Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
Supporting Information
Zinc phthalocyanine with PEG-400 as a recyclable catalytic
system for selective reduction of aromatic nitro compounds
Upendra Sharma, Neeraj Kumar,* Praveen Kumar Verma, Vishal Kumar and
Bikram Singh*
Natural Plant Products Division, CSIR-Institute of Himalayan Bioresource
Technology (Council of Scientific and Industrial research), Palampur, Himachal
Pradesh-176 061, INDIA
1
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
Table of Contents
1.
General Information
2.
General procedure
3.
Characterization of catalyst and products
4.
Spectra of reduction products
5.
IR spectra of Zinc phthalocyanine
6.
UV spectra
7.
References
2
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
1. General Information
High grade solvents were used for all reactions. Flash chromatography
was carried out with 230-400 mesh silica gel. 230-400 mesh silica gel,
TLC silica gel 60 F254 plates were purchased from Merck India Ltd.
Nitro compounds, NMR solvent were purchased from sigma Aldrich and
spectrochem. The GC-MS analysis was carried out on a Shimadzu (QP
2010) series Gas Chromatogram-Mass Spectrometer (Tokyo, Japan),
AOC-20i auto-sampler coupled, and a DB-5 MS capillary column, (30 m
x 0.25 mm i.d., 0.25µm). The initial temperature of column was 70°C
held for 4 min. and was programmed to 230 °C at 4°C/min., then held for
15 min. at 230°C; the sample injection volume was 2 µl in GC grade
dichloromethane. Helium was used as carrier gas at a flow rate of 1.1 ml
min-1 on split mode (1:50).
The IR spectra were recorded on a a NICOLET-6700 FT-IR
spectrometer with KBr disc.and the νmax are expressed in cm-1. The
electronic spectra were recorded on a Perkin Elmer Lambda-35 UV/Vis
spectrophotometer and the λmax are expressed in nanometers. 1H 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. Mass spectra were recorded on
QTOF-Micro of Waters Micromass.
3
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
2. General procedure
Synthesis of zinc (II) phthalocyanine: Zinc (II) phthalocyanine was
prepared by following the literature procedure from ZnCl2.1
Benzyl 4-nitrophenyl ether is prepared by the literature procedure.2
NO2
Ph
O
H NMR (300 MHz, CDCl3): δ 5.18 (s, 2H), 7.04 (d, J = 9.0 Hz, 2H),
1
7.28-7.44 (m, 5H), 8.21 (d, J = 9.0 Hz, 2H); 13C NMR (75 MHz, CDCl3):
δ 71.1, 115.3, 126.3, 127.9, 128.9, 129.2, 135.9, 142.1, 164.1. HRMS
calculated for [M+H] + is 230.0817 and found 230.0842.
N-benzyl-4-nitroaniline is prepared by following the literature
procedure.3
Ph
NH
NO 2
H NMR (300 MHz, CDCl3): δ 4.40 (s, 2H), 5.11 (bs, 1H), 6.55 (d, J =
1
6.5 Hz, 2H), 7.32 (m, 5H), 8.04 (d, J = 6.6 Hz, 2H); 13C NMR (75 MHz,
CDCl3): δ 48.3, 112.0, 127.1, 128.0, 128.5, 129.6, 138.2, 139.0, 153.9.
HRMS calculated for [M+H] + is 229.0997 and found 229.0954.
4
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
Representative experimental procedure for reduction of nitro
compounds: To a mixture of nitro compound (1.34 mmol) and catalyst (1
mol %) in PEG-400 (3 mL) was added hydrazine hydrate (2 equiv.). The
reaction mixture was stirred at 100 ºC for 8 h. Time was not optimized
separately for all substrates. After completion of reaction as monitored
by TLC (silica gel, hexane/ethyl acetate), the reaction mixture was cooled
to ambient temperature and 20 ml of ethyl acetate was added. PEG-400
was removed by washing with distilled water and ethyl acetate layer was
dried under reduced pressure using rotatory evaporator and analyzed by
GC-MS. In cases (Table 2, entries 9, 12, 15 and 32) where the products
are partially soluble in water the reaction mixture was dissolved in ethyl
acetate and directly analyzed by GC-MS. The initial temperature of
column was 70 ºC held for 4 min. and was programmed to 230 ºC at 4
ºC/min., then held for 15 min. at 230 ºC, the sample injection volume was
2 µl in GC grade dichloromethane. Helium was used as carrier gas at a
flow rate of 1.1 ml min-1 on split mode (1: 50). Whenever necessary,
crude products were purified by column chromatography (silica 230-400,
n-hexane/ethyl acetate mixture).
Representative experimental procedure for reduction of carbonyl
compounds: To a mixture of carbonyl compound (1.34 mmol) and
catalyst (1 mol%) in PEG-400 (3 mL) was added sodium borohydride
(0.5 equiv.). The reaction mixture was stirred at room temperature for
5
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
appropriate time. After completion of reaction as monitored by TLC
(silica gel, hexane/ethyl acetate) the crude product was extracted with
diethyl ether (3x10 ml). Diethyl ether fractions were combined and dried
under reduced pressure using rotatory evaporator. Crude products were
purified by column chromatography (silica 60-120, n-hexane/ethyl
acetate mixture).
