Supplementary material
Nickel Phthalocyanine Assisted Highly Efficient and Selective
Carbonyl Reduction in Polyethylene glycol-400
Praveen Kumar Verma · Upendra Sharma · Neeraj Kumar · Manju Bala · Vishal
Kumar · Bikram Singh
Natural Plant Products Division, CSIR-Institute of Himalayan Bioresource Technology,
Palampur, Himachal Pradesh, 176 061 (India)
Table of Contents
1. General information
2. General procedure
3. Characterization data of products
4. NMR spectra of isolated compounds
5. XRD spectra of nickel phthalocyanine
6. References
1
1. General information
High grade solvents were used for all reactions. Column chromatography was
carried out with 60-120 mesh silica gel. Silica (60-120 mesh) and TLC silica gel
60 F254 plates were purchased from Merck India Ltd. Carbonyl compounds,
amines, NMR solvents were purchased from sigma Aldrich and spectrochem.
1
H NMR and
13
C NMR experiments were performed on Bruker Avance-300
spectrometer. Chemical shifts are reported in parts per million (ppm) downfield
from an internal standard. The GC-MS analysis was carried out on a
Shimadzu (QP 2010) series GC-MS (Tokyo, Japan) equipped with a FID,
AOC-20i auto-sampler coupled, and a DB-5 capillary column, (30 m x
0.25 mm i.d., 0.25 µm). The initial temperature of column was 40° C held for
5min and was programmed to 230° C at 4° C/min, then held for 5 min at 230°
C; the sample injection volume was 2 µl in dichloromethane. Helium was
used as carrier gas at a flow rate of 1.1 ml min-1on split mode (1:50). XRD
analysis of NiPc was carried out on Bruker AXS GmbH Germany Model D8
Advance.
2. General procedure
General Procedure for the Synthesis of Nickel Phthalocyanine:
Nickel phthalocyanine was synthesised by using Hitoshi Uchida method.1
General Procedure for the Reduction of Carbonyl Compounds: To a
mixture of carbonyl compound (250 or 500 or 1000 mg) and catalyst (1.7x10-3
mmol) in PEG-400 (2 or 3 or 4 mL), sodium borohydride (0.5 equiv.) was
2
added. The reaction solution was stirred at room temperature and the progress of
the reaction was monitored by TLC (silica gel; hexane/ethyl acetate) and GCMS. After completion, the reaction mixture was extracted with diethyl ether (3
× 15 mL). The combined diethyl ether fractions were dried under reduced
pressure. The crude product was analysed directly by GC-MS. To obtain the
isolated yield product mixture was subjected to column chromatography (silica
60-120; n-hexane/ethyl acetate mixture).
General Procedure for the Reductive Amination: To a mixture of carbonyl
compound (250 mg), amine (1 equiv.) and catalyst (1.7x10-3 mmol) in PEG-400
(2 mL) was added. Sodium borohydride (0.5 equiv.) was added after the
formation of imine as monitored by TLC and the stirring was continued. The
progress of the reaction was monitored by TLC (silica gel; hexane/ethyl acetate)
and GC-MS. After completion, the reaction mixture was extracted with diethyl
ether (3 × 15 mL). The combined diethyl ether fractions were dried under
reduced pressure and analyzed directly by GC-MS.
3
3. Characterization data of products [2, 3]:
Benzyl alcohol (Table 2, entry 1):
OH
1
H NMR (300 MHz, CD3COCD3): δ 7.21-7.38 (m, 5H), 4.64 (d, J = 5.6 Hz, 2H),
4.19 (d, J = 5.7 Hz, 1H);
13
C NMR (75 MHz, CD3COCD3): δ 143.9, 129.4,
128.1, 127.8, 65.2; MS (EI): m/z 108 [M]+.
(4-Chlorophenyl) methanol (Table 2, entry 2):
OH
Cl
1
H NMR (300 MHz, CD3COCD3): δ 7.33-7.41 (m, 4H), 4.62-4.64 (m, 2H),
4.38-4.43 (m, 1H);
13
C NMR (75 MHz, CD3COCD3): δ 142.8, 133.2, 129.5,
64.3; MS (EI): m/z 142 [M]+.
