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Practical Multigram Synthesis of 3,3,3',3'-Tetramethyl-1,1'-spirobisindane-5,5'-diamino-6,6'-diol
Practical Multigram Synthesis of 3,3,3',3'-Tetramethyl-1,1'-spirobisindane-5,5'-diamino-6,6'-diol
Bulletin of the Korean Chemical Society. 2013. Dec, 34(12): 3888-3890
Copyright © 2013, Korea Chemical Society
  • Received : August 01, 2013
  • Accepted : September 20, 2013
  • Published : December 20, 2013
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About the Authors
Jee Soo Choi
Sang-Hyun Ahn
Kang Hyuck Lee
WCU Department of Energy Engineering, Hanyang University, Seoul 133-791, Korea
Young Moo Lee
WCU Department of Energy Engineering, Hanyang University, Seoul 133-791, Korea
Kee-Jung Lee

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Experimental Section
Spirobisindane derivatives 2 , 11 3a , and 4a 9 were prepared according to the procedures reported in the literatures.
6,6'-Dibenzyloxy-3,3,3',3'-tetramethyl-1,1'-spirobisin-dane (3b). A mixture of spirobisindanediol 2 (9.24 g, 30 mmol), benzyl chloride (11.3 g, 90 mmol) and K 2 CO 3 (12.4 g, 90 mmol) in CH 3 CN (120 mL) was stirred at reflux temperature for 8 h. The reaction mixture was poured into water, extracted with CH 2 Cl 2 (3 × 100 mL), and dried over MgSO 4 . The solvent was evaporated under reduced pre-ssure. The resulting solid was filtered with petroleum ether to produce pure 3b (10.5 g, 72%) as a white solid. mp 184-185 °C; IR (KBr) 1601, 1484, 1358, 1014 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 1.33 (s, 6H, two CH 3 ), 1.37 (s, 6H, two CH 3 ), 2.25 (d, J = 12.9 Hz, 2H, CH 2 ), 2.35 (d, J = 13.2 Hz, 2H, CH 2 ), 4.92 (s, 4H, C H 2 Ph), 6.43 (d, J = 2.3 Hz, 2H, aromatic), 6.87 (dd, J = 8.2 and 2.3 Hz, 2H, aromatic), 7.08 (d, J = 8.5 Hz, 2H, aromatic), 7.27-7.39 (m, 10H, two Ph); 13 C NMR (75 MHz, CDCl 3 ) δ 30.5, 31.8, 42.9, 57.8, 59.6, 70.1, 110.2, 114.0, 122.4, 127.6, 127.8, 128.4, 137.1, 144.9, 151.9, 158.5. Anal. Calcd for C 35 H 36 O 2 : C, 86.03; H, 7.43. Found: C, 85.85; H, 7.29.
6,6'-Dibenzyloxy-3,3,3',3'-tetramethyl-5,5'-dinitro-1,1'-spirobisindane (4b). To a chilled mixture (0 °C) of glacial acetic acid (130 mL), 60% HNO 3 (24.8 mL, 360 mmol), and 97% H 2 SO 4 (16.0 mL, 300 mmol), dibenzyloxyspirobi-sindane 3b (14.6 g, 30 mmol) were slowly added. The reaction mixture was stirred for 5 min at 0 °C and then at room temperature for 5 h. The reaction mixture was poured into ice water and the precipate was filtered off. The crude product was dissolved in CH 2 Cl 2 , dried over MgSO 4 , and evaporated under reduced pressure. The resulting solid was filtered with Et 2 O to produce pure 4b (13.0 g, 75%) as a slightly yellowish solid. mp 175-178 °C; IR (KBr) 1616, 1580, 1521, 1347, 1289 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 1.35 (s, 6H, two CH 3 ), 1.40 (s, 6H, two CH 3 ), 2.17 (d, J = 13.2 Hz, 2H, CH 2 ), 2.38 (d, J = 13.5 Hz, 2H, CH 2 ), 4.98 (two d, J = 12.3 Hz, 4H, CH 2 Ph), 6.31 (s, 2H, aromatic), 7.21-7.34 (m, 10H, two Ph), 7.66 (s, 2H, aromatic); 13 C NMR (75 MHz, CDCl 3 ) δ 30.1, 31.4, 43.4, 58.4, 58.8, 71.0, 110.4, 119.5, 126.9, 128.1, 128.6, 135.4, 140.1, 144.5, 151.8, 155.5. Anal. Calcd for C 35 H 34 N 2 O 6 : C, 72.65; H, 5.92; N, 4.84. Found: C, 72.53; H, 5.81; N, 4.98.
3,3,3',3'-Tetramethyl-1,1'-spirobisindane-5,5'-dinitro-6,6'-diol (5). To a chilled (0-5 °C) solution of 4a (8.52 g, 20 mmol) in CH 2 Cl 2 was added BBr 3 (5.8 mL, 60 mmol) dropwise manner. The reaction mixture was stirred at same temperature for 1 h. The mixture was poured into cold saturated aq. NaHCO 3 solution (500 mL), and extracted with CH 2 Cl 2 (200 mL × 3). The combined organic layers were dried (MgSO 4 ) and the solvent was evaporated under re-duced pressure. The resulting solid was filtered with Et 2 O-petroleum ether to produce pure 5 (6.77 g, 85%) as a yellow solid. mp 238-241 °C; 8 1 H NMR (300 MHz, CDCl 3 ) δ 1.37 (s, 6H, two CH 3 ), 1.44 (s, 6H, two CH 3 ), 2.28 (d, J = 13.2 Hz, 2H, CH 2 ), 2.42 (d, J = 13.2 Hz, 2H, CH 2 ), 6.54 (s, 2H, aromatic), 7.92 (s, 2H, aromatic), 10.61 (s, 2H, OH); 13 C NMR (75 MHz, CDCl 3 ) δ 30.1, 31.6, 43.4, 58.2, 58.7, 114.8, 118.7, 133.6, 145.1, 155.3, 160.5.
3,3,3',3'-Tetramethyl-1,1'-spirobisindane-5,5'-diamino-6,6'-diol (6). To a stirred suspension of 4b (11.6 g, 20 mmol) and 10% Pd-C (638 mg, 0.6 mmol) in refluxing ethanol (300 mL) was added NH 2 NH 2 ·H 2 O (19.4 mL, 400 mmol) drop-wise manner. After stirring at reflux temperature for 8 h, the reaction mixture was filtered with celite and washed with EtOH (20 mL). The organic phase was poured into water and the precipitate was filtered off and dried to give pure 6 (4.73 g, 70%) as a white solid. mp 262-265 °C; IR (KBr) 3492, 3376, 3285, 1616, 1506, 1322 cm −1 ; 1 H NMR (300 MHz, DMSO- d 6 ) δ 1.20 (s, 6H, two CH 3 ), 1.25 (s, 6H, two CH 3 ), 1.97 (d, J = 12.6 Hz, 2H, CH 2 ), 2.14 (d, J = 12.6 Hz, 2H, CH 2 ), 4.31 (s, 4H, NH 2 ), 6.04 (s, 2H, aromatic), 6.37 (s, 2H, aromatic), 8.65 (s, 2H, OH); 13 C NMR (75 MHz, DMSO- d 6 ) δ 30.7, 31.7, 42.3, 56.2, 59.7, 107.0, 109.1, 135.5, 138.7, 142.2, 143.8.
Acknowledgements
This research was supported by Korea CCS 2020 Program and Nano Material Technology Develop-ment Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2012M3A7B4049745).
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