S.N. Dmitrieva et al. / Tetrahedron 67 (2011) 2530e2535
2533
recorded on a Bruker DRX-500 instrument (500.13 and 125.76 MHz,
respectively) as solutions in CDCl3 or DMSO-d6 using the solvent as
an internal reference (dH 7.27 and 2.50, dC 77.00 and 39.43, re-
spectively); 2D homonuclear 1He1H COSY and NOESY spectra and
heteronuclear 1He13C COSY spectra were used to assign the proton
and carbon signals. Absorption spectra were recorded on a Shi-
madzu UV-3101PC spectrophotometer in the range of 200e550 nm,
C2e4¼2 10ꢁ5 M, 1-cm quartz cell, room temperature with an in-
crement of 1 nm. IR spectra in KBr pellets were recorded on Bruker
IFS-113V spectrophotometer. Mass spectra were measured with
a Varian MAT-311A instrument and high resolution mass spectra
were recorded with Finnigan MAT-212 instrument (per-
fluoroparaffin as a standard) with direct inlet of the sample into the
ionization zone; the energy of ionizing electrons was 70 and 60 eV,
respectively. Elemental analyses were performed at the Microan-
alytical Laboratory of the A.N. Nesmeyanov Institute of Organo-
element Compounds (Moscow, Russian Federation). The course of
the reactions was monitored by TLC on Merck DC-Kieselgel 60 F254
plates. Column chromatography was performed with Merck Kie-
selgel 60 (0.063e0.100 mm). 40,400(500)-Dinitrodibenzo-18-crown-6
ethers 1a,b were prepared according to known procedure.8
temperature to a stirred mixture of crown ethers 1a,b (450 mg,
1 mmol) and dry MeOH (10 mL). The reaction mixture was stirred at
reflux for 60 h, cooled, and concentrated in vacuo, and the residue
was diluted with water and extracted with EtOAc. The extract was
concentrated in vacuo. The residue was purified by column chro-
matography on silica gel using elution with benzene and then with
a benzene/EtOAc (1:1) solvent system. The podands 3a,b were
isolated as crystalline powders. Yield 3a: 233 mg (45%). Yield 3b:
226 mg (55%).
4.3.1. Podand 3a. Compound 3a was isolated as dark yellow crys-
tals; [found C, 51.49; H, 5.90; N, 5.44. C11H15NO6 requires C, 51.36;
H, 5.88; N, 5.45%]; mp 80e81 ꢀC; Rf 0.33 (EtOAc); UVevis (MeCN)
lmax 341 nm (
e
5700 L molꢁ1 cmꢁ1); nmax (KBr) 3329, 3244 (OeH),
1501 (NO2) cmꢁ1
;
dH (CDCl3) 2.30 (1H, br s, OH), 3.69 (2H, m, CH2O),
3.77 (2H, m, CH2O), 3.95 (2H, m, CH2CH2OAr), 3.96 (3H, s, MeO),
4.27 (2H, m, CH2OAr), 6.92 (1H, d, J 8.6 Hz, 3-H), 7.81 (1H, d, J 2.4 Hz,
6-H), 7.92 (1H, dd, J 8.6, 2.4 Hz, 4-H); dC (CDCl3) 56.55 (MeO), 61.93
(CH2O), 69.13 and 69.43 (CH2CH2OAr), 72.85 (CH2O), 108.55 and
110.37 (3-C, 6-C), 118.37 (4-C), 141.56 (5-C), 148.27 and 155.12 (1-C,
2-C); m/z 257 (54, Mþ), 169 (100), 123 (33), 94 (33), 89 (57), 79 (55),
76 (38), 65 (30), 63 (30), 59 (31).
