HÁBITOS DE CONSUMO DE CIGARRILLO

Ni(0Ac)2 • 4H2O H =

113

To an ethanolic solution containing ambch (0.13 g, 0.4 mmol, 60 mL) the stoichiometric amount o f nickel (H) acetate (0.1 g, 0.4 mmol) was added at once as a powder. The solution turned from yellow to dark red in only a few minutes. The reaction mixture was kept under stirring at 25 °C for 3 hours. Filtration o f the solution afforded a red precipitate o f the nickel (II) ambch complex 113 which was washed with cold ethanol (5 mL) and dried under vacuum (0.09 g, 60% yield). Dark-red crystals for X-ray experiments were grown from CH2CI2 and petroleum spirit.

'H-NMR (CDCI3): 5 ,7 .6 4 (IH, s, CH=N); 7.02 (IH , d, J = 7.8 Hz, H*); 6.94 (IH, t, J =

7.8 Hz, H"); 6.55 (IH, d, J = 7.8 Hz, H^); 6.22 (IH , t, J = 7.8 Hz, ); 3.21 (IH, m, aliph); 2.46 (IH, m, aliph); 1.95(1H, m, aliph); 1.56 (IH, m, aliph); 1.34 (IH, m, aliph).

'^C-NMR (CDCI3): 5, 153.74 (C’), 133.36 (C^), 133.25 (C ), 131.72 (C^), 119.35 (C'),

115.54 (C^), 111.56 (C^), 70.06 (C*), 29.13 (C*), 24.69 (C'“).

IR (KBr, cm”'): 3439 br, w, 3342 w, 3042 w, 2937 w , 2859 w, 1610 vs, 1540 s, 1459 s, 1389 m, 1366 m, 1340 w, 1307 w, 1241 m, 1218 w, 1192 w, 1155 w, 1122 w, 1045 w, 1022.2 w, 910 w, 932 w, 747 m, 735 m, 643 w, 571 w, 463 w, 445 w.

Elemental analysis calculated for: C2oH2 2N4Ni: C, 63.70; H, 5.88; N, 14.85. Found: C,

5.9.1.2 Synthesis of the Ni(5-Cl-ambch) complex

N=' = N

C l— (\ /)— N ' N —(\ />— 01 11 4

Synthesis o f this complex was performed using a procedure similar to that employed for N i ambch. The product ( 0.133 g), a red powder, was obtained in 91 % yield.

NMR (CDCI3): S, 7.59 (IH, s, CH=N); 7.00 (IH , d, J = 2.2 Hz, H®); 6.85 (IH , dd, J =

2.2 Hz, J = 9.0 Hz, H"); 6.49 (IH, d, J = 9.0 Hz, r f); 3.2-3.1 (IH, m, aliph); 2.5-2.4 (IH , m, aliph); 2.05-1.95 (IH, m, aliph); 1.6-1.2 (5H, m, aliph); 0.9-0.8 (2H, m, aliph). IR (KBr, cm”^): 3437 br, m, 3344 m, 2934 m, 2856 w, 1611 vs, 1535 m, 1472 s, 1435 m, 1391 m, 1344 w, 1304 w, 1229 m, 1178 m, 1130 w, 1042 w, 934 w, 870 w, 804 m, 737 m, 671 w, 638 w.

MS (FAB) (m/z) 445(95), 410(4.1), 367(2), 302(2), 252(4.4), 230(6), 117(14.6), 37(8.7) HRMS calculated for C2oH2oN4Cl2Ni (M+1) 445.0487, found 445.0496.

Elemental analysis calculated for C2oH2oN4Cl2Ni: C, 53.86; H, 4.52; N, 12.56. Found:

C, 53.66; H, 4.40; N, 12.60.

