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Synlett 2008(2): 286-288  
DOI: 10.1055/s-2007-1000881
LETTER
© Georg Thieme Verlag Stuttgart · New York

A Useful One-Pot Procedure for Obtaining 2-Aryl-5-nitrothiophenes from Bromonitromethane and 3-Aryl-3-chloro-propenals

Juan C. Rodríguez-Domíngueza, David Thomaea, Pierre Seckb, Gilbert Kirsch*a
a Laboratoire d’Ingénierie Moléculaire et Biochimie Pharmacologique, Institut Jean Barriol, FR CNRS 2843, Université Paul Verlaine-Metz, 1 Boulevard Arago, Metz, 57070, France
Fax: +33(3)87315801; e-Mail: kirsch@univ-metz.fr;
b Faculté des Sciences, de la Technologie et de la Communication, Université du Luxembourg, 162 A, Avenue de la Faiencerie, 1511 Luxembourg
Further Information

Publication History

Received 19 October 2007
Publication Date:
21 December 2007 (online)

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Abstract

A one-pot procedure was developed to prepare new 2-aryl-5-nitrothiophenes efficiently from bromonitromethane and 3-chloro-3-aryl-propenals. Nitrothiophenes were synthesized in good yields with a simple and easy workup procedure.

Key words

5-nitrothiophenes - bromonitromethane - 3-aryl-3-chloro-propenals

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Typical Experimental Procedure for Obtaining Mononitrophenylthiophenes
Sodium sulfide (Na2S·9H2O, 0.05 mol) was suspended in DMF (98 mL) and stirred at 40 °C for 30 min. After that time the corresponding 2-chloroacrolein (0.05 mol) was added. The mixture was then heated at 55 °C for 90 min and left to reach r.t. Bromonitromethane (0.05 mol) was slowly dropped at r.t. and left to stir at 55 °C for another 90 min. The reaction was followed by TLC (n-hexane-EtOAc, 3:1) and, once finished, NaOH (0.05 mol) in H2O (10 mL) was added and the mixture was left to stir 30 min at the same temperature. The mixture was poured onto H2O with good stirring and the obtained precipitate was filtered, washed with H2O, and dried at r.t. until the weight was constant.

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3-(3-Bromophenyl)-3-chloro-2-propenal
Yield 74.3%; orange solid, mp 64-65 °C (from EtOH). 1H NMR (250 MHz, DMSO-d 6): δ = 10.10 (d, J = 6.5 Hz, 1 H, HCO), 8.04 (d, J = 3.3 Hz, 1 H, PhH), 7.87 (dd, 1 H, PhH), 7.75 (dd, 1 H, PhH), 7.46 (m, 1 H, PhH), 7.04 (d, J = 6.6 Hz, 1 H, H2). 13C NMR (62.9 MHz, DMSO-d 6): δ = 191.30, 148.43, 136.99, 134.49, 130.96, 129.53, 126.25, 125.39, 122.23. Anal. Calcd for C9H6BrClO (245.50): C, 44.03; H, 2.46; Br, 32.55; Cl, 14.44. Found: C, 43.99; H, 2.50; Br, 32.59; Cl, 14.41.

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Purity was checked by 1H NMR spectroscopy using a Bruker 250 MHz instrument.

