N. Spreti, L. Brinchi, R. Germani, M. V. Mancini, G. Savelli
FULL PAPER
procedure.[25] The IR and 1H NMR spectra confirmed the struc-
ture.
3.89 (t, 4 H, 2 CH2–O–Ar), 6.79 (d, 4 H, Ar), 7.19 (d, 4 H,
Ar) ppm. C36H60N2O4 (584.98): calcd. C 73.92, H 10.34, N 4.78;
found C 73.70, H 10.39, N 4.82.
N,NЈ-Bis(p-octyloxybenzyl)-3,6-dioxaoctane-1,8-diamine
pODODA)
(bis-
Acknowledgments
i. Freshly recrystallized (from water) and dried 4-hydroxybenzalde-
hyde (29.31 g, 0.24 mol), anhydrous potassium carbonate (40.05 g,
0.29 mol), and acetonitrile (400 mL) were placed in a 1-L round-
bottomed flask fitted with a reflux condenser, nitrogen inlet, me-
chanical stirrer and pressure-equalizing dropping funnel. The reac-
tion mixture was heated to reflux and stirred. Once reflux was
reached, octyl bromide (44.42 g, 0.23 mol) was added dropwise
over 1 h and the mixture was then heated at reflux for 12 h. After
the mixture had cooled to room temperature, it was transferred to
a separating funnel (2 L), treated with water (500 mL), and ex-
tracted with petroleum ether. The organic layer was washed twice
with NaOH (10%) and finally with water until neutrality was
reached. The organic solution, after drying with Na2SO4, was con-
centrated in a rotary evaporator to give p-octyloxybenzaldehyde as
a pale yellow oil. The yield was 98% (52.82 g), and purity by GLC
Support of this work by the Ministero dell’Istruzione, Università e
Ricerca, Rome (COFIN 2003) is gratefully acknowledged.
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1
was 98%. No treatment of the oil followed. H NMR (200 MHz,
CDCl3, 25 °C): δ = 0.88 (t, 3 H, CH3), 1.01–1.75 (m, 10 H, 5 CH2),
1.80–1.95 (m, 2 H, CH2), 4.06 (t, 2 H, CH2–O), 7.00 (d, 2 H, Ar),
7.85 (d, 2 H, Ar), 9.01 (s, 1 H, COH) ppm. C15H22O2 (234.34):
calcd. C 76.88, H 9.46; found C 76.90, H 9.50.
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ii. 2,2Ј-(Ethylenedioxy)bis(ethylamine) (8.60 g, 0.058 mol) was
added to a solution of p-octyloxybenzaldehyde (28.36 g, 0.121 mol)
in chloroform (200 mL) in a 500-mL round-bottomed flask fitted
with a Dean–Stark separator. The mixture was heated to reflux
while the water/chloroform azeotrope was distilled off. Once distil-
lation had finished, a reflux condenser was substituted for the sepa-
rator, and molecular sieves (10 g, 4 Å) were added. After the system
had been heated at reflux for 12 h and cooled to room temperature,
the molecular sieves were removed by filtration. The organic solu-
tion was concentrated in a rotary evaporator to give a light yellow,
very viscous liquid, which was crystallized from petroleum ether
and recrystallized from acetonitrile to give, after drying under vac-
uum, a crystalline solid. Yield 88% (29.65 g), m.p. 51–52 °C. 1H
NMR (200 MHz, CDCl3, 25 °C): δ = 0.86 (t, 6 H, 2 CH3), 1.14–
1.41 (m, 20 H, 10 CH2), 1.60–1.81 (m, 4 H, 2 CH2), 3.60 (s, 4 H,
2 =N–CH2), 3.70 [s, 8 H, CH2–O–(CH2)2–O–CH2], 3.99 (t, 4 H, 2
CH2–O–Ar), 6.86 (d, 4 H, Ar), 7.60 (d, 4 H, Ar), 8.16 (s, 2 H, 2
CH=N) ppm. C36H56N2O4 (580.95): calcd. C 74.44, H 9.72, N 4.82;
found C 74.48, H 9.69, N 4.86.
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iii. NaBH4 (0.040 mol) was added in small aliquots to a stirred
solution of the diimine (see ii. above) (0.015 mol, 8.71 g) in meth-
anol (200 mL), in a round-bottomed flask fitted with a reflux con-
denser. The mixture was heated at reflux for 12 h, methanol was
removed in a rotary evaporator, and the crude product was reco-
vered and dissolved in diethyl ether. The organic layer was transfer-
red to a separating funnel and was washed twice with NaOH (10%)
and finally with water until neutrality was reached. After drying
with Na2SO4, the solvent was removed in a rotary evaporator. The
crude product was dissolved in petroleum ether and then cooled
to –20 °C to give white crystalline bis-pODODA, which was col-
lected on a Büchner and washed with small amounts of cold petro-
leum ether (–20 °C). The solid was dried under vacuum at 15–
20 °C. Yield 78% (6.84 g), m.p. 36–38 °C. 1H NMR (200 MHz,
CDCl3, 25 °C): δ = 0.85 (t, 6 H, 2 CH3), 1.05–1.45 (m, 20 H, 10
CH2), 1.60–1.75 (m, 6 H, 2 CH2 +2 NH), 2.73 (t, 4 H, 2 CH2–N),
3.51 (m, 8 H, 2 CH2–O+2 CH2–Ar), 3.66 [s, 4 H, O–(CH2)2–O],
Received: March 21, 2006
Published Online: August 3, 2006
4384
www.eurjoc.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2006, 4379–4384