Samarium(III) Triflate as an Efficient and Reusable Catalyst for Facile 
Synthesis of Benzoxazoles and Benzothiazoles in Aqueous Medium

Pratapsinha B. Gorepatil; Yogesh D. Mane; Vilas S. Ingle

doi:10.1055/s-0033-1339758

Synlett, Table of Contents

Synlett 2013; 24(17): 2241-2244
DOI: 10.1055/s-0033-1339758

letter

Samarium(III) Triflate as an Efficient and Reusable Catalyst for Facile Synthesis of Benzoxazoles and Benzothiazoles in Aqueous Medium

Authors

Pratapsinha B. Gorepatil

Department of Chemistry, S. C. S. College, Omerga, Dist-Osmanabad 413 606, India Fax: +91(2475)252020 Email: gorepatilpratap1986@gmail.com Email: Inglevilas71@yahoo.in
Yogesh D. Mane

Department of Chemistry, S. C. S. College, Omerga, Dist-Osmanabad 413 606, India Fax: +91(2475)252020 Email: gorepatilpratap1986@gmail.com Email: Inglevilas71@yahoo.in
Vilas S. Ingle*

Department of Chemistry, S. C. S. College, Omerga, Dist-Osmanabad 413 606, India Fax: +91(2475)252020 Email: gorepatilpratap1986@gmail.com Email: Inglevilas71@yahoo.in

Abstract

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Abstract

A simple, green, and efficient method is presented for the synthesis of benzoxazoles and benzothiazoles from reaction of o-aminophenols, o-aminothiophenols, and aliphatic or aromatic aldehydes using samarium triflate as a reusable acid catalyst under mild reaction conditions in aqueous medium.

Key words

benzoxazoles - benzothiazoles - samarium triflate

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References

References and Notes

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24 General Procedure To a mixture of the requisite o-aminophenol/o-amino-thiophenol (1 mmol) and aldehyde (1 mmol) in EtOH–H₂O (2:2 mL), samarium triflate catalyst (10 mol%) was added, and the resulting mixture was stirred at 60 °C. After completion of the reaction, as monitored by TLC, the mixture was diluted with H₂O–EtOAc (1:1, 10 mL) and catalyst recovered by filtration. The filtrate was extracted with Et₂O (2 × 10 mL) and dried with anhydrous Na₂SO₄. After filtration and evaporation of solvent, the crude product was recrystallized from EtOAc or MeOH. All the structures were confirmed by their analytical data and comparison with literature data.^25–30 Spectroscopic Data for Selected Compounds 2-Phenylbenzo[d]oxazole (Table 2 Entry 1) Mp 100–102 °C. ¹H NMR (300 MHz, DMSO-d ₆): δ = 7.39 (m, 2 H), 7.57 (m, 3 H), 7.64 (m, 1 H), 7.80 (m, 1 H), 8.29 (m, 2 H). ¹³C NMR (75 MHz, DMSO-d ₆): δ = 110.6, 119.9, 124.5, 125.1, 127.3, 127.5, 128.9, 131.5, 142.2, 150.8, 163.0. IR (KBr): 740, 1171, 1355, 1511, 1640, 3100 cm^–1. MS (EI): m/z = 195.1 [M⁺]. 2-(4-Methylphenyl)benzo[d]oxazole (Table 2 Entry 3) Mp 114–116 °C. ¹H NMR (300 MHz, DMSO-d ₆): δ = 2.45 (s, 3 H), 7.36 (d, 2 H, J = 8.1 Hz), 7.41 (t, 1 H, J = 8.4 Hz), 7.51 (t, 1 H, J = 8.4 Hz), 7.96 (d, 1 H, J = 8.0 Hz), 8.00–8.06 (m, 3 H). ¹³C NMR (75 MHz, DMSO-d ₆): δ = 21.2, 121.6, 122.9, 125.0, 126.2, 127.3, 129.7, 131.0, 135.0, 141.6, 154.2, 168.0. IR (KBr): 760, 1186, 1409, 1590, 1621, 2968 cm^–1. MS (EI): m/z = 209.07 [M⁺]. 2-(4-Chlorophenyl)benzo[d]oxazole (Table 2 Entry 4) Mp 147–149 °C. ¹H NMR (300 MHz, DMSO-d ₆): δ = 7.44 (t, 1 H, J = 7.6 Hz), 7.50–7.56 (m, 3 H), 7.98 (d, 1 H, J = 8.1 Hz), 8.05–8.09 (m, 3 H). ¹³C NMR (75 MHz, DMSO-d ₆): δ = 121.7, 123.2, 125.4, 126.5, 128.7, 129.2, 132.2, 135.1, 136.8, 154.1, 166.5. IR (KBr): 775, 1175, 1371, 1640, 2980 cm^–1. MS (EI): m/z = 229 [M⁺] and 231 [M + 2]. 2-(4-Nitrophenyl)benzo[d]thiazole (Table 2 Entry 11) Mp 225–227 °C. ¹H NMR (300 MHz, DMSO-d ₆): δ = 7.51 (t, 1 H, J = 7.5 Hz), 7.60 (t, 1 H, J = 7.6 Hz), 8.01 (d, 1 H, J = 7.8 Hz), 8.16 (d, 1 H, J = 8.1 Hz), 8.36 (q, 4 H, J = 9.4 Hz). ¹³C NMR (75 MHz, DMSO-d ₆): δ = 121.9, 123.8, 124.4, 126.1, 126.8, 128.2, 135.6, 139.2, 149.0, 154.1, 165.0. IR (KBr): 807, 1169, 1370, 1556, 1690, 3056 cm^–1. MS (EI): m/z = 256.0 [M⁺]. 2-(Pyridin-4-yl)benzo[d]thiazole (Table 2 Entry 14) Mp 130–132 °C. ¹H NMR (300 MHz, DMSO-d ₆): δ = 7.44–7.50 (m, 2 H), 7.57 (t, 1 H, J = 8.1 Hz), 8.01 (d, 1 H, J = 7.9 Hz), 8.13 (d, 1 H, J = 8.2 Hz), 8.40 (dt, 1 H, J = 8.0, 1.7 Hz), 8.73 (dd, 1 H, J = 4.8z, 1.7 Hz). ¹³C NMR (75 MHz, DMSO-d ₆): δ = 121.8, 123.3, 123.8, 125.6, 129.6, 134.4, 135.1, 148.5, 154.0, 164.7. IR (KBr): 690, 1150, 1400, 1653, 2360, 2905 cm^–1. MS (EI): m/z = 212.03 [M⁺]. 2-(4-Methoxyphenyl)benzo[d]thiazole (Table 2 Entry 15) Mp 122–124 °C. ¹H NMR (300 MHz, DMSO-d ₆): δ = 3.89 (s, 3 H), 7.02 (d, 2 H, J = 8.4 Hz), 7.39 (t, 1 H, J = 7.2 Hz), 7.51 (t, 1 H, J = 7.2 Hz), 7.94 (d, 1 H, J = 7.8 Hz), 8.06 (m, 3 H). ¹³C NMR (75 MHz, DMSO-d ₆): δ = 55.4, 114.3, 121.6, 122.7, 124.8, 126.2, 126.4, 129.0, 135.0, 154.3, 162.0, 167.7. IR (KBr): 781, 1170, 1450, 1597, 1650, 3010 cm^–1. MS (EI): m/z = 241 [M⁺].
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