A. Lüköová, P. Baran, V. Volarevic et al.
Journal of Molecular Structure 1246 (2021) 131144
Synthesis of 5,7-dibromo-8-quinolinol N-oxide (HdBrQNO)
According to [28], 8-HQNO (0.8 g, 4.964 mmol) was dissolved
in glacial acetic acid (10 mL) and bromine (1 mL, 4.964 mmol) dis-
solved in acetic acid (10 mL) was added dropwise to the solution.
The resulting mixture was stirred for 1 h and the resulting yel-
low precipitate was filtered off and rinsed with petroleum ether.
The precipitate of HdBrQNO was recrystallized in two ways a) from
glacial acetic acid (formation of orange prisms – HdBrQNOa) and
b) from acetone (formation of yellow needles – HdBrQNOb). The
identity of both types of crystals was proved by NMR spectroscopy.
HdBrQNO – Calc. for C9H5Br2NO2 (318.95 g mol−1): C, 33.89;
H, 1.58; N, 4.39%. Found: C, 33.77; H, 1.67; N, 4.23%. Yield: 1.27 g
(80%).
Synthesis of CuCl2(HdClQNO)2(H2O)2 (2) and Cu(dClQNO)2(CHCl3)
(3)
Et3N (0.073 mL, 1 mmol) was added to HdClQNO (0.23 g,
1 mmol) in chloroform (10 mL) to adjust the pH of the solu-
tion to ca. 7.5, observing a color change from yellow to orange.
CuCl2•2H2O (0.1705 g, 1 mmol) in methanol (5 mL) was added.
Yellow-brown precipitate of 2 was filtered out after 2 h of stirring.
Another portion of a yellow-brown precipitate of 3 was isolated
after two days from the filtrate. Both products were air dried.
CuCl2(HdClQNO)2(H2O)2 (2)
–
Calc. for CuCl6C18 H14 O6N2
(630.58 g mol−1): C, 34.29; H, 2.24; N, 4.44%. Found: C, 34.43; H,
1.97; N, 4.38%. Yield: 0.227 g (36%).
IR (ATR, cm−1): 3449(vw), 3336(vw), 3082(w), 3059(w),
1761(vw), 1586(m), 1545(s), 1506(m), 1439(s), 1402(m), 1372(s),
1331(m), 1285(w), 1268(w), 1243(w), 1206(w), 1188(w), 1177(w),
1141(m), 1081(w), 1067(m), 919(w), 877(w), 860(s), 808(m), 765(s),
749(m), 734(m), 697(m), 658(m), 650(m), 625(m), 567(w), 540(m),
505(w), 473(m), 455(w), 432(m).
1H NMR (DMSO-d6, 600 MHz): δ = 8.72 (dd, 1H, J = 6.1, 1.0 Hz,
H-1), 8.23 (s, 1H, H-6), 8.19 (dd, 1H, J = 8.8, 1.0 Hz, H-3), 7.72 (dd,
1H, J = 8.8, 6.1 Hz, H-2) ppm.
13C NMR (DMSO-d6, 151 MHz): δ = 151.1 (C-8), 136.6 (C-1),
136.1 (C-6), 129.9 (C-3), 129.6 (C-4, C-9), 123.5 (C-2), 107.3 (C-5),
106.9 (C-7) ppm.
Cu(dClQNO)2(CHCl3) (3)
–
Calc. for CuCl7C19 H9O4N2
15N NMR (DMSO-d6, 61 MHz): δ = -108.7 (N-1) ppm.
IR (ATR, cm−1): 3092(w), 3057(m), 1620(w), 1567(m), 1508(m),
1481(w), 1440(m), 1391(s), 1347(m), 1314(m), 1269(m), 1240(m),
1183(m), 1150(m), 1114(m), 1059(m), 898(m), 875(s), 829(m),
805(s), 750(s), 702(s), 643(s), 621(m), 600(s), 549(m), 528(s),
505(m), 474(m), 427(m).
(641.00 g mol−1): C, 35.60; H, 1.42; N, 4.37 %. Found: C, 35.39; H,
1.81; N, 4.55 %. Yield: 0.205 g (32 %).
IR (ATR, cm−1): 3102(w), 3082(m), 2940-2790 (w), 1759 (w),
1587(m), 1509(m), 1447(m), 1383(m), 1356(m), 1320(w), 1265(m),
1252(m), 1210(w), 1192(m), 1166(m), 1135(m), 1079(m), 1062(m),
995(w), 930(w), 877(m), 869(w), 856(s), 815(s), 738(s), 696(s),
649(s), 632(m), 617(m), 566(m), 548(m), 511(w), 485(w), 454(m).
Synthesis of Cu(dClQNO)2(H2O) (4)
Synthesis of 7-iodo-8-quinolinol N-oxide (HIQNO)
K2CO3 (0.069 g, 0.5 mmol) was added to HdClQNO (0.046 g,
0.2 mmol) in 15 mL DMF to adjust the pH of the solution to ca.
6.5. Unreacted K2CO3 was removed by filtration and CuCl2•2H2O
(0.017 g, 0.1 mmol) in 5 mL of ethanol was added to the filtrate.
Mixture was stirring for 1 h and then filtered. After a few weeks,
small hedgehog crystals of 4 were filtered out and dried in air.
Iodine monochloride (4 g, 24.82 mmol) in cold ethanol (20 mL)
was slowly added to warm (50 °C) solution of 8-HQNO (2 g,
12.41 mmol) in ethanol (25 mL) with vigorous stirring. Observed
brownish-yellow precipitate was filtered and air dried. Subse-
quently, the precipitate was recrystallized from acetone forming
brownish-yellow prismatic crystals of HIQNO.
