4.4. Synthetic Procedures
Compounds
6 [
14],
33 [
11],
37 [
17],
45 [
19],
46 [
20],
48 [
20],
69 [
17],
85 [
26],
86 [
27],
89 [
17],
91 [
17],
123 [
17],
125 [
76],
126 [
15],
127 [
77], and
128 [
77] have been synthesized as described.
4.4.1. Synthesis of Schiff Bases
New and reported substances were obtained according to the following general procedures. Method 1: To a solution of 2 or 6 (23.2 mmol) in 1M NaOH (25 mL) was added the appropriate aromatic aldehyde (25.0 mmol), and the mixture was stirred at room temperature. A solid precipitated and was collected by filtration and washed successively with cold water, cold ethanol, and ethyl ether, and dried under vacuum on silica gel. Method 2: Sodium hydrogen carbonate (0.50 g, 6.0 mmol) was added to a solution of 2 or 6 (4.7 mmol) in water (6 mL). To the resulting mixture, a solution of the appropriate aromatic aldehyde (4.7 mmol) in methanol (saturated solution) was added dropwise. The mixture was stirred at room temperature until precipitation, and then left in the refrigerator (~5 °C) overnight. The solid was collected, washed with cold water, ethanol, and ethyl ether, and dried in vacuo.
2-[(E
)-Benzylidenamino]-2-deoxy-α-d-glucopyranose (
30). Method 1 (60%). M.p: 169–171 °C; [α]
D +118.4°; [α]
578 +124.8°; [α]
546 +142.8°; [α]
436 +267.4° (
c 0.5, pyridine); [Lit. [
24] m.p. 156 °C (decomp.)]; IR (KBr)
max/cm
−1 3448, 3250 (OH), 2939, 2868 (CH), 1643 (C=N), 1581 (arom), 1154, 1085, 1010 (C-O), 758, 698 (arom);
1H NMR (500 MHz, DMSO-
d6) δ 8.33 (1H, s, N=CH), 7.77 (2H, m, arom), 7.45 (3H, m, arom), 6.22 (1H, d,
J1,OH 4.0 Hz, C1-OH), 4.95 (1H, t,
J1,OH =
J1,2 3.5 Hz, H-1), 4.92 (1H, d,
J3,OH 5.5 Hz, C3-OH), 4.71 (1H, d,
J4,OH = 5.5 Hz, C4-OH), 4.46 (1H, t,
J6,OH =
J6′,OH 5.5 Hz, C6-OH), 3.83 (1H, dt,
J3,OH 5.5 Hz,
J2,3 =
J3,4 9.5 Hz, H-3), 3.76 (1H, ddd,
J4,5 9.5 Hz,
J5,6 2.0 Hz,
J5,6′ 5.5 Hz, H-5), 3.68 (1H, ddd,
J6,OH 5.5 Hz,
J5,6′ 2.0
J6,6′ 11.5 Hz, H-6), 3.54 (1H, dt,
J6′,OH =
J5,6′ 5.5 Hz,
J6,6 11.5 Hz, H-6′), 3.20 (1H, dt,
J4,OH 5.5 Hz,
J3,4 =
J4,5 9.5 Hz, H-4), 3.14 (1H, dd,
J1,2 3.5 Hz,
J2,3 9.5 Hz, H-2);
13C{
1H} NMR (125 MHz, DMSO-
d6) δ 162.2 (N=C), 136.3, 130.6, 128.6 (2 C-arom), 128.2 (2 C-arom), 93.0 (C-1), 75.1 (C-2), 72.5 (C-5), 70.9 (C-3), 70.8 (C-4), 61.4 (C-6). Anal. Calcd. for C
13H
17NO
5: C, 58.42; H, 6.41; N, 5.24. Found: C, 58.27; H, 6.20; N, 5.11. HRMS [M+H]
+ calculated for C
13H
18NO
5: 268.1185. Found: 268.1170.
2-Deoxy-2-[(E)-(3-fluorobenzylidene)amino]-α-d-glucopyranose (31). Method 1 (60%). M.p. 183–185 °C; [α]D +154.0°; [α]578 +161.0°; [α]546 +185.4°; [α]436 +350.8° (c 0.5, pyridine); IR (KBr) max/cm−1 3449, 3243 (OH), 2940, 2867 (CH), 1644 (C=N) 1614, 1585, 1452, 1152, 1084, 1011 (C-O); 1H NMR (500 MHz, DMSO-d6) δ 8.34 (1H, s, N=CH), 7.59 (2H, m, arom), 7.50 (1H, m, arom), 7.29 (1H, dt, J 3.2 Hz, J 8.5 Hz, arom), 6.23 (1H, d, J1,OH 4.5 Hz, C1-OH), 4.95 (1H, t, J1,OH = J1,2 3.5 Hz, H-1), 4.92 (1H, d, J3,OH 5.5 Hz, C3-OH), 4.74 (1H, d, J4,OH = 5.5 Hz, C4-OH), 4.45 (1H, t, J6,OH = J6′,OH 6.0 Hz, C6-OH), 3.80 (1H, dt, J3,OH 5.5 Hz, J2,3 = J3,4 9.5 Hz, H-3), 3.76 (1H, ddd, J4,5 9.5 Hz, J5,6 2.0 Hz, J5,6′ 5.5 Hz, H-5), 3.67 (1H, ddd, J6,OH 5.5 Hz, J5,6′ = 2.0, J6,6′ 11.5 Hz, H-6), 3.54 (1H, dt, J6′,OH = J5,6′ 5.5 Hz, J6,6′ 12.0 Hz, H-6′), 3.20 (1H, dt, J4,OH 5.5 Hz, J3,4 = J4,5 9.9 Hz, H-4), 3.16 (1H, dd, J1,2 3.0 Hz, J2,3 10.0 Hz, H-2); 13C{1H} NMR (125 MHz, DMSO-d6) δ 162.4 (1JC,F = 242.5 Hz, C3 arom), 161.0 (4JC,F = 2.5 Hz, N=C), 138.9 (3JC,F = 7.5 Hz, C1 arom), 130.7 (4JC,F = 7.5 Hz, C5 arom), 124.7 (3JC,F = 1.25 Hz, C6 arom), 117.4 (2JC,F = 22.5 Hz, C2 arom), 113.8 (2JC,F = 22.5 Hz, C4 arom), 92.8 (C-1), 74.9 (C-2), 72.5(C-5), 70.8 (C-3), 70.7 (C-4), 61.6 (C-6). Anal. Calcd. for C13H16FNO5: C, 54.73; H, 5.65; N, 6.66. Found: C,54.92; H, 5.37; N, 5.58. HRMS [M+H]+ calculated for C13H17FNO5: 286.1091. Found: 286.1077.
2-Deoxy-2-[(E)-(3-bromobenzylidene)amino]-β-d-glucopyranose (32). Method 1 (86%). M.p. 167–170 °C; [α]D +51.6°; [α]578 +51.6°; [α]546 +55.0°; [α]436 +113.8° (c 0.5, pyridine); IR (KBr) max/cm−1 3484, 3304, 3191 (OH), 1650 (C=N) 1563, 1106, 1070, 1034 (C-O), 989, 880; 1H NMR (500 MHz, DMSO-d6) δ 8.19 (1H, s, CH=N), 7.95 (1H, s, arom), 7.73 (1H, d, J 8.0 Hz, H-arom), 7.65 (1H, dd, J 8.0 Hz, J 1.0 Hz, H-arom), 7.41 (1H, t, J 8.0 Hz, H-arom), 6.62 (1H, d, J1,OH 7.0 Hz, OH-1), 5.00 (1H, d, J3,OH 5.5 Hz, OH-3), 4.92 (1H, d, J4,OH 5.5 Hz, OH-4), 4.73 (1H, t, JOH,1 = J1,2 8.0 Hz, H-1), 4.59 (1H, t, J6,OH 5.5 Hz, OH-6), 3.72 (1H, ddd, J5,6 1.5 Hz, J6,OH 5.5 Hz, J6,6′ 11.5 Hz, H-6), 3.49 (1H, dt, J5,6′ = J6,OH 5.5 Hz, J6,6′ 11.5 Hz, H-6′), 3.45 (1H, m, H-3), 3.25 (1H, ddd, J5,6 2.0 Hz, J5,6′ 6.0 Hz, J6,6′ 9.0 Hz, H-5), 3.16 (1H, dt, J4,OH 5.5 Hz, J3,4 = J4,5 9.0 Hz, H-4), 2.85 (1H, dd~t, J1,2 8.0 Hz, J2,3 9.0 Hz, H-2); 13C{1H} NMR (125 MHz, DMSO-d6) δ 160.7 (C=N), 138.5 (C-arom), 133.2 (C-arom), 130.9 (C-arom), 130.1 (C-arom), 127.4 (C-arom), 122.1 (C-arom), 95.5 (C-1), 78.1 (C-2), 77.0 (C-5), 74.4 (C-3), 70.3 (C-4), 61.3 (C-6). Anal. Calcd. for C13H16BrNO5: C, 45.10; H, 4.66; N, 4.05. Found: C, 44.88; H, 4.84; N, 4.21. HRMS [M+H]+ calculated for C13H17BrNO5: 346.0290. Found: 346.0285.
2-Deoxy-2-[(E
)-(4-chlorobenzylidene)amino]-β-d-glucopyranose (
33) [
11]. Method 1 (76%). M.p. 178–180 °C; [α]
D +38.4°; [α]
578 +39.2°; [α]
546 +47.8°; [α]
436 +113.6° (
c 0.5, pyridine); IR (KBr)
max/cm
−1 3494, 3304, 3200 (OH), 1646 (C=N) 1597, 1085, 1068, 1030 (C-O), 987, 830;
1H NMR (500 MHz, DMSO-
d6) δ 8.21 (1H, s, CH=N), 7.78 (2H, d,
J 8.5 Hz, arom), 7.50 (2H, d,
J 8.5 Hz, arom), 6.59 (1H, d,
J1,OH 6.5 Hz, OH-1), 4.96 (1H, d,
J3,OH 5.5 Hz, OH-3), 4.89 (1H, d,
J4,OH 5.5 Hz, OH-4), 4.73 (1H, t,
JOH,1 =
J1,2 8.0 Hz, H-1), 4.57 (1H, t,
J6,OH 6.0 Hz, OH-6), 3.74 (1H, ddd,
J5,6 2.0 Hz,
J6,OH 5.5 Hz,
J6,6′ 12.0 Hz, H-6), 3.50 (1H, dt,
J6′,OH =
J5,6′ 6.0 Hz,
J6,6′ 12.0 Hz, H-6′), 3.45 (1H, dt,
J3,OH 5.5 Hz,
J2,3 ≈
J3,4 9.0 Hz, H-3), 3.26 (1H, ddd,
J5,6 2.0 Hz,
J5,6′ 6.0 Hz,
J4,5 9.0 Hz, H-5), 3.18 (1H, dt,
J4,OH 5.5 Hz,
J3,4 =
J4,5 9.0 Hz, H-4), 2.86 (1H, t,
J1,2 ≈
J2,3 8.0 Hz, H-2);
13C{
1H} NMR (125 MHz, DMSO-
d6) δ 160. 9 (C=N), 135.1 (C-arom), 135.1 (C arom), 129.7 (2 C-arom), 128.7 (2 C- arom), 95.5 (C-1), 78.2 (C-2), 76.9 (C-5), 74.4 (C-3), 70.3 (C-4), 61.3 (C-6). Anal. Calcd. for C
13H
16N
2O
7: C, 51.71; H, 5.35; N, 4.64. Found: C, 51.56; H, 5.53; N, 4.70. HRMS [M+H]
+ calculated for C
13H
17ClNO
5: 302.0795. Found: 302.0778.
2-Deoxy-2-[(E)-(4-cyanobenzylidene)amino]-β-d-glucopyranose (34). Method 1 (70%). M.p. 165–167 °C; [α]D +49.8°; [α]578 +52.0°; [α]546 +61.0°; [α]436 +138.0° (c 0.5, pyridine); IR (KBr) max/cm−1 3559, 3522, 3466, 3342, 3157 (OH), 2234 (CN), 1641 (C=N) 1369, 1096, 1080, 1048, 1018 (C-O), 835; 1H NMR (500 MHz, DMSO-d6) δ 8.30 (1H, s, CH=N), 7.92 (4H, m, arom), 6.65 (1H, d, J1,OH 6.5 Hz, OH-1), 4.99 (1H, d, J3,OH 5.5 Hz, OH-3), 4.94 (1H, d, J4,OH 5.5 Hz, OH-4), 4.76 (1H, t, JOH,1 = J1,2 7.0 Hz, H-1), 4.59 (1H, t, J6,OH 6.0 Hz, OH-6), 3.74 (1H, ddd, J5,6 1.5 Hz, J6,OH 5.5 Hz, J6,6′ 11.5 Hz, H-6), 3.50 (1H, dt, J6,OH = J5,6 6.0 Hz, J6,6′ 11.5 Hz, H-6′), 3.48 (1H, dt, J6,OH 5.5 Hz, J3,4 = J4,5 9.0 Hz, H-3,), 3.27 (1H, ddd, J4,5 9.5 Hz, J5,6 1.5 Hz, J5,6′ 6.0 Hz, H-5), 3.18 (1H, dt, J4,OH 5.5 Hz, J3,4 = J4,5 9.5 Hz, H-4), 2.91 (1H, dd≈t, J1,2 ≈ 7.5 J2,3 9.5 Hz, H-2); 13C{1H} NMR (125 MHz, DMSO-d6) δ 161.0 (C=N), 140.1 (C-arom), 132.7 (2 C-arom), 128.7 (2 C-arom), 118.7 (C≡N), 112.7 (C-arom), 95.4 (C-1), 78.4 (C-2), 77.0 (C-5), 74.3 (C-3), 70.2 (C-4), 61.3 (C-6). Anal. Calcd. for C14H16N2O5: C, 57.53; H, 5.52; N, 9.58. Found: C, 57.34; H, 5.28; N, 9.41. HRMS [M+H]+ calculated for C14H17N2O5: 293.1137. Found: 293.1137.
2-Deoxy-2-[(E)-(4-pyperidinylbenzylidene)amino]-β-d-glucopyranose (35). Method 1 (62%). M.p. 172–174 °C; [α]D +27.8°; [α]578 +30.0°; [α]546 +35.4°; [α]436 +84.0° (c 0.5, pyridine); IR (KBr) max/cm−1 3466, 3292, 3178 (OH), 2919, 2838 (CH), 1630 (C=N) 1609 (arom), 1522, 1254, 1191, 1129, 1109, 1089, 1028 (C-O), 807; 1H NMR (500 MHz, DMSO-d6) δ 8.03 (1H, s, CH=N), 7.55 (2H, d, J 8.5 Hz, arom), 6.93 (2H, d, J 8.5 Hz, arom), 6.50 (1H, d, J1,OH 7.0 Hz, OH-1), 4.90 (1H, d, J3,OH 5.0 Hz, OH-3), 4.77 (1H, d, J4,OH 5.5 Hz, OH-4), 4.68 (1H, t, JOH,1 = J1,2 7.5 Hz, H-1), 4.55 (1H, t, J6,OH = J6′,OH 6.0 Hz, OH-6), 3.73 (1H, dd, J6,OH 5.5 Hz, J6,6′ 12.0 Hz, H-6), 3.49 (1H, dt, J6′,OH = J5,6′ 6.0 Hz, J6,6′ 12.0 Hz, H-6′), 3.42 (1H, dt, J3,OH 6.0 Hz, J2,3 ≈ J3,4 9.0 Hz, H-3), 3.24 (5H, m, H-5, NCH2, piperidine), 3.16 (1H, dt, J4,OH 5.0 Hz, J3,4 = J4,5 9.5 Hz, H-4), 2.76 (1H, t, J1,2 = J2,3 8.5 Hz, H-2); 1.57 (6H, s, CH2 pyperidine); 13C{1H} NMR (125 MHz, DMSO-d6) δ 161.5 (C=N), 152.7 (arom), 129.3 (2 C-arom), 125.9 (C-arom), 114.3 (2 C-arom), 95.8 (C-1), 78.3 (C-2), 76.8 (C-5), 74.8 (C-3), 70.4 (C-4), 61.3 (C-6), 48. 6 (2C, piperidine), 25.0 (2C, piperidine), 24.0 (piperidine). Anal. Calcd. for C13H16N2O7: C, 61.70; H, 7.42; N, 7.99. Found: C, 62.01; H, 7.28; N, 8.26. HRMS [M+H]+ calculated for C18H27N2O5: 351.1920. Found: 351.1918.
