6
E. Karatas and H. I. Ucan
Vol 000
Scheme 3. Synthetic route for 5-aminomethyl-8-hydroxyquinoline (QN). Reagents and reaction condition: (i) formaldehyde, gaseous HCl, room tem-
perature 12 h; (ii) potassium phtalimide, DMF, 150°C 5 h, (iii) concentrated HCl, reflux.
Table 2
Some physical properties, effective magnetic moments, elemental analyses, and AAS analyses of the ligands and complexes.
Found (Calcd.)(%)
μeff
(BM)
mp
(°C)
Yield
(%)
Compound
Formula
Color
White
Greenish
Cream
Dark Brown
Dark Green
Brown
C
N
H
M
TRIPOD
QN
QN-TRIPOD
I
II
III
IV
C
24H15N3O6
C10H10N2O
C54H39N9O6
C102H78N15O12Fe3
C102H78N15O12Cr3
C114H78N15O12Fe3
C114H78N15O12Cr3
—
—
—
1.63
3.51
1.72
3.63
174
96
85
80
70
75
65
70
60
65.26 (65.31)
68.84 (68.95) 16.12 (16.08) 5.72 (5.79)
71.22 (71.28) 13.91 (13.85) 4.28 (4.32)
65.34 (65.40) 11.31 (11.22) 4.12 (4.20) 8.83 (8.94)
65.72 (65.80) 11.34 (11.28) 4.11 (4.22) 8.43 (8.38)
67.73 (67.87) 10.49 (10.41) 3.83 (3.90) 8.22 (8.30)
68.19 (68.26) 10.52 (10.47) 3.83 (3.92) 7.69 (7.78)
9.61 (9.52)
3.39 (3.43)
—
—
—
156
325a
350a
330a
365a
Green
aDecomposition temperature.
with 10% Na2CO3 twice and with H2O once. The organic
layer was dried over anhydrous Na2SO4 and then
concentrated. The white powder was recrystallized from
20mL of AcOEt.
mixture were refluxed for 4 h. The mixture was allowed
to cool to room temperature, and the obtained product
was filtered, washed with water, ethanol and diethyl
ether, and dried in vacuo (0.4 bar) at 60°C. The FTIR
(cmꢀ1) data for I: 2859 (CH), 1620 (ꢀCH¼N), 1574
(C¼N triazine), 1377 (COC), 547 (M–N), 469 (M–O). II:
2862 (CH), 1603 (–CH¼N), 1575 (C¼N triazine), 1369
(COC), 551 (M–N), 475 (M–O). III: 2824 (CH), 1615 (–
CH¼N ), 1578 (C¼N triazine), 1368 (COC), 549 (M–N),
464 (M–O). IV: 2829 (CH), 1600 (–CH¼N), 1578 (C¼N
triazine), 1368 (COC), 565 (M–N), 471 (M–O). The
elemental analyses, magnetic, and physical properties of
the synthesized complexes are given in Table 2.
Synthesis
of
QN-TRIPOD.
5-Aminomethyl-8-
hydroxyquinoline (0.522g, 3mmol) was added drop by
drop to a solution of 2,4,6-tris(p-formylphenoxy)-1,3,5-
triazine (0.442g, 1mmol) in 30mL methanol/chloroform
solution (1/1), and then three drops of concentrated H2SO4
was added as catalyst in 50mL methanol/chloroform
solution (1/1). The mixture was then stirred under reflux
for 24h. The mixture was cooled to room temperature and
yellow powder product was filtered. The precipitate was
washed with cool ethanol. FTIR (cmꢀ1): 3407 (ꢀOH),
1636 (ꢀCH¼N), 1562 (C¼Ntriazine); 1H NMR (DMSO-d6):
δ=4.41 (s, 6H, -CH2), 7.09 (d, 3H, ArH), 7.56 (d, 3H,
ArH), 7.63–7.67 (m, 15H, ArH), 8.1 (s, 3H, ꢀCH), 8.57 (d,
3H, ArH), 8.89 (d, 3H, ArH), 10.10 (s, 3H, OH).
Acknowledgment. We thank the Scientific Research Projects
Foundation of Selcuk University (SUBAP-Grant Number
2009/09101036) for financial support of this work produced
from a part of Erhan Karatas’s PhD Thesis.
Preperation of ligand complexes.
[Fe(Salen)]2O, [Fe
(Salophen)]2O, [Cr(Salen)]2O, and [Cr(Salophen)]2O
were prepared by addition of concentrated ammonia
solution until alkaline. It was to the hot EtOH solutions
of [Fe(Salen)]Cl, [Fe(Salophen)]Cl, [Cr(Salen)]Cl, and
[Cr(Salophen)]Cl, respectively [25].
REFERENCES AND NOTES
[1] Uysal, S.; Coskun, A. J Heterocyclic Chem 2011, 48, 936.
[2] Carmouma, M.; Blanchoud, H.; Teil, M. J.; Blanchard, M.;
Chevreuil, M. Water Air Soil Pollut 2001, 132, 1.
General procedure for the reaction of tripodal complexes
(I, II, III, and IV). A solution of QN-TRIPOD (1mmol)
in 20mL absolute methanol was added to the drop wise
suspension of {[Fe/Cr(Salen)]2O}/{[Fe/Cr(Salophen)]2O}
(1.6 mmol) in 20 mL of absolute methanol, and the
[3] Klenke, B.; Stewart, M.; Barrett, M. P.; Brun, R.; Gilbert, I. H.
J Med Chem 2001, 44, 3440.
[4] Patel, H. S.; Patel, V. C. Eur Polym J 2001, 37, 2263.
[5] Hoog, P.; Gamez, P.; Luken, M.; Roubeau, O.; Krebs, B.;
Reedijk, J. Inorg Chim Acta 2004, 357, 213.
[6] Timmerman, P.; Prins, L. J Eur J Org Chem 2001, 17, 3191.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet