Fluorinated azomethine ligands
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 9, September, 2010
1759
7.60, 7.72, 7.24, and 7.33 (all m, 8 H, 2 C6H4); 8.17 (s, 1 H, CH);
8.45 (s, 1 H, CH). 19F NMR (CDCl3), δ: 94.25 (s, 3 F, CF3).
Found (%): C, 51.56; H, 3.57; N, 6.13; F, 11.92. C20H15F3N2O4Ni.
Calculated (%): C, 51.88; H, 3.27; F, 12.31; N, 6.05.
(2ꢀEthoxycarbonylꢀ4,4,4ꢀtrifluoroꢀ1ꢀ{[2ꢀ(2ꢀoxidobenzylꢀ
ideneamino)phenyl]aminato}ꢀ3ꢀoxobutꢀ1ꢀene)copper(II) (3b). The
yield was 0.61 g (65%), m.p. 216—217 °C. IR, ν/cm–1: 3076,
2989 (CH str.); 1725 (CO2Et); 1607, 1583 (C=O, C=C, 1532
(C=N); 1273—1125 (C—F). Found (%): C, 50.99; H, 3.02;
F, 11.98; N, 5.75. C20H16F3N2O4Cu. Calculated (%): C, 51.34;
H, 3.23; F, 12.18; N, 5.99.
(2ꢀEthoxycarbonylꢀ4,4,5,5ꢀtetrafluoroꢀ1ꢀ{[2ꢀ(2ꢀoxidobenzylꢀ
ideneamino)phenyl]aminato}ꢀ3ꢀoxopentꢀ1ꢀene)nickel(II) (3c). The
yield was 0.72 g (73%), m.p. 218—220 °C. IR, ν/cm–1: 2991
(CH str.); 1710 (CO2Et); 1606, 1584 (C=O, C=C); 1525 (C=N);
1288—1092 (C—F). 1H NMR (CDCl3), δ: 1.37 (t, 3 H, OCH2CH3,
J = 7.1 Hz); 4.31 (q, 2 H, OCH2CH3, J = 7.1 Hz); 6.58 (tt, 1 H,
H(CF2)2, J = 53.5 Hz, J = 5.7 Hz); 6.66, 6.96, 7.54, 7.69, 7.22,
and 7.46 (all m, 8 H, 2 C6H4); 8.14 (s, 1 H, CH); 8.28 (s, 1 H,
CH). 19F NMR (CDCl3), δ: 23.4 (dm, 2 F, αꢀCF2, J = 53.4 Hz);
48.66 (m, 2 F, βꢀCF2). Found (%): C, 51.17; H, 3.18; F, 15.42;
N, 5.76. C21H16F4N2O4Ni. Calculated (%): C, 50.95; H, 3.26;
F, 15.35; N, 5.66.
(all m, 9 H, C6H5, C6H4); 8.66 (s, 1 H, CH=N); E (69%): 1.35
(t, 3 H, OCH2CH3, J = 7.1 Hz); 4.30 (q, 2 H, OCH2CH3,
J = 7.1 Hz); 6.69 (tt, 1 H, H(CF2)2, J = 53.7 Hz, J = 5.8 Hz);
8.64 (d, 1 H, CH=C, J = 14.6 Hz); 12.99 (br.d, 1 H, NH,
J = 14.6 Hz); Z (31%): 1.37 (t, 3 H, OCH2CH3, J = 7.1 Hz); 4.39
(q, 2 H, OCH2CH3, J = 7.1 Hz); 6.39 (tt, 1 H, H(CF2)2, J= 53.7 Hz,
J = 5.8 Hz); 8.54 (d, 1 H, CH=C, J = 14.6 Hz); 11.67 (br.d, 1 H,
NH, J = 13.9 Hz). 19F NMR (CDCl3), δ: E (69%): 23.64 (dm, 2 F,
CF2H, J= 53.7 Hz); 39.68 (m, 2 F, CF2); Z (31%): 22.19 (dm, 2 F,
CF2H, J= 53.7 Hz); 41.24 (m, 2 F, CF2H). Found (%): C, 59.84;
H, 4.05; F, 18.05; N, 6.48. C21H18F4N2O3. Calculated (%):
C, 59.72; H, 4.30; F, 17.99; N, 6.63.