2-Deoxy-2-[(E)-(4-morpholinylbenzylidene)amino]-β-d-glucopyranose (36). Method 1 (64%). M.p. 173–175 °C; [α]D +31.4°; [α]578 +33.2°; [α]546 +38.8°; [α]436 +88.8° (c 0.5, pyridine); IR (KBr) max/cm−1 3420, 3342, 3080 (OH), 2965, 2910, 2874, 2833 (CH), 1642 (C=N) 1610, 1518, 1117, 1070, 1029, 1011 (C-O), 923, 816; 1H NMR (500 MHz, DMSO-d6) δ 8.06 (1H, s, CH=N), 7.59 (2H, d, J 8.5 Hz, arom), 6.96 (2H, d, J 8.5 Hz, arom), 6.51 (1H, d, J1,OH 6.5 Hz, OH-1), 4.91 (1H, d, J3,OH 5.5 Hz, OH-3), 4.78 (1H, d, J4,OH 6.0 Hz, OH-4), 4.69 (1H, t, JOH,1 = J1,2 8.5 Hz, H-1), 4.55 (1H, t, J6,OH = J6′,OH 6.0 Hz, OH-6), 3.73 (5H, m, H-6, OCH2, morpholine), 3.49 (1H, dt, J6′,OH = J5,6′ 6.0 Hz, J6,6′ 12.0 Hz, H-6′), 3.42 (1H, dt, J3,OH 5.5 Hz, J2,3 ≈ J3,4 9.0 Hz, H-3), 3.24 (1H, ddd, J5,6 2.0 Hz, J5,6′ 6.0 Hz, J4,5 9.0 Hz, H-5), 3.19 (4H, m, NCH2, morpholine), 3.15 (1H, dt, J4,OH 6.0 Hz, J3,4 = J4,5 9.5 Hz, H-4), 2.77 (1H, t, J1,2 = J2,3 8.5 Hz, H-2); 13C{1H} NMR (125 MHz, DMSO-d6) δ 161.5 (C=N), 152.5 (C-arom), 129.3 (2 C-arom), 127.0 (C-arom), 114.1 (2 C-arom), 95.8 (C-1), 78.3 (C-2), 76.9 (C-5), 74.8 (C-3), 70.5 (C-4), 66.0 (2C, morpholine), 61.3 (C-6), 47.6 (2C, morpholine). Anal. Calcd. for C13H16N2O7: C, 57.94; H, 6.86; N, 7.95. Found: C, 58.13; H, 6.65; N, 7.92. HRMS [M+H]+ calculated for C17H25N2O6: 353.1713. Found: 353.1711.
2-Deoxy-2-[(E
)-(4-methoxybenzylidene)amino]-β-d-glycero
-l-gluco-
heptopyranose (
37) [
17]. Method 2 (83%). M.p. 189–190 °C (Lit. [
17] 190–192 °C);
1H NMR (500 MHz, DMSO-
d6) δ 8.11 (1H, s, CH=N), 7.68 (2H, d,
J 8.0 Hz, H-arom), 6.98 (2H, d,
J 8.0 Hz, H-arom), 6.46 (1H, d,
J1,OH 6.5 Hz, OH-1), 4.82 (1H, bs, OH-3), 4.78 (1H, bs, OH-4), 4.66 (1H, t,
J1,OH =
J1,2 7.0 Hz, H-1), 4.49 (1H, bs, OH-7), 4.27 (1H, d,
J6,OH 6.0 Hz, OH-6), 3.79 (4H, m, H-6, OCH
3), 3.86–3.44 (4H, m, H-3, H-4, H-7, H-7′), 3.27 (1H, d,
J4,5 8.0 Hz H-5), 2.78 (1H, t,
J1,2 ≈
J2,3 7.0 Hz, H-2);
13C{
1H} NMR (125 MHz, DMSO-
d6) δ 161.2 (C=N), 161.1 (C-arom), 131.9 (C-arom), 129.7 (2 C-arom), 113.9 (2 C-arom), 96.0 (C-1), 78.3 (C-2), 74.9 (C-3), 74.5 (C-5), 69.2 (C-4), 68.7 (C-6), 62.5 (C-7), 55.3 (OMe).
2-[(E)-Benzylidenamino]-2-deoxy-β-d-glycero-l-gluco-heptopyranose (38). Method 2 (37%). M.p. 155–157 °C (dec.); [α]D25 −49.1°; [α]57825 −51.9°; [α]54625 −60.0°; [α]43625 −120.9° (c 0.5, pyridine); IR (KBr) max/cm−1 3375, 3295 (OH), 1643 (C=N) 1090, 1063, 1014 (C-O); 1H NMR (500 MHz, DMSO-d6) δ 8.20 (1H, s, CH=N), 7.75 (2H, m, H-arom), 7.45 (3H, m, H-arom), 6.51 (1H, sa, C1-OH), 4.85 (1H, s, OH), 4.83 (1H, s, OH), 4.70 (1H, t, J1,OH ≈ J1,2 7.5 Hz, H-1), 4.51 (1H, sa, C7-OH), 4.29 (1H, d, J6,OH 6.5 Hz, C6-OH), 3.80 (1H, m, H-6), 3.5 (4H, m, H-3, H-4, H-7, H-7′), 3.29 (1H, d, J4,5 ≈ J5,6 8.0 Hz, H-5), 2.85 (1H, t, J1,2 ≈ J2,3 9.0 Hz, H-2); 13C{1H} NMR (125 MHz, DMSO-d6) δ 162.4 (C=N), 136.6, 131.0, 129.0, 128.5 (C-arom), 96.4 (C-1), 78.8 (C-2), 75.2 (C-3), 74.9 (C-5), 69.6 (C-4), 69.1 (C-6), 63.0 (C-7). Anal. Calcd. for C14H19NO6: C, 56.57; H, 6.40; N, 4.71. Found: C, 56.73; H, 6.23; N, 4.77. HRMS [M+H]+ calculated for C14H20NO6: 298.1285. Found: 298.1298.
2-Deoxy-2-[(E)-(4-nitrobenzylidene)amino]-β-d-glycero-l-gluco-heptopyranose (39). Method 2 (73%). M.p. 140–142 °C (dec.); [α]D −61.2°; [α]578 −62.3°; [α]546 −73.6°; [α]436 −170.2° (c 0.5, pyridine); IR (KBr) max/cm−1 3527, 3500–3100 (OH), 1649 (C=N), 1602 (arom), 1520 (NO2), 1429 (arom), 1345 (NO2), 1124, 1061, 1011 (C-O), 989, 838, 693, 682; 1H NMR (500 MHz, DMSO-d6) δ 8.36 (1H, s, CH=N), 8.30 (2H, d, H-arom), 8.03 (2H, d, H-arom), 6.60 (1H, s, C1-OH), 4.92 (1H, d, J 3.5 Hz, OH), 4.89 (1H, d, J 4.0 Hz, OH), 4.75 (1H, t, J1,OH ≈ J1,2 7.5 Hz, H-1), 4.51 (1H, t, J7,OH 6.5 Hz, C7-OH), 4.27 (1H, d, J6,OH 6.5 Hz, C6-OH), 3.80 (1H, c, J6,OH 6.5 Hz, H-6), 3.47 (4H, m, H-3, H-4, H-7, H-7′), 3.31 (1H, m, H-5), 2.93 (1H, t, J1,2 ≈ J2,3 8.5 Hz, H-2); 13C{1H} NMR (125 MHz, DMSO-d6) δ 160.9 (C=N), 148.9, 142.2, 129.5, 124.3 (C-arom), 96.2 (C-1), 78.9 (C-2), 75.0 (C-3), 74.9 (C-5), 69.5 (C-4), 69.1 (C-6), 62.9 (C-7). Anal. Calcd. for C14H18N2O8: C, 49.12; H, 5.26; N, 8.19. Found: C, 48.94; H, 5.23; N, 8.05. HRMS [M+H]+ calculated for C14H19N2O8: 343.1136. Found: 343.1149.
2-Deoxy-2-[(E)-(4-ethylbenzylidene)amino]-β-d-glycero-l-gluco-heptopyranose (40). Method 2 (60%). M.p. 182–184 °C (dec.); [α]D −44.0°; [α]578 −46.53°; [α]546 −54.5°; [α]436 −107.4° (c 0.5, pyridine); IR (KBr) max/cm−1 3367, 3284 (OH), 1644 (C=N),1609 (arom), 1081, 1014 (C-O); 1H NMR (500 MHz, DMSO-d6) δ 8.16 (1H, s, CH=N), 7.66 (2H, d, H-arom), 7.28 (2H, d, H-arom), 6.48 (1H, d, J1,OH 6.5 Hz, C1-OH), 4.82 (1H, d, J 3.5 Hz, OH), 4.78 (1H, d, J 4.5 Hz, OH), 4.68 (1H, t, J1,OH ≈ J1,2 7.0 Hz, H-1), 4.51 (1H, t, J7,OH 5.0 Hz, C7-OH), 4.27 (1H, d, J6,OH 6.5 Hz, C6-OH), 3.79 (1H, m, H-6), 3.45 (4H, m, H-3, H-4, H-7, H-7′), 3.28 (1H, d, J4,5 ≈ J5,6 8.0 Hz, H-5), 2.81 (1H, t, J1,2 ≈ J2,3 8.0 Hz, H-2), 2.64 (2H, c, J 7.0 Hz, CH2), 1.19 (3H, t, J 7.5 Hz, CH3); 13C{1H} NMR (125 MHz, DMSO-d6) δ 162.2 (C=N), 149.9, 134.4, 128.6, 128.4 (C-arom), 94.4 (C-1), 78.8 (C-2), 75.2 (C-3), 74.9 (C-5), 69.6 (C-4), 69.2 (C-6), 63.0 (C-7), 28.6 (CH2), 15.9 (CH3). Anal. Calcd. for C16H23NO6: C, 59.08; H, 7.08; N, 4.31. Found: C, 58.86; H, 6.97; N, 4.33. HRMS [M+H]+ calculated for C16H24NO6: 326.1598. Found: 326.1612.
2-Deoxy-2-[(E)-(2,4-dimethylbenzylidene)amino]-β-d-glycero-l-gluco-heptopyranose (41). Method 2 (40%). M.p. 175–177 °C (dec.); [α]D −45.9°; [α]578 −46.6°; [α]546 −54.1°; [α]436 −111.9° (c 0.5, pyridine); IR (KBr) max/cm−1 3367, 3294 (OH), 1634 (C=N),1613 (arom), 1084, 1010 (C-O); 1H NMR (500 MHz, DMSO-d6) δ 8.40 (1H, s, CH=N), 7.69 (2H, d, H-arom), 7.04 (2H, d, H-arom), 6.46 (1H, d, J1,OH 7.0 Hz, C1-OH), 4.81 (1H, d, J 5.0 Hz, OH), 4.76 (1H, d, J 5.0 Hz, OH), 4.67 (1H, t, J1,OH ≈ J1,2 7.5 Hz, H-1), 4.49 (1H, t, J7,OH 5.0 Hz, C7-OH), 4.26 (1H, d, J6,OH 7.0 Hz, C6-OH), 3.79 (1H, c, J6,OH 6.5 Hz, H-6), 3.43 (4H, m, H-3, H-4, H-7, H-7′), 3.28 (1H, d, J4,5 ≈ J5,6 8.5 Hz, H-5), 2.83 (1H, t, J1,2 ≈ J2,3 8.5 Hz, H-2), 2.43, 2.29 (9H, s, CH3); 13C{1H} NMR (125 MHz, DMSO-d6) δ 160.8 (C=N), 140.0, 137.7, 132.0, 131.8, 128.0, 127.0 (C-arom), 96.5 (C-1), 79.1 (C-2), 75.3 (C-3), 74.9 (C-5), 69.7 (C-4), 69.2 (C-6), 63.0 (C-7), 21.4, 19.4 (CH3). Anal. Calcd. for C16H23NO6: C, 59.08; H, 7.08; N, 4.31. Found: C, 59.15; H, 6.88; N, 4.26. HRMS [M+H]+ calculated for C16H24NO6: 326.1598. Found: 326.1609.
2,5-Bis(d-galacto-pentitol-1-yl)pyrazine (43). The title compound was obtained using Method 1 from 2-amino-2-deoxy-d-glycero-l-gluco-heptopyranose (6) and 2,4,6-trimethyl benzaldehyde. After partial solvent evaporation, a white solid was obtained, then isolated by filtration and washed with cold ethanol and ethyl ether. It decomposes without melting above 200 °C; [α]D −75.4°; [α]578 −82.0°; [α]546 −77.8°; [α]436 −86.8° (c 0.4, pyridine); IR(KBr) max/cm−1 3600–3100 (OH), 1637, 1491 (arom), 1043, 1028 (C-O), 870, 848 (arom.); 1H NMR (500 MHz, DMSO-d6) δ 8.63 (2H, s, H-arom), 5.28 (2H, s, C1-OH), 4.99 (2H, d, J 4.5 Hz, H-1), 4.45 (2H, s, C5-OH), 4.32 (2H, d, J 9.0 Hz, C4-OH), 4.30 (2H, d, J 8.5 Hz, C2-OH), 4.19 (2H, s, C3-OH), 3.74 (4H, s, H-3, H-4), 3.63 (2H, t, J 7.5 Hz, H-2); 3.44 (4H, t~s, H-5, H-5′); 13C{1H} NMR (125 MHz, DMSO-d6) δ 156.3 (C=N arom.), 141.3 (CH=, arom.), 72.7 and 69.9 (C-3, C-4), 71.3 (C-1), 69.4 (C-2), 63.1 (C-5). Anal. Calcd. for C14H24N2O10: C, 41.69; H, 5.96; N, 6.95. Found: C, 41.53; H, 5.86; N, 7.02. HRMS [M+H]+ calculated for C14H25N2O10: 381.1504; Found: 381.1518; [M+Na]+ calculated for C14H24N2O10Na: 403.1323. Found: 403.1332.
2,5-Bis(1′,2′,3′,4′,5′-penta-O-acetyl-d-galacto-pentitol-1-yl)pyrazine (44). To a suspension of 2,5-bis-(d-galacto-pentitol-1-yl)pyrazine (49) in pyridine (9.4 mL), acetic anhydride (9.0 mL) was added with stirring and external cooling. The mixture was allowed to warm at room temperature until dissolution. It was then poured into ice-water, and the resulting solid was filtered and washed with cold water and dried in vacuum over silica gel (62%). M.p. 217–219 °C; IR(KBr) max/cm−1 1742 (C=O, acetate), 1373, 1222 and 1206 (C-O-C, acetate), 1029 (C-O); 1H NMR (500 MHz, CDCl3) δ 8.44 (2H, s, H-arom), 6.02 (2H, d, J 1.5 Hz, H-1), 5.65 (2H, dd, J 1.5 Hz, J 10.0 Hz, H-2), 5.55 (2H, dd, J 10.0 Hz, J 1.5 Hz, H-3), 5.30 (2H, m, H-4), 4.31 (2H, dd, J 5.0 Hz, J 11.5 Hz, H-5), 3.90 (2H, dd, J 7.5 Hz, J 11.5 Hz, H-5′), 2.23 (6H, s, acetate), 2.16 (6H, s, acetate), 2.05 (6H, s, acetate), 2.04 (6H, s, acetate), 1.65 (6H, s, acetate); 13C{1H} NMR (125 MHz, CDCl3) δ 170.4, 170.2, 169.8, 168.6 (C=O), 151.1, 141.3 (C-arom), 71.8 (C-1), 68.9 (C-2), 67.8 (C-3), 67.6 (C-4), 62.0 (C-5), 20.7, 20.6, 20.6, 19.9 (CH3). Anal. Calc. for C34H44N2O20: C, 51.00; H, 3.50; N, 6.95. Found: C, 49.83; H, 3.60; N, 6.87. HRMS [M+H]+ calculated for C34H45N2O20: 801.2560; found: 801,2593; [M+Na]+ calculated for C34H44N2O20Na: 823.2380; found: 823.2399; [M+K]+ calculated for C34H44N2O20K: 839.2119; found: 839.2129.
2-[(E,E
)-Cinnamylideneamino]-2-deoxy-β-d-glucopyranose (
45) [
19]. Method 2 (40%); M.p. 173–175 °C; [α]
D +31.2°; [α]
578 +31.8°; [α]
546 +37.8°; [α]
436 +114.0° (
c 0.5, pyridine); [Lit. [
47] M.p. 187 °C, [α]
546 +57.6° (pyridine)]; IR (KBr)
max/cm
−1 3000–2922 (OH), 1632 (C=N), 1630 (C=C), 1096, 1010 (C-O), 758, 694, 631 (arom);
1H NMR (400 MHz, DMSO-
d6) δ 7.93 (1H, d,
J=CH-CH 8.8 Hz, N=C
H-CH), 7.59 (2H, d,
J 7.3 Hz H-arom), 7.36 (3H, m, H-arom), 7.11 (1H, d,
JCH=CH 16.1 Hz, CH=C
H-Ar), 6.90 (1H, dd,
JCH=CH 16.1 Hz,
JCH-CH 8.8 Hz, CH-C
H=CH), 6.56 (1H, d,
JC1,OH 6.7 Hz C1-OH), 4.95 (1H, d,
JC3,OH 4.7 Hz, C3-OH), 4.85 (1H, d,
JC4,OH 5.4 Hz, C4-OH), 4.64 (1H, d,
J1,2 7.7 Hz, H-1), 4.56 (1H, t,
JC6,OH 5.3 Hz, C6-OH), 3.72 (1H, dd,
J6,6′ 11.4 Hz,
J5,6 3.1 Hz, H-6), 3.47 (1H, m,
J6,6′ 11.9 Hz,
J5,6′ 5.8 Hz, H-6′), 3.36 (1H, m, H-3), 3.21 (1H, m,
J5,6′ 1.5 Hz,
J5,6 5.7 Hz, H-5), 3.13 (1H, dt,
J3,4 ≈
J4,5 9.0 Hz,
JC4-OH 4.2 Hz, H-4), 2.71 (1H, t,
J1,2 ≈
J2,3 8.5 Hz, H-2);
13C{
1H} NMR (100 MHz, DMSO-
d6) δ 163.9 (C=N), 141.4 (2C, CH=CH), 136.8, 129.1, 128.6, 127.4 (2 C-arom), 95.8 (C-1), 78.6 (C-2), 77.1 (C-5), 74.8 (C-3), 70.5 (C-4), 61.5 (C-6). Anal. Calcd. for C
15H
19NO
5: C, 61.42, H, 6.53, N, 4.78. Found: C, 61.20, H, 6.59, N, 4.86.
