 t (4H, J = 4.5 Hz, 2-H, 3-H), 4.65 s (2H,
18-H, 19-H), 5.40 s (2H, OH), 9.85 br.s (2H, NH).
13C NMR spectrum, δC, ppm: 15.48 q (14-CH3,
23-CH3), 23.72 t (C12, C25), 24.78 t (C7, C30); 29.03 t,
29.12 t, 29.16 t, 29.22 t (C8–C11, C26–C29); 34.04 t (C6,
C31), 34.09 t (C13, C24), 61.98 t (C2, C3), 71.76 d (C18,
C19), 158.40 s (C14, C23), 168.39 s (C17, C20), 173.54 s
(C5, C32). Mass spectrum, m/z (Irel, %): 569 (100)
[M + H]+, 567 (100) [M – H]–. Found, %: C 62.13;
14,22-Dimethyl-1,4-dioxa-15,16,20,21-tetraaza-
cyclohentriaconta-14,21-diene-5,17,19,31-tetraone
(5). Yield 0.46 g (83%), thick oil. IR spectrum, ν, cm–1:
1634 (C=N), 1661 (CONH), 1733 (O=CO), 3201
(NH). 1H NMR spectrum, δ, ppm: 1.27 s (6H, 14-CH3,
22-CH3), 1.35–1.70 m (8H, 9-H, 10-H, 26-H, 27-H),
1.80–2.15 m (16H, 7-H, 8-H, 11-H, 12-H, 24-H, 25-H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 4 2019