M. Misra et al. / Tetrahedron 67 (2011) 740e748
745
compound 1e (1.0g, 2.71 mmol), malononitrile (0.35 g, 5.41 mmol)
and K2CO3 (0.37g, 2.71 mmol) in water as Light yellow solid (0.76g,
yield 70%). Analysis found: C, 60.60; H, 5.49; N, 9.18 for C23H25N3O7
ArNH2), 5.23 (1H, d, J¼5.2 Hz, OH), 4.99 (1H, d, J¼4.2 Hz, OH), 4.94
(1H, br s, OH), 4.33 (1H, br s, OH), 3.67e3.65 (1H, m, H-600a),
3.37e3.31 (3H, m, 2ꢂCH, H-600b), 3.18 (1H, m, H-100), 3.07e3.02 (2H,
m, CH), 2.99e2.97 (1H, m, H-1b), 2.80 (1H, dd, J1¼8.6, J2¼14.2 Hz, H-
requires: C, 60.65; H, 5.53; N, 9.23; mp 135e138 ꢁC; Rf 0.55 (20%
25
MeOH/CHCl3); [
a
]
D
ꢀ57.0 (c 0.1, DMSO); IR (KBr) nmax cmꢀ1 3350
1a); 13C NMR (50 MHz, DMSO)
d
¼153.9 (AreC), 149.8 (AreC), 149.3
(OH), 2216 (C^N), 1638, 1581, 1518; 1H NMR (300 MHz, DMSO)
(AreC),135.6 (AreC), 133.3 (AreC),133.0 (AreC), 128.9 (AreCH),
128.5 (AreCH), 128.0 (AreCH), 127.5 (AreCH) 127.1 (AreCH),126.5
(AreCH), 120.0 (AreCH), 116.7 (C^N), 116.0 (C^N), 96.7 (AreC),
93.4 (AreC), 81.0 (CH), 78.8 (CH), 78.4 (CH), 74.0 (CH), 70.9 (CH),
61.9 (OCH2), 37.2 (CH2); ESMS m/z¼466 (Mþ21)þ.
d
¼7.17 (3H, m, ArH), 6.88 (1H, s, ArH), 6.48 (2H, s, ArNH2), 5.14 (1H,
br s, OH), 4.88 (2H, br s, OH), 4.20 (1H, br s, OH), 4.26 (1H, t,
J¼5.3 Hz, OH), 3.82 (6H, br s, 2ꢂOCH3), 3.64e3.57 (1H, m, H-600a),
3.40e3.34 (3H, m, 2ꢂCH, H-600b), 3.18e3.15 (1H, m, H-100),
3.07e3.05 (2H, m, CH), 3.00e2.94 (1H, m, H-1b), 2.77 (1H, dd,
J1¼8.9, J2¼14.7 Hz, H-1a); 13C NMR (50 MHz, DMSO)
d
¼153.9
4.2.9. 3-Amino-40-hydroxy-5-[(
b-D-glucopyranosyl)methyl]biphenyl-
(AreC), 150.2 (AreC), 149.5 (AreC), 149.3 (AreC), 148.9 (AreC),
130.4 (AreCH), 121.7 (AreCH), 119.5 (AreCH), 117.0 (C^N), 116.1
(C^N),112.5 (AreCH),112.1 (AreCH), 96.1 (AreC), 93.2 (AreC), 80.9
(CH), 79.6 (AreC), 78.8 (CH), 78.4 (CH), 74.1 (CH), 70.9 (CH), 61.9
(OCH2), 56.0 (OCH3), 37.2 (CH2); ESMS m/z 472 (MþH)þ.
2,4-dicarbonitrile (2i). It was obtained by the reaction of compound
1i (1.0g, 3.00 mmol), malononitrile (0.40 g, 6.10 mmol) and K2CO3
(0.42 g, 3.01 mmol) in water as yellow solid (0.58g, yield 52%).