Representative experimental procedure for reductive amination of
nitro-substituted benzaldehydes: To a mixture of nitrobenzaldehyde (1
mmol), 4-methoxyaniline (1 mmol) and catalyst (1 mol %) in ethanol (5
ml) was added sodium borohydride (1.0 equiv.). The reaction mixture was
stirred at room temperature for 1 h. After completion of reaction as
monitored by TLC (silica gel, hexane/ethyl acetate) the reaction mixture
was filtered and passed through anhydrous Na2SO4. The filtrate was dried
under vacuum and the crude products obtained were purified by column
chromatography (silica 60-120, n-hexane/ethyl acetate mixture).
6
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
Table S1 Evaluation of different solvents for reduction of 4nitrobenzonitrile.
NO2
NC
NH2
ZnPc (1 mol%)
N2H4.H2O (2 equiv.)
solvent, 100 oC, 8 h
NC
Entry Catalyst Solvent
Yield (%)a
1
ZnPc
Water
8b
2
ZnPc
Ethanol
92
3
ZnPc
Ethylacetate
No reaction
4
ZnPc
THF
6
5
ZnPc
[Bmim]BF4
97
6
ZnPc
[Bmim]HSO4
87
7
ZnPc
Water: Ethanol
46
(1: 1)
8
ZnPc
Ethylene glycol
93
9
ZnPc
Toluene
8
10
ZnPc
PEG-400
99
11
ZnPc
DMF
52
a
Yield is calculated on the basis of GC-MS analysis.
4-nitrobezamide was observed as major side product with yield 86%.
b
Optimization of the amount of catalyst: The minimum amount of
catalyst which can be used for the reaction was optimized (Table S2) by
initially starting with 0.025 mol% of catalyst and gradually increased the
7
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
amount upto 0.50 mol%. Full conversion was not observed with 0.025
mol% of the catalyst whereas 98% yield was observed with 0.050 mol %
of catalyst (Table S2, entry 2). Which indicates that the amount of
catalyst can be reduced to 0.050 mol %.
Table S2. Optimization of the amount of catalyst.
Entry
Catalyst
(mol%)
Yield (%)a
1
2
3
4
0.025 0.050 0.128 0.257
84
98
95
>99
5
0.50
>99
[a] GC-MS yield is reported.
Recyclability of the catalyst: The recyclability of catalytic system was
evaluated by using 4-nitrobenzonitrile as test substrate. After completion
of reaction the product was extracted with Et2O and remaining residue
was used as such after drying over rotary evaporator. Successive
reactions were carried out by sequential addition of fresh substrate and
hydrazine hydrate to the crude remains after extracting the product. The
catalytic system can be reused upto four cycles (Figure S1). However, the
reduction of the substrate was not complete in the fifth cycle.
8
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
Yield (%)
Con.
Selectivity
120
GC-MS based (%)
100
80
60
40
20
0
Cycle
Figure S1. Recyclability of the catalyst.
3. Characterization of catalyst and products:4
Zinc phthalocyanine: (Figure S2 for FT-IR and Figure S3 for UV-vis)
Obtained as a blue product from ZnCl2, IR (KBr) cm-1; 2927 (υC-H),
1637, 1621, 1401 (υC-N), 1317 (υC-C), 1116, (υC-H), 892, (γC-H), 615,
477 (ΦC-C). UV-vis (THF) max nm; 666, 602.
Characterization of nitro reduction products:
All compounds were identified by spectral comparison with literature
data.5, 6
Aniline (Table 2, entry 1):
NH2
H NMR (300 MHz, CDCl3): δ 3.68 (bs, 2H), 6.72-6.76 (m, 2H), 6.82-
1
6.87 (m, 1H), 7.21-7.27 (m, 2H);
C NMR (75 MHz, CDCl3): δ 115.1,
13
9
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
119.3, 129.7, 146.9. HRMS calculated for [M+H] + is 94.0657 and found
94.0691.
2-Fluroaniline (Table 2, entry 2):
NH2
F
H NMR (300 MHz, CDCl3): δ 3.60 (s, 2H), 6.59-6.65 (m, 2H), 6.86-6.93
1
(m, 2H); 13C NMR (75 MHz, CDCl3): δ 115.9, 116.2, 116.4, 116.5, 143.1,
155.2, 158.3. HRMS calculated for [M+H]
+
is 112.0563 and found
112.0537.
2-Chloroaniline (Table 2, entry 3):
NH 2
Cl
H NMR (300 MHz, CD3COCD3): δ 4.07 (bs, 2H), 6.69-6.72 (m, 1H),
1
6.75-6.79 (m, 1H), 7.04-7.07 (m, 1H), 7.22-7.26 (m, 1H), 13C NMR (75
MHz, CD3COCD3): δ 116.2, 119.3, 119.6, 128.0, 129.7, 143.3. HRMS
calculated for [M+H] + is 128.0267 and found 128.0264.
4-Chloroaniline (Table 2, entry 4):
10
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
NH2
Cl
H NMR (300 MHz, CDCl3): δ 3.59 (bs, 2H), 6.62 (d, J = 14.8 Hz, 2H),
1
7.11 (d, J = 14.8 Hz, 2H), 13C NMR (75 MHz, CDCl3): δ 116.6, 123.5,
129.5, 145.3. HRMS calculated for [M+H]
+
is 128.0267 and found
128.0249.