(4-Bromophenyl) methanol (Table 2, entry 3):
OH
Br
1
H NMR (300 MHz, CD3COCD3): δ 7.50 (d, J = 8.41 Hz, 2H), 7.32 (d, J =
8.48 Hz, 2H), 4.62 (d, J = 5.2 Hz, 2H), 4.45 (t, J = 5.5 Hz, 1H); 13C NMR (75
MHz, CD3COCD3): δ 142.9, 132.1, 129.5, 121.1, 64.1; MS (EI): m/z 186 [M]+.
(4-Methylphenyl) methanol (Table 2, entry 5):
OH
H3C
4
1
H NMR (300 MHz, CD3COCD3): δ 7.25 (d, J = 7.89 Hz, 2H), 7.14 (d, J = 7.84
Hz, 2H), 4.58 (s, 2H), 2.31 (s, 3H), 2.06 (bs, 1H);
13
C NMR (75 MHz,
CD3COCD3): δ 140.6, 137.2, 129.8, 127.8, 64.7, 21.4; MS (EI): m/z 122 [M]+.
(3-Methoxyphenyl) methanol (Table 2, entry 6):
OH
OCH3
1
H NMR (300 MHz, CD3COCD3): δ 7.24 (t, J = 7.8 Hz, 1H), 6.92-6.97 (m, 2H),
6.79-6.82 (m, 1H), 4.62 (s, 2H), 4.10 (brs, 1H), 3.79 (s, 3H); 13C NMR (75 MHz,
CD3COCD3): δ 160.2, 144.5, 129.4, 118.9, 112.5, 112.2, 64.0, 54.8; MS (EI):
m/z 138 [M]+.
(3-Cyanophenyl) methanol (Table 2, entry 7):
OH
CN
1
H NMR (300 MHz, CD3COCD3): δ 7.65-7.75 (m, 3H), 7.35-7.59 (m, 1H), 4.72
(d, J = 5.2 Hz, 2H), 4.58 (t, J = 5.1 Hz, 1H); 13C NMR (75 MHz, CD3COCD3):
δ 145.6, 132.2, 131.7, 131.0, 130.5, 119.9, 113.3, 63.9; MS (EI): m/z 133 [M]+.
Phthalide (Table 2, entry 8):
O
O
5
1
H NMR (300 MHz, CD3COCD3): δ 7.84-7.87 (m, 1H), 7.75-7.81 (m, 1H),
7.67-7.70 (m, 1H), 7.58-7.63 (m, 1H), 5.40 (s, 2H);
13
C NMR (75 MHz,
CD3COCD3): δ 172.1, 149.0, 135.6, 130.5, 127.3, 126.6, 124.4, 71.2; MS (EI):
m/z 134 [M]+.
(2-Nitrophenyl) methanol (Table 2, entry 9):
OH
NO 2
1
H NMR (300 MHz, CDCl3): δ 8.12 (d, J = 8.1 Hz, 1H), 7.66-7.77 (m, 2H),
7.47-7.52 (m, 1H), 4.99 (s, 2H);
13
C NMR (75 MHz, CDCl3): δ 148.1, 137.1,
134.4, 130.3, 128.8, 125.3, 62.9; MS (EI): m/z 153 [M]+.
(3-Nitrophenyl) methanol (Table 2, entry 10):
OH
NO 2
1
H NMR (300 MHz, CD3COCD3): δ 8.24 (s, 1H), 8.08-8.12 (m, 1H), 7.79 (d, J
= 7.6 Hz, 1H), 7.62 (t, J = 7.8 Hz, 1H), 4.78 (s, 2H), 3.12 (s, 1H); 13C NMR (75
MHz, CD3COCD3): δ 149.6, 146.1, 133.7, 130.5, 122.7, 122.0, 63.8; MS (EI):
m/z 153 [M]+.