Ethyl 4,4,5,5ꢀtetrafluoroꢀ2ꢀ{[2ꢀ(2ꢀfurylmethylideneamino)ꢀ
phenyl]aminomethylidene}ꢀ3ꢀoxopentanoate (5). A mixture of
ester 1b (3.34 g, 0.01 mol), furfural (0.97 g, 0.01 mol), and glacial
acetic acid (1 mL) was refluxed in benzene (30 mL) with azeoꢀ
tropic removal of water for 40 h. Then the reaction mixture was
concentrated. The precipitate that formed was filtered off
and recrystallized from ethanol. The yield was 2.84 g (69%),
m.p. 116—117 °C. IR, ν/cm–1: 3108 (NH); 2982, 2939, 2874
(C—H str.); 1699 (CO2Et); 1654 (CORF); 1623, 1605, 1589,
1
1578, 1562 (C=N, NH, C=C), 1283—1077 (C—F). H NMR
(DMSOꢀd6), δ, E, Z: 6.79—6.81 (m, 1 H, C4H3O); 7.32—7.39
(m, 4 H, C6H4); E (70%): 1.29 (t, 3 H, OCH2CH3, J = 7.1 Hz);
4.23 (q, 2 H, OCH2CH3, J = 7.1 Hz); 7.01 (tt, 1 H, H(CF2)2,
J = 52.6 Hz, J = 6.2 Hz); 7.57 (dd, 1 H, C4H3O, J = 7.8 Hz,
J = 1.3 Hz); 7.78 (dd, 1 H, C4H3O, J = 7.8 Hz, J = 1.3 Hz); 8.07
(br.d, 1 H, C4H3O, J = 1.5 Hz); 8.73 (s, 1 H, CH=N); 8.74 (d, 1 H,
CH=C, J = 14.8 Hz); 12.82 (br.d, 1 H, NH, J = 14.8 Hz);
Z (30%): 1.28 (t, 3 H, OCH2CH3, J = 7.1 Hz); 4.34 (q, 2 H,
OCH2CH3, J = 7.1 Hz); 6.87 (tt, 1 H, H(CF2)2, J= 52.6 Hz,
J = 6.2 Hz); 7.54 (dd, 1 H, C4H3O, J = 7.9 Hz, J = 1.3 Hz); 7.71
(dd, 1 H, C4H3O, J = 7.9 Hz, J = 1.3 Hz); 8.05 (br.d, 1 H,
C4H3O, J = 1.5 Hz); 8.70 (s, 1 H, CH=N); 8.58 (d, 1 H, CH=C,
J = 14.8 Hz); 11.67 (br.d, 1 H, NH, J = 14.8). 19F NMR
(DMSOꢀd6), δ: E (70%): 25.41 (dm, 2 F, CF2H, J = 52.6 Hz);
41.71 (m, 2 F, CF2); Z (30%): 24.24 (dm, 2 F, CF2H, J= 52.6 Hz);
42.31 (m, 2 F, CF2H). Found (%): C, 55.55; H, 3.75; F, 18.36;
N, 6.81. C19H16F4N2O4. Calculated (%): C, 55.34; H, 3.91;
F, 18.43; N, 6.79.
Chloro[1ꢀ(2ꢀaminophenylaminato)ꢀ2ꢀethoxycarbonylꢀ
4,4,5,5ꢀtetrafluoroꢀ3ꢀoxopentꢀ1ꢀene]copper(II) (6). A mixture of
compound 4 or 5 (0.002 mol) and copper(II) chloride (0.40 g,
0.003 mol) in ethanol (10 mL) was refluxed with stirring for 2 h.
The precipitate that formed was filtered off and recrystallized
from ethanol. The yield was 0.69 g (80% based on ester 4) and
0.73 g (81% based on ester 5), a darkꢀgreen powder, m.p.
205—207 °C (cf. lit. data10).
(2ꢀEthoxycarbonylꢀ4,4,5,5ꢀtetrafluoroꢀ1ꢀ{[2ꢀ(2ꢀoxidobenzylꢀ
ideneamino)phenyl]aminato}ꢀ3ꢀoxopentꢀ1ꢀene)copper(II) (3d).