2-Deoxy-2-[(E,E
)-(4-nitrocinnamylidene)amino]-β-d-glucopyranose (
46) [
20]. Method 2 (49%). M.p. 196–198 °C; [α]
D +31.2°; [α]
578 +31.8°; [α]
546 +37.8°; [α]
436 +114.0° (
c 0.5, pyridine); [Lit. [
47] M.p. 172–173 °C]; IR (KBr)
max/cm
−1 3545 (OH), 1634 (C=N), 1510 (arom), 1072, 1013 (C-O), 829, 750 (arom);
1H NMR (400 MHz, DMSO-
d6) δ 8.21 (2H, d,
J 8.7 Hz, H-arom), 7.99 (1H, d,
J=CH-CH 8.6 Hz, N=CH-CH), 7.87 (2H, d,
J 8.7 Hz, H-arom), 7.26 (1H, d,
J 16.1 Hz, CH=CH-Ar), 7.11 (1H, dd,
J 8.7 Hz,
JCH=CH 16.1 Hz, CH-CH=CH), 6.61 (1H, d,
JC1-OH 6.7 Hz, C1-OH), 4.98 (1H, d,
JC4-OH 5.2 Hz, C4-OH), 4.90 (1H, d,
JC3-OH 5.7 Hz, C3-OH), 4.68 (1H, t,
J1,2 7.2 Hz, H-1), 4.58 (1H, t,
JC6-OH 5.7 Hz, C6-OH), 3.72 (1H, dd,
J6,6′ 10.2 Hz,
J5,6 5.4 Hz, H-6), 3.48 (1H, m, H-6′, H-3), 3.23 (1H, m, H-5), 3.15 (1H, m, H-4), 2.76 (1H, t,
J1,2 ≈
J2,3 8.5 Hz, H-2);
13C{
1H} NMR (100 MHz, DMSO-
d6) δ 163.5 (C=N), 147.4, 142.6 (C-arom), 138.9 (CH=CH), 132.7, 128.4 (C-arom), 124.2 (CH=CH), 95.7 (C-1), 78.7 (C-2), 77.1 (C-5), 74.7 (C-3), 70.4 (C-4), 61.4 (C-6). Anal. Calcd. for C
15H
18N
2O
7: C, 53.25, H, 5.36, N, 8.28. Found: C, 53.03, H, 5.55, N, 8.36.
2-Deoxy-2-[(E,E)-(2-methoxycinnamylidene)amino]-β-d-glucopyranose (47). Method 2 (94%); M.p. 184–185 °C; [α]D −7.4°; [α]578 −8.4°; [α]546 −7.6°; [α]436 +2.4° (c 0.5, pyridine); IR (KBr) max/cm−1 3500–2800 (OH), 1635 (C=N), 1598 (CH=CH), 1488, 1462 (arom), 1249, 1160 (C-O-C, ester), 1079, 1024, 985 (C-O), 898, 754 (arom); 1H NMR (400 MHz, DMSO-d6) δ 7.92 (1H, d, J=CH-CH 8.9 Hz, N=CH-CH), 7.60 (1H, dd, J 7.7 Hz, J 1.2 Hz, H-arom), 7.33 (1H, dt, J 7.7 Hz, J 1.4 Hz, H-arom), 7.26 (1H, d, JCH=CH 16.2 Hz, CH=CH-Ar), 6.97 (1H, t, J 7.5 Hz, H-arom), 6.90 (1H, dd, JCH=CH 16.2 Hz, JCH-CH 8.9 Hz, CH-CH=CH), 6.55 (1H, d, JC1,OH 6.8 Hz, C1-OH), 4.96 (1H, d, JC3-OH 5.2 Hz, C3-OH), 4.84 (1H, d, JC4-OH 5.8 Hz, C4-OH), 4.63 (1H, d, J1,2 7.3 Hz, H-1), 4.57 (1H, t, JC6-OH 5.8 Hz, C6-OH), 3.85 (3H, s, OCH3), 3.71 (1H, ddd, J6,6′ 11.5 Hz, JC6,OH 5.5 Hz, J5,6 1.5 Hz, H-6), 3.47 (1H, dt, J6,6′ 11.6 Hz, JC6,OH ≈ J5,6′ 5.8 Hz, H-6′), 3.36 (1H, m, H-3), 3.18 (1H, m, J5,6 5.8 Hz, J5,6′ 1.6 Hz, H-5), 3.15 (1H, dt, J3,4 ≈ J4,5 8.9 Hz, JC4-OH 5.3 Hz, H-4), 2.70 (1H, t, J1,2 ≈ J2,3 8.5 Hz, H-2); 13C{1H} NMR (100 MHz, DMSO-d6) δ 164.4 (C=N), 157.2 (C-arom), 136.1 (CH=CH), 130.6, 129.2, 127.7, 124.3 (C-arom), 120.9 (CH=CH), 95.8 (C-1), 78.5 (C-2), 77.1 (C-5), 74.8 (C-3), 70.5 (C-4), 61.5 (C-6), 55.8 (OCH3). Anal. Calcd. for C16H21NO6: C, 59.43, H, 6.55, N, 4.33. Found: C, 58.83, H, 6.41, N, 4.44.
2-Deoxy-2-[(E,E
)-(4-hydroxy-3-methoxycinnamylidene)amino]-β-d-glucopyranose (
48) [
20]. Method 2 (97%). M.p. 202–204 °C; [α]
D +21.8°; [α]
578 +23.6°; [α]
546 +30.2° (
c 0.5, DMSO); IR (KBr)
max/cm
−1 3400–2800 (OH), 1635 (C=N), 1586 (CH=CH), 1520, 1441 (arom), 1294, 1204, 1155 (C-O-C, ester), 1086, 1029, 982 (C-O), 898, 754 (arom);
1H NMR (400 MHz, DMSO-
d6) δ 9.41 (1H, bs, OH-arom), 7.88 (1H, d,
J=CH-CH 8.9 Hz, N=C
H-CH), 7.15 (1H, d,
J 1.8 Hz H-arom), 6.97 (2H, m,
JCH=CH 16 Hz, H-arom, CH=C
H-Ar), 6.76 (2H, m, H-arom, CH-C
H=CH), 6.55 (1H, d,
JC1-OH 4.3 Hz, C1-OH), 4.97 (1H, bs, C3-OH), 4.85 (1H, bs, C4-OH), 4.62 (1H, bs, H-1), 4.58 (1H, bs, C6-OH), 3.80 (3H, s, OCH
3), 3.72 (1H, d,
J6,6′ 11.0 Hz, H-6), 3.47 (1H, m, H-6′), 3.36 (1H, t,
J2,3 ≈
J3,4 8.9 Hz H-3), 3.20 (1H, m, H-5), 3.15 (1H, q,
J3,4 ≈
J4,5 9.1 Hz, H-4), 2.69 (1H, t,
J1,2 ≈
J2,3 8.4 Hz, H-2);
13C{
1H} NMR (50.3 MHz, DMSO-
d6) δ 164.2 (C=N), 148.2 (C-arom), 148.2 (C-arom), 141.8 (CH=CH), 127.7, 125., 121.6, 115.9 (C-arom), 110.5 (CH=CH), 95.9 (C-1), 78.4 (C-2), 77.1 (C-5), 75.0 (C-3), 70.5 (C-4), 61.5 (C-6), 55.9 (OCH
3). Anal. Calcd. for C
16H
21NO
7: C, 56.63, H, 6.50, N, 4.17. Found: C, 56.07, H, 6.50, N, 4.12.
2-[(E,E)-Cinnamylideneamino]-2-deoxy-β-d-glycero-l-gluco-heptopyranose (49). Method 2 (25%). M.p. 159–161 °C; [α]D −22.0°; [α]578 −23.4°; [α]546 −27.6°; [α]436 −67.4° (c 0.5, pyridine); IR (KBr) max/cm−1 3300 (OH), 1634 (C=N, C=C, arom), 1082, 1018 (C-O), 868, 750, 586 (arom); 1H NMR (400 MHz, CDCl3) δ 7.92 (1H, d, J=CH-CH 8.8 Hz, N=CH-CH), 7.60 (2H, d, J 7.2 Hz H-arom), 7.37 (3H, m, H-arom), 7.11 (1H, d, JCH=CH 16.1 Hz, CH=CH-Ar), 6.91 (1H, dd, JCH=CH 16.1 Hz, JCH-CH 8.8 Hz, -CH=CH-Ar), 6.46 (1H, d, J1,OH 7.1, OH-1), 4.81 (1H, d, J3,OH 5.1 Hz, OH-3), 4.77 (1H, d, J4,OH 5.4 Hz, OH-4), 4.60 (1H, t, J1,2 ≈ J1,OH 7.5 Hz, H-1), 4.46 (1H, t, J7,OH 5.7 Hz, OH-7), 4.24 (1H, d, J6,OH 6.8 Hz, OH-6), 3.42 (5H, m, H-3, H-4, H-6, H-7, H-7′), 3.24 (1H, dd, J4,5 9.1 Hz, J5,6 0.82 Hz, H-5), 2.70 (1H, t, J1,2 ≈ J2,3 8.3 Hz, H-2); 13C{1H} NMR (100 MHz, DMSO-d6) δ 163.8 (C=N), 141.3 (2C=C), 136.0 (C-arom), 129.3 (C-arom), 129.1 (2 C-arom), 128.6 (C-arom), 127.4 (C-arom), 96.2 (C-1), 78.6 (C-2), 75.1 (C-3), 74.7 (C-5), 69.3 (C-4), 68.9 (C-6), 62.7 (C-7). Anal. Calculated. for C16H21NO6: C, 59.43; H, 6.55; N, 4.33. Found: C, 59.67; H, 6.32; N, 4.21.
2-Deoxy-2-[(E)-(1-naphthylmethylene)amino]-β-d-glucopyranose (50). Method 2 (42%). M.p. 99–100 °C; [α]D +37.0°; [α]578 +39.4°; [α]546 +46.8°; [α]436 +93.8° (c 0.5, pyridine); IR (KBr) max/cm−1 3339 (OH), 1638 (C=N, arom), 1512 (arom), 1236 (C-O-C), 1078 (C-O), 874, 773 (arom); 1H NMR (400 MHz, DMSO-d6) δ 9.07 (1H, d, J 8.3 Hz, H-arom), 8.81 (1H, s, N=CH), 7.99 (2H, m, H-arom), 7.92 (1H, d, J 7.1 Hz, H-arom), 7.59 (3H, m, H-arom), 6.64 (1H, d, JC1-OH 4.3 Hz, C1-OH), 5.00 (1H, d, JC4-OH 5.1 Hz, C4-OH), 4.94 (1H, d, JC3-OH 5.6 Hz, C3-OH), 4.85 (1H, t, J1,2 6.3 Hz, H-1), 4.61 (1H, t, JC6-OH 5.6 Hz, C6-OH), 3.77 (1H, dd, J6,6′ 10.9 Hz, J5,6 0 Hz, J6,OH 4.9 Hz, H-6), 3.53 (2H, m, J2,3 9.0 Hz, H-3, H-6′), 3.31 (1H, m, J5,6′ 1.2 Hz, J6,OH 5.5 Hz, H-5), 3.22 (1H, m, JC4-OH 4.9 Hz, J3,4 8.9 Hz, H-4), 2.98 (1H, t, J1,2 = J2,3 8.5 Hz, H-2); 13C{1H} NMR (100 MHz, DMSO-d6) δ 162.38 (N=C), 133.7, 131.7, 131.0, 130.9, 129.5, 128.8, 127.3, 126.4, 125.6, 125.1 (C-arom), 96.0 (C-1), 79.4 (C-2), 77.2 (C-5), 74.9 (C-3), 70.6 (C-4), 61.5 (C-6). Anal. Calculated for C17H19NO5: C, 64.34, H, 6.03, N, 4.41. Found: C, 64.12; H, 5.87; N. 4.37.
2-Deoxy-2-[(E)-(4-methoxy-1-naphthylmethylene)amino]-β-d-glucopyranose (51). Method 2 (15%). M.p. 140–142 °C; [α]578 +11.0°; [α]546 +12.4° (c 0.5, pyridine); IR (KBr) max/cm−1 3379 (OH), 1634 (C=N), 1578 (arom), 1097, 1011 (C-O), 764 (arom); 1H NMR (400 MHz, DMSO-d6) δ 9.24 (1H, s, arom), 8.64 (1H, s, N=CH), 8.22 (1H, d, J 8.5 Hz, arom), 7.83 (1H, d, J 8.1 Hz, arom), 7.63 (1H, t, J 7.7 Hz, arom), 7.55 (1H, t, J 7.3 Hz, arom), 7.06 (1H, d, J 8.1 Hz, arom), 6.58 (1H, d, JC1-OH 6.7 Hz, C1-OH), 4.94 (1H, d, JC4-OH 5.3 Hz, C4-OH), 4.87 (1H, d, JC3-OH 5.7 Hz, C3-OH), 4.80 (1H, d, J1,2 7.2 Hz, H-1), 4.57 (1H, t, JC6-OH 5.8 Hz, C6-OH), 4.03 (3H, s, OCH3), 3.74 (1H,dd, J6,6′ 10.2 Hz, JC6-OH 5.4 Hz, J6,5 1.3 Hz, H-6), 3.53 (2H, m, J6,6′ 10.1 Hz, JC6-OH 5.4 Hz, H-3, H-6′), 3.27 (1H, m, H-5), 3.20 (1H, m, JC4-OH 5.3 Hz, H-4), 2.88 (1H, dd~t, J1,2 = J2,3 8.5 Hz, H-2); 13C{1H} NMR (100 MHz, DMSO-d6) δ 162.5 (N=C), 156.8 (C-arom), 131.9 (C-arom), 131.9 (C-arom), 126.8 (C-arom), 125.8 (C-arom), 125.5 (C-arom), 125.1 (C-arom), 124.3 (C-arom), 122.0 (C-arom), 104.4 (C-arom), 96.0 (C-1), 79.4 (C-2), 77.2 (C-5), 75.1 (C-3), 70.6 (C-4), 61.5 (C-6), 56.1 (OCH3). Anal. Calcd. for C18H21NO6: C, 62.24, H, 6.09, N, 4.03. Found: C, 62.08, H, 6.13, N, 4.10.
2-Deoxy-2-[(E)-(4-methoxy-1-naphthylmethylene)]amino-α-d-glucopyranose (52). Method 2 (57%). [α]D +127.0°; [α]578 +134.0°; [α]546 +157.4°; [α]436 +30.7° (c 0.5, pyridine); 1H NMR (400 MHz, DMSO-d6) δ 9.32 (1H, s, arom), 8.99 (1H, s, N=CH), 8.22 (1H, d, J 8.2 Hz, arom), 7.85 (1H, d, J 8.1 Hz, arom), 7.62 (1H, t, J 7.3 Hz, arom), 7.55 (1H, t, J 7.4 Hz, arom), 7.23 (1H, d, J 10.5 Hz, arom), 6.28 (1H, d, JC1,OH 4.3 Hz, C1-OH), 5.00 (1H, t, J1,2 3.6 Hz, H-1), 4.91 (1H, d, JC4,OH 5.3 Hz, C4-OH), 4.72 (1H, d, JC3,OH 5.6 Hz, C3-OH), 4.48 (1H, t, JC6,OH 5.8 Hz, C6-OH), 4.03 (3H, s, OCH3), 3.89 (1H, dt, JC3,OH 5.7 Hz, J3,4 ≈ J2,3 9.2 Hz, H-3), 3.78 (1H, dd, J6,6′ 9.8 Hz, JC6,OH 5.4 Hz, H-6), 3.69 (1H, dd, J6,6′ 11.6 Hz, JC6,OH 5.4 Hz, H-6′), 3.53 (1H, m, H-5), 3.22 (1H, dt, JC4,OH 5.4, J4,5 ≈ J3,4 9.2 Hz, H-4), 3.15 (1H, dd, J1,2 3.3 Hz, J2,3 9.7 Hz, H-2); 13C{1H} NMR (100 MHz, DMSO-d6) δ 162.5 (N=C), 156.8 (C-arom), 131.9 (C-arom), 131.9 (C-arom), 126.8 (C-arom), 125.8 (C-arom), 125.5 (C-arom), 125.1 (C-arom), 124.3 (C-arom), 122.0 (C-arom), 104.4 (C-arom), 93.4 (C-1), 75.5 (C-2), 72.7 (C-5), 71.4 (C-3), 71.2 (C-4), 61.5 (C-6), 56.1 (OCH3). Anal. Calcd. for C18H21NO6: C, 62.24, H, 6.09, N, 4.03. Found: C, 62.34, H, 6.01, N, 3.87.