3-Bromoaniline (Table 2, entry 5):
NH2
Br
H NMR (300 MHz, CDCl3): δ 3.74 (bs, 2H), 6.59-7.06 (m, 4H);
1
13
C
NMR (75 MHz, CDCl3): δ 114.1, 118.2, 121.7, 123.4, 131.0, 148.2.
HRMS calculated for [M+H] + is 171.9762 and found 171.9798.
4-Bromoaniline (Table 2, entry 6):
NH2
Br
H NMR (300 MHz, CDCl3): δ 3.70 (bs, 2H) 6.57 (d, J = 8.4 Hz, 2H),
1
7.25 (d, J = 8.4 Hz, 2H);
C NMR (75 MHz, CDCl3): δ 110.5, 117.1,
13
132.02, 145.9. HRMS calculated for [M+H]
171.9793.
11
+
is 171.9762 and found
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
4-Iodoaniline (Table 2, entry 7):
NH2
I
H NMR (300 MHz, CDCl3): δ 3.50 (bs, 2H), 6.48 (d, J = 11.3, 2H), 7.41
1
(d, J = 11.3, 2H);
C NMR (75 MHz, CDCl3): δ 79.8, 117.7, 138.3,
13
146.3. HRMS calculated for [M+H] + is 219.9623 and found 219.9664.
4-Methoxyaniline (Table 2, entry 8):
NH2
H3CO
H NMR (300 MHz, CDCl3): δ 3.39 (bs, 2H), 3.77 (s, 3H), 6.65-6.79 (m,
1
4H);
C NMR (75 MHz, CDCl3): δ 56.1, 115.2, 116.8, 140.3, 153.2.
13
HRMS calculated for [M+H] + is 124.0762 and found 124.0736.
4-Amino-benzoic acid (Table 2, entry 9):
NH2
COOH
H NMR (300 MHz, CD3COCD3): δ 6.67-6.72 (m, 2H), 7.76-7.81 (m,
1
2H);
C NMR (75 MHz, CD3COCD3): δ 114.1, 118.7, 132.8, 154.4,
13
168.2. HRMS calculated for [M+H] + is 138.0555 and found 138.573.
3-Aminobenzonitrile (Table 2, entry 10):
12
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
NH 2
CN
H NMR (300 MHz, CDCl3): δ 3.96 (bs, 2H), 6.85-6.88 (m, 1H), 6.90 (s,
1
1H), 6.99-7.02 (m, 1H), 7.19-7.24 (m, 1H); 13C NMR (75 MHz, CDCl3):
δ 113.2, 117.8, 119.5, 122.2, 130.4, 147.4. HRMS calculated for [M+H] +
is 119.0609 and found 119.0624.
4-Aminobenzonitrile (Table 2, entry 11):
NH2
NC
H NMR (300 MHz, CDCl3): δ 4.23 (bs, 2H), 6.65 (d, J = 8.2 Hz, 2H),
1
7.41 (d, J = 8.3 Hz, 2H);
C NMR (75 MHz, CDCl3): δ 100.4, 114.8,
13
120.5, 134.1, 150.9. HRMS calculated for [M+H] + is 119.0609 and found
119.0658.
4-Aminobenzamide (Table 2, entry 12):
NH2
CONH2
H NMR (300 MHz, DMSO-d6): δ 3.62 (s, 2H), 4.88 (s, 2H, merged with
1
methanol signal), 6.67 (d, J = 7.9 Hz, 2H), 7.66 (d, J = 7.9 Hz, 2H); 13C
13
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
NMR (75 MHz, DMSO-d6): δ 114.5, 122.1, 130.3, 153.3, 172.6. HRMS
calculated for [M+H] + is 137.0715 and found 137.0746.
4-Amino-benzene-1-sulphonamide (Table 2, entry 13):
NH2
H2NO2S
H NMR (300 MHz, CD3OD): δ 6.70 (d, J = 14.0 Hz, 2H), 7.59 (d, J =
1
14.0 Hz, 2H); 13C NMR (75 MHz, CD3OD): δ 113.4, 127.9, 130.3, 152.5.
HRMS calculated for [M+H] + is 173.0385 and found 173.0354.
4-Methylaniline (Table 2, entry 14):
NH2
CH3
H NMR (300 MHz, CDCl3): δ 2.29 (s, 3H), 3.52 (bs, 2H), 6.65 (d, J =
1
8.0 Hz, 2H), 7.01 (d, J = 7.3 Hz, 2H);
C NMR (75 MHz, CDCl3): δ
13
20.8, 115.6, 128.1, 130.1, 144.2. HRMS calculated for [M+H]
108.0813 and found 108.0842.
4-Aminophenol (Table 2, entry 15):
NH2
OH
14
+
is
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
H NMR (300 MHz, CD3OD): δ 6.60-6.67 (m, 4H); 13C NMR (75 MHz,
1
CD3OD ): δ 115.7, 117.5, 139.2, 150.2. HRMS calculated for [M+H] + is
110.0606 and found 110.0575.
