F
A. S. Oshchepkov et al.
Paper
Synthesis
13С NMR (125 MHz, DMSO-d6): δ = 43.8 (C-17, C-22), 55.9 (C-16, C-
23), 57.5 (C-18, C-21), 67.1 (C-19, C-20), 68.9 (C-15, C-24), 113.1 (C-
13), 113.7 (C-10), 122.0 (C-14), 123.3 (C-4a), 123.8 (C-8), 124.39 (C-
3), 127.2 (C-1), 128.3 (C-9), 128.7 (C-8a), 129.4 (C-5), 129.9 (C-2),
130.1 (C-6), 132.7 (C-7), 148.9 (C-12),149.1 (C-11), 149.8 (C-4), 162.7
(C-8b), 163.5 (C-8c).
15-Nitro-2,3,5,6,8,9,11,12-octahydrobenzo[b][1,4,7,10,13]dioxa-
trithiacyclopentadecine (3d)
Prepared from dichloride 1a (84 mg, 0.30 mmol), thiol 2d (51 mg,
0.33 mmol), and Cs2CO3 (358 mg, 1.10 mmol) in MeCN. After elution
with benzene–EtOAc (5:1), 3d was obtained as a yellow solid; yield:
66 mg (63%); mp 157–159 °C (Lit.25 mp 159–161 °C).
1H NMR (400 MHz, CDCl3): δ = 2.85–2.88 (m, 4 H, 2 × CH2S), 2.99–3.03
(m, 4 H, 2 × CH2S), 3.08–3.11 (m, 4 H, 2 × CH2S), 4.33–4.36 (m, 4 H, 2 ×
CH2OAr), 7.21 (d, J = 8.9 Hz, 1 H, H-6), 7.77 (d, J = 2.5 Hz, 1 H, H-2),
7.93 (dd, J = 8.9, 2.5 Hz, 1 H, H-5).
MS (IES): m/z calcd for C28H30N4O7: 534.3; found: 536.1 [MH]+.
Anal. Calcd for C28H30N4O7: С, 62.91; Н, 5.66. Found: С, 62.88; Н, 5.62.
2-(4,13-Dimethyl-2,3,4,5,6,8,9,11,12,13,14,15-dodecahydroben-
zo[b][1,4,10,13,7,16]tetraoxadiazacyclooctadecin-18-yl)-6-nitro-
1H-benzo[de]isoquinoline-1,3(2H)-dione (5b)
15-Nitro-2,3,5,6,8,9,11,12-octahydrobenzo[b][1,4,10,7,13]trioxa-
dithiacyclopentadecine (3e)
Prepared from diiodide 5h (197 mg, 0.30 mmol), amine 2b (59 mg,
0.33 mmol), and K2CO3 (159 mg, 1.15 mmol) in MeCN. After elution
with benzene to benzene–EtOH (1:1), 5b obtained as a pale-yellow
solid; yield: 116 mg (67%); mp 137–142 °С (MeCN).
1H NMR (400 MHz, DMSO-d6): δ = 2.35 (s, 3 H, NCH3), 2.43 (s, 3 H,
NCH3), 2.82–2.89 (m, 4 H, 2 × CH2N), 3.00–3.08 (m, 4 H, 2 × CH2N),
3.63 (s, 4 H, 2 × CH2O), 3.63–3.70 (m, 4 H, 2 × CH2O), 4.08–4.12 (m, 2
H, CH2O), 4.15–4.18 (m, 2 H, CH2O), 6.79 (s, 1 H, ArH-10), 6.84 (d, J =
8.4 Hz, 1 H, ArH-14), 7.01 (d, J = 8.4 Hz, 1 H, ArH-13), 8.01 (t, J = 7.5
Hz, 1 Н, Н-6), 8.42 (d, J = 8.0 Hz, 1 Н, Н-3), 8.72 (d, J = 8.0 Hz, 1 Н, Н-2),
8.78 (d, J = 7.5 Hz, 1 Н, Н-7), 8.89 (d, J = 8.7 Hz, 1 Н, Н-5).
