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