Molecules 2019, 24, 1969
10 of 14
3-Cyano-4-methyl-2-(2”,3”,4”,6”-tetra-O-acetyl-
β
-d-galactoyranosyloxy)-6-phenyl-5-(40-chlorophenylazo)-
pyridine (8 ) υ
c): mp 178 ◦C; IR (KBr, cm−1 2228 (CN), 1757 (CO); COSY; NOESY; gHMBC; 1H-NMR
(400 MHz, CDCl3) = 1.97, 1.99, 2.01, and 2.02 (4s, 12H, 4CH3CO), 2.56 (s, 3H, CH3), 3.91-3.97 (m, 1H,
H-5”), 4.20 (t, 1H, H-4”, JH-4”-H-3” = 9.2 Hz), 4.26 (t, 1H, H-3”, JH-3”-H-4” = 9.2 Hz), 5.23 (t, 1H, H-2”,
JH-2”-H-1” = 7.8 Hz), 5.32–5.37 (m, 2H, H-6”), 5.99 (d, 1H, H-1”, J = 8.1 Hz), 7.33–7.81 (m, 9H, Ar-H);
13C-NMR (100 MHz, CDCl3)
δ = 18.7 (CH3), 20.6, 20.65, 20.7, and 20.8 (4CH3CO), 62.3 (C-6”), 68.4
(C-5”), 70.5 (C-4”), 72.9 (C-3”), 73.1 (C-2”), 94.8 (C-3), 98.1 (C-1”), 113.8 (CN), 124.2–154.7 (Ar-C), 159.7
(C-2), 168.3, 169.6, 170.0 and 170.9 (4CO); LC-MS (ionization method): m/z 679 [M + 1]; Anal. calcd for
C33H31ClN4O10: C, 58.37; H, 4.60; N, 8.25%. Found: C, 58.61; H, 4.73; N, 8.11%.
3-Cyano-4-methyl-2-(2”,3”,4”,6”-tetra-O-acetyl-
pyridine ( 2230 (CN), 1756 (CO); COSY; NOESY; (400 MHz, CDCl3) =
d): mp 168 ◦C; IR (KBr, cm−1
β
-d-galactopyranosyloxy)-6-phenyl-5-(30-nitrophenylazo)-
8
) υ
1.95, 2.01, 2.07, and 2.09 (4s, 12H, 4CH3CO), 2.60 (s, 3H, CH3), 3.99–4.03 (m, 1H, H-5”), 4.22 (t, 1H,
H-4”, JH-4”-H-3” = 9.2 Hz), 4.29 (t, 1H, H-3”, JH-3”-H-4” = 9.2 Hz), 5.33 (t, 1H, H-2”, JH-2”-H-1” = 7.8 Hz),
5.37–5.40 (m, 2H, H-6”), 6.09 (d, 1H, H-1”, J = 8.0 Hz), 7.33–7.81 (m, 9H, Ar-H); 13C-NMR (100 MHz,
CDCl3) δ = 18.7 (CH3), 20.5, 20.55, 20.6, and 20.7 (4CH3CO), 61.8 (C-6”), 68.4 (C-5”), 70.5 (C-4”), 72.3
(C-3”), 73.2 (C-2”), 94.8 (C-3), 97.9 (C-1”), 113.5 (CN), 123.2–154.7 (Ar-C), 160.2 (C-2), 168.8, 169.5, 170.3
and 170.5 (4CO); LC-MS (ionization method): m/z 690 [M + 1]; Anal. calcd for C33H31N5O12: C, 57.47;
H, 4.53; N, 10.16%. Found: C, 57.58; H, 4.62; N, 10.33%.
3-Cyano-4,6-dimethyl-2-(2”,3”,4”,6”-tetra-O-acetyl-
147 ◦C; IR (KBr, cm−1 2232 (CN), 1758 (CO); 1H-NMR (400 MHz, CDCl3)
2.05 (4s, 12H, 4CH3CO), 2.43 (s, 3H, CH3), 2.52 (s, 3H, CH3), 4.02–4.05 (m, 1H, H-5”), 4.24 (t, 1H, H-4”,
H-4”-H-3” = 9.2 Hz), 4.31 (t, 1H, H-3”, JH-3”-H-4” = 9.2 Hz), 5.31 (t, 1H, H-2”, JH-2”-H-1” = 7.8 Hz), 5.39–5.44
(m, 2H, H-6”), 6.02 (d, 1H, H-1”, JH-1”-H-2” = 8.0 Hz), 6.80 (s, 1H, pyridine H-5); 13C-NMR (100 MHz,
CDCl3) = 20.4 (CH3), 20.6, 20.7, 20.75, and 20.8 (4CH3CO), 24.3 (CH3), 61.3 (C-6”), 67.8 (C-5”), 70.7
β-d-galactopyranosylox-y) pyridine (11a): mp
)
υ
δ
= 2.01, 2.01, 2.03, and
J
δ
(C-4”), 72.8 (C-3”), 74.1 (C-2”), 93.8 (C-3), 95.0 (C-1”), 114.2 (CN), 120.2 (C-5), 154.8 (C-4), 160.8 (C-6),
161.7 (C-2), 169.1, 170.0, 170.5 and 170.8 (4CO); LC-MS (ionization method): m/z 479 [M + 1]; Anal.