Analysis found: C, 61.31; H, 5.14; N, 10.21 for C21H21N3O6 requires:
C, 61.40; H, 5.19; N, 10.18; mp 242e245 ꢁC; Rf 0.48 (20% MeOH/
25
CHCl3); [
a
]
ꢀ22.75 (c 0.1, DMSO); IR (KBr) nmax cmꢀ1 3361 (OH),
D
4.2.6. 3-Amino-40-chloro-5-[(
b
-
D
-glucopyranosyl)methyl]biphenyl-
2213 (C^N), 1648, 1582, 1229; 1H NMR (300 MHz, DMSO)
d¼9.98
2,4-dicarbonitrile (2f). It was obtained by the reaction of compound
2f (1.1g, 3.21 mmol), malononitrile (0.42 g, 6.40 mmol) and K2CO3
(0.44 g, 3.21 mmol) in water as white solid (0.87g, yield 64%).
Analysis found: C, 58.71; H, 4.61; Cl, 8.21; N, 9.72 for C21H20ClN3O5
requires: C, 58.68; H, 4.69; Cl, 8.25; N, 9.78; mp 130e132 ꢁC; Rf 0.52
(1H, s, ArOH), 7.46 (1H, d, J¼8.4 Hz, ArH), 6.88e6.82 (3H, m, ArH),
6.49 (2H, s, ArNH2), 5.19 (1H, d, J¼5.4 Hz, OH), 4.98 (1H, d, J¼4.4 Hz,
OH), 4.92 (1H, br s, OH), 4.26 (1H, t, J¼5.3 Hz, OH), 3.65 (1H, dd,
J1¼4.9, J2¼11.0 Hz, H-600a), 3.41e3.25 (3H, m, 2ꢂCH, H-600b),
3.17e3.16 (1H, m, H-100), 3.05 (2H, br s, CH), 2.99e2.92 (1H, m, H-
1b), 2.76 (1H, dd, J1¼8.9, J2¼14.6 Hz, H-1a); 13C NMR (50 MHz,
(20% MeOH/CHCl3); [
a
]
25 ꢀ136.99 (c 0.1, DMSO); IR (KBr) nmax cmꢀ1
D
3224 (OH), 2216 (C^N), 1644, 1577, 1428; 1H NMR (300 MHz,
DMSO)
d
¼159.0 (AreC), 153.9 (AreC), 149.5 (AreC), 130.5 (AreCH),
CD3OD)
d
¼7.60e7.47 (4H, m, ArH), 6.91 (1H, s, ArH), 3.81 (1H, dd,
128.7 (AreCH), 119.7 (AreCH), 117.0 (C^N), 116.0 (C^N), 115.8
(AreCH), 95.9 (AreC), 92.9 (AreC), 80.9 (CH), 78.9 (CH), 78.4 (CH),
74.0 (CH), 70.9 (CH), 61.9 (OCH2), 37.2 (CH2); ESMS m/z¼412
(MþH)þ.
J1¼3.51, J2¼17.5 Hz, H-600a), 3.64 (1H, dd, J1¼7.98, J2¼17.7 Hz, H-600b)
3.52e3.43 (2H, m, CH), 3.39e3.34 (1H, m, H-100), 3.31e3.26 (1H, m,
CH), 3.22e3.09 (2H, m, CH, H-1b), 2.96 (1H, dd, J1¼13.53,
J2¼21.9 Hz, H-1a); 13C NMR (50 MHz, DMSO)
¼154.9 (AreC), 150.5
d
(AreC), 149.8 (AreC), 138.0 (AreC), 136.5 (AreC), 131.4 (AreCH),
129.9 (AreCH), 117.0 (C^N), 116.7 (C^N), 98.4 (AreC), 94.7 (AreC),
81.5 (CH), 80.4 (CH), 79.7 (CH), 75.2 (CH), 71.9 (CH), 63.1 (OCH2),
38.3 (CH2); ESMS m/z 430.2 (MþH)þ.