Prepared from dichloride 1a (84 mg, 0.30 mmol), thiol 2e (51 mg,
0.33 mmol), and Cs2CO3 (358 mg 1.10 mmol) in MeCN. Ater elution
with benzene–EtOAc (5:1), 3e was obtained as yellow solid; yield: 61
mg (59%); mp 128–130 °C (Lit.24 mp 129–131 °C).
1H NMR (400 MHz, CDCl3): δ = 2.97–3.01 (m, 4 H, 2 × СH2S), 3.03–3.07
(m, 4 H, 2 × СH2S), 4.24–4.28 (m, 4 H, 2 × СH2ОAr), 6.82 (d, J = 8.7 Hz, 1
H, H-6), 7.69 (d, J = 2.3 Hz, 1 H, H-2), 7.82 (dd, J = 8.7, 2.3 Hz, 1 H, H-5).
18-Nitro-2,3,5,6,8,9,11,12,14,15-decahydroben-
zo[b][1,4,10,13,7,16]tetraoxadithiacyclooctadecine (3f)
13С NMR (125 MHz, DMSO-d6): δ = 43.5 (C-17, C-24), 55.6 (C-16, C-
25), 57.2 (C-18, C-23), 67.1 (C-19, C-22), 68.7 (C-15, C-26), 70.5 (C-20,
C-21), 113.2 (C-13), 113.6 (C-10), 122.2 (C-14), 123.4 (C-4a), 123.9 (C-
8), 124.39 (C-3), 127.1 (C-1), 128.3 (C-9), 128.7 (C-8a), 129.4 (C-5),
129.9 (C-2), 130.1 (C-6), 132.6 (C-7), 148.9 (C-12), 149.2 (C-11), 149.7
(C-4), 162.8 (C-8b), 164.3 (C-8c).
Prepared from dichloride 1a (84 mg, 0.30 mmol), dithiol 2f (60 mg,
0.33 mmol), and Cs2CO3 (358 mg 1.10 mmol) in MeCN. After elution
with benzene–EtOAc (10:1), 3f was obtained as a yellowish solid;
yield: 55 mg (52%); mp 128–130 °C (Lit.24 mp 128–129 °C).
1H NMR (400 MHz, CDCl3): δ = 2.97 (t, J = 6.6 Hz, 2 H, СH2S), 3.01 (t, J =
6.9 Hz, 2 H, СH2S), 3.15–3.19 (m, 2 H, СH2S), 3.19 (t, J = 6.6 Hz, 2 H,
СH2S), 3.63 (s, 4 H, 2 × СH2О), 3.74–3.79 (m, 4 H, 2 × СH2О), 4.25–4.29
(m, 4 H, 2 × СH2ОAr), 6.87 (d, J = 8.9 Hz, 1 H, H-6), 7.71 (d, J = 2.4 Hz, 1
H, H-2), 7.91 (dd, J = 8.9, 2.4 Hz, 1 H, H-5).
MS (IES): m/z calcd for C30H34N4O8: 578.4; found: 578.7 [M]+.
Anal. Calcd for C30H34N4O8: С, 62.27; Н, 5.92. Found: С, 62.30; Н, 5.89.
Benzothiacrown Ethers 3c–f and Benzothiacrown Naphthalimides
5c–f; General Procedure (Route 2)
2-(2,3,5,6,8,9-Hexahydrobenzo[b][1,4,7,10]dioxadithiacyclodo-
decin-12-yl)-6-nitro-1H-benzo[de]isoquinoline-1,3(2H)-dione (5c)
The procedure is a modified synthesis as described earlier.24 To a sus-
pension of Cs2CO3 (1.10 mmol) and dichloride 1a or 5g (or diiodide
1b, 5h for compounds 3c and 5c, respectively) (0.30 mmol) in MeCN
(30 mL) was added a solution of dithiol 2c–f (0.33 mmol) in MeCN (30
mL) dropwise under stirring. The reaction mixture was heated and re-
fluxed for 78 h. Then, it was concentrated in vacuo. H2O (150 mL) was
added to the residue, and the mixture was extracted with CHCl3
(compounds 5c–f were washed with H2O). The extracts were concen-
trated in vacuo, and the residue was purified by silica gel column
chromatography with eluent benzene–EtOAc (for 3c–f) or benzene–
EtOH (gradient) (for 5c–f).