2-Deoxy-2-[(E)-(2-naphthylmethylene)amino]-β-d-glucopyranose (53). Method 2 (75%). [α]D +16.0°; [α]578 +17.0°; [α]546 +20.6°; [α]436 +47.6° (c 0.5, pyridine); IR (KBr) max/cm−1 3373 (OH), 1635 (C=N, arom), 1014 (C-O), 831, 752 (arom); 1H NMR (400 MHz, DMSO-d6) δ 8.38 (1H, s, N=CH), 8.20 (1H, s, H-arom), 8.00 (2H, m, H-arom), 7.94 (2H, m, H-arom), 7.56 (1H, m, H-arom), 6.65 (1H, d, JC1-OH 6.7 Hz, C1-OH), 5.01 (1H, d, JC4-OH 5.2 Hz, C4-OH), 4.94 (1H, d, JC4-OH 5.6 Hz, C3-OH), 4.80 (1H, t, J1,2 7.3 Hz, H-1), 4.62 (1H, t, JC6-OH 5.8 Hz, C6-OH), 3.77 (1H, dd, J5,6 0 Hz, J6,OH 5.3 Hz, J6,6′ 10.3 Hz, H-6), 3.52 (2H, m, H-3, H-6′), 3.30 (1H, m, J5,6′ 1.5 Hz, H-5), 3.22 (1H, dd, JC4-OH 5.1 Hz, J3,4 ≈ J4,5 8.9 Hz, H-4), 2.95 (1H, t, J1,2 ≈ J2,3 8.5 Hz, H-2); 13C{1H} NMR (100 MHz, DMSO-d6) δ 162.3 (N=C), 134.2 (C-arom), 134.1 (C-arom), 132.9 (C-arom), 129.9 (C-arom), 128.7 (C-arom), 128.3 (C-arom), 128.0 (C-arom), 127.4 (C-arom), 126.8 (C-arom), 124.1 (C-arom), 95.8 (C-1), 78.6 (C-2), 77.1 (C-5), 74.7 (C-3), 70.5 (C-4), 61.5 (C-6). Anal. Calcd. for C17H19NO5: C, 64.34, H, 6.03, N, 4.41. Found: C, 64.49; H, 5.97; N. 4.33.
2-Deoxy-2-[(E)-(2-naphthylmethylene)amino]-α-d-glucopyranose (54). Method 2 (46%). M.p. 197–199 °C; [α]D +93.0°; [α]578 +97.2°; [α]546 +114.4°; [α]436 +229.6° (c 0.5, pyridine); IR (KBr) max/cm−1 3374 (OH), 1636 (C=N), 1410 (arom), 1148, 1015 (C-O), 831, 752 (arom); 1H NMR (400 MHz, DMSO-d6) δ 8.49 (1H, s, N=CH), 8.20 (1H, s, H-arom), 8.00 (2H, m, H-arom), 7.94 (2H, m, H-arom), 7.56 (1H, m, H-arom), 6.29 (1H, d, JC1,OH 4.3 Hz, C1-OH), 5.01 (1H, t, J1,2 3.8 Hz, H-1), 4.96 (1H, d, JC4,OH 5.4 Hz, C4-OH), 4.78 (1H, d, JC3,OH 5.7 Hz, C3-OH), 4.50 (1H, t, JC6,OH 5.8 Hz, OH-6), 3.87 (1H, dt, JC3,OH 5.6 Hz, J3,4 ≈ J2,3 9.1 Hz, H-3), 3.80 (1H, ddd, JC6,OH 5.4 Hz, J5,6 1.8 Hz, J6,6′ 9.8 Hz, H-6), 3.70 (1H, dd, J4,5 9.5 Hz, J5,6 1.8 Hz, H-5), 3.57 (1H, m, J4,5 ≈ J3,4 9.3 Hz JC4,OH 5.6 Hz H-4), 3.22 (1H, dd, J1,2 3.3 Hz, J2,3 9.9 Hz, H-2); 13C{1H} NMR (100 MHz, DMSO-d6) δ 162.3 (N=C), 134.3 (C-arom), 134.2 (C-arom), 132.9 (C-arom), 130.1 (C-arom), 128.7 (C-arom), 128.3 (C-arom), 128.0 (C-arom), 127.4 (C-arom), 126.8 (C-arom), 124.1 (C-arom), 93.1 (C-1), 75.4 (C-2), 72.7 (C-5), 71.1 (C-3), 71.0 (C-4), 61.5 (C-6). Anal. Calcd. for C17H19NO5: C, 64.34, H, 6.03, N, 4.41. Found: C, 64.12, H, 6.09, N, 4.47.
2-Deoxy-2-[(E)-(9-phenantrylmethylene)amino]-β-d-glucopyranose (55). Method 2 (41%). M.p. 156–158 °C; [α]D +41.6°; [α]578 +44.2°; [α]546 +51.6°; [α]436 +115.6° (c 0.5, pyridine); IR (KBr) max/cm−1 3358 (OH), 1645 (C=N, arom), 1450 (arom), 1078, 1037 (C-O), 723 (arom); 1H NMR (400 MHz, DMSO-d6) δ 9.26 (1H, dd, J 8.0 Hz, J 1.4 Hz, H-arom), 8.90 (1H, d, J 9.0 Hz, H-arom), 8.85 (1H, d, J 8.3 Hz, H-arom), 8.83 (1H, s, H-arom), 8.26 (1H, s, N=CH), 7.73 (4H, m, H-arom), 6.68 (1H, d, JC1-OH 6.9 Hz, C1-OH), 5.00 (1H, m, JC4-OH 5.31 Hz, C4-OH), 4.98 (1H, d, JC3-OH 5.75 Hz, C3-OH), 4.87 (1H, t, J1,2 7.3 Hz, H-1), 4.61 (1H, t, JC6-OH 5.8 Hz, C6-OH), 3.78 (1H, dd, J6,6′ 9.9 Hz, J5,6 1.4 Hz, H-6), 3.56 (2H, m, H-3, H-6′), 3.32 (1H, m, J5,6 1.8 Hz, H-5), 3.25 (1H, m, JC4,OH 4.7 Hz, J3,4 8.9 Hz, H-4), 3.01 (1H, t, J1,2 = J2,3 8.5 Hz, H-2); 13C{1H} NMR (50.3 MHz, DMSO-d6) δ 162.8 (C=N), 131.5, 130.8, 130.4, 130.3, 129.6, 129.5, 128.5, 127.4, 127.4, 127.2, 126.2, 123.1 (C-arom), 95.9 (C-1), 79.5 (C-2), 77.2 (C-5), 74.9 (C-3), 70.6 (C-4), 61.5 (C-6). Anal. Calcd. for C21H21O5N: C, 68.65, H, 5.76, N, 3.81. Found: C, 68.42; H, 5.54; N, 3.85.
2-[(E)-(9-Antrylmethylene)amino]-2-deoxy-β-d-glucopyranose (56). Method 2 (80%). M.p. 162–164 °C; [α]578 +3.0°; [α]546 –5.0° (c 0.5, pyridine); IR (KBr) max/cm−1 3401 (OH), 1649 (C=N), 1570, 1452 (arom), 1099, 1028 (C-O), 897, 731 (arom); 1H NMR (400 MHz, DMSO-d6) δ 9.31 (1H, s, N=CH), 8.66 (1H, s, arom), 8.60 (2H, d, arom), 8.12 (2H, dd, arom), 7.54 (4H, dd, arom), 4.88 (1H, d, J1,2 7.7 Hz, H-1), 3.78 (1H, d, J6,6′ 11.4 Hz, H-6), 3.65–3.38 (4H, m, H-3, 4, 5, 6′), 3.27 (1H, t, J1,2 = J2,3 8.6 Hz, H-2); 13C{1H} NMR (100 MHz, DMSO-d6) δ 161.6 (N=C), 131.0 (2C-arom), 129.7 (C-arom), 129.4 (2 C-arom), 128.7 (2 C-arom), 128.6 (C-arom), 126.6 (3 C-arom), 125.7 (3 C-arom), 95.8 (C-1), 79.6 (C-2), 77.3 (C-5), 74.6 (C-3), 70.8 (C-4), 61.4 (C-6). Anal. Calcd. for C21H21NO5: C, 68.65, H, 5.76, N, 3.81. Found: C, 68.39; H, 5.92; N. 3.75.
2-Deoxy-2-[(E)-(10-methyl-9-antrylmethylene)amino]-β-d-glucopyranose (57). Method 2 (35%). M.p. 219–221 °C; [α]D +1.6°; [α]578 +0.6°; [α]546 +0.4° (c 0.5, pyridine); IR (KBr) max/cm−1 3414 (OH), 1659 (C=N), 1444 (arom), 1099, 1036 (C-O), 893, 750 (arom); 1H NMR (400 MHz, DMSO-d6) δ 9.23 (1H, s, CH=N), 8.58 (2H, d, J 8.5 Hz, H-arom), 8.39 (2H, d, J 8.7 Hz, H-arom), 7.56 (4H, m, H-arom), 6.88 (1H, d, JC1-OH 7.2 Hz, C1-OH), 5.19 (1H, d, JC4-OH 6.4 Hz, C4-OH), 5.06 (1H, d, JC3-OH 4.7 Hz, C3-OH), 4.89 (1H, t, J1,2 7.5 Hz, H-1), 4.65 (1H, t, JC6-OH 5.8 Hz, C6-OH), 3.80 (1H, dd, J6,6′ 11.1 Hz, J6,OH 5.8 Hz, H-6), 3.64 (1H, m, J2,3 ≈ J3,4 8.3 Hz, H-3), 3.56 (1H, m, J6,6′ 11.6 Hz, JC6-OH 5.8 Hz, H-6′), 3.32 (2H, m, H-4, H-5), 3.26 (1H, t, J1,2 ≈ J2,3 8.5 Hz, H-2), 3.10 (3H, s, CH3); 13C{1H} NMR (50.3 MHz, DMSO-d6) δ 162.2 (N=C), 132.3, 129.4, 129.0, 128.7, 126.5, 126.0, 125.7, 125.3 (C-arom), 95.9 (C-1), 79.8 (C-2), 77.4 (C-5), 74.7 (C-3), 70.9 (C-4), 61.5 (C-6), 14.4 (CH3). Anal. Calcd. for C22H23NO5: C, 69.28, H, 6.08, N, 3.67. Found: C, 69.04, H, 5.97, N, 3.61.
2-Deoxy-2-[(E)-(9-antrylmethylene)amino]-β-d-glycero-l-gluco-heptopyranose (58). Method 2 (48%). M.p. 161–163 °C; [α]578 −5.8°; [α]546 6.3° (c 0.5, pyridine); IR (KBr) max/cm−1 3256 (OH), 1644 (C=N), 1445 (arom), 1074, 1018 (C-O), 876, 733 (arom); 1H NMR (400 MHz, DMSO-d6) δ 9.26 (1H, s, CH=N), 8.67 (1H, s, H-arom), 8.59 (2H, m, H-arom), 8.12 (2H, d, J 5.0 Hz, H-arom), 7.55 (4H, m, H-arom), 6.77 (1H, d, J1,OH 7.3 Hz, OH-1), 5.09 (1H, d, J3,OH 5.2 Hz, OH-3), 4.90 (1H, d, J4,OH 4.0 Hz, OH-4), 4.84 (1H, t, J1,2 ≈ J1,OH 7.6 Hz, H-1), 4.50 (1H, t, J7,OH 5.2 Hz, OH-7), 4.32 (1H, d, J6,OH 6.7 Hz, OH-6), 3.85 (1H, c, J6,7 ≈ J6,7′ ≈ J6,OH 6.5 Hz, H-6), 3.61 (2H, m, H-3, H-4), 3.50 (2H, m, H-7, H-7′), 3.37 (1H, m, H-5), 3.24 (1H, t, J1,2 ≈ J2,3 8.2 Hz, H-2); 13C{1H} NMR (100 MHz, DMSO-d6) δ 161.6 (C=N), 131.0 (2 C-arom), 129.7 (2 C-arom), 129.4 (2 C-arom), 128.8 (2 C-arom), 128.6 (2 C-arom), 126.7 (2 C-arom), 125.8 (3 C-arom), 96.2 (C-1), 79.8 (C-2), 75.0 (C-3), 74.9 (C-5), 69.7 (C-4), 69.0 (C-6), 63.0 (C-7). Anal. Calcd. for C22H23NO6·2H2O: C, 60.96, H, 6.28, N, 3.23. Found: C, 60.77, H, 6.32, N, 3.33.
4.4.2. Synthesis of Acetyl Derivatives
As general protocol, acetic anhydride (9.0 mL) was added to a suspension of the corresponding 2-(arylmethylene)amino-2-deoxy-β-d-aldopyranose (7.1 mmol) in pyridine (9.4 mL) with stirring and external cooling, and the mixture was left at room temperature until dissolution. Then, it was poured into ice-water (ca. 300 mL) with stirring. The solid formed was collected by filtration and washed repeatedly with cold water and dried over silica gel.
1,3,4,6-Tetra-O
-acetyl-2-deoxy-2-[(E
)-(phenylmethylene)amino]-β-d-glucopyranose (
63). From
30 (35%). M.p. 162–164 °C; [α]
D +89.0°; [α]
578 +93.2°; [α]
546 +109.4°, [α]
436 +216.4° (
c 0.5, chloroform) (Lit. [
13] m.p. 160–162 °C, [α]
D +79.0° (c 0.5, chloroform)); IR (KBr)
max/cm
−1 1752 (C=O), 1646 (C=N), 1581 (arom.), 1216 (C-O-C), 1083, 1055, 1055 (C-O), 755, 690 (arom.);
1H NMR (500 MHz, Cl
3CD) δ 8.24 (1H, s, CH=), 7.71 (2H, d,
J 7.0 Hz, arom), 7.46 (1H, t,
J 7.0 Hz, arom), 7.40 (2H, t,
J 7.0 Hz, arom), 5.97 (1H, d,
J1,2 8.0 Hz, H-1), 5.46 (1H, t,
J2,3 =
J3,4 10.0 Hz, H-3), 5.15 (1H, t,
J3,4 =
J4,5 10.0 Hz, H-4), 4.38 (1H, dd,
J5,6 4.5 Hz,
J6,6′ 12.5 Hz, H-6), 4.14 (1H, dd,
J5,6′ 2.0 Hz,
J6,6′ 12.5 Hz, H-6′), 3.99 (1H, ddd,
J4,5 10.0 Hz,
J5,6 4.5 Hz,
J5,6′ 2.0 Hz, H-5), 3.50 (1H, dd~t,
J1,2 8.0 Hz,
J2,3 10.0 Hz, H-2), 2.10, 2.04, 2.02, 1.89 (4 × 3H, s, CH
3);
13C{
1H} NMR (125 MHz, Cl
3CD) δ 170.7 (C=O), 169.9 (C=O), 169.5 (C=O), 168.8 (C=O), 165.2 (CH=N), 135.3 (C-arom), 131.6 (C-arom), 128.7 (2 C-arom), 128.6 (2 C-arom), 93.1 (C-1), 73.1, 73.0 and 72.8 (C-2, C-3, C-5), 68.0 (C-4), 61.8 (C-6), 20.8, 20.8, 20.7, 20.5 (CH
3). Anal. Calc. for C
21H
25O
9N: C, 57.93, H, 5.79, N, 3.22. Found: C, 58.06, H, 5.58, N, 3.01. HRMS [M+H]
+ calculated for C
21H
26NO
9: 436.1608; Found: 436.1618; [M
2+Na]
+ calculated for C
42H
50N
2O
18Na: 893.2956. Found: 893.2990.
1,3,4,6-Tetra-O-acetyl-2-deoxy-2-[(E)-(3-fluorophenylmethylene)amino]-β-d-glucopyranose (64). From 31, we obtained 64. This reaction was conducted at −10 °C (37%); M.p.: 150–152 °C; [α]D +87.0°; [α]578 +90.4°; [α]546 +105.4°, [α]436 +211.0° (c 0.5, chloroform); IR (KBr) max/cm−1 1755 (C=O), 1648 (C=N), 1587 (arom.), 1216 (C-O-C), 1081, 1057, 1033 (C-O), 788 (arom.); 1H NMR (500 MHz, Cl3CD) δ 8.22 (1H, s, CH=), 7.45 (2H, m, arom), 7.39 (1H, m, arom), 7.16 (1H, m, arom), 5.96 (1H, d, J1,2 8.5 Hz, H-1), 5.45 (1H, t, J2,3 = J3,4 10.0 Hz, H-3), 5.15 (1H, t, J3,4 = J4,5 10.0 Hz, H-4), 4.39 (1H, dd, J5,6 4.5 Hz, J6,6′ 12.5 Hz, H-6), 4.14 (1H, dd, J5,6′ 2.0 Hz, J6,6′ 12.5 Hz, H-6′), 3.99 (1H, ddd, J4,5 10.0 Hz, J5,6 4.5 Hz, J5,6′ 2.0 Hz, H-5), 3.51 (1H, dd~t, J1,2 8.0 Hz, J2,3 10.0 Hz, H-2), 2.10, 2.04, 2.03, 1.90 (4 × 3H, s, CH3); 13C{1H} NMR (125 MHz, Cl3CD) δ 170.9 (C=O), 167.0 (C=O), 169.5 (C=O), 168.7 (C=O), 163.8 (4JC,F = 2.5 Hz, CH=N), 163.0 (1JC,F = 246.3 Hz, C3 arom), 137.5 (3JC,F = 7.5 Hz, C1 arom), 130.3 (3JC,F = 7.5 Hz, C5 arom), 124.7 (4JC,F = 2.5 Hz, C6 arom), 118.6 (2JC,F = 21.3 Hz, C4 arom), 114.7 (2JC,F = 21.3 Hz, C2 arom), 93.0 (C-1), 73.0 (C-2), 72.8 (2C, C-3, C-5), 68.0 (C-4), 61.8 (C-6), 20.8, 20.8, 20.7, 20.5 (CH3). HRMS [M+H]+ calculated for C21H25NO9F: 454.1513; Found: 454.1513; [M2+Na]+ calculated for C42H50N2O18Na: 929.2768. Found: 929.2766.