(4-Nitrophenyl) methanol (Table 2, entry 11):
OH
O2N
6
1
H NMR (300 MHz, CD3OD): δ 8.19 (d, J = 8.71 Hz, 2H), 7.58 (d, J = 8.79 Hz,
2H), 4.73 (s, 2H); 13C NMR (75 MHz, CD3OD): δ 149.8, 147.4, 127.2, 123.4,
63.0; MS (EI): m/z 153 [M]+.
Benzene-1,2-dimethanol (Table 2, entry 12):
OH
OH
1
H NMR (300 MHz, CD3COCD3): δ 7.38-7.43 (m, 2H), 7.24-7.28 (m, 2H), 4.70
(s, 4H), 4.26-4.33 (m, 2H);
13
C NMR (75 MHz, CD3COCD3): δ 141.1, 129.1,
128.3, 63.3; MS (EI): m/z 120 [M-H2O]+.
(3-carboxyphenyl) methanol (Table 2, entry 13):
OH
O
1
H
H NMR (300 MHz, CD3OD): δ 7.99-8.05 (m, 1H), 7.53-7.56 (m, 1H), 7.35-
7.47 (m, 2H), 5.38-5.45 (m, 2H); 13C NMR (75 MHz, CD3OD): δ 184.5, 168.5,
138.8, 129.6, 126.9, 126.8, 103.5; MS (EI): m/z 136 [M]+.
(4-carboxyphenyl) methanol (Table 2, entry 14):
OH
H
O
7
1
H NMR (300 MHz, CD3COCD3): δ 10.02 (s, 1H), 7.88-7.95 (m, 2H), 7.58-7.65
(m, 2H), 4.76 (s, 2H); 13C NMR (75 MHz, CD3COCD3): δ 192.9, 150.7, 136.8,
130.6, 127.8, 64.4; MS (EI): m/z 136 [M]+.
(4-Hydroxy-3-methoxyphenyl) methanol (Table 2, entry 15):
OH
HO
OCH3
1
H NMR (300 MHz, CD3COCD3): δ 7.55 (s, 1H), 6.97 (s, 1H), 6.79 (s, 2H),
4.53 (s, 2H), 4.19 (brs, 1H), 3.82 (s, 1H); 13C NMR (75 MHz, CD3COCD3): δ
148.2, 146.5, 134.8, 120.4, 115.5, 111.4, 64.8, 56.2.
(3,4-Methylenedioxy-6-nitrophenyl) methanol (Table 2, entry 16):
O
OH
O
1
NO2
H NMR (300 MHz, CD3COCD3): δ 7.54 (s, 1H), 7.34 (s, 1H), 6.21 (s, 2H),
4.91 (s, 2H); 13C NMR (75 MHz, CD3COCD3): δ 153.11, 147.1, 140.9, 137.1,
107.0, 105.1, 102.6, 61.4; MS (EI): m/z 197 [M]+.
1-Phenylethanol (Table 3, entry 1):
OH
CH3
1
H NMR (300 MHz, CD3COCD3): δ 7.42-7.45 (m, 2H), 7.32-7.37 (m, 2H),
7.23-7.27 (m, 1H), 4.88-4.90 (m, 1H), 4.48 (s, 1H), 1.46 (d, J = 6.5 Hz, 3H); 13C
8
NMR (75 MHz, CD3COCD3): δ 148.0, 128.8, 127.4, 126.1, 70.8, 26.2; MS (EI):
m/z 122 [M]+.
1-(4-Bromophenyl) ethanol (Table 3, entry 2):
OH
CH3
Br
1
H NMR (300 MHz, CD3COCD3): δ 7.49 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 8.4
Hz, 2H), 4.82-4.88 (m, 1H), 4.50 (brs, 1H), 1.40 (d, J = 6.4 Hz, 3H); 13C NMR
(75 MHz, CD3COCD3): δ 147.4, 131.8, 128.2, 120.6, 69.2, 26.1; MS (EI): m/z
200 [M]+.