5.9.1.3. Synthesis o f the Ni(3-MeO-ambch) complex

N='

115

Procedure 1

To an ethanolic solution o f 3-MeO-ambch (0.116 g, 0.3 nunol, 20 mL) was added N i(0 Ac) 2 • 4H20(0.076 g, 0.3 mmol) and the obtained solution was kept at room

temperature under stirring for 3 h. No precipitate was formed and after the mentioned time, solution was concentrated under vacuum, transferred to a sample tube and layered with petroleum spirit. Next day the liquid phase was separated with a pipette from the purple precipitate formed at the bottom o f the tube and the solid was washed two times

with petroleum spirit. Both the solution and the purple solid were analysed by ' H-NMR. The NMR o f the solution indicated that it contained only unreacted ligand. The purple solid had low solubility in CDCI3 and it presented no signals in the aromatic region o f

the spectrum.

IR (KBr, cm“^): 3600 s, 3427 vs, 3292 vs, 3270 vs, 3171 s, 3157 s, 2947 s, 2926 vs, 2899 m, 2859 m, 1598 vs, 1576 vs, 1456 m, 1440 m, 1406 s, 1343 w, 1232 w, 1123 m, 1021 vs, 925 w, 859 w, 6 6 8 m, 558 w, 497 w.

Complexation was also attempted in the presence o f stoichiometric amount o f NEt] which was added as a solution in ethanol, after the metal salt. The reaction took place under stirring at room temperature for 4 h. However, at the end o f this period the NMR o f a sample indicated only unreacted ligand.

Procedure 2

The reaction was performed using a similar procedure as described before, with the difference that after addition o f all the reagents, the mixture was heated to 60-65 °C and stirred at this temperature for 3 h. After this time, a dark brown precipitate o f Ni (3- MeO-ambch) 115 (0.082 g, 62 % yield) was separated by filtration fi*om a dark-brown solution.

'H-NMR (Precipitate, CDCI3): 5,7.67 (IH, s, CH=N); 6.72 (IH, d, H‘ , J = 7.5 Hz); 6.45

(IH, d, H^, J = 7.5 Hz); 6.17 (IH, t, , J = 7.5 Hz); 4.16 (IH, br, NH); 3.85 (3H, s, OCH3); 3.18 (IH, m, aliph); 2.5 (IH, m, aliph); 1.96 (IH, m, aliph); 1.3-1.26 (2H, m,

aliph). '^C-NMR (CDCI3): S, 152.96 (C’), 148.55 (C^), 145.88 (C^), 124.71 (C®), 115.00 (C ), 109.68 (C*), 108.20 (C'), 70.14 (C*), 55.62 (OCH3), 29.22 (C®), 24.77 (C'°). IR (KBr, cm”'): 3446 br, m, 3351 m, 2932 w, 1611 vs, 1543 w, 1481 s, 1442 m, 1386 w, 1344 w, 1227 vs, 1164 w, 1095 w, 1074 w, 1040 w, 975 w, 872 w, 725 m, 673 w. MS (FAB) (tw/z) 437(100), 422(9), 371(3), 301(3), 268(3), 248(6), 225(8), 213(4), 183(2.2), 158(4.3), 129(4), 99(7);

Elemental analysis calculated for C2 2H2 6N4 0 2Ni: C, 60.44; H, 5.99; N, 12.81. Found: C,

5.9.1.4. Synthesis of the Ni(3-Me-ambch) complex

N='

CH

1 1 6

Synthesis o f this complex was performed using a procedure similar to that employed for the nickel (II) ambch-3MeO. The compound (0.247 g) was obtained in 85 % yield. 'H-NMR (CDCI3): 5, 7.70 (IH, s, CH=N); 6.99 (IH, d, H*, J = 7.5 Hz); 6.94 (IH, d, H^,

J = 7.5 Hz); 6.20 (IH, t, H^ J = 7.5 Hz); 5.31 (IH, br, NH); 3.20 (IH, m, aliph); 2.53- 2.50 (IH, m, aliph); 2.17 (3H, s, CH3); 1.97 (IH, m, aliph); 1.39-1.25 (2H, m, aliph).

