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Synthesis of 10-Amino-5,6,7,9-tetrahydro-1-thia-4,9-diazacyclohepta[f]inden-8-one Derivatives using Schmit Reaction
Synthesis of 10-Amino-5,6,7,9-tetrahydro-1-thia-4,9-diazacyclohepta[f]inden-8-one Derivatives using Schmit Reaction
Journal of the Korean Chemical Society. 2009. Jun, 53(3): 387-391
Copyright © 2009, The Korean Chemical Society
  • Received : May 06, 2009
  • Published : June 20, 2009
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Han Mi Lee
Yang-Heon Song

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EXPERIMENTAL
All products were characterized by IR, 1 H NMR, MS and elemental analysis. Melting points were measured by using the capillary tubes on Büchi apparatus and are uncorrected. Each compound of the reactions was checked on thin-layer chromatography of Merck Kieselgel 60F 254 and purified by column chromatography using Merck silica gel (70-230 mesh). IR spectra were recorded on the FT-IR Brucker Tensor 27. The 1 H NMR spectra were recorded on Bruker DRX-300 FTNMR spectrometer (300 MHz) with Me 4 Si as internal standard and chemical shifts are given in ppm (δ). Electron ionization mass spectra were recorded on a HP 59580 B spectrometer. Elemental analyses were performed on a Carlo Erba 1106 elemental analyzer.
- General procedure for the preparation of 10-amino-5,6,7,9-tetrahydro-1-thia-4,9-diazacyclohe pta[f]inden-8-one derivatives (4):
To a solution of 8 (0.01 mole) in concentrated H 2 SO 4 (10 mL) and CHCl 3 (10 mL), sodium azide (0.03 mole) was slowly added over 1 h. The solution was stirred for 5 h at room temperature. The reaction mixture was basified with dilute NH 4 OH and extracted with CHCl 3 . After evaporation the precipitate was filtered and recrystallized from EtOH.
- 10-Amino-5,6,7,9-tetrahydro-1-thia-4,9-diazac yclohepta[f]inden-8-one (4a):
Yield 58%; mp 231 ℃ (dec); IR (KBr): 1670 cm -1 ; 1 H NMR (DMSO-d 6 ): δ 8.71 (s, 1H, NH), 7.78 (d, J = 5.9 Hz, 1H, thiophene H-2), 7.24 (d, J = 5.9 Hz, 1H, H-3), 6.18 (s, 2H, NH 2 ), 2.78 (m, 2H, H-5), 2.13-2.07 (m, 4H, H-6 and H-7); MS: (m/z) 233 (M + ), 204, 190. Anal . Calcd. for C 11 H 11 N 3 OS: C, 56.63; H, 3.14; N, 18.01. Found: C, 56.50; H, 3.30; N, 18.22.
- 1,3,4,5-Tetrahydro-9-thia-1,2,6-triazacyclopen ta[d]acenaphthylene (9a):
Yield 14%; mp 283-284 ℃; 1 H NMR (DMSO-d 6 ):
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13.30 (s, 1H, NH), 7.91 (d, J = 5.9 Hz, 1H, thiophene H-8), 7.59 (d, J = 5.9 Hz, 1H, H-9), 3.00-2.94 (m, 4H, H-3 and H-5), 2.19 (q, 2H, H-4); MS: (m/z) 215 (M + ), 186, 160. Anal . Calcd. for C 11 H 9 N 3 S: C, 61.37; H, 4.21; N, 19.52. Found: C, 61.49; H, 4.10; N, 19.70.
- 10-Amino-6,6-dimethyl-5,6,7,9-tetrahydro-1-thia-4,9-diazacyclohepta[f]inden-8-one (4b):
Yield 52%; mp 227 ℃ (dec); 1 H NMR (DMSO-d 6 ):
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8.77 (s, 1H,NH), 7.76 (d, J = 5.9 Hz, 1H, thiophene H-2), 7.29 (d, J = 5.9 Hz, 1H, H-3), 6.18 (s, 2H, NH 2 ), 2.90 (s, 2H, H-5), 2.58 (s, 2H, H-7), 1.00 (s, 6H, diMe); MS: (m/z) 261 (M + ), 246, 218, 178, 135. Anal . Calcd. for C 13 H 15 N 3 OS: C, 59.75; H, 5.78; N, 16.08. Found: C, 59.90; H, 5.59; N, 16.20.
