696 Bhowmik et al.
Asian J. Chem.
13
1H, -OH); C NMR (75 MHz, CDCl3) δ 45.9, 47.4, 68.03,
Compound 2i: Yellow solid; yield: 75 %; m.p.: 158-162 °C;
1H NMR (300 MHz, DMSO-d6) δ 1.13-1.023 (m, 4H, C6H11),
1.77-1.45 (m, 10H, C6H11, OCH2CH2CH2CH2NH), 1.83 (m,
1H, -C6H11), 2.51 (brs, 1H, OCH2CH2CH2CH2NH), 2.65 (t,
J = 6.0 Hz, 2H, OCH2CH2CH2CH2NH), 4.03 (t, J = 4.8 Hz,
2H, OCH2CH2CH2CH2NH), 6.29 (s, 1H, Ar-H), 6.7 (s, 1H,
Ar-H), 6.9 (s, 1H, Ar-H), 7.52 (d, J = 7.5Hz, 3H, Ar-H), 8.02
(d, J = 6.6 Hz, 2H, Ar-H), 12.62 (s, 1H, -OH); 13C NMR (75
MHz, DMSO-d6) δ 24.8, 27.6 (2C), 29.6 (2C), 31.5 (2C), 44.2,
56.8, 66.3, 92.9, 98.7, 105.0, 105.9, 126.0 (2C), 129.0, 131.1
93.09, 98.6, 105.8 (2C), 107.2, 110.1, 126.2 (2C), 129.0, 131.8
(3C), 142.0 (2C), 157.7, 162.1, 164.0, 164.7, 182.4; IR (KBr,
ν
max, cm-1): 3470, 3417, 2924, 2851, 1662, 1644, 1373, 1179;
MS/GCMS: Calcd. for C22H19NO5: m/z 377.39 (M+). Found:
377.
Compound 2e: Yellow solid; yield: 70 %; m.p.: 130-132
°C; H NMR (300 MHz, CDCl3) δ 0.86 (t, J = 7.2 Hz, 3H,
1
HNCH2CH2CH2CH3), 1.33 (m, 2H, HNCH2CH2CH2CH3), 1.52
(m, 2H, HNCH2CH2CH2CH3), 1.92 (s, 1H NHCH2CH2CH2CH3),
2.68 (t, J = 7.5 Hz, 2H, HNCH2CH2CH2CH3), 3.03 (t, J = 7.2
Hz, 2H, OCH2CH2NH), 4.11 (t, J = 4.5 Hz, 2H, OCH2CH2NH),
6.27 (s, 1H, Ar-H), 6.41 (s, 1H, Ar-H), 6.56 (s, 1H, Ar-H),
7.44 (dd, J = 5.7 Hz, J = 5.1 Hz, 3H, Ar-H), 7.77 (dd, J = 6.0
Hz, J = 2.1 Hz, 2H, Ar-H), 12.62 (s, 1H, -OH); 13C NMR (75
MHz, CDCl3) δ13.8, 20.3, 31.1, 47.72, 48.9, 67.0, 92.9, 98.6,
105.8 (2C), 126.2 (2C), 129.0 (3C), 131.8, 162.1 (2C), 164.5
(2C), 182.4; IR (KBr, νmax, cm-1): 3477, 3416, 3060, 2955,
2926, 1664, 1614, 1359, 1176; MS/GCMS: Calcd. for
C21H23NO4: m/z 353.41 (M+). Found: 353.
Compound 2f: Yellow solid; yield: 80 %; m.p.: 140 °C;
1H NMR (300 MHz, CDCl3) 0.85 (t, J = 7.2 Hz, 3H,
NCH2CH2CH2CH3), 1.28 (m, 2H, NCH2CH2CH2CH3), 1.43
(m, 2H, NCH2CH2CH2CH3), 2.56 (t, J = 7.5 Hz, 2H
NCH2CH2CH2CH3), 2.93 (t, J = 7.2 Hz, 4H, OCH2CH2N), 4.02
(t, J = 5.7 Hz, 4H, OCH2CH2N), 6.24 (s, 2H, Ar-H), 6.35 (s,
2H, Ar-H), 6.49 (s, 2H, Ar-H), 7.37 (dd, J = 6 Hz, J = 3Hz,
6H, Ar-H), 7.73 (dd, J = 6.3 Hz, J = 1.2 Hz, 4H, Ar-H), 12.58
(s, 2H, -OH); 13C NMR (75 MHz, CDCl3) δ 14.0, 20.4, 29.5,
53.4, 55.6 (2C), 67.6 (2C), 93.1 (2C), 98.5 (2C), 105.7 (4C),
126.2 (4C), 129.0 (2C), 131.2 (4C), 131.7 (2C), 157.6 (2C),
(2C), 131.8, 157.6, 162.0, 164.0, 164.2, 182.4; IR (KBr, νmax
,
cm-1): 3436, 3065, 2928, 2853, 1663, 1612, 1383, 1173; MS/
GCMS: Calcd. for C25H29NO4: m/z 407.50 (M+). Found: 408.