Benzyl-4-aminophenyl ether (Table 2, entry 16):
NH2
Ph
O
H NMR (300 MHz, CDCl3): δ 3.33 (bs, 2H), 5.02 (s, 2H), 6.66 (d, J =
1
8.7 Hz, 2H), 6.84 (d, J = 8.7 Hz, 2H), 7.35-7.46 (m, 5H); 13C NMR (75
MHz, CDCl3): δ 71.2, 116.5, 116.7, 127.9, 128.2, 128.9, 137.9, 140.6,
152.4.
Methyl- 3-Amino-benzoate (Table 2, entry 19):
NH2
COOCH3
H NMR (300 MHz, CDCl3): δ 6.85-6.88 (m, 1H), 7.19-7.24 (m, 2H);
1
C NMR (75 MHz, CDCl3): δ 114.1, 118.7, 132.8, 154.4, 168.2. HRMS
13
calculated for [M+H] + is 152.0712 and found 152.0715.
6-Aminoisoquinoline (Table 2, entry 26):
H2N
N
15
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
H NMR (300 MHz, CDCl3): δ 4.32 (bs, 2H), 6.93 (bs, 1H), 7.36 (s, 3H),
1
7.58 (d, J = 5.3, 1H), 8.44 (d, J = 4.98, 1H) 9.15 (s, 1H) 13C NMR (75
MHz, CDCl3): δ 113.4, 114.7, 118.1, 126.3, 128.2, 129.8, 142.1, 153.1.
HRMS calculated for [M+H] + is 145.0766 and found 145.0731.
4-Amino-2, 1, 3-benzothiadiazole (Table 2, entry 28):
NH2
N
S
N
H NMR (300 MHz, CDCl3): δ 4.71 (bs, 2H) 6.62 (d, J = 6.8, 1H), 7.33-
1
7.43 (m, 2H); 13C NMR (75 MHz, CDCl3): δ 107.0 110.4, 131.6, 139.2,
148.1, 156.1. HRMS calculated for [M+H]
+
is 152.0282 and found
152.0257.
6-Aminobenzothiazole (Table 2, entry 29):
N
S
H2N
H NMR (300 MHz, CDCl3): δ 3.91 (bs, 2H), 6.85-6.88 (m, 1H), 7.15 (s,
1
1H), 7.89 (d, J = 8.6, 1H), 8.70 (s, 1H); 13C NMR (75 MHz, CDCl3): δ
106.0, 116.1, 124.3, 135.8, 145.2, 147.1, 150.2. HRMS calculated for
[M+H] + is 151.0330 and found 151.0352.
1-Aminonaphthalene (Table 2, entry 30):
NH 2
16
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
H NMR (300 MHz, CDCl3): δ 4.12 (bs, 2H), 6.81 (d, J = 6.084 Hz, 1H),
1
7.33-7.51 (m, 3H), 7.75-7.84 (m, 2H),
C NMR (75 MHz, CDCl3): δ
13
110.1, 119.4, 121.3, 124.1, 125.3, 126.3, 126.8, 129.0, 134.8, 142.6.
HRMS calculated for [M+H] + is 144.0813 and found 144.837.
2-Aminofullrene (Table 2, entry 31):
NH2
H NMR (300 MHz, CDCl3): δ 3.74 (brs, 2H), 3.85(s, 2H), 6.73-6.76 (m,
1
1H), 6.8 (s, 1H), 7.24-7.29 (m, 1H), 7.37-7.41 (m, 1H), 7.50 (d, J = 7.3,
1H), 7.62 (d, J = 8.0, 1H), 7.70 (d, J = 7.5, 1H),;
13
C NMR (75 MHz,
CDCl3): δ 37.2, 112.2, 114.4, 119.0, 121.0, 125.2, 125.5, 127.1, 133.3,
142.6, 142.7, 145.6, 146.2. HRMS calculated for [M+H]
+
is 182.0970
and found 182.0953.
2-Aminodiphenylamine (Table 2, entry 31):
NH2
N
H
H NMR (300 MHz, CD3OD): δ 5.30 (brs, 1H), 6.67-6.74 (m, 4H), 6.82-
1
6.85 (m, 1H), 6.91-6.96 (m, 1H), 7.05-7.15 (m, 3H); 13C NMR (75 MHz,
CD3OD): δ 116.4, 117.9, 119.9, 120.2, 126.1, 126.5, 130.4, 130.9, 143.8,
148.0. HRMS calculated for [M+H] + is 185.1079 and found 185.1054.
17
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
3-Aminostyrene (Table 2, entry 33):
NH2
H NMR (300 MHz, CDCl3) δ 5.22 (d, J = 10.8 Hz, 1H), 5.72 (d, J = 17.6
1
Hz, 1H), 6.60-6.63 (m, 2H), 6.76 (s, 1H), 6.85 (d, J = 7.4 Hz, 1H), 7.117.16 (m, 1H), 13C NMR (300 MHz, CDCl3) δ 113.1, 113.9, 115.1, 117.3,
129.8, 137.4, 139.1, 146.9. HRMS calculated for [M+H]
+
is 120.0813
and found 120.0801.