4.2. Synthesis of podands 2a,b
4.3.2. Podand 3b. Compound 3b was isolated as light yellow crys-
tals; [found C, 50.23, H, 4.70, N, 6.30. C18H20N2O9$H2O requires C,
50.70; H, 5.20; N, 6.57%]; 188e190 ꢀC; Rf 0.78 (EtOAc); UVevis
A mixture of crown ethers 1a,b (225 mg, 0.5 mmol) and a 35%
solution of MeNH2 in dry EtOH (5 mL) was heated at 100 ꢀC (a water
bath) for 9 days in a sealed tube, the tube being shaken every 10 h
after cooling to w20 ꢀC. After tube opening, the solvent was
evaporated in vacuo, and the residue was extracted with hot EtOAc
and filtered to give 7 mg (0.016 mmol) of EtOAc-insoluble trans
isomer 1a, mp 245e248 ꢀC (Ref. 9: mp 245e248 ꢀC). The filtrate
was evaporated and the residue was purified by column chroma-
tography on silica gel using EtOAc as the eluent. The podands 2a,b
were isolated as crystalline powders. Yield 2a: 108 mg (44%). Yield
2b: 103 mg (52%).
(MeCN) lmax 339 nm (
e
12,400 L molꢁ1 cmꢁ1); nmax (KBr) 1511, 1501
(NO2) cmꢁ1
;
dH (CDCl3) 3.85 (6H, s, 2MeO), 3.93 (4H, m,
2CH2CH2OAr), 4.20 (4H, m, 2CH2OAr), 6.80 (2H, d, J 8.7 Hz, 2 3-H),
7.70 (2H, d, J 2.3 Hz, 2 6-H), 7.81 (2H, dd, J 8.7, 2.3 Hz, 2 4-H); dC
(CDCl3) 55.91 (2MeO), 69.08 and 69.76 (2CH2CH2OAr), 108.49 and
110.19 (2 3-C, 2 6-C),118.10 (2 4-C),140.00 (2 5-C),148.13 and 155.01
(2 1-C, 2 2-C); m/z 408 (87, Mþ), 196 (84), 151 (78), 150 (65), 124
(53), 122 (70), 109 (51), 106 (59), 89 (91), 79 (100).
4.4. Synthesis of dibenzodiazacrown ethers 4a-c from
dibenzo-18-crown-6 ethers 1a,b (general procedure)
4.2.1. Podand 2a. Compound 2a was isolated as orange crystals;
[found C, 51.43; H, 6.20; N, 10.49. C11H16N2O5 requires C, 51.56; H,
6.29; N, 10.93%]; mp 114e116 ꢀC; Rf 0.23 (EtOAc); UVevis (MeCN)
A mixture of crown ethers 1a,b (360 mg, 0.8 mmol) and a 5%
solution of alkanediamine (16 mmol) in dry EtOH was heated at
130 ꢀC (an oil bath) for 9 days in a sealed tube. After tube opening,
the solvent was evaporated in vacuo. Water (100 mL) and con-
centrated HCl (dropwise, to pH 3) were added to the residue. An
aqueous solution was extracted with EtOAc, and the extract was
concentrated in vacuo. The residue was purified by column chro-
matography on silica gel using EtOAc as the eluent. The compounds
4aec were isolated as light yellow crystalline powders.
lmax 398 nm (
e
14,100 L molꢁ1 cmꢁ1); nmax (KBr) 3453, 3343 (NeH,
OeH), 1482 (NO2) cmꢁ1
;
dH (CDCl3) 2.17 (1H, br s, OH), 2.96 (3H, d, J
4.6 Hz, MeN), 3.67 (2H, m, CH2O), 3.79 (2H, m, CH2O), 3.90 (2H, m,
CH2CH2OAr), 4.24 (2H, m, CH2OAr), 5.30 (1H, br s, NH), 6.49 (1H, d, J
8.9 Hz, 3-H), 7.66 (1H, d, J 2.3 Hz, 6-H), 7.94 (1H, dd, J 8.9, 2.3 Hz, 4-
H); dC (CDCl3) 29.55 (MeN), 61.61 (CH2O), 68.32 (CH2OAr), 69.26
(CH2CH2OAr), 72.47 (CH2O), 106.34 (3-C, 6-C), 120.41 (4-C), 136.63
(5-C), 144.10 (1-C), 145.64 (2-C); m/z 256 (100, Mþ), 168 (94), 167
(42), 150 (45), 148 (57), 138 (22), 122 (20), 121 (45), 93 (34), 78 (46).