The yield was 0.69 g (69%), m.p. 215—216 °C. IR, ν/cm–1: 2988
(CH str.); 1700 br. (CO2Et); 1609, 1582 (C=O, C=C); 1521
(C=N); 1228—1168 (C—F). Found (%): C, 50.15; H, 3.26;
N, 5.48; F, 15.42. C21H16F4N2O4Cu. Calculated (%): C, 50.45;
H, 3.23; F, 15.20; N, 5.60.
(2ꢀEthoxycarbonylꢀ4,4,5,5,6,6,6ꢀheptafluoroꢀ1ꢀ{[2ꢀ(2ꢀoxidoꢀ
benzylideneamino)phenyl]aminato}ꢀ3ꢀoxohexꢀ1ꢀene)nickel(II)
(3e). The yield was 0.79 g (70%), m.p. 193—194 °C. IR, ν/cm–1
:
3060, 2984 (CH str.); 1703 (CO2Et); 1605, 1580 (C=O, C=C);
1
1519 (C=N); 1218—1118 (C—F). H NMR (CDCl3), δ: 1.34
(t, 3 H, OCH2CH3, J = 7.1 Hz); 4.30 (q, 2 H, OCH2CH3,
J = 7.1 Hz); 6.69, 7.06, 7.62, 7.72, and 7.29 (all m, 4 H, 2 C6H4);
8.18 (s, 1 H, CH); 8.35 (s, 1 H, CH). 19F NMR (CDCl3), δ:
38.75 (m, 2 F, βꢀCF2); 51.51 (m, 2 F, αꢀCF2); 81.91 (t, 3 F, CF3,
J = 9.8 Hz). Found (%): C, 46.62; H, 2.59; F, 23.42; N, 4.66.
C22H15F7N2O4Ni. Calculated (%): C, 46.93; H, 2.69; F, 23.62;
N, 4.98.
(2ꢀEthoxycarbonylꢀ4,4,5,5,6,6,6ꢀheptafluoroꢀ1ꢀ{[2ꢀ(2ꢀoxidoꢀ
benzylideneamino)phenyl]aminato}ꢀ3ꢀoxohexꢀ1ꢀene)copper(II)
(3f). The yield was 0.77 g (68%), m.p. 159—161 °C. IR, ν/cm–1
:
3071, 2986 (CH str.); 1705 (CO2Et); 1605, 1581 (C=O, C=C);
1524 (C=N); 1281—1095 (C—F). Found (%): C, 46.23; H, 2.96;
F, 23.50; N, 4.66. C22H15F7N2O4Cu. Calculated (%): C, 46.53;
H, 2.66; F, 23.42; N, 4.93.
This study was financially supported by the Russian
Academy of Sciences (Programs of the Presidium of the
Russian Academy of Sciences Nos 09ꢀMꢀ23ꢀ2006 and
09ꢀCꢀ3ꢀ1002) and the Russian Foundation for Basic
Research (Project No. 10ꢀ03ꢀ96017).
Ethyl 2ꢀ{[2ꢀ(benzylideneamino)phenyl]aminomethylidene}ꢀ
4,4,5,5ꢀtetrafluoroꢀ3ꢀoxopentanoate (4). A mixture of ester 1b
(3.34 g, 0.01 mol) and benzaldehyde (1.06 g, 0.01 mol) was
refluxed in benzene (30 mL) with azeotropic removal of water
for 30 h. Then the reaction mixture was concentrated, and the
residue was dissolved in diethyl ether (15 mL). Hexane (40 mL)
was added to the reaction solution, and the precipitate that
formed was filtered off and recrystallized from ethanol. The yield
was 2.63 g (62%), m.p. 109—111 °C. IR, ν/cm–1: 3170, 3114
(NH); 2979, 2932, 2905 (C—H str.); 1717 (CO2Et); 1697
(CORF); 1633, 1622, 1597, 1586 (C=N, NH, C=C); 1317—1097
References
1. K. C. Gupta, A.K. Sutar, Coord. Chem. Rev., 2008, 252, 1420.
2. A. D. Garnovskii, I. S. Vasil´chenko, Usp. Khim., 2002, 71,
1064 [Russ. Chem. Rev. (Engl. Transl.), 2002, 71].
1
(C—F). H NMR (CDCl3), δ, E, Z: 7.22—7.56 and 8.10—8.16