Synthesis of 7-(O) substituted chrysin-triazole hybrids
(3a-c, 4a-c, 5a-c): The key intermediates 1(a-c) was prepared
according to the standard method as described in Scheme-I.
Then to the solution of an intermediate 1(a-c) (about 0.2-0.5
mmol in about 3 mL anhydrous DMF) was added alkyne (1.5
equiv.), Cu/CuO (50 mol %) and heated at 60-80 °C for several
hours until completion of the reaction was indicated on TLC.
The residue was then extracted and purified by similar chroma-
tographic techniques as before to afford 3a-c, 4a-c, 5a-c (Fig. 1).
Compound 3a: Yellow solid; yield: 75 %; m.p.: 186 °C;
1H NMR (400 MHz, CDCl3) δ 2.5 (s, 1H, CH2-OH), 4.49 (brs,
2H, OCH2CH2N), 4.74 (brs, 2H, OCH2CH2N), 4.82 (s, 2H,
CH2-OH), 6.35 (s, 1H, Ar-H), 6.57 (s, 1H, Ar-H), 6.7 (s, 1H,
Ar-H), 7.56 (s, 1H, triazole-H), 7.9 (m, 5H, Ar-H), 12.62 (s,
1H -OH); 13C NMR (100 MHz, CDCl3) δ 48.7, 55.3, 66.3,
92.6, 98.1, 105.1, 105.4, 125.8, 128.6 (3C), 130.4 (2C), 131.5,
157.1 (2C), 161.4, 163.2, 163.6, 181.8; IR (KBr, νmax, cm-1):
3440, 2926, 2857, 1657.9, 1614, 1353; MS/GCMS: Calcd.
for C20H17N3O5: m/z 379.37 (M+). Found: 379.
162.1 (2C), 163.8 (2C), 164.7 (2C), 182.3 (2C); IR (KBr, νmax
,
cm-1): 3416, 3075, 2958, 2855, 1662, 1617, 1353, 1170; MS/
GCMS: Calcd. for C38H35NO8: m/z 633.69 (M+). Found: 634.
Compound 2g: Yellow solid; yield: 55 %; m.p.: 162 °C;
1H NMR (300 MHz, CDCl3) δ 3.58 (t, J = 5.1 Hz, 2H,
OCH2CH2NH), 4.26 (t, J = 4.8 Hz, 2H, OCH2CH2NH), 6.29
(s, 1H, Ar-H), 6.42 (s, 1H, Ar-H), 6.47 (s, 1H, Ar-H), 6.58 (s,
1H, Ar-H), 6.64 (s, 1H, NHC6H4Cl), 7.0 (m, 1H, Ar-H), 7.1
(d, J = 3.6 Hz, 2H, Ar-H), 7.4 (d, J = 3.3 Hz, 3H, Ar-H), 7.79
(d, J = 1.8 Hz, 2H, Ar-H), 12.64 (s, 1H, -OH); 13C NMR (75
MHz, CDCl3) δ43.7, 67.0, 93.1, 98.6, 105.9 (2C), 114.2 (2C),
115.9 (2C), 126.2 (2C), 127.6, 129.0 (2C), 131.8, 137.8, 151.2,
157.7, 163.2, 164.0, 164.5, 182.4; IR (KBr, νmax, cm-1): 3445,
3416, 3025, 2958, 2852, 1666, 1617, 1339, 1179; MS/GCMS:
Calcd. for C23H18NO4Cl: m/z 407.85 (M+). Found: 408.
