solid. The product was purified by chromatography eluting
with methylene chloride–hexane (3:1 v/v). Evaporation of the
solvent gave the product as a light yellow solid which was
recrystallized from thf–MeOH. Yield 90%. H NMR (CDCl3):
δ 0.85 (t, CH3, 3 H), 1.24–1.81 (m, CH2, 20 H), 1.95 (s, CNCH3,
3 H), 3.33 (q, CH2OH, 2 H), 3.68 (t, NCH3 2 H), 3.92 (t, OCH2,
2 H), 5.55 (s, COHCH, 1 H), 6.83 (d, C6H3, 2 H), 7.76 (d, C6H4,
2 H) and 11.25 (s, COHCH, 1 H). 13C NMR (CDCl3): δ 14.03,
19.21, 22.53, 25.14, 29.08, 29.18, 29.31, 29.40, 31.79, 32.51,
39.82, 59.04, 67.89, 91.42, 113.75, 128.46, 132.57, 161.08,
164.80 and 186.67.
Table 4 Elemental analyses of dicopper complexes with calculated
values in parentheses
1
Analysis (%)
Compound
n
C
H
N
3
12
14
16
18
12
16
8
64.23 (63.90)
64.96 (65.17)
65.85 (66.30)
67.44 (67.32)
68.65 (68.43)
71.09 (70.96)
61.85 (61.67)
64.61 (64.56)
67.11 (66.82)
8.30 (8.27)
3.12 (3.10)
2.75 (2.92)
2.66 (2.76)
2.67 (2.62)
2.17 (2.16)
1.91 (1.84)
3.45 (3.43)
3.11 (3.01)
2.71 (2.69)
8.52 (8.62)
8.70 (8.94)
9.36 (9.23)
9.99 (9.78)
10.57 (10.45)
7.66 (7.64)
8.58 (8.45)
9.23 (9.09)
5
4
3,5-Bis(dodecyloxy)phenyl
2-(3-hydroxypropyl)iminopropyl
ketone. Light yellow solid, yield 89%. 1H NMR (CDCl3): δ 0.79
(t, CH3, 6 H), 1.24–1.80 (m, CH2, 40 H), 1.96 (s, CNCH3, 3 H),
3.34 (q, CH2OH, 2 H), 3.65 (t, NCH3, 2 H), 3.93 (t, OCH2, 4
H), 5.53 (s, COHCH, 1 H), 6.45 (s, C6H3, 1 H), 6.91 (s, C6H3,
2 H) and 11.32 (s, COHCH, 1 H). 13C NMR (CDCl3): δ 14.12,
19.35, 21.03, 22.69, 26.04, 29.36, 29.63, 31.92, 32.47, 39.96,
59.45, 60.41, 68.16, 92.27, 103.83, 105.16, 142.46, 160.08,
165.34 and 187.24.
12
16
â-Enaminoketones.1-(4-Dodecyloxyphenyl)-3-(3-hydroxyprop-
ylimino)propan-1-one. Sodium metal (0.75 g, 32.6 mmol) was
freshly cut into small pieces and stirred in dry diethyl ether (25
cm3) for 0.5 h. A mixture of 4-dodecyloxyacetophenone (5.0 g,
16.45 mmol) in diethyl ether (20 cm3) and ethyl formate (6.60
cm3, 16.45 mmol) was slowly added and allowed to stir at room
temperature under a nitrogen atmosphere for 12 h. The solution
was concentrated to give a light greenish solid mixed with
some sodium metal. Methanol was slowly added to quench the
sodium metal, and the solution filtered to remove inorganic
salts. It was transferred to a round-bottom flask (250 cm3), and
then neutralized with acetic acid. At this time the solution
turned from cloudy yellow to clear red. 3-Aminopropan-1-ol
(1.06 g, 16.45 mmol) was added dropwise and the mixture
gently refluxed for 24 h. It was concentrated in vacuum to give
the crude product as a brown solid. A light orange solid was
obtained after recrystallization from hexane–dichloromethane
(9:1). Yield 96%. 1H NMR (CDCl3): δ 0.88 (t, CH3, 3 H), 1.15–
1.86 (m, CH2, 20 H), 3.44 (q, OCH2, 2 H), 3.78 (t, NCH2, 2 H),
4.01 (t, OCH2, 2 H), 5.66 (d, CH2, 1 H), 6.89 (d, C6H4, 2 H),
7.10 (t, CHN, 1 H), 7.30 (d, C6H4, 2 H) and 10.20 (t, CNH,
1 H). 13C NMR (CDCl3): δ 14.13, 22.72, 25.87, 29.21, 31.93,
33.35, 45.75, 59.43, 68.14, 89.71, 113.92, 128.87, 132.24, 153.98,
161.54 and 189.15. IR (thin film): 3420, 2941, 2848, 1663, 1606,
1586, 1532, 1490, 1478, 1382, 1297, 1254, 1173, 1115, 1069,
Copper complexes of 1-(4-alkoxyphenyl)-3-(3-hydroxypropyl-
imino)propan-1-one 3. A solution of 1-(4-dodecyloxyphenyl)-
3-(3-hydroxypropylimino)propan-1-one (0.30 g, 0.77 mmol)
dissolved in dichloromethane (10 cm3) was added to a hot
methanol solution (10 cm3) of copper acetate monohydrate
(0.158 g, 0.79 mmol). The mixture was stirred at room temper-
ature for 1 h and then gently refluxed for 1 h. The crude green
solid was collected and then recrystallized from dichloro-
methane–methanol (2:3) to give a light green solid. Yield 78%.