4.2.10. 3-Amino-40-(dimethylamino)-5-[(
b-D-glucopyranosyl)methyl]
biphenyl-2,4-dicarbonitrile (2j). It was obtained by the reaction of
compound 1j (1.2g, 3.41 mmol), malononitrile (0.45 g, 6.81 mmol)
and K2CO3 (0.47 g, 3.41 mmol) in water as yellow solid (0.83g, yield
58%). Analysis found: C, 63.12; H, 6.01; N, 12.69 for C23H26N4O5
requires: C, 63.00; H, 5.98; N, 12.78; mp 230e233 ꢁC; Rf 0.45 (20%
4.2.7. 3-Amino-40-fluoro-5-[(
b-D-glucopyranosyl)methyl]biphenyl-
2,4-dicarbonitrile (2g). It was obtained by the reaction of com-
pound 1g (1.0g, 3.00 mmol), malononitrile (0.40 g, 6.13 mmol) and
K2CO3 (0.42 g, 3.06 mmol) in water as yellow solid (0.73g, yield
69%). Analysis found: C, 61.11; H, 4.91; N, 10.21 for C21H20FN3O5
requires: C, 61.01; H, 4.88; N, 10.16; mp 168e171 ꢁC; Rf 0.58 (20%
MeOH/CHCl3); [
a
]
25 ꢀ26.93 (c 0.1, DMSO); IR (KBr) nmax cmꢀ1 3449
D
(OH), 2563, 1777, 1626; 1H NMR (300 MHz, DMSO)
d
¼7.49 (2H, d,
J¼8.7 Hz, ArH), 6.83 (3H, m, ArH), 6.43 (2H, s, ArNH2), 5.17 (1H, d,
J¼5.4 Hz, OH), 4.95 (1H, d, J¼4.6 Hz, OH), 4.89 (1H, br s, OH), 4.25
(1H, t, J¼5.5 Hz, OH), 3.65 (1H, dd, J1¼5.0, J2¼11.2 Hz, H-600a),
3.36e3.24 (3H, m, 2ꢂCH, H-600b), 3.17e3.15 (1H, m, H-100), 3.05 (2H,
br s, CH), 2.97e2.85 (7H, m, 2ꢂNCH3, H-1b), 2.74 (1H, dd, J1¼8.9,
MeOH/CHCl3); [
a]
25 ꢀ71.69 (c 0.1, DMSO); IR (KBr) nmax cmꢀ1 3344
D
(OH), 2218 (C^N), 1646, 1579, 1236; 1H NMR (300 MHz, DMSO)
d
¼7.67 (2H, m, ArH), 7.36 (2H, m, ArH), 6.86 (1H, s, ArH), 6.58 (2H, s,
J2¼14.8 Hz, H-1a); 13C NMR (50 MHz, DMSO)
¼154.0 (AreC), 151.1
d
ArNH2), 5.15 (1H, d, J¼5.4 Hz, OH), 4.92e4.90 (1H, d, J¼4.6 Hz, OH),
4.87e4.85 (1H, d, J¼4.2 Hz, OH), 4.22 (1H, t, J¼5.4 Hz, OH), 3.65 (1H,
dd, J1¼5.3, J2¼11.3 Hz, H-600a), 3.39e3.27 (3H, m, 2ꢂCH, H-600b),
3.18e3.13 (m, 1H, H-100), 3.06 (m, 2H, CH), 3.00 (dd, J1¼5.5,
J2¼8.8 Hz, 1H, H-1b), 2.78 (dd, J1¼8.8, J2¼14.7 Hz, 1H, H-1a); 13C
(AreC), 149.6 (AreC),149.1 (AreC), 129.9 (AreCH), 125.3 (AreCH),
119.1 (AreCH), 117.2 (C^N), 116.3 (C^N), 112.5 (AreCH), 95.2
(AreC), 92.4 (AreC), 80.8 (CH), 78.8 (AreC), 78.4 (CH), 74.0 (CH),
70.8 (CH), 61.8 (OCH2), 37.1 (CH2); ESMS m/z 439 (MþH)þ.