3-Nitroaniline (Table 2, entry 35):
NH2
NO2
H NMR (300 MHz, CDCl3): δ 4.05 (bs, 2H), 6.95 (d, J = 9.3 Hz, 1H),
1
7.24-7.29 (m, 1H), 7.48 (s, 1H), 7.56 (d, J = 8.0 Hz, 1H),; 13C NMR (75
MHz, CDCl3): δ 109.3, 113.4, 121.0, 130.3, 147.9, 149.6. HRMS
calculated for [M+H] + is 139.0508 and found 139.0563.
4-Nitroaniline (Table 2, entry 36):
NH2
O 2N
H NMR (300 MHz, CDCl3): δ 4.43 (bs, 2H), 6.63 (d, J = 8.7 Hz, 2H),
1
8.08 (d, J = 8.7 Hz, 2H),;
C NMR (75 MHz, CDCl3): δ 113.7, 126.7,
13
18
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
139.4, 152.9. HRMS calculated for [M+H]
+
is 139.0508 and found
139.0531.
Benzotriazole
H
N
N
N
H NMR (300 MHz, CDCl3): δ 7.40-7.43 (m, 2H), 7.92-7.95 (m, 2H),;
1
C NMR (75 MHz, CDCl3): δ 115.3, 126.4, 139.2; HRMS calculated for
13
[M+H] + is 120.0562 and found 120.0562.
Characterization of carbonyl reduction products:
2-Nitro-benzylalchol (Table 3, entry 1)
CH2OH
NO2
H NMR (300 MHz, CDCl3): δ 2.58 (brs, 1H), 4.99 (s, 2H), 7.47-7.52 (m,
1
1H), 7.67-7.77 (m, 2H), 8.12 (d, J = 8.17 Hz, 1H); 13C NMR (75 MHz,
CDCl3): δ 62.9, 125.4, 128.9, 130.3, 134.5, 137.1, 148.0.
3-Nitro-benzylalchol (Table 3, entry 2)
CH2OH
NO2
H NMR (300 MHz, CDCl3): δ 3.12 (brs, 1H), 4.76 (s, 2H), 7.46-7.51 (m,
1
1H), 7.64-7.66 (m, 1H), 8.05-8.08 (m, 1H), 8.17 (s, 1H);
13
C NMR (75
MHz, CDCl3): δ 64.1, 121.7, 122.7, 129.8, 133.1, 143.3, 148.6.
19
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
4-Nitro-benzylalchol (Table 3, entry 3)
CH2OH
O2N
H NMR (300 MHz, CDCl3): δ 2.55 (brs, 1H), 4.82 (s, 2H), 7.52 (d, J =
1
8.3Hz, 2H), 8.18 (d, J = 8.6 Hz, 1H); 13C NMR (75 MHz, CDCl3): δ 64.3,
124.0, 127.3, 147.5, 148.7.
4-(4-Nitrophenyl)-furfural alcohol (Table 3, entry 5)
CH2OH
O
O2N
H NMR (300 MHz, CD3COCD3): δ 4.75 (brs, 1H), 4.65 (s, 2H), 6.51 (d,
1
J = 3.3Hz, 1H), 7.12 (d, J = 3.3 Hz, 1H), 7.94 (d, J = 11.1Hz, 2H), 8.28
(d, J = 11.2 Hz, 1H);
C NMR (75 MHz, CD3COCD3): δ 56.8, 110.0,
13
110.7, 124.1, 124.5, 136.9, 146.7, 151.2, 158.2.
(Table 3, entry 6)
OH
OH
+
O2N
O2N
H NMR (300 MHz, CD3COCD3): δ 2.04-2.09 (m, 2H), 2.87-2.91 (m,
1
2H), 4.73 (t, J =7.1, 1H), 5.46 (d, J =5.3, 1H), 6.74-6.76 (m, 1H), 6.876.89 (m, 1H), 7.24-7.42 (m, 7H), 7.46-7.55 (m, 5H), 7.69-7.72 (m, 2H),
8.13-8.19 (m, 4H); 13C NMR (75 MHz, CD3COCD3): δ 33.3, 42.1, 73.8,
20
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
75.3, 124.9, 125.3, 127.3, 127.9, 128.2, 128.4, 128.7, 128.8, 129.6, 129.8,
131.0, 139.7, 145.1, 145.4, 147.3, 147.8, 148.3, 152.3.
3,4-methylenedioxy-6-nitrobenzylalchol (Table 3, entry 7)
O
O
CH2OH
NO2
H NMR (300 MHz, CD3OD): δ 4.86 (s, 2H), 6.15 (s, 2H), 7.29 (s, 1H),
1
7.58 (s, 1H); 13C NMR (75 MHz, CD3OD): δ 61.2, 103.6, 105.0, 106.8,
136.4, 140.9, 147.2, 153.1.
(Table 3, entry 8)
O
O2N
OH
H NMR (300 MHz, CD3OD): δ 1.89-1.98 (m, 1H), 2.01-2.10 (m, 1H),
1
3.54 (brs, 1H), 4.25-4.29 (m, 2H), 4.69 (overlapped with MeOD signal),
6.81 (d, J = 10.8, 1H), 7.95 (d, J = 11.6, 1H), 8.18 (s, 1H); 13C NMR (75
MHz, CD3OD): δ 31.9, 63.9, 65.2, 118.9, 126.2, 127.3, 127.6, 142.7,
161.9
4-Bromo-benzylalchol (Table 3, entry 10)
CH2OH
Br
H NMR (300 MHz, CD3OD): δ 4.56 (s, 2H), 7.25 (d, J = 8.2Hz, 2H),
1
7.47 (d, J = 8.3 Hz, 1H);
13
C NMR (75 MHz, CD3OD): δ 63.4, 120.9,
128.8, 131.4, 141.0.
