One-Pot Synthesis of 5-Ene-4-aminothiazol-2(5H)-ones and Chromeno[2,3-d]thiazol-2-ones

Abstract

Herein, we describe a one-pot, three-component method for the synthesis of 5-arylidene-4-aminothiazol-2(5H)-ones based on the reaction of isorhodanine, aromatic aldehydes, and ethanolamine. The one-pot procedure for chromeno[2,3-d]thiazol-2-one synthesis starting from 4-aminothiazol-2(5H)-one was proposed following the study of 5-(2-hydroxybenzylidene)-thiazolidinones. Structural features of the starting 4-thioxo-2-thiazolidinone, 4-aminothiazol-2(5H)-one, and target compounds are discussed.

Key words

one-pot method - 5-ene-thiazolidinones - 4-aminothiazol-2(5H)-ones - chromeno[2,3-d]thiazol-2-ones - X-ray

• References and Notes


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• 14 General Procedure for 5-Ene-4-aminothiazol-2(5H)-ones 1 A mixture of isorhodanine (5 mmol), aldehyde (5 mmol), and ethanolamine (5 mmol) was heated at reflux for 2 h in EtOH (10 mL). After cooling, the precipitate was filtered off, washed and recrystallized from EtOH. Representative Analytical Data for (Z)-5-(4-Chlorophenylmethylidene)-4-(2-hydroxyethylamino)-thiazol-2(5H)-one (1a) Yield 63%; mp 237–239 °C. ¹H NMR (400 MHz, DMSO-d₆ ): δ = 3.59 (t, 2 H, J = 5.2 Hz, CH₂), 3.65 (t, 2 H, J = 5.2 Hz, CH₂), 4.77 (t, 1 H, J = 5.1 Hz, OH), 7.47 (d, 2 H, J = 8.4 Hz, arom.), 7.52 (d, 2 H, J = 8.4 Hz, arom.), 7.81 (s, 1 H, CH), 9.31 (br s, 1 H, NH). ¹³C NMR (100 MHz, DMSO-d₆ ): δ = 176.4, 173.3, 144.3, 134.3, 133.2, 131.2, 129.5, 126.0, 58.7, 47.4. LCMS (ESI⁺): m/z = 283/285 [M + H]⁺. Anal. Calcd (%) for C₁₂H₁₁ClN₂O₂S: C, 50.98; H, 3.92; N, 9.91. Found: C, 51.10; H, 4.00; N, 9.80.
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• 19 General Procedure for Chromeno[2,3-d]thiazol-2-ones (2) A mixture of 4-aminothiazol-2(5H)-one (5 mmol), salicylic aldehyde (5 mmol), and NaOAc (5 mmol) was heated at reflux for 2 h in a mixture of AcOH and Ac₂O (10 mL, 1:1). After cooling, the precipitate was filtered off, washed with AcOH (3 mL), H₂O (3 mL), and EtOH (3 mL), and recrystallized from AcOH or a mixture of DMF–EtOH (1:1). Representative Analytical data for Chromeno[2,3-d]thiazol-2-one (2a) Yield 77%; mp 223–225 °C. ¹H NMR (400 MHz, DMSO-d₆ ): δ = 7.56 (t, J = 7.3 Hz, 1 Н), 7.75–7.82 (m, 2 Н), 7.85 (d, J = 7.7 Hz, 1 H), 8.46 (s, 1 Н).¹³C NMR (100 MHz, DMSO-d₆ ): δ = 177.2, 175.9, 150.9, 132.8, 132.7, 128.6, 127.9, 126.8, 120.8, 118.0. LCMS (ESI⁺): m/z = 204 [M + H]⁺. Anal. Calcd (%) for C₁₀H₅NO₂S: C, 59.10; H, 2.48; N, 6.89. Found: C, 59.30; H, 2.60; N, 6.70.

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