1,3,4,6-Tetra-O-acetyl-2-deoxy-2-[(E)-(3-bromophenylmethylene)amino]-β-d-glucopyranose (65). From 32 we obtained 65 (71%); M.p.: 113–115 °C; [α]D +75.4°; [α]578 +78.8°; [α]546 +93.0°, [α]436 +189.0° (c 0.5, chloroform); IR (KBr) max/cm−1 1744 (C=O), 1646 (C=N), 1564, 1381 (arom.), 1223 (C-O-C), 1064, 1034 (C-O), 794 (arom.); 1H NMR (500 MHz, Cl3CD) δ 8.18 (1H, s, CH=), 7.87 (1H, t, J 1.5 Hz, arom), 7.63 (1H, d, J 7.5 Hz, arom), 7.58 (1H, d, J 7.5 Hz, arom), 7.29 (1H, t, J 7.5 Hz, arom), 5.96 (1H, d, J1,2 8.5 Hz, H-1), 5.44 (1H, t, J2,3 = J3,4 9.5 Hz, H-3), 5.15 (1H, t, J3,4 = J4,5 9.5 Hz, H-4), 4.39 (1H, dd, J5,6 4.5 Hz, J6,6′ 12.0 Hz, H-6), 4.14 (1H, dd, J5,6′ 2.0 Hz, J6,6′ 12.0 Hz, H-6′), 3.99 (1H, ddd, J4,5 9.5 Hz, J5,6 4.5 Hz, J5,6′ 2.0 Hz, H-5), 3.50 (1H, dd~t, J1,2 8.0 Hz, J2,3 9.5 Hz, H-2), 2.10, 2.04, 2.03, 1.90 (4× 3H, s, CH3); 13C{1H} NMR (125 MHz, Cl3CD) δ 170. 7 (C=O), 169.9 (C=O), 169.5 (C=O), 168.7 (C=O), 163.6 (CH=N), 137.2 (C-arom), 134.5 (C-arom), 131.3 (2 C-arom), 130.3 (C-arom), 127.2 (C-arom), 123.0 (C-arom), 92.9 (C-1), 73.0, 72.9 and 72.8 (C-2, C-3, C-5), 68.0 (C-4), 61.8 (C-6), 20.8, 20.8, 20.7, 20.5 (CH3). HRMS [M+H]+ calculated for C21H25NO9Br: 514.0713; Found: 514.0692.
1,3,4,6-Tetra-O-acetyl-2-deoxy-2-[(E)-(4-chlorophenylmethylene)amino]-β-d-glucopyranose (66). From 33, we obtained 66 (76%); M.p.: 177–180 °C; [α]D +96.2°; [α]578 +101.4°; [α]546 +118.2°, [α]436 +242.0° (c 0.5, chloroform); IR (KBr) max/cm−1 1752 (C=O), 1643 (C=N), 1597, 1573 (arom.), 1222 (C-O-C), 1088, 1062, 1035 (C-O), 824 (arom.); 1H NMR (500 MHz, Cl3CD) δ 8.20 (1H, s, CH=), 7.65 (2H, d, J 8.5 Hz, arom), 7.39 (2H, d, J 8.5 Hz, arom), 5.95 (1H, d, J1,2 8.5 Hz, H-1), 5.44 (1H, t, J2,3 = J3,4 10.0 Hz, H-3), 5.15 (1H, t, J3,4 = J4,5 10.0 Hz, H-4), 4.38 (1H, dd, J5,6 4.5 Hz, J6,6′ 12.5 Hz, H-6), 4.14 (1H, dd, J5,6′ 2.0 Hz, J6,6′ 12.5 Hz, H-6′), 3.98 (1H, ddd, J4,5 10.0 Hz, J5,6 4.5 Hz, J5,6′ 2.0 Hz, H-5), 3.49 (1H, dd~t, J1,2 8.5 Hz, J2,3 10.0 Hz, H-2), 2.10, 2.04, 2.03, 1.90 (4× 3H, s, CH3); 13C{1H} NMR (125 MHz, Cl3CD) δ 170.7 (C=O), 169.9 (C=O), 169.5 (C=O), 168.7 (C=O), 163.7 (CH=N), 137.7 (C-arom), 133.7 (C-arom), 129.8 (2 C-arom), 129.0 (C-arom), 93.0 (C-1), 73.0, 72.9 and 72.8 (C-2, C-3, C-5), 68.0 (C-4), 61.8 (C-6), 20.8, 20.7, 20.6, 20.5 (CH3). HRMS [M+H]+ calculated for C21H25NO9Cl: 470.1218; Found: 470.1216.
1,3,4,6-Tetra-O-acetyl-2-deoxy-2-[(E)-(4-piperidinylbenzylidene)amino]-β-d-glucopyranose (67). From 35, we obtained 67 (82%); M.p.: 153–155 °C; [α]D +113.6°; [α]578 +119.2°; [α]546 +142.0°, [α]436 +343.4° (c 0.5, chloroform); IR (KBr) max/cm−1 2954, 2872, 2811 (CH aliphatic), 1751 (C=O), 1637 (C=N), 1608, 1519 (arom.), 1366 (CH2), 1519 (arom.), 1220 (C-O-C), 1127, 1080, 1032 (C-O), 813 (arom.); 1H NMR (500 MHz, Cl3CD) δ 8.09 (1H, s, CH=), 7.57 (2H, d, J 9.0 Hz, arom), 6.87 (2H, d, J 9.0 Hz, arom), 5.93 (1H, d, J1,2 8.0 Hz, H-1), 5.42 (1H, t, J2,3 = J3,4 9.5 Hz, H-3), 5.14 (1H, t, J3,4 = J4,5 9.5 Hz, H-4), 4.38 (1H, dd, J5,6 4.5 Hz, J6,6′ 12.5 Hz, H-6), 4.13 (1H, dd, J5,6′ 2.0 Hz, J6,6′ 12.5 Hz, H-6′), 3.96 (1H, ddd, J4,5 10.0 Hz, J5,6 4.5 Hz, J5,6′ 2.0 Hz, H-5), 3.49 (1H, dd~t, J1,2 8.0 Hz, J2,3 10.0 Hz, H-2), 3.29 (4H, t, J 5.5 Hz, NCH2 piperidine), 2.10, 2.03, 2.02, 1.88 (4 × 3H, s, CH3), 1.68 (6H, m, CH2 piperidine); 13C{1H} NMR (125 MHz, Cl3CD) δ 170.7 (C=O), 169.9 (C=O), 169.6 (C=O), 168.8 (C=O), 164.6 (CH=N), 153.8 (C-arom), 130.0 (C-arom), 125.2 (2 C-arom), 114.5 (C-arom), 93.3 (C-1), 73.4 (C-3,), 73.1 (C-2), 72.7 (C-5), 68.1 (C-4), 62.0 (C-6), 49.1 (2C, NCH2), 25.5 (2C, CH2 piperidine), 24.3 (C, CH2 piperidine), 20.9, 20.8, 20.7, 20.6 (CH3). HRMS [M+H]+ calculated for C26H35N2O9: 519.2343; Found: 519.2354.
1,3,4,6-Tetra-O-acetyl-2-deoxy-2-[(E)-(4-morpholinylbenzylidene)amino]-β-d-glucopyranose (68). From 36, we obtained 68 (42%); M.p.: 182–184 °C; [α]D +120.2°; [α]578 +126.8°; [α]546 +151.4°, [α]436 +350.6° (c 0.5, chloroform); IR (KBr) max/cm−1 2970, 2917, 2876, 2823 (CH aliphatic), 1761, 1752 (C=O), 1638 (C=N), 1610, 1519 (arom.), 1366 (CH2), 1250, 1229 (C-O-C), 1080, 1058, 1035 (C-O), 825 (arom.); 1H NMR (500 MHz, Cl3CD) δ 8.12 (1H, s, CH=), 7.62 (2H, d, J 8.5 Hz, arom), 6.88 (2H, d, J 8.5 Hz, arom), 5.94 (1H, d, J1,2 8.0 Hz, H-1), 5.42 (1H, t, J2,3 = J3,4 10.0 Hz, H-3), 5.14 (1H, t, J3,4 = J4,5 10.0 Hz, H-4), 4.38 (1H, dd, J5,6 4.5 Hz, J6,6′ 12.5 Hz, H-6), 4.13 (1H, dd, J5,6′ 2.0 Hz, J6,6′ 12.5 Hz, H-6′), 3.97 (1H, ddd, J4,5 10.0 Hz, J5,6 4.5 Hz, J5,6′ 2.0 Hz, H-5), 3.86 (4H, t, J 5.0 Hz, CH2O), 3.43 (1H, dd~t, J1,2 8.0 Hz, J2,3 10.0 Hz, H-2), 3.26 (4H, t, J 5.0 Hz, CH2N), 2.10, 2.04, 2.02, 1.88 (4 × 3H, s, CH3); 13C{1H} NMR (125 MHz, Cl3CD) δ 170.7 (C=O), 169.9 (C=O), 169.6 (C=O), 168.8 (C=O), 164.4 (CH=N), 153.4 (C-arom), 130.0 (2 C-arom), 126.6 (C-arom), 114.3 (2 C-arom), 93.3 (C-1), 73.4 (C-2), 73.0, 72.8 (C-3, C-5), 68.1 (C-4), 66.7 (2C, CH2O), 61.9 (C-6), 48.1 (2C, CH2N), 20.8, 20.8, 20.7, 20.5 (CH3). HRMS [M+H]+ calculated for C25H33N2O10: 521.2135; Found: 521.2136; [M2+Na]+ calculated for C42H50N2O18Na: 929.2768. Found: 929.2766.
1,3,4,6,7-Penta-O
-acetyl-2-deoxy-2-[(E
)-(4-methoxybenzylidene)amino]-β-d-glycero
-l-gluco-
heptopyranose (
69) [
17]. (89%). M.p. 187–189 °C;
1H NMR (500 MHz, CDCl
3) δ 8.15 (1H, s, CH=N), 7.65 (2H, d,
J 8.5 Hz, arom), 6.91 (2H, d,
J 8.5 Hz, arom), 5.87 (1H, d,
J1,2 8.5 Hz, H-1), 5.42 (1H, t,
J2,3 =
J3,4 10.0 Hz, H-3), 5.36 (1H, m, H-6), 5.13 (1H, t,
J3,4 =
J4,5 10.0 Hz, H-4), 4.35 (1H, dd,
J6,7 5.0 Hz,
J7,7 11.5 Hz, H-7), 4.17 (1H, dd,
J6,7 8.0 Hz,
J7,7′ 11.5 Hz, H-7′), 4.01 (1H, dd,
J4,5 10.0 Hz,
J5,6 2.0 Hz, H-5), 3.84 (3H, s, OCH
3), 3.46 (1H, dd,
J1,2 8.5 Hz,
J2,3 9.0, H-2), 2.12, 2.06, 2.02, 2.01, 1.88 (5 × 3H, s, CH
3);
13C{
1H} NMR (125 MHz, CDCl
3) δ 170.5, 170.3, 167.0, 169.5, 168.6 (acetate), 164.3 (N=C), 162.3 (C-arom), 130.3 (2 C-arom) 128.3, 114.1 (2 C-arom), 93.6 (C-1), 73.4 (C-2), 73.0 (C-3), 72.9 (C-5), 67.2 (C-4), 66.8 (C-6), 62.1 (C-7), 55.4 (OCH
3), 20.8, 20.7, 20.7, 20.6, 20.5 (CH
3). HRMS [M+H]
+ calculated for C
25H
32NO
12: 538.1919. Found: 538.1929.
1,3,4,6,7-Penta-O-acetyl-2-deoxy-2-[(E)-(4-nitrobenzylidene)amino]-β-d-glycero-l-gluco-heptopyranose (70). (63%). M.p. 208–210 °C; [α]D −61.4°; [α]578 −64.6°; [α]546 −79.4°; [α]436 −191.2° (c 0.5, chloroform); IR (KBr) max/cm−1 1755 (C=O), 1646 (C=N), 1602, 1522 (arom), 1246, 1221 (C-O-C, ester), 1082, 1062, 1037 (C-O), 835 (arom); 1H NMR (500 MHz, CDCl3) δ 8.31 (1H, s, CH=N), 8.25 (2H, d, J 8.8 Hz, H-arom), 7.08 (2H, d, J 8.8 Hz, H-arom), 5.91 (1H, d, J1,2 9.0 Hz, H-1), 5.44 (1H, t, J2,3 = J3,4 9.0 Hz, H-3), 5.35 (1H, m, J5,6 2.0 Hz, J6,7 5.3 Hz, J6,7′ 7.5 Hz, H-6), 5.13 (1H, t, J3,4 = J4,5 10.0 Hz, H-4), 4.33 (1H, dd, J6,7′ 5.3 Hz, J7,7′ 12.5 Hz, H-7), 4.12 (1H, dd, J6,7′ 8.0 Hz, J7,7′ 12.5 Hz, H-7′), 3.97 (1H, dd, J4,5 10.0 Hz, J5,6 2.0 Hz, H-5), 3.56 (1H, t, J1,2 = J2,3 9.0 Hz, H-2), 2.10, 2.05, 2.02, 2.00, 1.87 (5 × 3H, s, CH3); 13C{1H} NMR (125 MHz, CDCl3) δ 170.5, 170.1, 169.9, 169.3, 168.4 (C=O), 162.8 (N=CH), 149.6, 140.3, 129.3 (2 C-arom), 123.3, (2 C-arom), 93.2 (C-1), 73.0 (C-2), 72.9 (C-3, C-5), 67.0 (C-4), 66.6 (C-6), 62.0 (C-7), 20.7, 20.6, 20.5, 20.4 (2 CH3). Anal. Calcd. for C24H28N2O13: C, 57.73, H, 6.32, N, 5.85. Found: C, 57.52; H, 6.16; N, 5.80. HRMS [M+H]+ calculated for C24H29N2O13: 553.1664. Found: 553.1645.
1,3,4,6,7-Penta-O-acetyl-2-deoxy-2-[(E)-(4-ethylbenzylidene)amino]-β-d-glycero-l-gluco-heptopyranose (71). (54%) M.p. 141–144 °C; [α]D −41.0°; [α]578 −43.0°; [α]546 −52.0°; [α]436 −118.6° (c 0.5, chloroform); IR (KBr) max/cm−1 1750 (C=O), 1644 (C=N), 1610 (arom), 1222 (C-O-C), 1078, 1033 (C-O), 895 and 832 (arom); 1H NMR (500 MHz, CDCl3) δ 8.20 (1H, s, CH=N), 7.63 (2H, d, J 8.0 Hz, H-arom), 7.25 (2H, d, J 8.0 Hz, H-arom), 5.88 (1H, d, J1,2 8.5 Hz, H-1), 5.43 (1H, t, J2,3 = J3,4 9.5 Hz, H-3), 5.36 (1H, m, J6,7 5.5 Hz, J6,7′ 8.0 Hz, H-6), 5.13 (1H, t, J3,4 = J4,5 10.0 Hz, H-4), 4.35 (1H, dd, J6,7′ 5.5 Hz, J7,7′ 12.0 Hz, H-7), 4.17 (1H, dd, J6,7′ 8.0 Hz, J7,7′ 12.0 Hz, H-7′), 4.02 (1H, dd, J4,5 10.0 Hz, J5,6 2.0 Hz, H-5), 3.48 (1H, t, J1,2 = J2,3 9.0 Hz, H-2), 2.68 (1H, c, J 7.5 Hz, CH2), 2.12, 2.06, 2.02, 1.88 (5 × 3H, s, CH3), 2.68 (1H, c, J 7.5 Hz, CH3); 13C{1H} NMR (125 MHz, CDCl3) δ 170.5, 170.2, 170.0, 169.5, 168.5 (C=O), 165.0 (N=CH), 148.3, 132.9, 128.7 (2 C-arom), 128.2, (2 C-arom), 93.5 (C-1), 73.2 (C-2), 73.0 and 72.9 (C-3, C-5), 67.2 (C-4), 66.7 (C-6), 62.1 (C-7), 28.9 (CH2CH3), 20.7, 20.7, 20.6, 20.6, 20.5 (CH3 acetyl), 15.3 (CH2CH3). Anal. Calcd. for C26H33NO11: C, 57.73, H, 6.32, N, 5.85. Found: C, 57.58; H, 6.11; N, 5.92. HRMS [M+H]+ calculated for C26H34NO11: 536.2126. Found: 536.2112.