21
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
3-Metoxy-4-hydroxybenzylalchol (Table 3, entry 11)
CH2OH
HO
OCH3
H NMR (300 MHz, CD3OD): δ 3.84 (s, 3H), 4.51 (s, 2H), 6.78 (s, 2H),
1
6.94 (s, 1H);
C NMR (75 MHz, CD3OD): δ 55.3, 64.3, 111.1, 115.0,
13
120.1, 133.2, 145.9, 147.9.
2,3,4-Trimethoxybenzylalchol (Table 3, entry 12)
CH2OH
OCH3
H3CO
OCH3
H NMR (300 MHz, CDCl3): δ 3.76 (s, 3H), 3.78 (s, 3H), 3.83 (s, 3H),
1
4.51 (s, 2H), 6.56 (d, J = 8.4Hz, 2H), 6.92 (d, J = 8.4 Hz, 1H); 13C NMR
(75 MHz, CDCl3): δ 56.3, 61.0, 61.4, 107.5, 123.6, 127.4, 142.3, 151.9,
153.7.
Thalide (Table 3, entry 13)
O
O
H NMR (300 MHz, CDCl3): δ 5.33 (s, 2H), 7.53 (t, J = 8.4, 2H), 7.69 (t,
1
J = 7.5, 1H), 7.91 (d, J = 7.4, 2H); 13C NMR (75 MHz, CDCl3): δ 69.7,
122.2, 125.8, 129.1, 134.1, 146.6, 171.2.
3-Cyano-benzylalchol (Table 3, entry 14)
22
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
CH2OH
CN
H NMR (300 MHz, CD3OD): δ 4.66 (s, 2H), 7.50-7.55 (m, 1H), 7.61-
1
7.71 (m, 3H); 13C NMR (75 MHz, CD3OD): δ 62.9, 112.3, 118.7, 129.4,
130.1, 130.8, 131.3, 143.8.
1-(4-Bromophenyl)ethanol (Table 3, entry 16)
OH
CHCH 3
Br
H NMR (300 MHz, CDCl3): δ 1.40 (d, J = 6.4Hz, 3H), 4.75 (q, J =
1
19.3Hz, 2H), 7.17 (d, J = 8.3Hz, 2H), 7.43 (d, J = 8.3 Hz, 1H); 13C NMR
(75 MHz, CDCl3): δ 25.5, 69.9, 121.4, 127.6, 131.8, 145.2.
Characterization of carbonyl reductive amination products:
4-Methoxy-N-(2׳-nitrobenzyl)aniline
OCH3
N
H
NO2
H NMR (300 MHz, CDCl3): δ 3.74 (s, 3H), 4.67 (s, 2H), 6.54 (d, J = 8.9
1
Hz, 2H), 6.76 (d, J = 8.9 Hz, 2H), 7.39-7.44 (m, 1H), 7.54-7.59 (m, 1H),
7.68 (d, J = 7.7 Hz, 1H), 8.05 (d, J = 8.1 Hz, 1H); 13C NMR (75 MHz,
CDCl3): δ 47.0, 56.1, 114.6, 115.3, 125.4, 128.3, 130.3, 133.9, 136.2,
142.0, 148.7, 152.8.
23
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
4-Methoxy-N-(3׳-nitrobenzyl)aniline
OCH3
N
H
NO2
H NMR (300 MHz, CDCl3): δ 3.74 (s, 3H), 4.41 (s, 2H), 6.58 (d, J = 8.9
1
Hz, 2H), 6.78 (d, J = 8.9 Hz, 2H), 7.47-7.52 (m, 1H), 7.72 (d, J = 7.6 Hz,
1H), 8.11 (d, J = 8.0 Hz, 1H), 8.24 (s, 1H); 13C NMR (75 MHz, CDCl3): δ
48.8, 56.1, 114.7, 115.4, 122.5, 129.8, 133.7, 142.0, 142.8, 149.0, 153.0.
4-Methoxy-N-(4׳-nitrobenzyl)aniline
OCH3
N
H
O2N
H NMR (300 MHz, CDCl3): δ 3.74 (s, 3H), 4.44 (s, 2H), 6.55 (d, J = 8.9
1
Hz, 2H), 6.78 (d, J = 8.9 Hz, 2H), 7.54 (d, J = 8.5 Hz, 2H), 8.18 (d, J =
8.5 Hz, 2H);
C NMR (75 MHz, CDCl3): δ 48.9, 56.1, 114.6, 115.4,
13
124.2, 128.1, 141.9, 147.5, 148.2, 152.9.