Prepared from diiodide 5h (197 mg, 0.30 mmol), dithiol 2c (31 mg,
0.33 mmol), and Cs2CO3 (358 mg 1.10 mmol) in MeCN. After elution
with benzene to benzene–EtOH (2:1), 5c was obtained as a yellow
solid; yield: 61 mg (41%); mp 268–269 °С (AcOH).
IR (KBr): 1717 cm–1
.
1H NMR (500 MHz, DMSO-d6): δ = 2.90–2.92 (m, 2 H, CH2-16), 2.95–
2.97 (m, 2 H, CH2-19), 3.02 (s, 4 H, CH2S-17, 18), 4.22–4.24 (m, 2 H,
CH2OAr-15), 4.36–4.38 (m, 2 H, CH2OAr-20), 6.95 (dd, 4J = 2.2 Hz, 3J =
8.6 Hz, 1 H, ArH-14), 7.05 (d, 4J = 2.2 Hz, 1 H, ArH-10), 7.09 (d, 3J = 8.6
3
3
Hz, 1 H, ArH-13), 8.13 (dd, J = 7.4 Hz, J = 8.6 Hz, 1 Н, Н-6), 8.60 (d,
3J = 8.0 Hz, 1 Н, Н-3), 8.62 (d, 3J = 8.0 Hz, 1 Н, Н-2), 8.64 (d, 3J = 7.4 Hz,
1 Н, Н-7), 8.76 (d, 3J = 8.6 Hz ,1 Н, Н-5).
12-Nitro-2,3,5,6,8,9-hexahydrobenzo[b][1,4,7,10]dioxadithiacy-
clododecine (3c)
13С NMR (125 MHz, DMSO-d6): δ = 30.8 (C-18, C-17) 33.5 (C-16, C-19),
72.6 (C-15, C-20), 112.9 (C-13), 114.0 (C-10), 121.9 (C-14), 123.3 (C-
4a), 123.9 (C-8), 124.8 (C-3), 127.8 (C-1), 128.8 (C-9), 129.2 (C-8a),
129.3 (C-5), 130.1 (C-2), 130.6 (C-6), 132.2 (C-7), 148.4 (C-12),148.5
(C-11), 149.7 (C-4), 163.0 (C-8b), 163.8 (C-8c).
Prepared from diiodide 1b (139 mg, 0.30 mmol), dithiol 2c (31 mg,
0.33 mmol), and Cs2CO3 (358 mg, 1.10 mmol) in MeCN: After elution
with benzene 3c, was obtained as a white-yellowish solid; yield: 54
mg (61%); mp 157–159 °C (Lit.24 mp 159–161 °C).
1H NMR (400 MHz, CDCl3): δ = 2.99–3.02 (m, 4 H, 2 × СH2S), 3.07 (s, 4
H, 2 × СH2S), 4.44–4.47 (m, 4 H, 2 × СH2ОAr), 6.86 (d, J = 8.9 Hz, 1 H, H-
6), 7.70 (d, J = 2.2 Hz, 1 H, H-2), 7.94 (dd, J = 8.9, 2.2 Hz, 1 H, H-5).
MS: m/z (%) = 496.08 (100.0), 497.08 (28.0), 498.07 (9.1), 498.08 (5.1),
499.08 (2.8).
Anal. Calcd for C24H20N2O6S2: C, 58.05; H, 4.06; N, 5.64. Found: С,
57.99; Н, 4.08; N, 5.61.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–J