1,3,4,6,7-Penta-O-acetyl-2-deoxy-2-[(E)-(2,4-dimethylbenzylidene)amino]-β-d-glycero-l-gluco-heptopyranose (72). (48%); 1H NMR (500 MHz, CDCl3) δ 8.50 (1H, s, CH=N), 7.65 (2H, d, J 7.8 Hz, H-arom), 7.06 (2H, d, J 7.8 Hz, H-arom), 7.02 (1H, s, H-arom), 5.91 (1H, d, J1,2 9.0 Hz, H-1), 5.47 (1H, t, J2,3 = J3,4 9.5 Hz, H-3), 5.38 (1H, m, J6,7~J6,7′ 5.5 Hz, H-6), 5.15 (1H, t, J3,4 = J4,5 10.0 Hz, H-4), 4.36 (1H, dd, J6,7′ 5.3 Hz, J7,7′ 11.8 Hz, H-7), 4.33 (1H, dd, J6,7′ 8.0 Hz, J7,7′ 11.8 Hz, H-7′), 4.04 (1H, dd, J4,5 10.0 Hz, J5,6 2.0 Hz, H-5), 3.49 (1H, t, J1,2 = J2,3 9.0 Hz, H-2), 2.46, 2.35 (2xMe, arom), 2.13, 2.08, 2.05, 2.04, 1.92 (5 × 3H, s, CH3). Anal. Calcd. for C26H33NO11: C, 57.73, H, 6.32, N, 5.85. Found: C, 57.61; H, 6.07; N, 5.83. HRMS [M+H]+ calculated for C26H34NO11: 536.2126. Found: 536.2121.
1,3,4,6-Tetra-O-acetyl-2-[(E,E)-cinnamylideneamino]-2-deoxy-β-d-glucopyranose (73). (45%). M.p. 217–218 °C; [α]D +58.8°; [α]578 +62.4°; [α]546 +75.0°; [α]436 +185.2°; [α]365 +530.0° (c 0.5, chloroform); IR (KBr) max/cm−1 2912 (OCH3), 1757 (C=O), 1638 (C=N, arom), 1229 (C-O-C), 1169, 1036 (C-O), 760, 694 (arom); 1H NMR (400 MHz, CDCl3) δ 7.99 (1H, d, J=CH-CH 8.8 Hz, N=CH-CH), 7.49 (2H, d, J 8.4 Hz, H-arom), 7.36 (3H, m, H-arom), 7.03 (1H, d, JCH=CH 16.1 Hz, CH=CH-Ar), 6.86 (1H, dd, JCH=CH 16.1 Hz, JCH-CH 8.8 Hz, CH-CH=CH), 5.99 (1H, d, J1,2 8.1 Hz, H-1), 5.38 (1H, t, J2,3 = J3,4 9.5 Hz, H-3), 5.13 (1H, t, J3,4 = J4,5 9.8 Hz, H-4), 4.37 (1H, dd, J6,6′ 12.4 Hz, J5,6 4.5 Hz, H-6), 4.12 (1H, dd, J6,6′ 12.4 Hz, J5,6′ 2.1 Hz, H-6′), 3.95 (1H, ddd, J4,5 10.1 Hz, J5,6 4.5 Hz, J5,6′ 2.1 Hz, H-5), 3.38 (1H, t, J1,2 = J2,3 9.0 Hz, H-2), 2.10, 2.07, 2.04, 1.96 (4 × 3H, s, CH3); 13C{1H} NMR (100 MHz, CDCl3) δ 170.7, 169.9. 169.6, 168.7 (4C=O), 166.8 (N=C), 143.9 (2C, CH=CH), 135.1, 129.8, 128.9 (C-arom), 127.5 (2 C-arom), 127.3 (C-arom), 93.1 (C-1), 73.2 (C-2), 73.0 (C-5), 72.7 (C-3), 68.0 (C-4), 61.8 (C-6), 20.8, 20.7, 20.7, 20.5 (CH3). Anal. Calcd. for C23H27NO9: C, 59.86, H, 5.90, N, 3.04. Found: C, 59.80, H, 5.94, N, 2.76.
1,3,4,6-Tetra-O-acetyl-2-deoxy-2-[(E,E)-(4-nitrocinnamylidene)amino]-β-d-glucopyranose (74). (73%). M.p. 87–89 °C; [α]D +54.0°; [α]578 +59.8°; [α]546 +71.0°; [α]436 +174.0° (c 0.5, chloroform); IR (KBr) max/cm−1 2955 (OCH3), 1753 (C=O), 1682 (C=N), 1522 (arom), 1219 (C-O-C), 1034 (C-O), 746 (arom); 1H NMR (400 MHz, CDCl3) δ 8.26 (1H, dd, J 9.0 Hz, H-arom), 8.03 (1H, d, J=CH-CH 8.5 Hz, N=CH-CH), 7.63 (2H, dd, J 11.1 Hz, J 2.2 Hz, H-arom), 7.08 (1H, d, JCH=CH 16.1 Hz, CH=CH-Ar), 6.97 (1H, dd, JCH=CH 16.2 Hz, JCH-CH 8.5 Hz, CH-CH=CH), 5.91 (1H, d, J1,2 8.3 Hz, H-1), 5.41 (1H, t, J2,3 = J3,4 9.7 Hz, H-3), 5.14 (1H, t, J3,4 = J4,5 9.8 Hz, H-4), 4.38 (1H, dd, J6,6′ 12.5 Hz, J5,6 4.5 Hz, H-6), 4.13 (1H, dd, J6,6′ 12.4 Hz, J5,6′ 1.9 Hz, H-6′), 3.97 (1H, ddd, J4,5 10.1 Hz, J5,6 4.5 Hz, J5,6′ 2.0 Hz, H-5), 3.43 (1H, dd, J1,2 8.4 Hz, J2,3 9.6 Hz, H-2), 2.10, 2.07, 2.06, 1.97 (4 × 3H, s, CH3); 13C{1H} NMR (100 MHz, CDCl3) δ 170.7, 169.9, 169.5, 168.6 (C=O), 165.7 (C=N), 148.0 (C-arom), 140.6 (CH=CH), 131.3, 129.0, 128.0 (C-arom), 124.2 (CH=CH), 92.9 (C-1), 73.0 (C-2), 72.7 (C-5), 67.8 (C-3), 67.8 (C-4), 61.6 (C-6), 20.8, 20.7, 20.6, 20.5 (CH3). Anal. Calcd. for C23H26N2O11: C, 54.54, H, 5.17, N, 5.53. Found: C, 54.71; H, 5.34; N, 5.38.
1,3,4,6,7-Penta-O-acetyl-2-[(E,E)-cinnamylideneamino]-2-deoxy-β-d-glycero-l-gluco-heptopyranose (75). (50%). M.p. 184–187 °C; [α]D −10.0°; [α]578 −11.0°; [α]546 −14.6°; [α]436 −58.2° (c 0.5, chloroform); IR (KBr) max/cm−1 1750 (C=O), 1636 (C=N), 1433 (C=C, arom), 1215 (C-O-C), 1036 (C-O), 754, 692 (arom); 1H NMR (400 MHz, CDCl3) δ 7.98 (1H, s, CH=N), 7.46 (2H, m, H-arom), 7.37 (3H, m, H-arom), 7.02 (1H, d, JCH=CH 16.0 Hz, CH=CH-Ar), 6.85 (1H, dd, JCH=CH 16.0 Hz, JCH-CH 8.8 Hz, -CH=CH-Ar), 5.64 (1H, d, J1,2 8.8 Hz, H-1), 5.36 (2H, m, J2,3 = J3,4 9.6 Hz, H-3 y 6), 5.13 (1H, t, J3,4 = J4,5 9.7 Hz, H-4), 4.33 (1H, dd, J6,7 5.1 Hz, J7,7′ 11.7 Hz, H-7), 4.15 (1H, dd, J6,7′ 7.9 Hz, J7,7′ 11.5 Hz, H-7′), 3.98 (1H, dd, J5,6 2.0 Hz, J4,5 10.1 Hz, H-5), 3.39 (1H, t, J1,2 ≈ J2,3 9.0 Hz, H-2), 2.14, 2.11, 1.95 (4 × 3H, s, CH3); 13C{1H} NMR (100 MHz, CDCl3) δ 170.5, 170.2, 169.9, 168.5 (C=O), 166.8 (C=N), 144.0 (2C=C), 135.0 (C-arom), 129.8 (C-arom), 128.9 (C-arom), 127.4 (2 C-arom), 127.2 (C-arom), 93.4 (C-1), 73.2 (C-2), 72.9 (C-3), 72.9 (C-5), 67.1 (C-4), 66.7 (C-6), 62.1 (C-7), 20.6, 20.5, 20.5 (CH3, acetate). Anal. Calcd. for C26H31NO11: C, 58.53, H, 5.86, N, 2.63. Found: C, 58.31, H, 5.89, N, 2.73.
1,3,4,6-Tetra-O-acetyl-2-deoxy-2-[(E)-(1-naphthylmethylene)amino]-β-d-glucopyranose (76). From 50 as an oil (43%). 1H NMR (400 MHz, CDCl3) δ 8.89 (1H, s, CH=N), 8.79 (1H, d, J 8.8 Hz, H-arom), 7.95 (1H, d, J 8.8 Hz, H-arom), 7.90 (1H, d, J 8.4 Hz, H-arom), 7.84 (1H, d, J 7.2 Hz, H-arom), 7.61 (1H, c, J 7.0 Hz, H-arom), 7.53 (1H, c, J 8.3 Hz, H-arom), 6.07 (1H, d, J1,2 8.3 Hz, H-1), 5.58 (1H, t, J2,3 = J3,4 9.8 Hz, H-3), 5.21 (1H, t, J3,4 = J4,5 9.8 Hz, H-4), 4.42 (1H, dd, J6,6′ 12.4 Hz, J5,6 4.4 Hz, H-6), 4.17 (1H, dd, J6,6′ 12.6 Hz, J5,6′ 1.4 Hz, H-6′), 4.04 (1H, ddd, J4,5 10.0 Hz, J5,6 4.0 Hz, J5,6′ 2.1 Hz, H-5), 3.61 (1H, t, J1,2 8.8 Hz, H-2), 2.12, 2.06, 2.02, 1.89 (4 × 3H, s, CH3); 13C{1H} NMR (100 MHz, CDCl3) δ 170.7, 169.9, 169. 6, 168.7 (C=O), 165.1 (C=N), 132.0, 128.7, 127.6, 126.3 (C-arom), 93.1 (C-1), 73.9 (C-2), 73.2 (C-5), 72.8 (C-3), 68.0 (C-4), 61.8 (C-6), 20.7, 20.7, 20.5, 18.4 (CH3). Anal. Calcd. for C25H27NO9: C, 61.85, H, 5.61, N, 2.89. Found: C, 62.03; H, 5.50; N, 2.87.
1,3,4,6-Tetra-O-acetyl-2-deoxy-2-[(E)-(4-methoxy-1-naphthylmethylene)amino]-β-d-glucopyranose (77). From 51 (50%). M.p. 150–152 °C; [α]D +87.2°; [α]578 +91.0°; [α]546 +106.4°; [α]436 +231.0° (c 0.5, chloroform); IR (KBr) max/cm−1 2953 (OCH3), 1753 (C=O), 1640 (C=N), 1514 (arom), 1219 (C-O-C), 1032 (C-O), 765 (arom); 1H NMR (400 MHz, CDCl3) δ 8.88 (1H, d, J 8.5 Hz, H-arom), 8.74 (1H, s, CH=N), 8.32 (1H, d, J 7.6 Hz, H-arom), 7.77 (1H, d, J 8.1 Hz, H-arom), 7.61 (1H, t, J 7.8 Hz, H-arom), 7.53 (1H, t, J 8.0 Hz, H-arom), 6.84 (1H, d, J 8.2 Hz, H-arom), 6.04 (1H, d, J1,2 8.5 Hz, H-1), 5.55 (1H, t, J2,3 = J3,4 9.5 Hz, H-3), 5.20 (1H, t, J3,4 = J4,5 9.8 Hz, H-4), 4.40 (1H, dd, J6,6′ 12.3 Hz, J5,6 4.4 Hz, H-6), 4.16 (1H, dd, J6,6′ 12.3 Hz, J5,6′ 1.8 Hz, H-6′), 4.05 (1H, ddd, J4,5 10.2 Hz, J5,6 4.5 Hz, J5,6′ 2.3 Hz, H-5), 3.53 (1H, dd, J1,2 8.4 Hz, J2,3 9.6 Hz, H-2), 2.12, 2.05, 2.02, 1.87 (4 × 3H, s, CH3); 13C{1H} NMR (100 MHz, CDCl3) δ 170.7, 169.56, 169.0, 160.8 (C=O), 160.8 (C=N), 139.6, 132.5, 127.9, 125.6, 124.5, 123.5, 122.4 (C-arom), 93.3 (C-1), 73.4 (C-2), 72.8 (C-5), 71.7 (C-3), 68.1 (C-4), 61.8 (C-6), 55.9 (OCH3), 21.0, 20.7, 20.7, 20.6 (CH3). Anal. Calcd. for C29H29NO10: C, 60.58, H, 5.67, N, 2.72. Found: C, 60.29, H, 5.67, N, 2.59.
1,3,4,6-Tetra-O-acetyl-2-deoxy-2-[(E)-(4-methoxy-1-naphthylmethylene)amino]-α-d-glucopyranose (78). From 52, a mixture of 77 and 78 was isolated. Crystallization from ethanol gave 78 (32%); 1H NMR (400 MHz, CDCl3) δ 9.01 (1H, d, J 8.1 Hz, H-arom), 8.74 (1H, s, CH=N), 8.31 (1H, d, J 8.1 Hz, H-arom), 7.71 (1H, d, J 8.1 Hz, H-arom), 7.56 (1H, dt, J 7.6 Hz, J 1.5 Hz, H-arom), 7.51 (1H, dt, J 8.1 Hz, J 1.2 Hz, H-arom), 6.83 (1H, d, J 8.1 Hz, H-arom), 6.32 (1H, d, J1,2 3.6 Hz, H-1), 5.70 (1H, t, J2,3 = J3,4 9.8 Hz, H-3), 5.23 (1H, t, J3,4 = J4,5 9.9, H-4), 4.38 (1H, dd, J6,6′ 12.3 Hz, J5,6 4.1 Hz, H-6), 4.29 (1H, ddd, J4,5 10.2 Hz, J5,6 4.0 Hz, J5,6′ 2.1 Hz, H-5), 4.14 (1H, dd, J5,6′ 2.0 Hz, J6,6′ 12.3 Hz, H-6′), 3.73 (1H, dd, J1,2 3.6 Hz, J2,3 10.1 Hz, H-2), 2.25, 2.13, 2.06, 1.88 (4 × 3H, s, CH3); 13C{1H} NMR (100 MHz, CDCl3) δ 170.7, 169.6, 169.0, 160.8 (C=O), 158.3 (CH=N), 139.6, 132.5, 127.9, 125.6, 124.5, 123.5, 122.4 (C-arom), 91.9 (C-1), 71.8 (C-2), 71.3 (C-5), 70.1 (C-3), 68.3 (C-4), 61.9 (C-6), 55.7 (OCH3), 21.0, 20.7, 20.7, 20.6 (4 × CH3). Anal. Calcd. for C29H29NO10: C, 60.58, H, 5.67, N, 2.72. Found: C, 60.81, H, 5.53, N, 2.75.
1,3,4,6-Tetra-O-acetyl-2-deoxy-2-[(E)-(2-naphthylmethylene)amino]-β-d-glucopyranose (79). From 53 (30%); [α]D +86.2°; [α]578 +91.0°; [α]546 +106.4°; [α]436 +224.4°; [α]365 +500.4° (c 0.5, chloroform); max/cm−1 1752 (C=O), 1641 (C=N), 1430 (arom), 1222 (C-O-C), 1024 (C-O); 1H NMR (400 MHz, CDCl3) δ 8.55 (1H, s, CH=N), 8.23 (1H, d, arom), 8.00 (1H, m, arom), 7.90 (3H, m, arom), 7.57 (2H, m, arom), 6.18 (1H, d, J1,2 8.4 Hz, H-1), 5.56 (1H, t, J3,4 = J4,5 9.8 Hz, H-4), 5.06 (1H, t, J2,3 = J3,4 9.6 Hz, H-3), 4.33 (1H, dd, J5,6 3.2 Hz, J4,5 8.0 Hz, H-5), 4.27 (1H, dd, J5,6 4.4 Hz, J6,6′ 12.0 Hz, H-6), 4.06 (1H, d, J6,6′ 11.2 Hz, H-6′), 3.88 (1H, t, J1,2 = J2,3 8.8 Hz, H-2), 2.03, 2.00, 1.98, 1.83 (4 × 3H, s, CH3); 13C{1H} NMR (100 MHz, CDCl3) δ 170.5, 169.8, 169.4, 168.6 (C=O), 165.0 (N=CH), 134.9, 132.9, 132.7, 130.7, 128.5, 127.8, 127.5, 126.5, 123.7 (C-arom), 93.0 (C-1), 73.0 (C-2), 73.0 (C-5), 72.7 (C-3), 67.9 (C-4), 61.7 (C-6), 20.7, 20.6, 20.4 (4 CH3). Anal. Calcd. for C25H27NO9: C, 61.85, H, 5.61, N, 2.89. Found: C, 61.68; H, 5.73; N, 2.95.