'^C-NMR (CDCI3): S, 154.1 (C’), 152.34 (C^), 131.9 (C"), 131.8 (C*), 123.97 (C^),

115.28 (C^), 1 1 1 . 2 1 (C'), 70.20 (C*), 29.09 (C’), 24.73 (C'“), 17.56 (CH3)

IR (KBr, cm''): 3444 w, 3375 w, 3364 w, 3050 w, 3024 w, 2962 w, 2933 m, 2855 w, 1609 vs, 1548 s, 1459 s, 1440 m, 1412 w, 1377 w, 1342 w, 1311 w, 1226 s, 1089 m, 1044 m, 1032 w, 741 m, 733 s, 623 m, 571 w, 509 w.

Elemental analysis calculated for C2 2H2 6N4Ni: C, 65.22; H, 6.46; N, 13.83. Found: C,

64.11; H, 6.42; N, 13.42.

5.9.1.5 Synthesis o f the Ni(5-Me-ambch) complex

N='

11 7

Synthesis o f this complex was performed using a procedure similar to that employed for the nickel (II) 3-MeO-ambch. The product (0.098 g, dark-red powder) was obtained in 32 % yield.

'H-NMR (CDCI3): 6, 7.60 (IH, s, CH=N); 6.80 (IH , s, H‘); 6.78 (IH , d, S ', J = 8.4

Hz); 6.50 (IH , d, , J = 8.4 Hz); 3.15 (IH, m, aliph); 2.47 (IH, m, aliph); 2.14 (3H, s, CHj); 1.95 (IH, m, aliph); 1.36 (2H, m, ahph).

IR (KBr, cm”^): 3439 br, w, 3337 w, 3012 w, 2928 m, 2855 m, 1622 vs, 1601 vs, 1541 vs, 1479 vs, 1452 s, 1393 s, 1348 s, 1306 w, 1246 s, 1200 m, 1165 s, 1130 w, 1045 w, 945 w, 870 w, 808 m, 781 w, 638 m, 563 w, 451 w.

MS (FAB) {m/z) 405(100), 352(3.2), 267(2.7), 192(12.5), 145(6), 58(3) HRMS calculated for C2 2H2 6N4N1 (M ^ 404.1501, found 404.1511.

Elemental analysis calculated for C22H26N4N1: C, 65.22; H, 6.46; N, 13.83. Found: C, 62.81; H, 6.25; N, 12.91.

5.9.2 Synthesis o f Copper amch complexes

5.9.2.1 Synthesis o f Cu(ambch) complex

N = = N

:cu

132

A solution o f triethylamine (0.06 g, 0.6 mmol) in ethanol (2.5 mL) was added to a stirred ethanolic solution o f the free ligand (0.1 g, 0.3 mmol, 40mL). The stoichiometric amount o f copper(II) acetate (0.06 g, 0.3 mmol) was then added as a powder to the above solution. The latter changed its colour in few minutes from yellow to brown indicating the formation o f the complex. After 3 h at 25 °C the solution was filtered to give a brown precipitate which was washed with cold ethanol and dried under vacuum. The desired product (0.07 g) was obtained in 59 % yield. Brown crystals for X-ray experiments were grown from CH2CI2 and petroleum spirit.

IR (KBr, cm"^): 3440 br, w, 3340 br, w, 2935 w, 2856 w, 1616 vs, 1535 s, 1475 sh, m, 1450 s, 1389 m, 1355 m, 1309 w, 1235 m, 1179 m, 1157 m, 1117 m, 1022 m, 909 w, 746 sh, m, 738 m, 664 w, 566 w, 460 w, 414 w.

MS (FAB) {m/z) 382(60.4), 321(2), 263(9.6), 182(7.2), 131(9.1), 81(2.8) HRMS calculated for C2 0H2 2N4CU (M ^ 381.1134, found 381.1140.

Elemental analysis calculated for C2 0H2 2N4CU: C, 62.89; H, 5.80; N, 14.67; Found: C,