S₈-Mediated Cyclization of Bis(2-aminophenyl) Disulfide/Diselenide with Arylacetylenes/Styrenes: Access to 2-(Arylmethyl)-1,3-benzothiazoles/benzoselenazoles

Abstract

A novel S₈-mediated approach to benzothiazoles/benzoselenazoles from bis(2-aminophenyl) disulfides/diselenides and phenylacetylenes or styrenes has been developed. 2-(Arylmethyl)-1,3-benzoselenazoles were comprehensively synthesized for the first time. The reactions proceeded in moderate to excellent yields, and with a gram-scale application.

Key words

benzothiazoles - benzoselenazoles - aralkynes - styrenes - cyclization - sulfur

• References and Notes

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• 9 2-Benzyl-1,3-benzothiazole (3aa) and 2-Benzyl-1,3-benzoselenazole (7aa); Typical Procedures From ethynylbenzene: A mixture of ethynylbenzene (1a; 23 μL, 0.2 mmol), bis(2-aminophenyl) disulfide 2a (50 mg, 0.2 mmol) [or bis(2-aminophenyl) diselenide 6a (69 mg, 0.2 mmol)], elemental S (12.8 mg, 0.4 mmol), NaHCO₃ (33.6 mg, 0.4 mmol), and DMF (or NMP) (0.6 mL) was placed in a sealed pressure vessel (10 mL) containing a magnetic stirring bar. The vessel was then capped and the mixture was stirred at 110 °C for 16 h under air (or at 130 °C for 24 h under N₂) until the reaction was complete (TLC). The mixture was cooled to rt and treated with EtOAc (15 mL) and H₂O (10 mL). The organic phase was then separated, washed with brine, dried, filtered, concentrated under vacuum, and purified by column chromatography [silica gel, PE–EtOAc (40:1 or 50:1)] to afford 3aa as a light-yellow oil (yield: 42 mg, 94%) [or 7aa as a light-yellow solid (yield: 46 mg, 85%)].From styrene: A mixture of styrene 4a (24 μL, 0.2 mmol), bis(2-aminophenyl) disulfide 2a (0.2 mmol), elemental S (12.8 mg, 0.4 mmol), NaHCO₃ (33.6 mg, 0.4 mmol), and DMF (0.6 mL) was placed in a sealed pressure vessel (10 mL) containing a magnetic stirring bar. The vessel was then capped and the mixture was stirred at 110 °C for 16 h under air until the reaction was complete (TLC). Similar workup to the above gave 3aa as a light-yellow oil; yield: 42 mg (93%).From 2,2′-trisulfanediyldianiline: A mixture of ethynylbenzene (1a; 23 μL, 0.2 mmol), 2,2′-trisulfanediyldianiline (5a; 56 mg, 0.2 mmol), elemental S (12.8 mg, 0.4 mmol), NaHCO₃ (33.6 mg, 0.4 mmol), and DMF (0.6 mL) was placed in a sealed pressure vessel (10 mL) containing a magnetic stirring bar. The vessel was then capped and the mixture was stirred at 110 °C for 16 h under air until the reaction was complete (TLC). Similar workup to the above gave 3aa as a light-yellow oil; yield: 36 mg (79%).2-Benzyl-1,3-benzothiazole (3aa)[CAS Reg. No. 6265-94-7]Light-yellow oil. ¹H NMR (400 MHz, CDCl₃): δ = 7.95 (d, J = 8.1 Hz, 1 H), 7.71 (d, J = 8.0 Hz, 1 H), 7.36–7.40 (m, 1 H), 7.23–7.33 (m, 6 H), 4.37 (s, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 171.1, 153.1, 137.1, 135.5, 129.0, 128.8, 127.2, 125.9, 124.7, 122.6, 121.4, 40.5.The spectral data agreed with those reported in the literature; see ref. 3c.2-Benzyl-1,3-benzoselenazole (7aa)[CAS Reg. No.854053-83-1]Light-yellow solid. ¹H NMR (500 MHz, CDCl₃): δ = 8.01 (d, J = 8.1 Hz, 1 H), 7.77 (d, J = 7.9 Hz, 1 H), 7.39–7.42 (m, 1 H), 7.31–7.35 (m, 4 H), 7.26–7.29 (m, 1 H), 7.21 (t, J = 7.6 Hz, 1 H), 4.36 (s, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 176.6, 154.8, 139.1, 137.5, 129.2, 128.8, 127.4, 125.9, 124.8, 124.7, 124.2, 43.7.