1-(3-Hydroxyphenyl) ethanol (Table 3, entry 3):
OH
CH3
OH
1
H NMR (300 MHz, CD3COCD3): δ 8.27 (brs, 1H), 7.11-7.16 (m, 1H), 6.92 (s,
1H), 6.85 (d, J = 7.5 Hz, 1H), 6.69-6.72 (m, 1H), 4.77-4.81 (m, 1H), 4.31 (brs,
1H), 1.39 (d, J = 6.4 Hz, 3H); 13C NMR (75 MHz, CD3COCD3): δ 157.6, 149.3,
129.4, 116.9, 114.0, 112.6, 69.5, 25.6.
1-(4-Methoxyphenyl) ethanol (Table 3, entry 4):
OH
CH3
H3CO
9
1
H NMR (300 MHz, CD3COCD3): δ 7.33-7.36 (m, 2H), 6.89-6.94 (m, 2H), 4.81
(q, J = 6.4 Hz, 1H), 4.50 (brs, 1H), 3.77 (s, 3H), 1.45 (d, J = 6.4 Hz, 3H); 13C
NMR (75 MHz, CD3COCD3): δ 159.1, 139.5, 127.0, 113.8, 69.2, 55.1, 25.8.
1-(4-Nitrophenyl) ethanol (Table 3, entry 5):
OH
CH3
O2N
1
H NMR (300 MHz, CD3COCD3): δ 8.17 (d, J = 8.6 Hz, 2H), 7.65 (d, J = 8.5
Hz, 2H), 5.02 (q, J = 6.48 Hz, 1H), 4.52 (brs, 1H), 1.45 (d, J = 6.5 Hz, 3H); 13C
NMR (75 MHz, CD3COCD3): δ 155.2, 147.2, 126.7, 123.9, 68.8, 25.5; MS (EI):
m/z 167 [M]+.
1-(2,4-Dimethoxyphenyl) ethanol (Table 3, entry 6):
OH
CH3
H3CO
1
OCH3
H NMR (300 MHz, CD3COCD3): δ 7.38-7.43 (m, 1H), 6.48-6.53 (m, 2H), 5.11
(q, J = 6.3 Hz, 2H), 3.81 (s, 3H), 3.78 (s, 3H), 1.37 (d, J = 6.3 Hz, 3H);
13
C
NMR (75 MHz, CD3COCD3): δ 160.9, 158.0, 128.7, 127.2, 105.4, 99.1, 64.6,
55.9, 25.1.
4-Chlorobenzhydrol (Table 3, entry 8):
10
OH
Cl
1
H NMR (300 MHz, CD3COCD3): δ 7.47-7.50 (m, 4H), 7.34-7.39 (m, 4H),
7.25-7.30 (m, 1H), 5.90 (s, 1H), 5.19 (s, 1H); 13C NMR (75 MHz, CD3COCD3):
δ 145.3, 144.7, 132.6, 128.7, 127.0, 126.5, 75.4; MS (EI): m/z 218 [M]+.
1-(3,4-methylenedioxyphenyl) ethanol (Table 3, entry 9):
OH
O
CH3
O
1
H NMR (300 MHz, CD3COCD3): δ 6.72-6.92 (m, 3H), 5.95 (s, 2H), 4.78 (q, J
= 6.4 Hz, 1H), 2.05-2.09 (m, 1H), 1.37 (d, J = 6.4 Hz, 3H), );
13
C NMR (75
MHz, CD3COCD3): δ 147.9, 146.7, 141.9, 118.7, 107.9, 106.2, 101.2, 69.2,
25.8; MS (EI): m/z 166 [M]+.
7-Decenol (Table 4, entry 1):
OH
1
H NMR (300 MHz, CD3COCD3): δ 5.28-5.40 (m, 2H), 3.65 (brs, 1H), 3.53 (t,
J = 6.4 Hz, 2H), 2.00-2.07 (m, 4H), 1.49-1.53 (m, 2H), 1.30-1.41 (m, 6H), 0.95
(t, J = 7.5 Hz, 3H); 13C NMR (75 MHz, CD3COCD3): δ 132.3, 130.1, 62.7, 33.9,
31.1, 30.9, 27.9, 26.4, 21.3, 14.9.