calcd for C22H26N2O10: C, 55.23; H, 5.48; N, 5.86%. Found: C, 55.46; H, 5.72; N, 5.98%.
3-Cyano-4-methyl-2-(2”,3”,4”,6”-tetra-O-acetyl-
β
-d-galactopyranosyloxy)-6-phenyl-pyridine (11b): mp
167 ◦C; IR (KBr, cm−1 2230 (CN), 1764 (CO); 1H-NMR (400 MHz, CDCl3)
)
υ
δ
= 2.00, 2.01, 2.02, and 2.03
(4s, 12H, 4CH3CO), 2.57 (s, 3H, CH3), 3.90–3.94 (m, 1H, H-5”), 4.12 (t, 1H, H-4”, JH-4”-H-3” = 9.2 Hz),
4.11 (t, 1H, H-3”, JH-3”-H-4” = 9.2 Hz), 5.22 (t, 1H, H-2”, JH-2”-H-1” = 7.8 Hz), 5.40-5.46 (m, 2H, H-6”),
5.97 (d, 1H, H-1”, JH-1”-H-2” = 8.0 Hz), 7.40 (s, 1H, pyridine H-5), 7.39–7.45 (m, 3H, Ar-H), 7.94–7.99
(m, 2H, Ar-H); 13C-NMR (100 MHz, CDCl3)
δ = 20.4, 20.5, 20.6, and 20.7 (4CH3CO), 24.2 (CH3), 62.4
(C-6”), 68.6 (C-5”), 70.5 (C-4”), 72.8 (C-3”), 73.1 (C-2”), 93.7 (C-3), 96.3 (C-1”), 113.8 (CN), 116.3 (C-5),
127.2–137.1 (Ar-C), 155.6 (C-4), 157.5 (C-6), 161.4 (C-2), 168.3, 168.9, 169.8, and 170.8 (4CO); LC-MS
(ionization method): m/z 563 [M + Na]+; Anal. calcd for C27H28N2O10: C, 60.00; H, 5.22; N, 5.18%.
Found: C, 59.88; H, 5.42; N, 5.30%.
3-Cyano-2-(2”,3”,4”,6”-tetra-O-acetyl-
β
-d-galactopyranosyloxy)-4-trifluromethyl-6-phenyl-pyridine
(
11c): mp 161 ◦C; IR (KBr, cm−1 2230 (CN), 1753 (CO); 1H-NMR (400 MHz, CDCl3)
)
υ
δ
= 2.00, 2.01,
2.02, and 2.03 (4s, 12H, 4 CH3CO), 3.97–4.01 (m, 1 H, H-5”), 4.19 (t, 1H, H-4”, JH-4”-H-3” = 9.2 Hz), 4.08
(t, 1H, H-3”, JH-3”-H-4” = 9.2 Hz), 5.19 (t, 1H, H-2”, JH-2”-H-1” = 7.8 Hz), 5.42-5.47 (m, 2H, H-6”), 6.12 (d,
1H, H-1”, JH-1”-H-2” = 8.0 Hz), 7.51–7.53 (m, 3H, Ar-H), 7.68 (s, 1H, pyridine H-5), 7.84–8.03 (m, 2H,
Ar-H); 19F-NMR (376 MHz, CDCl3)
δ δ = 20.0,
= (-63.81) (s, 3F, CF3); 13C-NMR (100 MHz, CDCl3)
20.1, 20.15 and 20.2 (4CH3CO), 61.8 (C-6”), 68.0 (C-5”), 70.1 (C-4”), 72.3 (C-3”), 73.0 (C-2”), 91.8 (C-1”),
94.3 (C-3), 110.7 (CN), 110.9 (C-5), 119.8 (CF3), 127.2–135.2 (Ar-C), 144.9 (C-4), 160.0 (C-6), 162.2 (C-2),
168.3, 168.8, 169.3, and 170.4 (4 CO); LC-MS (ionization method): m/z 595 [M + 1]; Anal. calcd for
C27H25F3N2O10: C, 54.55; H, 4.24; N, 4.71%. Found: C, 54.76; H, 4.51; N, 4.52%.