- 10-Amino-6-phenyl-5,6,7,9-tetrahydro-1-thia-4,9-diazacyclohepta[f]inden-8-one (4c):
Yield 62%; mp 196-197 ℃; 1 H NMR (DMSO-d 6 ):
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8.94 (s, 1H,NH), 7.81 (d, J = 6.0 Hz, 1H, thiophene H-2), 7.29-7.22 (m, 6H, H-3 and phenyl), 6.27 (s, 2H, NH2), 3.65 (m, 1H, H-6), 3.15 (m, 1H, H-5a), 2.98 (m, 1H, H-5b), 2.49 (m, 1H, H-7a), 2.29 (m, 1H, H-7b); MS: (m/z) 309 (M + ), 284, 179. Anal . Calcd. for C 17 H 15 N 3 OS: C, 66.00; H, 4.89; N, 13.58. Found: C, 65.84; H, 4.73; N, 13.70.
- 10-Amino-6-p-tolyl-5,6,7,9-tetrahydro-1-thia-4,9-diazacyclohepta[f]inden-8-one (4d):
Yield 44%; mp 169-171 ℃; 1 H NMR (DMSO-d 6 ): δ 8.92 (s, 1H,NH), 7.81 (d, J = 6.0 Hz, 1H, thiophene H-2), 7.29 (d, J = 5.9 Hz, 1H, H-3), 7.25 (d, 2H, phenyl H-2’and H-6’), 7.09 (d, 2H, phenyl H-3’and H-5’), 6.26 (s, 2H, NH 2 ), 3.57 (m, 1H, H-6), 3.12 (m, 1H, H-5a), 2.96 (m, 1H, H-5b), 2.50 (m, 1H, H-7a), 2.27-2.20 (m, 4H, H-7b and Me); MS: (m/z) 323 (M + ), 295, 280, 179, 145. Anal . Calcd. for C 18 H 17 N 3 OS: C, 66.85; H, 5.30; N, 12.99. Found: C, 66.99; H, 5.48; N, 13.19.
- 4-p-Tolyl-1,3,4,5-tetrahydro-9-thia-1,2,6-triaza cyclopenta[d]acenaphthylene (9d):
Yield 10%; mp 246-247 ℃; 1 H NMR (DMSO-d 6 ): δ 13.60 (s, 1H, NH), 7.95 (d, J = 5.9 Hz, 1H, thiophene H-8), 7.34 (d, J = 5.9 Hz, 1H, H-9), 7.24 (d, 2H, phenyl H-2’and H-6’), 7.07 (d, 2H, phenyl H-3’and H-5’), 3.40 (m, 1H, H-4), 3.11-2.95 (m, 4H, H-3 and H-5), 2.22(s, 3H, Me); MS: (m/z) 305 (M + ), 299, 286. Anal . Calcd. for C 18 H 15 N 3 S: C,70.79; H, 4.95; N, 13.76. Found: C, 70.62; H, 4.76; N, 13.90.
- 10-Amino-6-(4-chlorophenyl)-5,6,7,9-tetrahyd ro-1-thia-4,9-diazacyclohepta[f]inden-8-one (4e):
Yield 65%; mp 189-190 ℃; 1 H NMR (DMSO-d 6 ): δ 8.97 (s, 1H,NH), 7.83 (d, J = 5.9 Hz, 1H, thiophene H-2), 7.48 (d, 2H, phenyl H-3’and H-5’), 7.31 (d, 2H, phenyl H-2’and H-6’), 7.28 (d, J = 5.9 Hz, 1H, H-3), 6.35 (s, 2H, NH 2 ), 3.67 (m, 1H, H-6), 3.16 (m, 1H, H-5a), 2.98 (m, 1H, H-5b), 2.49 (m, 1H, H-7a), 2.28 (m, 1H, H-7b); MS: (m/z) 344 (M + ), 316, 300, 219, 180, 165. Anal . Calcd. for C 17 H 14 ClN 3 OS: C, 59.39; H, 4.10; N, 12.22. Found: C, 59.22; H, 4.28; N, 12.10.
- 10-Amino-6-(4-bromophenyl)-5,6,7,9-tetrahyd ro-1-thia-4,9-diazacyclohepta[f]inden-8-one (4f):
Yield 56%; mp 252-254 ℃; 1 H NMR (DMSO-d 6 ): δ 8.96 (s, 1H,NH), 7.82 (d, J = 5.9 Hz, 1H, thiophene H-2), 7.47 (d, 2H, phenyl H-3’and H-5’), 7.31 (d, 2H, phenyl H-2’and H-6’), 7.27 (d, J = 5.9 Hz, 1H, H-3), 6.30 (s, 2H, NH 2 ), 3.66 (m, 1H, H-6), 3.15 (m, 1H, H-5a), 2.96 (m, 1H, H-5b), 2.49 (m, 1H, H-7a), 2.26 (m, 1H, H-7b); MS: (m/z) 388 (M + ), 360, 218, 190, 179. Anal . Calcd. for C 17 H 14 BrN 3 OS: C, 52.59; H, 3.63; N, 10.82. Found: C, 52.75; H, 3.48; N, 11.01.
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