Molecular-Iodine-Catalyzed One-Pot Synthesis of 1,5-Benzodiazepine Derivatives under Solvent-Free Conditions

Wei-Yi Chen; Jun Lu

doi:10.1055/s-2005-868516

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Synlett 2005(8): 1337-1339
DOI: 10.1055/s-2005-868516

LETTER

Molecular-Iodine-Catalyzed One-Pot Synthesis of 1,5-Benzodiazepine Derivatives under Solvent-Free Conditions

Wei-Yi Chen*, Jun Lu
College of Chemistry and Chemical Engineering, Suzhou University, Suzhou, 215006, P. R. China
Fax: +86(512)65112371; e-Mail: suzhoucwy@163.com;

Further Information

Publication History

Received 7 March 2005
Publication Date:
03 May 2005 (online)

Abstract
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Abstract

2,3-Dihydro-1H-1,5-benzodiazepines have been synthesized from o-phenylenediamine (OPDA) and ketones under solvent-free conditions in the presence of a catalytic amount of molecular iodine. All of the ketones, including cyclic ketones and acyclic ketones, reacted smoothly with OPDA to furnish products. Compared to other reaction conditions, this new protocol has the advantage of excellent yield and short reaction time at room temperature.

Key words

benzodiazepine - o-phenylenediamine - iodine - ketones - solvent-free

References

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21

General Experimental Procedure: A mixture of OPDA (1 mmol), ketone (2 mmol), and iodine (0.1 mmol) were ground together in a mortar with a pestle at room temperature for several minutes. After completion of the reaction (TLC), the reaction was treated with aqueous Na₂S₂O₃ to furnish the crude products, which were further purified by column chromatography.
3a: Mp 145-146 °C. IR (KBr): 3341, 1637, 1600 cm^-1. ¹H NMR (CDCl₃): δ = 1.37 (s, 6 H), 2.25 (s, 2 H), 2.39 (s, 3 H), 3.44 (br s, 1 H), 6.64-7.41 (m, 4 H). ¹³C NMR (CDCl₃): δ = 29.4, 30.8, 44.9, 68.1, 121.6, 122.3, 126.1, 126.8, 138.2, 140.9, 171.6.
3b: Mp 137-138 °C. IR (KBr): 3328, 1640, 1608 cm^-1.¹H NMR (CDCl₃): δ = 0.98 (t, 3 H, J = 6.8 Hz), 1.24 (t, 3 H, J = 7.1 Hz), 1.72 (q, 2 H, J = 6.8 Hz), 2.18 (m, 2 H), 2.34 (s, 3 H), 2.71 (q, 2 H, J = 7.1 Hz), 3.28 (br s, 1 H), 6.78-7.33 (m, 4 H). ¹³C NMR (CDCl₃): δ = 8.8, 11.2, 26.8, 35.9, 36.0, 42.3, 70.8, 121.9, 125.2, 126.4, 126.8, 137.6, 140.9, 175.8.
3c: Mp 142-144 °C. IR (KBr): 3320, 1638, 1596 cm^-1.¹H NMR (CDCl₃): δ = 0.81-1.15 (m, 10 H), 1.22-1.42 (m, 4 H), 1.52-1.66 (m, 2 H), 2.38-2.56 (m, 2 H), 2.91 (q, 1 H, J = 7.0 Hz), 3.78 (br s, 1 H), 6.56-7.38 (m, 4 H). ¹³C NMR (CDCl₃): δ = 7.6, 7.9, 11.9, 12.4, 28.1, 28.5, 35.5, 46.4, 68.4, 117.6, 118.2, 126.4, 132.7, 139.1, 142.2, 173.9.
3d: Mp 118-120 °C. IR (KBr): 3265, 1651, 1600 cm^-1. ¹H NMR (CDCl₃): δ = 0.96-1.085 (m, 12 H), 1.34 (s, 3 H), 1.50-1.52 (m, 2 H), 1.66-1.75 (m, 1 H), 2.07-2.26 (m, 3 H), 2.25 (d, 2 H, J = 12.7 Hz), 6.60-7.15 (m, 4 H). ¹³C NMR (CDCl₃): δ = 22.6, 22.9, 24.1, 24.8, 25.1, 26.2, 28.3, 43.4, 51.7, 51.9, 70.9, 121.4, 121.5, 125.3, 127.4, 137.9, 140.5, 173.9.
3e: Mp 150-152 °C. IR (KBr): 3268, 1640, 1601 cm^-1. ¹H NMR (CDCl₃): δ = 1.81 (s, 3 H), 3.01 (d, 1 H, J = 12.8 Hz), 3.16 (d, 1 H, J = 12.8 Hz) 3.45 (br s, 1 H), 6.56-7.02 (m, 3 H), 7.14-7.40 (m, 7 H), 7.56-7.65 (m, 4 H). ¹³C NMR (CDCl₃): δ = 29.8, 42.9, 73.5, 121.2, 121.5, 125.3, 126.1, 126.7, 126.9, 127.8, 128.2, 128.5, 129.6, 137.9, 139.4, 139.9, 147.5, 167.6.
3f: Mp 141-143 °C. IR (KBr): 3270, 1644, 1602 cm^-1. ¹H NMR (CDCl₃): δ = 2.11 (s, 9 H,), 3.05 (d, 1 H, J = 13.6 Hz), 3.17 (d, 1 H, J = 13.6 Hz,), 3.60 (br s, 1 H), 7.12-7.61 (m, 11 H). ¹³C NMR (CDCl₃): δ = 21.3, 24.4, 28.4, 29.0, 46.4, 52.5, 114.7, 122.2, 126.2, 127.1, 128.6, 132.7, 133.1, 133.6, 135.5, 136.1, 164.9.
3g: Mp 136-138 °C. IR (KBr): 3342, 1656, 1604 cm^-1. ¹H NMR (CDCl₃): δ = 1.29-1.88 (m, 12 H), 2.31-2.58 (m, 3 H), 4.36 (br s, 1 H), 6.71-7.39 (m, 4 H). ¹³C NMR (CDCl₃): δ = 23.5, 24.1, 24.4, 28.9, 33.4, 38.5, 39.4, 54.4, 67.3, 118.6, 119.5, 126.9, 132.3, 139.3, 143.3, 178.4.
3h: Mp 137-139 °C. IR (KBr): 3321, 1654, 1600 cm^-1. ¹H NMR (CDCl₃): δ = 1.88-2.58 (m, 16 H), 2.46-2.79 (m, 3 H), 4.55 (br s, 1 H), 6.65-7.36 (m, 4 H). ¹³C NMR (CDCl₃): δ = 21.5, 21.7, 23.3, 24.5, 25.4, 33.4, 34.4, 39.3, 40.5, 52.4, 63.2, 121.1, 121.4, 126.3, 129.7, 138.2, 142.4, 178.8.