Synthesis of b-amino alcohols
641
3
CuCl , 5 mmol), and 20 cm water were mixed and the
reaction mixture was refluxed with stirring for 24 h. The
3
polymer was filtered and washed with hexane (5 cm 9 5),
2
reaction mixture was stirred at room temperature for 24 h.
3
The polymer was filtered, washed with water (20 cm 9
3
water–methanol (2:1 v/v, 20 cm 9 3), and water
3
20 cm 9 5). The yellow solid was dried under vacuum at
3
5), water–methanol mixture (2:1 v/v, 20 cm 9 3), and
(
3
methanol (20 cm 9 2), and dried under vacuum at room
room temperature.
temperature. Characterization data for Cu(II) complex 6a
and Ni(II) complex 7a are given below. As the complexes
with other polymer-supported Schiff bases showed inferior
catalytic performance, they were not fully characterized.
PVC-supported 2-[(2-aminoethylimino)methyl]phenol(5a)
FTIR (KBr): vꢀ = 3,600 (O–H), 3,064 (aromatic), 2,900
-
1 1
(
CH ), 1,682 (C=N), 1,463 (CH ) cm ; H NMR: d = 8.0
2
2
(
s, CH=N), 6.73–7.42 (m, aromatic), 5.5 (s, OH), 3.59 (t,
CH , CH –N=CH), 3.00 (m, CH , CH –NH), 2.86–2.56
2
Cu(II) complex of PVC-supported 2-[(2-aminoethylimi-
no)methyl]phenol (6a)
2
2
2
(
m, CH, polymer), 2.02 (br, NH), 1.76–1.27 (m, CH ,
2
1
3
polymer chain) ppm; C NMR: d = 161.1, 132.5, 130.5,
24.5, 121.1, 115.7 (aromatic), 160.8 (C=N), 55.4, 48.0
=NCH CH NH), 49.0, 35.8, 29.5, 24.9, 14.0 (polymer
FTIR (KBr): vꢀ = 3,064 (aromatic), 2,900 (CH ), 1,642
2
-
1 1
1
(C=N), 1462 (CH ), 635 (Cu–N) cm ; H NMR: d = 8.0
2
(
(s, CH=N), 6.73–7.42 (m, aromatic), 3.59 (t, CH , CH –N=CH),
2
2
2
2
chain) ppm.
3.00 (m, CH , CH –NH), 2.86–2.56 (m, CH, polymer),
2 2
2
.02 (br, NH), 1.76–1.27 (m, CH , polymer chain) ppm;
2
PVC-supported 4-[(2-aminoethylimino)methyl]-
2
1
3
C NMR: d = 158.0, 133.0, 130.9, 124.8, 120.4, 115.9
aromatic), 163.0 (C=N), 49.0, 41.1 (=NCH CH NH),
-methoxyphenol (5b)
FTIR (KBr): vꢀ = 3,600 (O–H), 3,060 (aromatic), 2,910
(
2 2
49.0, 35.4, 29.1, 24.0, 13.9 (polymer chain) ppm; UV–
-
1 1
(
CH ), 1,663 (C=N), 1,460 (CH ) cm ; H NMR: d = 8.1
2
2
Vis (powder): kmax = 422, 543 nm. ICP-AES analysis of
the complex showed that the loading of metal ion was
(
s, CH=N), 6.62–7.00 (m, aromatic), 5.1 (s, OH), 3.9 (s,
OCH ), 3.60 (t, CH , CH –N=CH), 3.01 (m, CH , CH –
3
2
2
2
2
4
.26 mmol/g polymer.
NH), 2.84–2.52 (m, CH, polymer), 2.00 (br, NH), 1.79–
1
3
1
1
4
1
.29 (m, CH , polymer chain) ppm; C NMR: d = 151.1,
Ni(II) complex of PVC-supported 2-[(2-aminoethylimi-
no)methyl]phenol (7a)
2
48.0, 133.4, 122.8, 117.0 (aromatic), 160.1 (C=N), 55.4,
8.3 (=NCH CH NH), 56.0 (OCH ), 49.0, 35.4, 29.1, 24.3,
3
FTIR (KBr): vꢀ = 3,400 (H O), 3,064 (aromatic), 2,900
2
2
2
-
1 1
4.0 (polymer chain) ppm.