Cinnamylalcohol (Table 4, entry 6):
11
OH
1
H NMR (300 MHz, CD3COCD3): δ 7.22-7.48 (m, 5H), 6.68 (d, J = 15.9 Hz,
1H), 6.44 (dt, J = 21.2, 5.2 Hz, 1H), 4.33 (s, 1H);
13
C NMR (75 MHz,
CD3COCD3): δ 134.8, 130.4, 129.8, 128.4, 128.3, 126.9, 63.5; MS (EI): m/z 134
[M]+.
2-Furanmethanol (Table 4, entry 1):
O
OH
1
H NMR (300 MHz, CD3OD): δ 7.45 (s, 1H), 6.30-6.37 (m, 2H), 5.05 (brs, 1H),
4.53 (s, 2H); 13C NMR (75 MHz, CD3OD): δ 155.0, 142.5, 110.3, 107.4, 56.4;
MS (EI): m/z 98 [M]+.
5-Methyl-2-furanmethanol (Table 4, entry 2):
H3C
1
O
OH
H NMR (300 MHz, CD3OD): δ 4.50 (s, 1H), 4.27 (s, 1H), 3.34 (brs, 1H), 2.80
(s, 2H), 0.58(s, 3H); 13C NMR (75 MHz, CD3OD): δ 151.5, 150.5, 106.9, 104.7,
54.9, 11.1; MS (EI): m/z 112 [M]+.
12
4. NMR spectra of isolated compounds
Benzyl alcohol (Table 2, entry 1):
OH
10
9
8
7
6
5
4
3
2
ppm
1
OH
220
200
180
160
140
120
100
80
60
40
20
ppm
13
α-Deuterated benzyl alcohol:
H
D
OH
9
8
7
6
5
4
3
2
1
ppm
14
(4-Chlorophenyl) methanol (Table 2, entry 2):
OH
Cl
9
8
7
6
5
4
3
2
1
ppm
OH
Cl
220
200
180
160
140
120
100
80
60
40
20
ppm
15
(4-Bromophenyl) methanol (Table 2, entry 3):
OH
Br
10
9
8
7
6
5
4
3
2
ppm
1
OH
Br
220
200
180
160
140
120
100
80
60
40
20
ppm
16
(4-Methylphenyl) methanol (Table 2, entry 5):
OH
H3C
9
8
7
6
5
4
3
2
ppm
1
OH
H3C
220
200
180
160
140
120
100
80
60
40
20
ppm
17
(3-Methoxyphenyl) methanol (Table 2, entry 6):
OH
OCH3
9
8
7
6
5
4
3
2
1
20
ppm
ppm
OH
OCH3
220
200
180
160
140
120
100
80
60
40
18
(3-Cyanophenyl) methanol (Table 2, entry 7):
OH
CN
9
8
7
6
5
4
3
2
1
ppm
OH
CN
220
200
180
160
140
120
100
80
60
40
20
ppm
19
Phthalide (Table 2, entry 8):
O
O
9
8
7
6
5
4
3
2
ppm
1
O
O
220
200
180
160
140
120
100
80
60
40
20
ppm
20
(2-Nitrophenyl) methanol (Table 2, entry 9):
OH
NO 2
9
8
7
6
5
4
3
2
1
100
80
60
40
ppm
OH
NO 2
220
200
180
160
140
120
20
ppm
21
(3-Nitrophenyl) methanol (Table 2, entry 10):
OH
NO 2
9
8
7
6
5
4
3
2
1
0 ppm
OH
NO 2
220
200
180
160
140
120
100
80
60
40
20
ppm
22
(4-Nitrophenyl) methanol (Table 2, entry 11):
OH
O2N
9
8
7
6
5
4
3
2
ppm
1
OH
O2N
220
200
180
160
140
120
100
80
60
40
20
ppm
23
Benzene-1,2-dimethanol (Table 2, entry 12):
OH
OH
9
8
7
6
5
4
3
2
0 ppm
1
OH
OH
220
200
180
160
140
120
100
80
60
40
20
ppm
24
(3-carboxyphenyl) methanol (Table 2, entry 13): NMR of crude reaction
mixture without purification.