24
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
4. Spectra of Compounds
Aniline (Table 2, entry 1)
NH2
9
8
7
6
5
4
3
2
ppm
1
NH2
220
200
180
160
140
120
100
25
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
2-Floroaniline (Table 2, entry 2)
NH2
F
9
8
7
6
5
4
3
2
ppm
1
NH2
F
220
200
180
160
140
120
100
26
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
2-Chloroaniline (Table 2, entry 3)
NH2
Cl
9
8
7
6
5
4
27
3
2
1
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
4-Chloroaniline (Table 2, entry 4)
NH2
Cl
9
8
7
6
5
4
3
2
ppm
1
NH2
Cl
220
200
180
160
140
120
100
28
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
3-Bromoaniline (Table 2, entry 5)
NH2
Br
9
8
7
6
5
4
3
2
ppm
1
NH2
Br
220
200
180
160
140
120
100
29
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
4-Bromoaniline (Table 2, entry 6)
NH2
Br
9
8
7
6
5
4
3
2
1
ppm
NH2
Br
220
200
180
160
140
120
100
30
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
4-Iodoaniline (Table 2, entry 7)
NH2
I
9
8
7
6
5
4
3
2
1
ppm
NH2
I
220
200
180
160
140
120
100
31
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
4-Methoxyaniline (Table 2, entry 8)
NH2
OCH3
9
8
7
6
5
4
120
100
3
2
ppm
1
NH2
OCH3
220
200
180
160
140
32
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
4-Aminobenzoic acid (Table 2, entry 9)
NH2
8.1
8.0
7.9
7.8
7.7
7.6
7.5
7.4
7.3
7.2
7.1
7.0
6.9
6.8
ppm
6.7
COOH
9
8
7
6
5
4
3
2
ppm
1
NH2
COOH
220
200
180
160
140
120
100
33
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
3-aminobenzonitrile (Table 2, entry 10)
NH2
CN
9
8
7
6
5
4
3
2
1
ppm
NH2
CN
220
200
180
160
140
120
100
34
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
4-aminobenzonitrile (Table 2, entry 11)
NH2
CN
9
8
7
6
5
4
3
2
ppm
1
NH2
CN
220
200
180
160
140
120
100
35
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
4-Aminobenzamide (Table 2, entry 12)
NH 2
CONH 2
9
8
7
6
5
4
3
2
ppm
1
NH 2
CONH 2
220
200
180
160
140
120
100
36
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
4-Aminosulphonamide (Table 2, entry 13)
NH 2
SO2NH 2
9
8
7
6
5
4
3
2
0 ppm
1
NH 2
SO2NH 2
220
200
180
160
140
120
100
37
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
4-Methylaniline (Table 2, entry 14)
NH2
CH3
9
8
7
6
5
4
3
2
1
ppm
NH2
CH3
220
200
180
160
140
120
100
38
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
4-Aminophenol (Table 2, entry 15)
9
8
7
6
5
4
3
2
1
ppm
NH2
OH
220
200
180
160
140
120
100
39
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
Benzyl-4-aminophenyl ether (Table 2, entry 16)
NH2
O
9
8
7
6
5
4
3
2
ppm
1
NH2
O
220
200
180
160
140
120
100
40
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
Methy-3-aminobenzoate (Table 2, entry 19)
NH2
COOCH3
9
8
7
6
5
140
120
4
3
2
ppm
1
NH2
COOCH3
220
200
180
160
100
41
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
6-Aminoisoquinoline (Table 2, entry 28)
H2N
N
9
8
7
6
5
4
3
2
ppm
1
H2N
N
220
200
180
160
140
120
100
42
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
Table 2, entry 30
43
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
6-Aminobenzothiazole (Table 2, entry 31)
N
S
H2N
9
8
7
6
5
4
3
2
ppm
1
N
S
H2N
220
200
180
160
140
120
100
44
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
1-Aminonaphthalene (Table 2, entry 32)
NH2
9
8
7
6
5
4
3
2
ppm
1
NH2
220
200
180
160
140
120
100
45
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
2-Aminofluorene (Table 2, entry 33)
NH2
7.9
7.8
9
7.7
7.6
8
7.5
7.4
7
7.3
7.2
7.1
6
7.0
6.9
6.8
6.7
5
ppm
4
3
2
0 ppm
1
NH2
220
200
180
160
140
120
100
46
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
2-Aminobiphenylamine (Table 2, entry 34)
NH2
H
N
NH2
H
N
NH2
H
N
47
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
3-Aminostyrene (Table 2, entry 35)
9
220
8
200
180
7
160
6
140
5
4
120
100
48
3
80
2
60
ppm
1
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
3-Nitroaniline (Table 2, entry 37)
NH2
NO2
9
8
7
6
5
4
3
2
1
ppm
NH2
NO2
220
200
180
160
140
120
100
49
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
4-Nitroaniline (Table 2, entry 38)
NH2
NO2
9
8
7
6
5
4