1,3,4,6-Tetra-O-acetyl-2-deoxy-2-(E)-(9-phenantrylmethylene)amino]-β-d-glucopyranose (81). From 55 (90%). M.p. 99–100 °C; [α]D +69.6°; [α]578 +74.0°; [α]546 +87.4°; [α]436 +199.8° (c 0.5, chloroform); IR (KBr) max/cm−1 1755 (C=O), 1641 (C=N, arom), 1219 (C-O-C), 1036 (C-O), 752, 601 (arom); 1H NMR (400 MHz, CDCl3) δ 8.96 (1H, dd, J 8.0 Hz, J 1.6 Hz, H-arom), 8.89 (1H, s, H-arom), 8.74 (1H, dd, H-arom), 8.68 (1H, d, J 8.3 Hz, H-arom), 8.09 (1H, s, N=CH), 7.96 (1H, d, J 7.6 Hz, H-arom), 7.68 (4H, m, H-arom), 6.10 (1H, d, J1,2 6.2 Hz, H-1), 5.61 (1H, t, J2,3 = J3,4 9.6 Hz, H-3), 5.23 (1H, t, J3,4 = J4,5 9.8 Hz, H-4), 4.42 (1H, dd, J6,6′ 12.4 Hz, J5,6 4.5 Hz, H-6), 4.18 (1H, dd, J6,6′ 12.4 Hz, J5,6′ 2.1 Hz, H-6′), 4.06 (1H, ddd, J4,5 10.1 Hz, J5,6 4.4 Hz, J5,6′ 2.0 Hz, H-5), 3.63 (1H, dd, J1,2 8.3 Hz, J2,3 9.7 Hz, H-2), 2.11, 2.08, 2.06, 1.90 (4 × 3H, s, CH3); 13C{1H} NMR (100 MHz, DMSO-d6) δ 170.7, 169.9, 169.6, 168.7 (C=O), 165.7 (C=N), 132.5, 131.6, 130.6, 129.7, 127.4, 127.0 (2 C-arom), 125.2, 123.0, 122.6 (C-arom), 93.1 (C-1), 74.0 (C-2), 73.2 (C-5), 72.8 (C-3), 68.0 (C-4), 61.8 (C-6). 20.8 (2 CH3), 20.7 (CH3), 20.5 (2 CH3) Anal. Calcd. for C29H29NO9: C, 65.04, H, 5.46, N, 2.62. Found: C, 64.82, H, 5.57, N, 2.74.
1,3,4,5-Tetra-O-acetyl-2-[(E)-(9-antrylmethylene)amino]-2-deoxy-β-d-glucopyranose (82). From 56 (68%). M.p. 164–167 °C; [α]D +21.2°; [α]578 +21.8°; [α]546 +26.2° (c 0.5, chloroform); IR (KBr) max/cm−1 1753 (C=O), 1651 (C=N, arom), 1217 (C-O-C), 1041 (C-O), 903, 733 (arom); 1H NMR (400 MHz, CDCl3) δ 9.46 (1H, s, CH=N), 8.37 (1H, d, arom), 8.08 (1H, s, arom), 8.03 (1H, d, arom), 7.50 (4H, m, arom), 7.30 (2H, m, arom), 6.14 (1H, d, J1,2 8.1 Hz, H-1), 5.71 (1H, t, J2,3 = J3,4 9.6 Hz, H-3), 5.27 (1H, t, J3,4 = J4,5 9.8 Hz, H-4), 4.45 (1H, dd, J5,6 4.4 Hz, J6,6′ 12.3 Hz, H-6), 4.20 (1H, dd, J5,6′ 1.6 Hz, J6,6′ 12.4 Hz, H-6′), 4.10 (1H, ddd, J4,5 9.8 Hz, J5,6 4.5 Hz, J5,6′ 1.7 Hz, H-5), 3.88 (1H, t, J1,2 = J2,3 9.1 Hz, H-2), 2.14, 2.08, 2.07, 2.03 (4 × 3H, s, CH3); 13C{1H} NMR (100 MHz, CDCl3) δ 170.6, 170.0, 169.8, 169.7 (C=O), 165.6 (N=CH), 138.1, 137.9, 137.8, 137.7, 130.2, 128.1, 127.6, 127.3, 126.8, 123.5, 121.9, 121.6 (C-arom), 93.0 (C-1), 73.2 (C-2), 72.8 (C-5), 72.8 (C-3), 68.3 (C-4), 61.7 (C-6), 20.7, 20.6 (4 CH3). Anal. Calcd. for C29H29NO9: C, 65.04, H, 5.46, N, 2.62; Found: C, 64.79, H, 5.23, N, 2.83.
1,3,4,6-Tetra-O-acetyl-2-deoxy-2-[(E)-(10-methyl-9-antrylmethylene)amino]-β-d-glucopyranose (83). From 57 (92%). M.p. 225–226 °C; [α]D +59.2°; [α]578 +63.8°; [α]546 +80.2° (c 0.5, chloroform); IR (KBr) max/cm−1 2915 (OCH3), 1746 (C=O), 1647 (C=N, arom), 1215 (C-O-C), 1084, 1032 (C-O), 750 (arom); 1H NMR (400 MHz, CDCl3) δ 9.43 (1H, s, C=N), 8.34 (4H, m, H-arom), 7.52 (4H, m, H-arom), 6.13 (1H, d, J1,2 8.3 Hz, H-1), 5.71 (1H, t, J2,3 = J3,4 9.6 Hz, H-3), 5.28 (1H, t, J3,4 = J4,5 9.7 Hz, H-4), 4.45 (1H, dd, J6,6′ 12.5 Hz, J5,6 4.4 Hz, H-6), 4.19 (1H, dd, J6,6′ 12.5 Hz, J5,6′ 1.9 Hz, H-6′), 4.07 (1H, ddd, J4,5 10.1 Hz, J5,6 4.3 Hz, J5,6′ 1.9 Hz, H-5), 3.89 (1H, dd, J1,2 8.5 Hz, J2,3 9.7 Hz, H-2), 2.17, 2.14, 2.08, 2.06 (4 × 3H, s, CH3); 13C{1H} NMR (100 MHz, DMSO-d6) δ 170.7, 170.0, 169.7, 168.6 (C=O), 166.3 (C=N), 134.2, 129.6, 129.4, 126.3, 125.8, 125.4, 125.3, 124.6 (C-arom), 92.9 (C-1), 74.6 (C-2), 73.2 (C-5), 72.8 (C-3), 68.2 (C-4), 61.7 (C-6), 20.8 (2 CH3), 20.7 (2 CH3), 14.6 (CH3). Anal. Calcd. for C30H31NO9: C, 65.56, H, 5.69, N, 2.55; Found: C, 65.03, H, 5.37, N, 2.39.
1,3,4,6,7-Penta-O-acetyl-2-deoxy-2-[(E)-(9-antrylmethylene)amino]-β-d-glycero-l-gluco-heptopyranose (84). From 58 (99%). M.p. 176–177 °C; [α]578 −25.6°; [α]546 −32.6° (c 0.5, chloroform); IR (KBr) max/cm−1 1751 (C=O), 1634 (C=N), 1443 (arom), 1219 (C-O-C), 1035 (C-O), 737 (arom); 1H NMR (400 MHz, CDCl3) δ 9.45 (1H, s, CH=N), 8.53 (1H, s, H-arom), 8.35 (2H, d, J 8.2 Hz, H-arom), 8.02 (2H, d, J 7.7 Hz, H-arom), 7.52 (4H, m, H-arom), 6.06 (1H, d, J1,2 8.3 Hz, H-1), 5.71 (1H, t, J3,4 = J4,5 9.6 Hz, H-4), 5.42 (1H, ddd, J5,6 1.4 Hz, J6,7 5.4 Hz, J6,7′ 7.8 Hz, H-6), 5.25 (1H, t, J2,3 = J3,4 9.7, H-3), 4.39 (1H, dd, J6,7 5.2 Hz, J7,7′ 11.4 Hz, H-7), 4.12 (1H, dd, J6,7′ 7.9 Hz, J7,7′ 11.4 Hz, H-7′), 4.12 (1H, dd, J4,5 10.0 Hz, J5,6 1.4 Hz, H-5), 3.89 (1H, dd, J1,2 ≈ J2,3 9.0 Hz, H-2), 2.16, 2.14, 2.08, 2.06, 2.03 (4 × 3H, s, CH3); 13C{1H} NMR (100 MHz, CDCl3) δ 170.5, 170.2, 169.6, 168.5 (C=O), 165.7 (C=N), 132.0 (2 C-arom), 131.1, 130.3 (C-arom), 129.2 (2 C-arom), 129.1 (2 C-arom), 127.1, 126.7 (C-arom), 125.4 (2 C-arom), 123.9 (2 C-arom), 93.9 (C-1), 74.5 (C-2), 73.3 (C-3), 73.0 (C-5), 67.5 (C-4), 66.7 (C-6), 62.1 (C-7), 20.7 (3C, CH3, acetate), 20.6 (3C, CH3, acetate). Anal. Calcd. for C32H33NO11: C, 63.26, H, 5.47, N, 2.31. Found: C, 63.53, H, 5.62, N, 2.45. HRMS [M+H]+ calculated for C32H34NO11: 608.2132. Found: 608.2120.
1,3,4,5-Tetra-O-acetyl-2-deoxy-2-[(2-methoxy-1-naphthyl)methylene]amino-β-d-glucopyranose (87). To a solution of 1,3,4,5-tetra-O-acetyl-2-amino-2-deoxy-β-d-glucopyranose hydrochloride (85) (1.3 g, 3.3 mmol) in ethanol (14 mL), anhydrous sodium acetate (0.25 g) dissolved in water (2 mL) and 2-methoxynaphthaldehyde (0.6 g, 3.0 mmol) were added. The solution was heated in a water bath, filtered to remove impurities, and then cooled. The crystalline solid crystallized was filtered and washed with 96% aqueous ethanol to afford the title compound in 21% yield. M.p.: 196–198 °C; [α]D +73.6°; [α]578 +76.4°; [α]546 +90.2° (c 0.5, chloroform); IR (KBr) max/cm−1 1752 (C=O), 1650 (C=N), 1256, 1218 (C-O-C, ester), 1086, 1033 (C-O), 818 (arom); 1H NMR (400 MHz, CDCl3) δ 8.97 (1H, s, N=CH), 8.90 (1H, d, J 8.8 Hz, H-arom), 7.91 (1H, d, J 9.2 Hz, H-arom), 7.49 (1H, t, J 8.6 Hz, H-arom), 7.36 (1H, t, J 7.0 Hz, H-arom), 7.25 (1H, d, J 9.6 Hz, H-arom), 6.10 (1H, d, J1,2 7.6 Hz, H-1), 5.58 (1H, t, J3,4 = J4,5 9.4 Hz, H-4), 5.21 (1H, t, J2,3 = J3,4 9.8 Hz, H-3), 4.41 (1H, dd, J5,6 4.8 Hz, J6,6′ 12.4 Hz, H-6), 4.17 (1H, dd, J5,6′ 2.4 Hz, J6,6′ 12.4 Hz, H-6′), 4.05 (1H, ddd, J4,5 10.0 Hz, J5,6′ 2.4 Hz, H-5), 3.98 (3H, s, OCH3), 3.61 (1H, dd, J1,2 8.6 Hz, J2,3 9.4 Hz, H-2), 2.12, 2.08, 2.06, 1.97 (4 × 3H, s, CH3); 13C{1H} NMR (100 MHz, CDCl3) δ 170.6, 169.9, 169.7, 168.8 (C=O), 163.5 (N=CH), 158.2, 133.3, 131.7, 128.9, 128.2, 128.1, 125.0, 124.1, 116.4, 112.2 (C-arom), 93.2 (C-1), 74.0 (C-2), 73.2 (C-5), 72.8 (C-3), 68.1 (C-4), 61.8 (C-6), 56.3 (OMe), 20.7, 20.4 (4 CH3). Anal. Calcd. for C26H29NO10: C, 60.58, H, 5.67, N, 2.72. Found: C, 60.83; H, 5.78; N, 2.67.
1,3,4,6-Tetra-O-acetyl-2-[(E,E)-cinnamylideneamino]-2-deoxy-α-d-glucopyranose (88). To a suspension of 1,3,4,6-tetra-O-acetyl-2-amino-2-deoxy-α-d-glucopyranose hydrobromide (86) (1.4 g, 3.0 mmol) in 96% aqueous ethanol (14 mL), sodium acetate trihydrate (0.41 g, 3.0 mmol) dissolved in water (2 mL) and pyridine (0.8 mL), and cinnamylidene aldehyde (0.6 mL) were added. The solution was heated in a water bath and filtered to remove impurities, then cooled. The crystalline solid crystallized was collected by filtration and washed with 50% aqueous ethanol to give the title compound in 57% yield. M.p.: 177–179 °C; [α]D +81.8°; [α]578 +87.2°; [α]546 +93.0° (c 0.5, chloroform); IR (KBr) max/cm−1 1747 (C=O), 1635 (C=N), 1251, 1221 (C-O-C, ester), 1027 (C-O); 1H NMR (400 MHz, CDCl3) δ 8.07 (1H, d, JCH=N 8.4 Hz, CH-CH=N), 7.48 (2H, d, J 7.2 Hz, H-arom), 7.38 (3H, m, H-arom), 7.02 (1H, d, JCH=CH-Ar 16.0 Hz, =CH-Ar), 6.88 (1H, dd, JCH-CH=CH 8.8 Hz, JCH-CH=CH 16.0 Hz, N=CH-CH), 6.18 (1H, d, J1,2 3.6 Hz, H-1), 5.61 (1H, t, J2,3 = J3,4 9.8 Hz, H-3), 5.17 (1H, t, J3,4 = J4,5 9.8, H-4), 4.36 (1H, dd, J6,6′ 12.2 Hz, J5,6 4.2 Hz, H-6), 4.24 (1H, d, J4,5 10.0 Hz, H-5), 4.10 (1H, d, J6,6′ 12.0 Hz), 3.60 (1H, dd, J1,2 3.0 Hz, J2,3 10.2 Hz, H-2), 2.22, 2.10, 2.05, 1.95 (4 × 3H, s, CH3); 13C{1H} NMR (100 MHz, CDCl3) δ 170.5, 169.6, 168.9, 167.1 (C=O), 167.1 (C=N), 144.0 (C-arom), 135.0, 129.6, 128.7, 127.4, 127.2 (C-arom), 91.4 (C-1), 71.0 (C-2), 70.9 (C-5), 69.8 (C-3), 68.1 (C-4), 61.7 (C-6), 21.0, 20.6, 20.5, 20.4 (CH3). Anal. Calcd. for C23H27NO9: C, 59.86, H, 5.90, N, 3.04. Found: C, 59.75, H, 5.83, N, 3.06.
2-Acetamido-1,3,4,6,7-penta-O
-acetyl-2-deoxy-α-d-glycero
-l-gluco
-heptopyranose (
90). To a suspension of 1,3,4,6,7-penta-
O-acetyl-2-amino-2-deoxy-α-
d-
glycero-
l-
gluco-heptopyranose hydrobromide (
89) [
17] (0.51 g, 0.75 mmol) in pyridine (3.0 mL), acetic anhydride (2.9 mL) was added. The mixture was kept under stirring at room temperature for 30 min until complete dissolution. After 12 h in the refrigerator, it was poured into ice-water and a white solid was filtered, washed with cold water and dried under vacuum over silica gel (0.16 g, 33%). M.p. 90–92 °C (lit. [
16] m.p. 82–84 °C); IR (KBr)
max/cm
−1 3257 (NH), 1751, 1661 (C=O), 1227 (C-O-C), 1047, 1012 (C-O);
1H NMR (500 MHz, CDCl
3) δ 6.15 (1H, d,
J1,2 3.5 Hz, H-1), 5.67 (1H, d,
J2,NH 9.0 Hz, NH), 5.20 (1H, t,
J2,3 ≈
J3,4 9.5 Hz, H-3), 5.17 (1H, m,
J5,6 2.0 Hz,
J6,7 5.0 Hz,
J6,7′ 7.0 Hz, H-6), 5.15 (1H, t,
J3,4 ≈
J4,5 10.0 Hz, H-4), 4.47 (1H, td,
J1,2 4.0 Hz,
J2,NH 9.5 Hz,
J2,3 10.5 Hz, H-2), 4.21 (1H, dd,
J6,7 5.0 Hz,
J7,7′ 11.5 Hz, H-7), 4.10 (1H, dd,
J6,7′ 7.0 Hz,
J7,7′ 11.5 Hz, H-7′), 4.03 (1H, dd,
J5,6 2.0 Hz,
J4,5 9.5 Hz, H-5), 2.17, 2.10, 2.02, 2.00, 1.99 (12H, s, OAc), 1.92 (3H, s, NAc);
13C{
1H} NMR (125 MHz, CDCl
3) δ 171.6, 170.5, 170.3, 169.9, 169.0, 168.4 (C=O), 90.6 (C-1), 70.9 (2C, C-3, C-6), 69.9 (C-5), 66.6 (C-4), 62.1 (C-7), 51.0 (C-2), 23.0, 20.8, 20.6, 20.6, 20.4 (CH
3). HRMS [M+H]
+ calculated for C
19H
28NO
12: 462.1606. Found: 462.1618.