NMR (50 MHz, DMSO)
d¼153.8(AreC), 150.0 (AreC), 148.1 (AreC),
4.2.11. 2-Amino-40-(thiophen-2-yl)-6-[(
b-D-glucopyranosyl)methyl]
137.3 (AreC),132.0 (AreCH), 131.1 (AreCH), 123.3 (AreC), 119.5
(AreCH), 116.5 (C^N), 115.9 (C^N), 97.0 (AreC), 93.0 (AreC), 81.0
(CH), 78.7 (CH), 78.4 (CH), 74.0 (CH), 70.9 (CH), 61.8 (OCH2), 37.2
(CH2); ESMS m/z¼437 (MþNaþH)þ.
isophthalonitrile (2k). It was obtained by the reaction of compound
1k (1.2 g, 3.81 mmol), malononitrile (0.50 g, 7.64 mmol) and K2CO3
(0.52 g, 3.82 mmol) in water as light yellow solid (0.83g, yield 55%).
Analysis found C, 56.85; H, 4.77; N, 10.47 for C19H19N3O5S requires:
56.79; H, 4.56; N, 10.36; mp 209e212 ꢁC; Rf 0.52 (20% MeOH/
25
4.2.8. 2-Amino-40-(naphthalen-2-yl)-6-[(
b
-
D
-glucopyranosyl)
CHCl3); [
a]
ꢀ79.22 (c 0.1, DMSO); IR (KBr) nmax cmꢀ1 3457 (OH),
D
methyl]isophthalonitrile (2h). It was obtained by the reaction of
compound 1h (1.1g, 3.07 mmol), malononitrile (0.40 g, 6.14 mmol)
and potassium carbonate (0.42 g, 3.07 mmol) in water as yellow
solid (0.94g, yield 70%). Analysis found: C, 67.50; H, 5.12; N, 9.38 for
2214 (C^N), 1635, 1580, 1290; 1H NMR (300 MHz, DMSO)
d
¼7.82e7.80 (1H, m, ArH), 7,69e7.68 (1H, m, ArH), 7.24e7.21 (1H,
m, ArH), 6.99 (1H, s, ArH), 6.66 (2H, s, ArNH2), 5.21 (1H, d, J¼5.5 Hz,
OH), 5.00 (1H, d, J¼4.5 Hz, OH), 4.93 (1H, d, J¼4.0 Hz, OH), 4.26 (1H,
t, J¼5.5 Hz, OH), 3.64 (1H, dd, J1¼5.2, J2¼10.9 Hz, H-600a), 3. 39e3.25
(3H, m, 2ꢂCH, H-600b), 3.17e3.12 (1H, m, H-100), 3.09e3.07 (2H, m,
C25H23N3O5 requires: C, 67.41; H, 5.20; N, 9.43; Rf 0.6 (20% MeOH/
25
CHCl3); mp 230e233 ꢁC; [
a]
ꢀ51.99 (c 0.1, DMSO); IR (KBr) nmax
D
cmꢀ1 3351(OH), 2216 (C^N), 1637, 1579, 1288; 1H NMR (300 MHz,
DMSO)
¼8.18 (1H, s, ArH), 8.05e8.01 (3H, m, ArH), 7.74 (1H, d,
J¼8.2 Hz, ArH), 7.61 (2H, m, ArH), 7.00 (1H, s, ArH) 6.67 (2H, s,
CH), 2.99 (1H, m, H-1b), 2.77 (1H, dd, J1¼8.9, J2¼14.8 Hz, H-1a); 13
C
d
NMR (50 MHz, DMSO)
d¼154.2 (AreC), 150.0 (AreC), 141.1 (AreC),
139.1 (AreC), 129.8 (AreCH), 129.3 (AreCH), 128.8 (AreCH), 118.8