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Synlett 2015; 26(13): 1819-1822
DOI: 10.1055/s-0034-1378724
DOI: 10.1055/s-0034-1378724
letter
Novel Route to Thiophene-2,4-diamines
Further Information
Publication History
Received: 05 April 2015
Accepted after revision: 07 May 2015
Publication Date:
25 June 2015 (online)
Abstract
A novel and simple procedure for the construction of fully substituted thiophene-2,4-diamines using tertiary thioamides was developed. Thus, thioacetomorpholides undergo self-condensation to the corresponding 3,5-diarylthiophene-2,4-diamine derivatives in the presence of iodine and potassium carbonate in a suitable solvent and under mild conditions.
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References and Notes
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- 13 General Procedure for the Synthesis of 3,5-Diarylthiophene-2,4-diamines To a stirred solution of thioacetomorpholide (2 mmol) in DMF (1 mL), I2 (1.1 mmol, 280 mg) and anhydrous K2CO3 (3 mmol, 415 mg) were added. The reaction mixture was heated at 65 °C and stirred for 120 min. Then the reaction mixture was poured in H2O (10 mL) and extracted with EtOAc (20 mL). The organic phase was separated, dried, and subjected to flash column chromatography (EtOAc–hexane, 1: 4) to afford the desired compounds as white solids.
- 14 Selected Spectral Data for Compound 4,4′-(3,5-Di-p-tolylthiophene-2,4-diyl)dimorpholine (2b) Yield: 343 mg (79%); white crystals, mp 181–183 °C. 1H NMR (400 MHz, CDCl3): δ = 2.31 (s, 6 H), 2.65 (t, 3 J HH = 4.4 Hz, 4 H), 2.74 (t, 3 J HH = 4.4 Hz, 4 H), 3.35 (t, 3 J HH = 4.4 Hz, 4 H), 3.54 (t, 3 J HH = 4.4 Hz, 4 H), 7.09–7.13 (m, 4 H), 7.29 (d, 3 J HH = 8.0 Hz, 2 H), 7.39 (d, 3 J HH = 8.0 Hz, 2 H). 13C NMR (100 MHz, CDCl3): δ = 21.2, 21.3, 51.6, 52.6, 66.8, 67.3, 120.4, 126.5, 128.7, 128.8, 129.8, 130.1, 132.0, 132.8, 136.3, 137.1, 143.9, 151.4. Anal. Calcd for C26H30N2O2S: C, 71.86; H, 6.96; N, 6.45; S, 7.38. Found: C, 71.83; H, 6.93; N, 6.52; S, 7.34.