(CH ), 1,650 (C=N), 1,462 (CH ), 540 (Ni–N) cm ; H
2 2
NMR: d = 8.2 (s, CH=N), 6.73–7.42 (m, aromatic), 3.59
1
PVC-supported N -(3,4-dimethoxybenzylidene)ethane-
(t, CH , CH –N=CH), 3.00 (m, CH , CH –NH), 2.86–2.56
2 2 2 2
1
,2-diamine (5c)
(
m, CH, polymer), 2.02 (br, NH), 1.76–1.27 (m, CH ,
2
FTIR (KBr): vꢀ = 3,065 (aromatic), 2,920 (CH ), 1,631
2
13
polymer chain) ppm; C NMR: d = 157.3, 132.3, 130.1,
24.1, 120.4, 115.1 (aromatic), 162.8 (C=N), 48.0, 40.0
=NCH CH NH), 49.5, 35.8, 29.5, 24.9, 14.0 (polymer
-
1 1
(
C=N), 1,467 (CH ) cm ; H NMR: d = 8.21 (s, CH=N),
2
1
6
.69–7.10 (m, aromatic), 3.73 (s, OCH ), 3.67 (t, CH ,
3 2
(
2
2
CH –N=CH), 3.00 (m, CH , CH –NH), 2.87–2.55 (m, CH,
2
2
2
chain) ppm; UV–Vis (powder): kmax = 262, 326, 416 nm.
ICP-AES analysis of the complex showed that the loading
of metal ion was 4.00 mmol/g polymer.
polymer), 2.10 (br, NH), 1.75–1.23 (m, CH , polymer
2
1
3
chain) ppm; C NMR: d = 152.1, 149.9, 133.2, 122.5,
15.4 (aromatic), 161.0 (C=N), 55.9, 48.9 (=NCH CH2
1
2
NH), 56.4 (OCH ), 50.0, 35.8, 29.6, 22.9, 14.0 (polymer
3
General procedure for ring opening of epoxides
chain) ppm.
1
2
PVC-supported N -methyl-N (1,7,7-trimethylbicyclo-
2.2.1]heptan-2-ylidene)ethane-1,2-diamine (5d)
In a round-bottom flask epoxide 8 (5 mmol) and amine 9
3
(5.1 mmol) were dissolved in 10 cm 1,4-dioxane. Cata-
[
-
1 1
FTIR (KBr): vꢀ = 1,617 (C=N) cm ; H NMR: d = 2.87–
.60 (m, CH, polymer and camphor unit), 2.00 (br, NH),
lyst 7a (62.5 mg, 5 mol% of Ni with respect to the
epoxide) was added. The reaction mixture was stirred at
50 °C. The progress of the reaction was monitored by TLC
on silica-coated alumina plates with hexane–ethyl acetate
(10:1) as eluent. After the completion of the reaction the
catalyst was filtered and washed with methanol. The fil-
trate and washings were combined and evaporated. The
final product 10 was isolated using column chromatogra-
phy on a small silica column using hexane–ethyl acetate
2
1
.99–1.10 (m, CH , polymer chain and camphor unit) ppm;
2
1
3
C NMR: d = 174.1 (C=N), 50.3, 48.9 (=NCH CH NH),
0.0, 38.7, 35.4, 29.1, 24.3, 20.0, 14.0 (polymer chain and
2
2
5
camphor) ppm.
General procedure for the synthesis of metal complex
of polymer-supported Schiff bases
(
10:1) as eluent. All products were previously reported
1
3
In a 50-cm round-bottom flask 2 g of the polymer sup-
[12–25] and were characterized by FTIR and H NMR
spectroscopy.
ported Schiff base (10 mmol), the metal salt (NiCl or
2
123