Naphthaldehyde derived ligands
279
6,7,8,9,10,11,12,13,14,15,23,24,25,26-Tetra-
decahydrodinaphtho[2,3-b:20,30-n][1,16,5,12]-
J = 7.3 Hz, 2H), 7.58 (s, 2H), 7.68 (d, J = 8.2 Hz, 2H),
7.71 (d, J = 8.2 Hz, 2H) ppm; 13C NMR (C6D6):
d = 26.4, 30.8, 48.2, 51.1, 66.9, 106.1, 123.9,126.3,
126.6, 129.5, 130.2, 131.5, 134.7, 156.4 ppm; ESI–MS:
m/z = 441.2 (MH?).
dioxadiazacycloicosine (3, C32H38N2O2)
A solution of 4 % (v/v) 1,6-diaminohexane in ethanol
(1.7 cm3) was added at 0.3 cm3/h to a stirred solution of
0.10 g dialdehyde 7 (0.25 mmol) in 25 cm3 chloroform
and 25 cm3 ethanol. The resultant mixture was heated
under reflux for 2 h, then it was kept at room temperature
for 0.5 h. NaBH4 (0.038 g, 1.0 mmol) was added and the
mixture was heated to reflux for 1 h. Water (25 cm3) was
added and the products were extracted using chloroforme
(3 9 50 cm3). The combined chloroform extract was dried
over Na2SO4, filtered, and then the chloroform was
evaporated. The residue was purified by column chroma-
tography eluting with methanol/25 % ammonia (9.9:0.1,
v/v) to afford the product 3 (0.07 g, 58 %). M.p.:
156–157 °C; IR (KBr): vꢀ = 3394, 3052, 2927, 2848,
Complex formation
To obtain the association constants (K) corresponding to
complex formation, changes in the chemical shifts (Dd) as
a function of [Ni(II)] were determined. Amounts of 2 mg
of the host compound (1, 2, or 3) were dissolved in
2.00 cm3 of DMSO-d6. A 0.60-cm3 portion of this solution
was transferred into an NMR tube, to which were added
portions of NiCl2 solution prepared using the ligand solu-
tion as a solvent to eliminate the dilution effect. At least
8–10 data points were collected for each run, and each run
was conducted in duplicate. The changes in chemical shifts
(Dd) were plotted against [Ni(II)] for each run, and the
resulting mole ratio plots level off at around a 1:1 ratio of
Ni(II) and 1, 2,or 3, indicating the formation of a 1:1
complex in each case. The stoichiometry of each complex
was confirmed using the method of continuous variation
(Job’s plot). Figure 3 shows a typical 1:1 Job’s plot for the
1:Ni(II) complex. The other ligands showed similar
behavior. To calculate K values, the slopes and the inter-
cepts obtained from linear regression analyses of the
Benesi–Hildebrand plot were used (Fig. 2).
1631, 1598, 1594, 1502, 1456 cm-1 1H NMR (C6D6):
;
d = 1.06 (s, 4H), 1.24 (t, J = 6.4 Hz, 4H), 1.41 (s, 4H),
2.40 (t, J = 6.4 Hz, 4H), 3.35 (s, 4H), 3.76 (s, 4H), 6.68 (s,
2H), 6.98 (t, J = 7.4 Hz, 2H), 7.08 (t, J = 7.5 Hz, 2H),
7.40 (s, 2H), 7.43 (s, 2H), 7.44 (s, 2H) ppm; 13C NMR
(C6D6): d = 26.5, 26.7, 29.7, 48.9, 49.7, 67.6, 106.1,
124.0, 126.2, 126.7, 129.4, 129.5, 131.5, 134.5, 156.3 ppm;
ESI–MS: m/z = 483.3 (M?H).
6,7,8,9,10,11,12,13,21,22,23,24-Dodecahydrodinaph-
tho[2,3-b:20,30-l][1,14,5,10]dioxadiazacyclooctadecine
(2, C30H34N2O2)
Using the same general procedure as for 3, reaction of 7
with 1,4-diaminobutane afforded the product 2 (0.085 g,
75 %). M.p.: 157–158 °C; IR (KBr): vꢀ = 3324, 3054,
Acknowledgments We thank the Deanship of Research at Jordan
University of Science and Technology for financial support.
2930, 1630, 1600, 1504, 1460 cm-1 1H NMR (C6D6):
;
References
d = 1.62 (s, 4H), 1.68 (s, 4H), 2.70 (s, 4H), 3.64 (s, 4H),
3.98 (s, 4H), 6.97 (s, 2H), 7.27 (t, J = 7.4 Hz, 2H), 7.37 (t,
J = 7.4 Hz, 2H), 7.60 (s, 2H), 7.78 (d, J = 8.1 Hz, 2H),
7.72 (d, J = 8.2 Hz, 2H) ppm; 13C NMR (C6D6):
d = 26.3, 27.8, 49.3, 50.6, 67.4, 106.3, 124.0, 126.3,
126.6, 129.4, 129.9, 131.2, 134.6, 156.4 ppm; ESI–MS:
m/z = 455.5 (MH?).
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¨
8,9,10,18,19,20,21,22,23,24-Decahydro-7H-dinaph-
tho[2,3-b:20,30-k][1,5,9,13]dioxadiazacycloheptadecine
(1, C29H32N2O2)
Using the same general procedure as for 3, reaction of 7
with 1,3-diaminopropane afforded the product 1 (0.08 g,
73 %). M.p.: 204–205 °C; IR (KBr): vꢀ = 3321, 3051,
2930, 1631, 1597, 1501, 1459, 1440 cm-1 1H NMR
;
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13. Benesi A, Hildebrand JH (1949) J Am Chem Soc 71:2703
(C6D6): d = 1.55 (broad s, 2H), 1.74 (s, 4H), 1.82 (q,
J = 6.3 Hz, 2H), 2.78 (t, J = 6.3 Hz, 4H), 3.64 (s, 4H),
3.95 (s, 4H), 6.95 (s, 2H), 7.27 (t, J = 7.4 Hz, 2H), 7.37 (t,
123