Chemistry of Heterocyclic Compounds 2015, 51(1), 67–72
2-(2-Acetamido-2-deoxy--D-glucopyranosyloxy)-
(CDCl3), δ, ppm (J, Hz): 1.76 (3H, s, NHCOCH3); 1.92
(3H, s, COCH3); 1.98 (6H, s, 2COCH3); 2.32 (6H, s,
6,7-CH3); 3.95–4.28 (3H, m, 6'-CH2, 5'-CH); 4.37–4.41
(1H, m, 2'-CH); 5.13–5.30 (2H, m, 3'-CH, 4'-CH); 6.12
(1H, d, J = 7.3, NH); 6.26 (1H, d, J = 9.8, 1'-CH); 7.43
(1H, s, H Ar); 7.65 (1H, s, H Ar); 8.33 (1H, s, CH).
13C NMR spectrum (DMSO-d6), δ, ppm: 19.8 (CH3); 20.0
(CH3); 20.2 (CH3); 20.6 (CH3); 23.1 (2CH3); 53.5 (C-6');
61.8 (C-5'); 69.5 (C-2'); 72.9 (C-4'); 73.8 (C-3'); 94.7
(C-1'); 128.5 (C Ar); 129.1 (C Ar); 135.2 (C Ar); 136.7
(C Ar); 138.2 (C Ar); 142.3 (C Ar); 154.3 (C Ar); 168.6
(COCH3); 169.8 (COCH3); 171.8 (COCH3); 172.4
(COCH3). Found, %: C 57.02; H 6.15; N 8.09. C24H29N3O9.
Calculated, %: C 57.25; H 5.81; N 8.35.
quinoxaline (8a). Yield 2.56 g (68%), white crystals, mp
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221–222°C. H NMR spectrum (CDCl3), δ, ppm (J, Hz):
1.73 (3H, s, NHCOCH3); 3.29–3.67 (2H, m, 6'-CH2); 3.83–
3.79 (2H, m, 2',5'-CH); 4.61 (3H, m, OH, 3',4'-CH); 5.16
(2H, br. s, OH, D2O-exchangeable); 6.08 (1H, d, J = 9.7,
1'-CH); 7.61–7.80 (4H, m, H Ar); 7.88 (1H, d, J = 7.6,
NH); 8.43 (1H, s, CH). Found, %: C 54.81; H 5.15;
N 11.78. C16H19N3O6. Calculated, %: C 55.01; H 5.48;
N 12.03.
2-(2-Acetamido-2-deoxy--D-glucopyranosyloxy)-
3-methylquinoxaline (8b). Yield 2.73 g (59%), white
crystals, mp 241–242°C. 1H NMR spectrum (CDCl3),
δ, ppm (J, Hz): 1.76 (3H, s, NHCOCH3); 2.39 (3H, s, CH3);
3.71–3.23 (2H, m, 6'-CH2); 4.01–3.85 (2H, m, 2',5'-CH);
4.56 (1H, t, J = 7.0, OH, D2O-exchangeable); 5.20 (1H, br. s,
OH, D2O-exchangeable); 5.51 (2H, m, 3',4'-CH); 6.24 (1H,
d, J = 9.7, 1'-CH); 6.73 (1H, br. s, OH, D2O-exchangeable);
7.45–7.53 (3H, m, H Ar); 7.59–7.64 (1H, m, H Ar); 7.82
(1H, d, J = 7.8, NH). Found, %: C 55.87; H 6.03; N 11.91.
C17H21N3O6. Calculated, %: C 56.19; H 5.83; N 11.56.
2-(2-Acetamido-2-deoxy--D-glucopyranosyloxy)-
3-phenylquinoxaline (8c). Yield 2.45 g (61%), white
2-(2-Acetamido-3,4,6-tri-O-acetyl-2-deoxy--D-gluco-
pyranosyloxy)-3,6,7-trimethylquinoxaline (7e). Yield
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3.05 g (59%), white crystals, mp 125–126°C. H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 1.84 (3H, s, NHCOCH3);
2.05 (3H, s, COCH3); 2.08 (6H, s, 2COCH3); 2.43 (6H, s,
6,7-CH3); 2.61 (3H, s, 3-CH3); 3.98–4.18 (2H, m, 6'-CH2);
4.32–4.41 (1H, m, 5'-CH); 4.52–4.63 (1H, m, 2'-CH);
5.24–5.31 (2H, m, 3',4'-CH); 5.84 (1H, d, J = 9.0, NH);
6.27 (1H, d, J = 9.7, 1'-CH); 7.53 (1H, s, H Ar); 7.70 (1H,
s, H Ar). 13C NMR spectrum (DMSO-d6), δ, ppm: 19.9
(CH3); 20.0 (CH3); 20.1 (CH3); 20.7 (CH3); 22.6 (CH3);
23.2 (2CH3); 53.3 (C-6'); 61.9 (C-5'); 68.3 (C-2'); 72.5
(C-4'); 72.8 (C-3'); 94.4 (C-1'); 126.2 (C Ar); 127.5 (C Ar);
137.2 (C Ar); 137.4 (C Ar); 138.2 (C Ar); 139.3 (C Ar);
146.6 (C Ar); 153.8 (C Ar); 169.3 (COCH3); 170.0
(COCH3); 170.7 (COCH3); 171.3 (COCH3). Found, %:
C 57.86; H 6.32; N 8.41. C25H31N3O9. Calculated, %:
C 58.02; H 6.04; N 8.12.
2-(2-Acetamido-3,4,6-tri-O-acetyl-2-deoxy--D-gluco-
pyranosyloxy)-6,7-dimethyl-3-phenylquinoxaline (7f).
Yield 3.70 g (64%), white crystals, mp 158–159°C.
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 1.83 (3H, s,
NHCOCH3); 2.02 (3H, s, COCH3); 2.07 (6H, s, 2COCH3);
2.45 (6H, s, 6,7-CH3); 4.00–4.29 (3H, m, 6'-CH2, 5'-CH);
4.47–4.54 (1H, m, 2'-CH); 5.18–5.41 (2H, m, 3'-CH,
4'-CH); 5.98 (1H, d, J = 9.3, NH); 6.42 (1H, d, J = 9.8,
1'-CH); 7.33–7.45 (3H, m, H Ar); 7.58 (1H, s, H Ar); 7.84
(1H, s, H Ar); 7.94–8.03 (2H, m, H Ar). 13C NMR
spectrum (DMSO-d6), δ, ppm: 19.3 (CH3); 19.9 (CH3);
20.0 (CH3); 20.5 (CH3); 23.0 (2 CH3); 53.2 (C-6'); 61.8
(C-5'); 68.2 (C-2'); 72.3 (C-4'); 73.0 (C-3'); 94.0 (C-1');
126.1 (C Ar); 128.2 (C Ar); 129.3 (C Ar); 129.5 (C Ar);
135.2 (C Ar); 137.4 (C Ar); 137.7 (C Ar); 138.6 (C Ar);
140.2 (C Ar); 144.7 (C Ar); 152.8 (C Ar); 169.2 (COCH3);
170.0 (COCH3); 170.6 (COCH3); 171.0 (COCH3). Found,
%: C 62.04; H 6.12; N 7.11. C30H33N3O9. Calculated, %:
C 62.17; H 5.74; N 7.25.
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crystals, mp 262–263°C. H NMR spectrum (CDCl3), δ,
ppm (J, Hz): 1.84 (3H, s, NHCOCH3); 3.73–3.21 (2H, m,
6'-CH2); 3.98–3.83 (2H, m, 2',5'-CH); 4.63 (1H, br. s, OH,
D2O-exchangeable); 5.19 (1H, br. s, OH, D2O-exchange-
able); 5.40–5.45 (2H, m, 3',4'-CH); 6.01 (1H, d, J = 8.7,
1'-CH); 6.69 (1H, br. s, OH, D2O-exchangeable); 7.59–7.63
(4H, m, H Ar); 7.72–7.82 (5H, m, H Ar); 7.86 (1H, d,
J = 9.0, NH). Found, %: C 61.83; H 5.38; N 9.64.
C22H23N3O6. Calculated, %: C 62.11; H 5.45; N 9.88.
2-(2-Acetamido-2-deoxy--D-glucopyranosyloxy)-
6,7-dimethylquinoxaline (8d). Yield 2.61 g (72%), white
crystals, mp 195–196°C. 1H NMR (CDCl3), δ, ppm (J, Hz):
1.77 (3H, s, NHCOCH3); 2.51 (6H, s, 2CH3); 3.29–3.72
(2H, m, 6'-CH2); 3.87–3.98 (2H, m, 2',5'-CH); 4.66 (1H, br.
s, OH, D2O-exchangeable); 5.21 (1H, br. s, OH, D2O-
exchangeable); 5.51–5.72 (2H, m, 3',4'-CH); 6.04 (1H, d,
J = 8.7, 1'-CH); 6.72 (1H, br. s, OH, D2O-exchangeable);
7.59–7.73 (2H, m, H Ar); 7.93 (1H, d, J = 7.3, NH), 8.37
(1H, s, CH). 13C NMR spectrum (DMSO-d6), δ, ppm: 19.7
(COCH3); 22.8 (2CH3); 54.7 (C-6'); 60.5 (C-5'); 70.0
(C-2'); 73.7 (C-4'); 77.7 (C-3'); 95.2 (C-1'); 126.6 (C Ar);
127.1 (C Ar); 127.8 (C Ar); 129.3 (C Ar); 138.5 (C Ar);
147.8 (C Ar); 154.3 (C Ar); 169.3 (COCH3). Found, %:
C 57.63; H 6.33; N 11.46. C18H23N3O6. Calculated, %:
C 57.29; H 6.14; N 11.13.
2-(2-Acetamido-2-deoxy--D-glucopyranosyloxy)-
3,6,7-trimethylquinoxaline (8e). Yield 2.54 g (60%),
white crystals, mp 216–217°C. 1H NMR spectrum (CDCl3),
δ, ppm (J, Hz): 1.78 (3H, s, NHCOCH3); 2.31 (6H, s,
2CH3); 2.45 (3H, s, CH3); 3.29–3.62 (2H, m, 6'-CH2);
3.91–4.01 (2H, m, 2',5'-CH); 4.58 (1H, t, J = 6.1, OH, D2O-
exchangeable); 5.21 (1H, br. s, OH, D2O-exchangeable);
5.54 (2H, m, 3',4'-CH); 6.35 (1H, d, J = 8.7, 1'-CH); 6.72
(1H, br. s, NH); 7.34 (1H, br. s, OH, D2O-exchangeable);
7.42–7.62 (2H, m, H Ar). 13C NMR spectrum (DMSO-d6),
δ, ppm: 19.9 (COCH3); 22.2; 22.4; 22.5 (3CH3); 54.6
Synthesis of deprotected nucleosides 8a–f (General
Method). Conc. ammonia (25%, 30 ml) was added to a
solution of acetylated quinoxaline nucleosides 7a–f
(1.0 mmol) in methanol (30 ml). The reaction mixture was
stirred at room temperature for 2 h, then evaporated to
dryness. The resulting crude product was purified by
column chromatography using CH2Cl2–MeOH, 10:1, as
eluent.
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