4.4.1. Compound 4a. Compound 4a was isolated in yield 29 mg
(18% based on cis isomer 1b); mp 256e257 ꢀC; Rf 0.70 (EtOAc);
4.2.2. Podand 2b. Compound 2b was isolated as light yellow crys-
tals; [found C, 53.47; H, 5.47; N,13.93. C18H22N4O7 requires C, 53.20;
H, 5.46; N, 13.79%]; mp 161e163 ꢀC; Rf 0.65 (EtOAc); UVevis
UVevis (MeCN) lmax 402 nm (
e
24,400 L molꢁ1 cmꢁ1); nmax (KBr)
3395, 3385 (NeH), 1504 (NO2) cmꢁ1
;
dH (CDCl3) 3.59 (4H, m,
(MeCN) lmax 398 nm (
e
33,100 L molꢁ1 cmꢁ1); nmax (KBr) 3438, 3424
2CH2N), 3.85 (4H, m, 2CH2O), 4.32 (4H, m, 2CH2OAr), 5.44 (2H, br s,
2NH), 6.60 (2H, d, J 8.9 Hz, 2 3-H), 7.66 (2H, d, J 2.0 Hz, 2 6-H), 7.93
(2H, dd, J 8.9, 2.0 Hz, 2 4-H); dC (DMSO-d6) 40.03 (2CH2N), 69.11 and
69.77 (2CH2CH2OAr), 106.93 and 107.84 (2 3-C, 2 6-C), 120.42 (2 4-
C), 136.45 (2 5-C), 145.41 (2 1-C, 2 2-C); m/z 404 (36, Mþ), 387 (27),
386 (100),193 (37),165 (28), 147 (29),146 (91), 135 (36), 119 (34), 77
(43). HRMS: Mþ, found 404.1333. C18H20N4O7 requires 404.1332.
(NeH), 1488 (NO2) cmꢁ1
;
dH (CDCl3) 2.92 (6H, d, J 5.3 Hz, 2MeN),
3.95 (4H, m, 2CH2CH2OAr), 4.28 (4H, m, 2CH2OAr), 5.18 (2H, br q,
2NH), 6.48 (2H, d, J 8.9 Hz, 2 3-H), 7.68 (2H, d, J 2.3 Hz, 2 6-H), 7.94
(2H, dd, J 8.9, 2.3 Hz, 2 4-H); dC (CDCl3) 29.61 (2MeN), 68.42
(2CH2OAr), 69.49 (2CH2CH2OAr), 106.47 (2 3-C), 106.53 (2 6-C),
120.49 (2 4-C), 136.81 (2 5-C), 144.05 (2 1-C), 145.57 (2 2-C); m/z
406 (45, Mþ), 312 (64), 167 (100), 148 (69), 135 (58), 134 (86), 121
(65), 93 (58), 90 (50), 79 (47), 78 (83).
4.4.2. Compound 4b. Compound 4b was isolated in yield 51 mg
(31% based on cis isomer 1b); mp 246e247 ꢀC; Rf 0.54 (EtOAc);
4.3. Synthesis of podands 3a,b
UVevis (MeCN) lmax 401 nm (
e
20,800 L molꢁ1 cmꢁ1); nmax (KBr)
3417, 3383 (NeH), 1497 (NO2) cmꢁ1
;
dH (CDCl3) 2.17 (2H, m,
An alcohol solution of MeONa, prepared by dissolving Na (1.15 g,
50 mmol) in dry MeOH (50 mL), was added dropwise at room
CH2CH2N), 3.49 (4H, m, 2CH2N), 3.90 (4H, m, 2CH2O), 4.30 (4H, m,
2CH2OAr), 5.50 (2H, br s, 2NH), 6.56 (2H, d, J 8.9 Hz, 2 3-H), 7.64 (2H,