Cu(dClQNO)2(H2O)
(4)
–
Calc.
for
CuCl4C18 H10O5N2
HIQNO – Calc. for C9H6INO2 (287.05 g mol−1): C, 37.66; H, 2.11;
N, 4.88%. Found: C, 37.31; H, 1.89; N, 4.65 %. Yield: 3.38 g (95%).
1H NMR (DMSO-d6, 600 MHz): δ = 8.59 (dd, 1H, J = 6.0, 1.0
Hz, H-1), 8.13 (dd, 1H, J = 8.5, 1.0 Hz, H-3), 7.94 (s, 1H, H-6), 7.55
(dd, 1H, J = 8.5, 6.0 Hz, H-2), 7.26 (d, 1H, J = 8.5 Hz, H-5) ppm.
13C NMR (DMSO-d6, 151 MHz): δ = 153.1 (C-8), 138.7 (C-6),
135.5 (C-1), 131.8 (C-4), 130.7 (C-3), 128.0 (C-9), 122.2 (C-2), 118.2
(C-5), 83.1 (C-7) ppm.
(539.64 g mol−1): C, 40.06; H, 1.87; N, 5.19%. Found: C, 39.91; H,
2.01; N, 5.13%. Yield: 0.031 g (58%).
IR (ATR, cm−1): 3476(m), 3352(w), 3084(vw), 3051(w), 1658(w),
1577(m), 1541(m), 1504(m), 1444(s), 1407(m), 1374(s), 1332(s),
1286(m), 1248(m), 1209(m), 1189(w), 1173(m), 1139(m), 1085(w),
971(w), 871(m), 858(s), 797(s), 762(s), 747(s), 729(m), 655(s),
626(m), 602(m), 536(s), 505(w), 476(w), 434(w).
15N NMR (DMSO-d6, 61 MHz): δ = -110.0 (N-1) ppm.
Synthesis of {[Cu(dBrQNO)2]•2H2O}n (5)
IR (ATR, cm−1): 3056(m), 1568(m), 1508(m), 1441(m), 1386(m),
1362(w), 1327(m), 1301(m), 1236(m), 1185(w), 1150(m), 1097(m),
1063(w), 1040(m), 913(m), 815(s), 752(m), 683(s), 638(m), 606(m),
588(w), 567(s), 537(m), 477(m), 429(m).
K2CO3 (0.069 g, 0.5 mmol) was added to HdBrQNOa (0.064 g,
0.2 mmol) in 15 mL DMF to adjust the pH of the solution to ca.
6.5. Unreacted K2CO3 was removed by filtration and CuCl2•2H2O
(0.017 g, 0.1 mmol) in 5 mL of ethanol was added to the filtrate.
Mixture was stirring for 1 h and then filtered. After a few weeks,
small hedgehog crystals of 5 were filtered out and dried in air.
{[Cu(dBrQNO)2]•2H2O}n (5)
(735.46 g mol−1): C, 29.40; H, 1.64; N, 3.81 %. Found: C, 29.85;
–
Calc. for CuBr4C18 H12O6N2
Synthesis of CuCl2(8-HQNO)2(H2O) (1)
Aqueous solution (50 mL) of 8-HQNO (0.161 g, 1 mmol) was ad-
justed to the pH of 9 by 0.5 mL of 1 mol dm−3 aqueous KOH and
heated under reflux for 1 h followed by the addition of CuCl2 so-
lution (0.085 g CuCl2•2H2O, 0.5 mmol) in 25 mL H2O. The pH was
again adjusted to 9 and the mixture was refluxed for 8 h. Yellow
precipitate of 1 was filtered from a hot mixture and dried in the
air.
H, 1.79; N, 3.96 %. Yield: 0.049 g (67 %).
IR (ATR, cm−1): 3480(m), 3360(w), 3081(w), 3050(w),
2969(vw), 1747(w), 1651(m), 1573(m), 1537(s), 1500(m), 1436(s),
1403(s), 1368(s), 1327(s), 1275(w), 1246(m), 1208(m), 1188(m),
1171(m), 1132(m), 1080(m), 1059(s), 874(m), 852(m), 837(m),
795(s), 741(s), 703(w), 689(m), 650(s), 628(m), 596(m), 534(s),
471(m), 429(w).
CuCl2(8-HQNO)2(H2O) (1)
–
Calc. for CuCl2C18 H16 O5N2
(474.78 g mol−1): C, 45.53; H, 3.39; N, 5.90%. Found: C, 45.30; H,
3.35; N, 5.77%. Yield: 0.173 g (73 %).
Synthesis of CuCl2(HIQNO)2(H2O)4 (6)
IR (ATR, cm−1): 3625-3200(m), 3063(vw), 3006(vw), 1567(s),
1511(w), 1452(m), 1423(w), 1387(s), 1347(m), 1307(s), 1297(m),
1198(w), 1136(w), 1111(w), 1052(m), 1033(s), 810(s), 791(m),
737(s), 715(s), 607(s), 573(w), 509(s).
CuCl2•2H2O (0.017 g, 0.1 mmol) in methanol (5 mL) was added
drop by drop to the solution of HIQNO (0.057 g, 0.2 mmol) in
methanol (15 mL) under stirring. After 1 h of stirring, a yellow pre-
cipitate was isolated by filtration and dried in air.
3