Compound 2h: Shining crystalline solid; yield: 50 %; m.p.:
130-132 °C; 1H NMR (CDCl3, 300 MHz) δ 3.44 (t, J = 4.8 Hz,
2H, OCH2CH2NH), 4.12 (t, J = 5.1 Hz, 2H, OCH2CH2NH),
6.28 (s, 1H, Ar-H), 6.4 (s, 1H, Ar-H), 6.51 (s, 1H, Ar-H), 6.53
(s, 1H, NHC6H4F), 6.57 (t, J = 2.4 Hz, 2H, Ar-H), 6.82 (t, J =
8.7 Hz, 2H, Ar-H), 7.44 (m, 3H, Ar-H), 7.78 (d, J = 6.0 Hz,
2H, Ar-H), 12.62 (s, 1H, -OH); 13C NMR (75 MHz, CDCl3) δ
43.7, 67.0, 93.1, 98.6, 105.9 (2C), 115.9 (2C), 126.2 (2C),
129.1, 131.2 (2C), 131.8 (3C), 143.8, 157.7, 162.2 (2C), 164.0,
164.5, 182.4; IR (KBr, νmax, cm-1): 3447, 3350, 2926, 2851,
1672, 1617, 1333, 1177; MS/GCMS: Calcd. for C23H18NO4F:
m/z 391.39 (M+). Found: 391.
Compound 3b: Yellow solid; yield: 45 %; m.p.: 160-162
°C; 1H NMR (400 MHz, CDCl3) δ 4.4 (brs, 2H, OCH2CH2N),
4.8 (brs, 2H, OCH2CH2N), 5.35 (s, 2H, CH2OC10H7), 6.3 (s,
1H, Ar-H), 6.4 (s, 1H, Ar-H), 6.6 (s, 1H, Ar-H), 7.18 (s, 1H,
Ar-H), 7.28 (m, 3H, Ar-H), 7.31 (d, J = 6.7 Hz, 2H, Ar-H),
7.34 (s, 1H, triazole-H), 7.54 (d, J = 7.2 Hz, 1H, Ar-H), 7.75
(d, J = 7.2 Hz, 3H, Ar-H), 7.87 (dd, J = 6.4 Hz, J = 4.8 Hz,
2H, Ar-H), 12.75 (s, 1H, -OH); 13C NMR (100 MHz, CDCl3)
δ 49.4, 61.9, 66.3, 93.0, 98.4, 105.9, 106.2, 107.7, 118.7, 123.9,
126.3, 126.4, 126.8, 127.6, 129.1, 129.5 (3C), 131.1 (3C),
132.0, 134.3, 144.4, 156.0 (2C), 162.3, 163.0, 164.1, 182.4;
IR (KBr, νmax, cm-1): 3410, 2927, 2858, 1658, 1614, 1357;
MS/GCMS: Calcd. for C30H23N3O5: m/z 505.52 (M+). Found:
506.
Compound 3c: White brown solid; yield: 45 %; m.p.: 178-
180 °C; 1HNMR(400MHz, CDCl3) δ2.3(s, 6H, OC6H2 (CH3)2Cl),
4.4 (brs, 2H, OCH2CH2N), 4.8 (brs, 2H, OCH2CH2N), 5.1 (s,
2H, CH2OC6H2 (Me2)Cl), 6.3 (s, 1H, Ar-H), 6.4 (s, 1H, Ar-H),
6.6 (s, 1H, Ar-H), 6.7 (s, 2H, Ar-H), 7.54 (s, 1H, triazole-H),
7.78 (brs, 3H, Ar-H), 7.8 (d, J = 6 Hz, 2H, Ar-H), 12.75 (s,
13
1H, -OH); C NMR (100 MHz, CDCl3) δ 20.9 (2C), 49.4,
61.9, 66.2, 92.2, 98.2, 105.7 (2C), 114.2 (2C), 123.1, 126.8,
129.1 (3C), 131.2 (3C), 137.2 (2C), 142.0, 158.0, 159.8, 162.2,
164.1, 165.0, 182.4; IR (KBr, νmax, cm-1): 3435, 2920, 2853,
1651.7, 1614, 1349.7; MS/GCMS: Calcd. for C28H24N3O5Cl:
m/z 517.96 (M+). Found: 518.