OH
O
9
8
H
7
6
5
4
3
2
1
ppm
OH
O
220
200
180
160
140
H
120
100
80
60
40
20
ppm
25
(4-carboxyphenyl) methanol (Table 2, entry 14):
OH
H
O
10
9
8
7
6
5
4
3
2
1
0 ppm
OH
H
O
220
200
180
160
140
120
100
80
60
40
20
ppm
26
(4-Hydroxy-3-methoxyphenyl) methanol (Table 2, entry 15):
OH
HO
OCH3
9
8
7
6
5
4
3
2
ppm
1
OH
HO
OCH3
220
200
180
160
140
120
100
80
60
40
20
ppm
27
(3,4-Methylenedioxy-6-nitrophenyl) methanol (Table 2, entry 16):
O
OH
O
9
8
7
6
5
O
200
180
160
140
3
2
ppm
1
OH
O
220
4
NO2
NO2
120
100
80
60
40
20
ppm
28
1-Phenylethanol (Table 3, entry 1):
OH
CH3
9
8
7
6
5
4
3
2
ppm
1
OH
CH3
220
200
180
160
140
120
100
80
60
40
20
ppm
29
1-(4-Bromophenyl) ethanol (Table 3, entry 2):
OH
CH3
Br
9
8
7
6
5
4
3
2
0 ppm
1
OH
CH3
Br
220
200
180
160
140
120
100
80
60
40
20
ppm
30
1-(3-Hydroxyphenyl) ethanol (Table 3, entry 3):
OH
CH3
OH
9
8
7
6
5
4
3
2
ppm
1
OH
CH3
OH
220
200
180
160
140
120
100
80
60
40
20
ppm
31
1-(4-Methoxyphenyl) ethanol (Table 3, entry 4):
OH
CH3
H3CO
9
8
7
6
5
4
3
2
ppm
1
OH
CH3
H3CO
220
200
180
160
140
120
100
80
60
40
20
ppm
32
1-(4-Nitrophenyl) ethanol (Table 3, entry 5):
OH
CH3
O2N
9
8
7
6
5
4
3
2
0 ppm
1
OH
CH3
O2N
220
200
180
160
140
120
100
80
60
40
20
ppm
33
2-Bromo-1-phenylethanol (Table 3, entry 7): NMR of crude reaction mixture
without purification.
OH
CH2Br
9
8
7
6
5
4
3
2
0 ppm
1
OH
CH2Br
220
200
180
160
140
120
100
80
60
40
20
ppm
34
4-Chlorobenzhydrol (Table 3, entry 8):
OH
Cl
9
8
7
6
5
4
3
2
ppm
1
OH
Cl
220
200
180
160
140
120
100
80
60
40
20
ppm
35
1-(3,4-methylenedioxyphenyl) ethanol (Table 3, entry 9):
OH
O
CH3
O
9
8
7
6
5
4
3
2
ppm
1
OH
O
CH3
O
220
200
180
160
140
120
100
80
60
40
20
ppm
36
7-Decenol (Table 4, entry 1):
OH
9
8
7
6
5
4
3
2
ppm
1
OH
220
200
180
160
140
120
100
80
60
40
20
ppm
37
Cinnamylalcohol (Table 4, entry 6):
OH
10
9
8
7
6
5
4
3
2
1
ppm
OH
220
200
180
160
140
120
100
80
60
40
20
ppm
38
2-Furanmethanol (Table 4, entry 1):
O
OH
9
8
7
6
5
4
3
2
1
ppm
O
OH
220
200
180
160
140
120
100
80
60
40
20
ppm
39
5-Methyl-2-furanmethanol (Table 4, entry 2):
O
H3C
9
8
7
H3C
220
200
180
160
OH
6
5
4
3
2
1
0 ppm
O
OH
140
120
100
80
60
40
20
ppm
40
5. XRD spectra of NiPc
41
42
6. References
1. Jung K S, Kwon J H, Shon S M, Ko J P, Shin J S, Park S S (2004) J
Mater Sci 39:723
2. Castro L C M, Bezier D, Sortais J B, Darcel C (2011) Adv Synth Catal
353:1279
3. Shaikh N S, Junge K, Beller M (2007) Org Lett 9:5429
43