IR (thin film): 3458, 2929, 2840, 1606, 1532, 1505, 1463, 1432,
1389, 1297, 1243, 1181, 1173, 1092, 1019, 845, 718 and 617
cmϪ1
.
Bis[3,5-dialkoxyphenyl 2-(3-hydroxypropyl)iminopropyl keto-
nato]copper(II) complexes 5. To a stirred solution of 3,5-
bis(dodecyloxy)phenyl
2-(3-hydroxypropyl)iminopropyl
ketone (0.30 g, 0.53 mmol) in dichloromethane (10 cm3) was
added a solution of copper acetate monohydrate (0.11 g, 0.55
mmol) in hot methanol (5.0 cm3). The reaction mixture was
stirred for 1 h and then gently refluxed for 2 h. The mixture was
concentrated to give a brown-green solid. The green-gray prod-
uct was obtained by recrystallization from ethyl acetate–
methanol. Yield 83%. IR (thin film): 3440, 2936, 2848, 1576,
1516, 1457, 1416, 1349, 1300, 1274, 1268, 1167, 1100, 1051, 998,
1019, 853 and 780 cmϪ1
.
3,5-Bis(dodecyloxy)acetophenone. White crystals, yield 83%.
1H NMR (CDCl3): δ 0.82 (t, CH3, 6 H), 1.25–1.80 (m, CH2, 40
H), 2.51 (s, COCH3, 3 H), 3.93 (t, OCH2, 4 H), 6.59 (s, C6H3, 1
H) and 7.02 (s, C6H3, 2 H). 13C NMR (CDCl3): δ 14.00, 22.59,
25.96, 26.55, 29.17, 29.28, 31.75, 68.17, 105.97, 106.45, 138.80,
160.25 and 197.58.
965, 937, 917, 838, 770, 723 and 615 cmϪ1
.
Crystal-structure determination of complex 5 (n ؍
8)
1-(4-Dodecyloxyphenyl)butane-1,3-dione. Yellow solid, yield
79%. H NMR (CDCl3): δ 0.85 (s, CH3, 3 H), 1.24–1.78 (m,
Single-crystal X-ray diffraction data were measured on a
Seimens SMART CCD diffractometer. Reflections were
collected using four different φ setting angles, each setting
covers a ω range of 180Њ with a 0.3Њ interval between frames.
Each frame was exposed for 20 s. The detector was located
4.0 cm away from the crystal. An empirical absorption correc-
tion was applied. The structure was solved by direct methods.
Hydrogen atoms were fixed at calculated positions and refined
using a riding model. Anisotropic displacement parameters
were used for all non-H atoms, while the given isotropic
displacement parameters were used for H atoms (1.2 and 1.5
times the equivalent isotropic displacement parameter of the
atom to which they are attached respectively for methylene H
atoms and methyl H atoms).
1
CH2, 20 H), 2.10 (s, COCH3, 3 H), 3.97 (t, OCH2, 2 H), 6.06 (s,
COHCH, 1 H), 6.88 (d, C6H4, 2 H), 7.87 (d, C6H4, 2 H) and
16.32 (s, COHCH, 1 H). 13C NMR (CDCl3): δ 14.04, 22.63,
25.14, 25.94, 29.09, 29.32, 29.51, 31.85, 68.09, 95.61, 114.32,
127.21, 129.03, 162.70, 184.12 and 191.36.
1-[3,5-Bis(dodecyl)oxyphenyl]butane-1,3-dione. Yellow solid,
1
yield 77%. H NMR (CDCl3): δ 0.81 (s, CH3, 6 H), 1.24–1.82
(m, CH2, 40 H), 2.05 (s, COCH3, 3 H), 3.91 (t, OCH2, 4 H), 6.03
(s, COHCH, 1 H), 6.53 (t, C6H3, 1 H), 6.93 (t, C6H3, 2 H) and
16.10 (s, COHCH, 1 H). 13C NMR (CDCl3): δ 13.99, 19.61,
22.59, 25.41, 25.98, 29.12, 29.23, 29.18, 29.65, 31.76, 68.17,
96.68, 105.28, 105.37, 136.76, 160.28, 183.65 and 192.93.
CCDC reference number 186/938.
Schiff bases of iminopropyl ketones. 4-Dodecyloxyphenyl 2-(3-
hydroxypropyl)iminopropyl ketone. 1-(4-Dodecyloxyphenyl)-
butane-1,3-dione (3.0 g, 8.7 mmol), 3-aminopropan-1-ol (0.73
cm3, 9.6 mmol) and glacial acetic acid (0.20 cm3) were mixed in
dried thf (100 cm3) under a nitrogen atmosphere. The mixture
was refluxed for 24 h then concentrated to give a brown crude
Acknowledgements
We thank the National Science Council of Taiwan, ROC for
funds (NSC-87-2113-M-008-007) in generous support of this
work.
J. Chem. Soc., Dalton Trans., 1998, Pages 1857–1862
1861