3
2
ppm
1
NH2
NO2
220
200
180
160
140
120
100
50
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
Benzotriazole
H
N
N
N
9
8
7
6
5
4
3
2
ppm
1
H
N
N
N
220
200
180
160
140
120
100
H
N
N
N
51
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
Spectra of carbonyl reduction products
2-Nitro-benzylalchol (Table 3, entry 1)
CH2OH
NO2
9
8
7
6
5
4
3
2
60
40
ppm
1
CH2OH
NO2
220
200
180
160
140
120
100
52
80
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
3-Nitro-benzylalchol (Table 3, entry 2)
8.2
8.1
8.0
7.9
7.8
7.7
7.6
7.5
7.4
7.3
CH2OH
ppm
NO2
9
8
7
6
5
4
3
2
1
ppm
CH2OH
NO2
220
200
180
160
140
120
100
53
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
4-Nitro-benzylalchol (Table 3, entry 3)
CH2OH
O2N
9
8
7
6
5
4
3
2
ppm
1
CH2OH
O2N
220
200
180
160
140
120
100
54
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
4-(4-Nitrophenyl) furfural alcohol (Table 3, entry 5)
CH2OH
O
O2N
9
8
7
6
5
4
3
2
ppm
1
CH2OH
O
O2N
220
200
180
160
140
120
100
55
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
(Table 3, entry 6)
OH
OH
+
O2N
O2N
9
8
7
6
5
4
3
2
ppm
1
OH
OH
+
O2N
O2N
220
200
180
160
140
120
56
100
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
3,4-methylenedioxy-6-nitrobenzylalchol (Table 3, entry 7)
CH2OH
O
O
9
1
220
8
200
180
7
160
6
140
5
120
4
100
57
NO2
3
80
60
2
40
ppm
1
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
(Table 3, entry 8)
O
O2N
OH
9
8
7
6
5
4
3
2
1
20
ppm
O
O2N
OH
220
200
180
160
140
120
100
58
80
60
40
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
4-Bromo-benzylalchol (Table 3, entry 10)
CH2OH
Br
9
8
7
6
5
4
3
2
1
ppm
CH2OH
Br
220
200
180
160
140
120
100
59
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
3-Metoxy-4-hydroxybenzylalchol (Table 3, entry 11)
CH2OH
HO
OCH3
9
8
7
6
5
4
3
2
1
20
ppm
CH2OH
HO
OCH3
220
200
180
160
140
120
100
60
80
60
40
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
2,3,4-Trimethoxy-benzylalchol (Table 3, entry 12)
CH2OH
OCH3
H3CO
OCH3
9
8
7
6
5
4
3
2
ppm
1
CH2OH
OCH3
H3CO
OCH3
220
200
180
160
140
120
61
100
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
Thalide (Table 3, entry 13)
O
O
9
8
7
6
5
4
3
2
1
ppm
O
O
220
200
180
160
140
120
62
100
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
3-Cyano-benzylalchol (Table 3, entry 14)
CH2OH
CN
9
8
7
6
5
4
3
2
ppm
1
CH2OH
CN
220 200 180 160 140 120 100
63
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
1-(4-Bromophenyl)ethanol (Table 3, entry 16)
OH
CHCH 3
Br
9
8
7
6
5
4
3
2
1
ppm
OH
CHCH 3
Br
220
200
180
160
140
120
64
100
80
60
40
20
ppm
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
Spectra of reductive amination product
4-Methoxy-N-(4׳-nitrobenzyl)aniline
OCH3
N
H
O2N
9
8
7
6
5
4
3
2
1
ppm
OCH3
N
H
O2N
220
200
180
160
140
120
65
100
80
60
40
20
ppm
45
40
15
10
4000
1 6 3 7 .1
55
50
3500
3000
2500
Fig. S2 IR spectra of ZnPc.
66
2000
Wavenumbers (cm-1)
1500
1000
35
30
25
20
5
500
4 0 2 .8
4 7 7 .1
6 1 5 .2
2 4 1 4 .5
1 1 1 6 .2
2 4 0 9 .8
2 4 7 5 .3
2 5 5 2 .8
75
1 6 2 1 .3
2 4 2 9 .9
60
2 5 6 2 .0
65
3 4 7 0 .6
70
3 4 1 4 .6
80
1 4 0 1 .9
2 0 7 3 .1
2 3 9 4 .4
3 9 0 6 .7
8 9 2 .7
1 3 1 7 .5
2 0 3 7 .4
2 3 5 8 .4
2 4 2 7 .0
2 4 8 6 .0
2 5 4 6 .1
3 8 2 9 .4
2 9 2 7 .9
2 5 3 7 .8
3 8 4 0 .6
3 9 1 3 .6
85
3 8 6 7 .9
90
3 8 7 7 .7
95
3 9 1 7 .9
%T
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
5. IR of Zinc Phthalocyanine
** Zn
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
6. UV-vis spectra of ZnPc
Fig. S2 Uv-vis spectra of ZnPc in THF.
67
Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2012
7. References
1. K. S. Jung, J. H. Kwon, S. M. Shon, J. P. Ko, J. S. Shin, S. S. Park,
J. Mater. Sci. 2004, 39, 723.
2. N. M. T.Lourenco, C. A. M. Afonso, Tetrahedron 2003, 59, 789.
3. J. L. Romera, J. M. Cid, A. A. Trabanco Tetrahedron Lett. 2004,
45, 8797.
4. D. Villemin, M. Hammadi2, M. Hachemi, N. Bar, Molecules 2001,
6, 831.
5. M. Takasaki, Y. Motoyama, K. Higashi, S. H. Yoon, I. Mochida,
H. Nagashima, Org. Lett. 2008, 10, 1601.
6. G. de Noronha, C. C. Romao, A. C. Fernandes J. Org. Chem. 2009,
74, 6960
68