2-Acetamido-1,3,4,6,7-penta-O
-acetyl-2-deoxy-β-d-glycero
-l-gluco
-heptopyranose (
92). The title compound was obtained from 1,3,4,6,7-penta-
O-acetyl-2-amino-2-deoxy-β-
d-
glycero-
l-
gluco-heptopyranose hydrochloride (
91) [
17] (0.26 g, 0.4 mmol) with pyridine (1.5 mL) and acetic anhydride (1.0 mL) using the procedure described for
74 (0.07 g, 27%). M.p. 226–228 °C (Lit. [
16] m.p. 221–223 °C); IR (KBr)
max/cm
−1 3354 (NH), 1754, 1667 (C=O), 1220 (C-O-C), 1073, 1034 (C-O);
1H NMR (500 MHz, CDCl
3) δ 5.76 (1H, d,
J2,NH 9.0 Hz, NH), 5.66 (1H, d,
J1,2 9.0 Hz, H-1), 5.24 (1H, ddd,
J5,6 2.0 Hz,
J6,7 5.0 Hz,
J6,7′ 7.5 Hz, H-6), 5.16 (1H, t,
J2,3 ≈
J3,4 9.5 Hz, H-3), 5.11 (1H, t,
J3,4 ≈
J4,5 10.0 Hz, H-4), 4.30 (1H, dd,
J6,7 5.0 Hz,
J7,7′ 11.5 Hz, H-7), 4.24 (1H, c,
J1,2 =
J2,NH ≈
J2,3 9.5 Hz, H-2), 4.10 (1H, dd,
J6,7′ 8.0 Hz,
J7,7′ 11.5 Hz, 1H, H-7′), 3.85 (1H, dd,
J5,6 2.0 Hz,
J4,5 9.5 Hz, H-5), 2.10, 2.09, 2.02, 2.01 (12H, s, OAc), 1.92 (3H, s, NAc);
13C{
1H} NMR (125 MHz, CDCl
3) δ 171.1, 170.5, 170.3, 170.1, 169.3, 169.2 (C=O), 92.8 (1C,
1J 120 Hz, C-1), 73.0, 72.6 (C-3, C-5), 66.9, 66.5 (C-4, C-6), 62.2 (C-7), 53.1 (C-2), 23.1, 20.8, 20.6, 20.6, 20.5 (CH
3). HRMS [M+H]
+ calculated for C
19H
28NO
12: 462.1606; found: 462.1613; [M+Na]
+ calculated for C
19H
27NO
12Na: 484.1425; found: 484.1435.; [M+K]
+ calculated for C
19H
27NO
12K: 500.1165, found: 500.1174.
4.4.3. Mutarotational Equilibrium in Schiff Bases Derived from 2-Amino-2-deoxyaldoses
Imine samples (~15 mg) were dissolved in DMSO-d6 (0.5 mL) or pyridine-d5 (0.5 mL), and the corresponding 1H NMR spectra were immediately recorded, followed by temporal monitoring until equilibration (as inferred from unaltered 1H and 13C NMR spectra over time).
2-Deoxy-2-[(E)-(3-bromobenzylidene)amino]-α-d-glucopyranose (95). 13C{1H} NMR (100 MHz, DMSO-d6) δ 161.0 (C=N), 138.8, 137.4, 132.3, 127.8 (C-arom), 93.1 (C-1), 75.6 (C-2), 72.7 (C-5), 70.9 (C-3, C-4), 61.5 (C-6).
2-[(E,E)-Cinnamylideneamino]-2-deoxy-α-d-glucopyranose (105). 1H NMR (400 MHz, DMSO-d6) δ 8.06 (1H, d, J=CH-CH 8.7 Hz, N=CH-CH), 7.59 (2H, d, J 7.3 Hz H-arom), 7.36 (3H, m, H-arom), 7.11 (1H, d, JCH=CH 16.1 Hz, CH=CH-Ar), 6.90 (1H, dd, JCH=CH 16.1 Hz, JCH-CH 8.8 Hz, CH-CH=CH), 6.24 (1H, d, JC1,OH 4.2 Hz, C1-OH), 4.91 (2H, m, J1,2 ≈ JC1,OH 4.0 Hz H-1, C3-OH), 4.71 (1H, d, JC4-OH 5.3 Hz, C4-OH), 4.57 (1H, t, JC6-OH 5.3 Hz, C6-OH), 3.78 (1H, m, H-3), 3.65 (1H, m, H-6), 3.54 (1H, m, H-6′), 3.00 (1H, t, J1,2 3.1 Hz, J2,3 9.7 Hz, H-2); 13C{1H} NMR (100 MHz, DMSO-d6) δ 164.1 (C=N), 141.6 (2C, CH=CH), 136.0, 129.1, 128.6, 127.4 (2 C-arom), 93.2 (C-1), 75.5 (C-2), 72.6 (C-5), 71.1 (C-3, C-4), 61.5 (C-6).
2-Deoxy-2-[(E,E)-(4-nitrocinnamylidene)amino]-α-d-glucopyranose (106). 1H NMR (400 MHz, DMSO-d6) δ 8.21 (2H, d, J 8.7 Hz, H-arom), 8.10 (1H, d, J=CH-CH 8.5 Hz, N=CH-CH), 7.87 (2H, d, J 8.7 Hz, H-arom), 7.25 (1H, d, J 16.1 Hz, CH=CH-Ar), 7.11 (1H, dd, J 8.7 Hz, JCH=CH 16.1 Hz, CH-CH=CH), 6.28 (1H, d, JC1-OH 4.4 Hz, C1-OH), 4.93 (1H, d, J1–2 5.2 Hz, H-1), 4.74 (1H, m, JC3-OH 5.7 Hz, C3-OH), 4.47 (1H, t, JC6-OH 5.8 Hz, C6-OH), 4.13 (1H, c, J4,5 ≈ J5,6 5.2 Hz, H-5), 3.78 (1H, m, J3,4 9.4 Hz, J2,3 5.3 Hz, H-3), 3.66 (1H, ddd, J6,6′ 11.6 Hz, J5,6 2.2 Hz, JC6-OH 5.4 Hz, H-6), 3.48 (1H, d, JC6-OH 5.9 Hz, H-6′), 3.14 (1H, m, H-4), 3.03 (1H, dd, J1,2 3.5 Hz, J2,3 9.4 Hz, H-2); 13C{1H} NMR (100 MHz, DMSO-d6) δ 163.5 (C=N), 147.4, 142.6 (C-arom), 139.1 (CH=CH), 132.7, 128.4 (C-arom), 124.2 (CH=CH), 93.0 (C-1), 75.6 (C-2), 71.0 (C-3, C-5), 70.4 (C-4), 61.4 (C-6).
2-Desoxi-2-[(E,E)-(2-methoxycinnamylidene)amino]-α-d-glucopyranose (107). 1H NMR (400 MHz, DMSO-d6) δ 8.04 (1H, d, J=CH-CH 8.8 Hz, N=CH-CH), 7.60 (1H, dd, J 7.7 Hz, J 1.2 Hz, H-arom), 7.33 (1H, dt, J 7.7 Hz, J 1.4 Hz, H-arom), 7.26 (1H, d, JCH=CH 16.2 Hz, CH=CH-Ar), 6.97 (1H, t, J 7.5 Hz, H-arom), 6.90 (1H, dd, JCH=CH 16.2 Hz, JCH-CH 8.9 Hz, CH-CH=CH), 6.22 (1H, d, JC1,OH 4.5 Hz, C1-OH), 4.90 (1H, d, JC3-OH 5.4 Hz, C3-OH), 4.88 (1H, t, J1,2 4.0 Hz, H-1), 4.68 (1H, d, JC4-OH 5.7 Hz, C4-OH), 4.46 (1H, t, JC6-OH 5.9 Hz, C6-OH), 3.85 (3H, s, OCH3), 3.76 (1H, m, H-3), 3.66 (1H, t, H-4), 3.63 (1H, dd, H-6), 3.52 (1H, dd, J5,6 6.2 Hz, J6,6′ 12.3 Hz, H-6′), 2.97 (1H, dd, J1,2 3.1 Hz, J2,3 9.7 Hz, H-2); 13C{1H} NMR (100 MHz, DMSO-d6) δ 164.7 (C=N), 136.4 (C-arom), 136.1 (CH=CH), 130.6, 129.2, 127.7, 124.3 (C-arom), 120.9 (CH=CH), 93.2 (C-1), 75.5 (C-2), 72.6 (C-5), 71.1 (C-3), 71.0 (C-4), 61.5 (C-6), 55.8 (OCH3).
2-Desoxi-2-[(E,E)-(4-hydroxy-3-methoxycinnamylidene)amino]-α-d-glucopyranose (108). 13C NMR (50.3 MHz, DMSO-d6) δ 164.2 (C=N), 148.3 (C-arom), 148.2 (C-arom), 141.8 (CH=CH), 127.7, 126.0, 121.6, 115.9 (C-arom), 111.8 (CH=CH), 93.3 (C-1), 75.4 (C-2), 72.7 (C-5), 71.2 (C-3), 71.1 (C-4), 61.5 (C-6), 55.9 (OCH3).
2-Deoxy-2-[(E,E)-(4-nitrocinnamylidene)amino]-β-d-glucopyranose (46). 1H NMR (400 MHz, pyridine-d5) δ 9.06 (1H, d, J 5.8 Hz, H-arom), 8.47 (1H, d, J 8.7 Hz, H-arom), 8.16 (1H, d, J=CH-CH 8.7 Hz, N=CH-CH), 7.32 (1H, dd, J 8.7 Hz, JCH=CH 16.1 Hz, CH-CH=CH), 6.93 (1H, d, J 16.1 Hz, CH=CH-Ar), 6.71 (1H, t, C6-OH), 5.77 (1H, ddt, J1–2 ≈ JC1-OH 7.3 Hz, H-1), 4.67 (1H, d, J6–6′ 11.8 Hz, J5–6 2.3 Hz, H-6), 4.57 (1H, t, J2–3 ≈ J3–4 8.8 Hz, H-3), 4.50 (1H, dd, J5–6 5.4 Hz, J6–6′ 11.1 Hz, H-6′), 4.41 (1H, t, J2–3 ≈ J3–4 9.0 Hz, H-4), 4.20 (1H, ddd, J4–5 8.2 Hz, J5–6 5.6 Hz, J5–6′ 2.5 Hz, H-5), 3.79 (1H, t, J1,2 ≈ J2,3 8.4 Hz, H-2).
2-Deoxy-2-[(E)-(4-methoxy-1-naphthylmethylene)amino]-β-d-glucopyranose (51). 1H NMR (400 MHz, pyridine-d5) δ 9.69 (1H, dd, J 2.4 Hz, J 6.7 Hz, H-arom), 9.24 (1H, s, CH=N), 8.46 (1H, m, H-arom), 7.93 (1H, d, J 8.1 Hz, H-arom), 7.57 (2H, m, H-arom), 7.28 (1H, sa, OH), 6.85 (1H, d, J 8.1 Hz, H-arom), 5.85 (1H, d, J1,2 7.4 Hz, H-1), 4.72 (1H, dd, J6,6′ 11.6 Hz, J5,6 2.1 Hz, H-6), 4.66 (1H, t, J4,5 ≈ J3,4 8.2 Hz, H-4), 4.53 (1H, dd, J6,6′ 11.6 Hz, J5,6′ 5.6 Hz, H-6′), 4.46 (1H, t, J3,4 ≈ J2,3 9.2 Hz, H-3) 4.26 (1H, ddd, J4,5 8.9 Hz, J5,6 2.5 Hz J5,6′ 6.0 Hz, H-5), 3.92 (1H, t, J1,2 ≈ J2,3 8.4 Hz, H-2), 3.83 (3H, s, OCH3); 13C{1H} NMR (100 MHz, DMSO-d6) δ 163.8 (N=C), 157.9 (C-arom), 133.3 (C-arom), 132.6 (C-arom), 128.2 (C-arom), 126.4 (C-arom), 126.1 (C-arom), 122.9 (C-arom), 124.3 (C-arom), 104.3 (C-arom), 98.1 (C-1), 81.9 (C-2), 79.1 (C-5), 77.1 (C-3), 72.4 (C-4), 63.5 (C-6), 56.0 (OCH3).
2-Deoxy-2-[(E)-(4-methoxy-1-naphthylmethylene)amino]-α-d-glucopyranose (52). 1H NMR (400 MHz, pyridine-d5) δ 9.83 (1H, m, H-arom), 9.22 (1H, s, CH=N), 8.46 (2H, m, H-arom), 7.98 (1H, d, J 8.1 Hz, H-arom), 7.54 (3H, m, H-arom), 7.21 (3H, m, OH), 6.87 (1H, d, J 8.08 Hz, H-arom), 6.40 (1H, t, C6-OH), 5.90 (1H, t, J1,2 ≈ JC1-OH 2.8 Hz, H-1), 5.21 (1H, t, J2,3 ≈ J3,4 9.1 Hz, H-3), 5.05 (1H, ddd, J4,5 7.9 Hz, J5,6 5.4 Hz J5,6 2.7 Hz, H-5), 4.68 (1H, dd, J6,6′ 12.9 Hz, J5,6′ 1.4 Hz, H-6′), 4.56 (1H, dd, J6,6′ 11.3 Hz, J5,6 4.9 Hz, H-6), 4.48 (1H, t, J3,4 ≈ J4,5 9.3 Hz, H-4), 3.96 (1H, dd, J1,2 3.4 Hz, J2,3 9.6 Hz, H-2), 3.83 (3H, s, OCH3); 13C{1H} NMR (100 MHz, DMSO-d6) δ 163.8 (N=C), 157.9 (C-arom), 133.3 (C-arom), 132.6 (C-arom), 128.2 (C-arom), 126.4 (C-arom), 126.1 (C-arom), 122.9 (C-arom), 124.3 (C-arom), 104.3 (C-arom), 95.6 (C-1), 79.0 (C-2), 74.6 (C-5), 73.4 (C-3), 73.2 (C-4), 63.8 (C-6), 56.0 (OCH3).
2-Deoxy-2-[(E)-(2-naphthylmethylene)amino]-β-d-glucopyranose (53). 1H NMR (400 MHz, pyridine-d5) δ 9.08 (1H, d, J 5.0 Hz, H-arom), 8.90 (1H, s, CH=N), 8.32 (1H, dd, J 9.7 Hz, J 1.0 Hz, H-arom), 8.12 (1H, s, H-arom), 7.89 (2H, s, H-arom), 7.50 (2H, m, H-arom), 7.34 (1H, sa, OH), 7.23 (2H, sa, OH), 6.78 (1H, sa, C6-OH), 5.86 (1H, t, J1,2 7.5 Hz, H-1), 4.70 (1H, d, J6,6′ 11.8 Hz, H-6), 4.64 (1H, t, J3,4 = J4,5 9.0 Hz, H-4), 4.50 (1H, dd, J6,OH 5.5 Hz, J6,6′ 11.6 Hz, H-6), 4.45 (1H, t, J2,3 = J3,4 9.1 Hz, H-3), 4.25 (1H, m, J4,5 8.8 Hz, J5,6 2.0 Hz, H-5), 3.96 (1H, t, J1,2 ≈ J2,3 8.4 Hz, H-2).
2-Deoxy-2-[(E,E)-(4-nitrocinnamylidene)amino]-α-d-glucopyranose (106). 1H NMR (400 MHz, pyridine-d5) δ 8.50 (2H, d, J 8.7 Hz, H-arom), 8.46 (2H, d, J 8.7 Hz, H-arom), 7.59 (1H, d, J=CH-CH 8.7 Hz, N=CH-CH), 7.32 (1H, dd, J 8.7 Hz, JCH=CH 16.0 Hz, CH-CH=CH), 7.00 (1H, d, J 16.1 Hz, CH=CH-Ar), 6.41 (1H, t, JC6-OH 5.7 Hz, C6-OH), 5.83 (1H, t, J1–2 3.2 Hz, H-1), 4.67 (1H, d, J6–6′ 11.8 Hz, J5–6 2.3 Hz, H-6), 4.57 (1H, t, J2–3 ≈ J3–4 8.8 Hz, H-3), 4.50 (1H, dd, J5–6 5.4 Hz, J6–6′ 11.1 Hz, H-6′), 4.41 (1H, t, J2–3 ≈ J3–4 9.0 Hz, H-4), 4.20 (1H, ddd, J4–5 8.2 Hz, J5–6 5.6 Hz, J5–6′ 2.5 Hz, H-5), 3.85 (1H,dd, J1,2 3.3 Hz, J2,3 9.6 Hz, H-2).
2-Deoxy-2-[(E)-(2-naphthylmethylene)amino]-α-d-glucopyranose (54). 1H NMR (400 MHz, pyridine-d5) δ 8.87 (1H, s, CH=N), 8.51 (1H, d, J 3.2 Hz, H-arom), 8.34 (1H, d, J 9.6 Hz, H-arom), 8.19 (1H, s, H-arom), 7.88 (2H, m, H-arom), 7.50 (2H, m, arom), 7.26 (2H, sa, OH), 6.48 (1H, t, C6-OH), 5.88 (1H, t, H-1), 5.16 (1H, m, J3,4 ≈ J2,3 9.9 Hz, H-3), 5.05 (1H, dddd, J5,6 2.3 Hz, J5,6′ 5.4 Hz, J4,5 7.5 Hz, H-5), 4.66 (1H,d, J6,6′ 10.3 Hz, H-6), 4.56 (1H, dd, J6,6′ 11.3 Hz, J5,6 4.5 Hz, H-6′), 4.47 (1H, t, J3,4 ≈ J4,5 9.1 Hz, H-4), 4.00 (1H, t, J2,3 9.6 Hz, J1,2 3.2 Hz, H-2).