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Reagents were purchased from ACROS Organics. Thin-layer chromatography (TLC) was carried out by using SilicaGel 60 F-254 plates and n-hexane-EtOAc (3:1) as an eluent. Melting points were determined on a Stuart Scientific SMP 3 capillary melting point apparatus and are uncorrected. IR spectra were performed in a Perkin Elmer Spectrum BxFT-IR spectrophotometer. Elemental analyses were conducted in a LECO CHNS 932 instrument.
2-(4-Chlorophenyl)-5-nitrothiophene (1): mp 121-124 °C (from EtOH). IR (KBr): ν = 1534 (NO2), 1333 (NO2) cm-1. 1H NMR (250 MHz, DMSO-d 6): δ = 8.19 (d, J 4,3 = 7.5 Hz, 1 H, H4), 7.88 (d, J = 10.0 Hz, 2 H, HPh), 7.72 (d, J 3,4 = 5.0 Hz, 1 H, H3), 7.58 (d, J = 10 Hz, 2 H, HPh). 13C NMR (62.9 MHz, DMSO-d 6): δ = 149.83, 149.57, 134.86, 131.27, 129.44, 129.31, 127.79, 124.56. Anal. Calcd for C10H6ClNO2S (239.68): C, 50.11; H, 2.52; Cl, 14.79; N, 5.84; S, 13.38. Found: C, 50.20; H, 2.60; Cl, 14.70; N, 5.80; S, 13.32.
2-(4-Fluorophenyl)-5-nitrothiophene (2): mp 124-126 °C (from EtOH); mpLit 129-130 °C.2 IR (KBr): ν = 1536 (NO2), 1334 (NO2) cm-1. 1H NMR (250 MHz, DMSO-d 6): δ = 8.14 (d, J = 4.25 Hz, 1 H), 7.87 (dd, 2 H, HPh), 7.63 (d, J = 4.25 Hz, 1 H), 7.33 (m, 2 H, HPh). 13C NMR (62.9 MHz, DMSO-d 6): δ = 161.1, 150.2, 131.3, 128.6, 128.4, 124.1, 116.8, 116.5.
2-(4-Methylphenyl)-5-nitrothiophene (3): mp 86-87 °C (from diisopropyl ether). IR (KBr): ν = 1510 (NO2), 1333 (NO2) cm-1. 1H NMR (250 MHz, DMSO-d 6): δ = 8.13 (d, J = 4.45 Hz, 1 H), 7.71 (d, J = 8.07 Hz, 2 H, HPh), 7.61 (d, J = 4.37 Hz, 1 H), 7.30 (d, J = 7.72 Hz, 2 H, HPh), 2.34 (s, 3 H, CH3). 13C NMR (62.9 MHz, DMSO-d 6): δ = 151.85, 140.36, 131.37, 130.02, 128.71, 126.12, 123.38, 20.85. Anal. Calcd for C11H9NO2S (219.26): C, 60.26; H, 4.14; N, 6.39; S, 14.62. Found: C, 60.30; H, 4.19; N, 5.32; S, 14.68.
2-(4-Methoxyphenyl)-5-nitrothiophene (4): mp 129-131 °C (from cyclohexane); mpLit 135 °C.5 IR (KBr): ν = 1536 (NO2), 1337 (NO2) cm-1. 1H NMR (250 MHz, DMSO-d 6): δ = 8.14 (d, J = 5.0 Hz, 1 H, H4), 7.79 (d, J = 7.5 Hz, 2 H, HPh), 7.57 (d, J 3,4 = 5.0 Hz, 1 H, H3), 7.06 (d, J = 7.5 Hz, 2 H, HPh), 3.83 (s, 3 H, OCH3). 13C NMR (62.9 MHz, DMSO-d 6): δ = 160.95, 152.04, 148.05, 130.44, 127.47, 123.71, 122.66, 114.86, 55.19. Anal. Calcd for C11H9NO3S (235.26): C, 50.11; H, 2.52; Cl, 14.79; N, 5.84; S, 13.38. Found: C, 56.16; H, 3.86; N, 5.95; S, 13.63.
2-(4-Nitrophenyl)-5-nitrothiophene (5): mp 166-170 °C (from EtOH); mpLit 179 °C (from EtOH-H2O).3 IR (KBr): ν = 1516 (NO2), 1345 (NO2) cm-1. 1H NMR (250 MHz, DMSO-d 6): δ = 8.29 (d, J = 8.65 Hz, 2 H, HPh), 8.21 (dd, 1 H), 8.09 (d, J = 8.75 Hz, 2 H, HPh), 7.87 (dd, 1 H). 13C NMR (62.9 MHz, DMSO-d 6): δ = 151.17, 147.81, 137.35, 131.02, 130.27, 127.24, 126.51, 124.41.
2-[1,1′-Biphenyl]-4-yl-5-nitrothiophene (6): mp 166-169 °C (from EtOH). IR (KBr): ν = 1485 (NO2), 1300 (NO2) cm-1. 1H NMR (250 MHz, DMSO-d 6): δ = 8.37-7.82 (m, 11 H). 13C NMR (62.9 MHz, DMSO-d 6): δ = 152.2, 148.8, 148.7, 138.3, 132.1, 131.1, 128.3, 128.1, 127.5, 125.4, 125.1, 124.7. Anal. Calcd for C16H11NO2S (281.33): C, 68.31; H, 3.94; N, 4.98; S, 11.40. Found: C, 68.38; H, 4.01; N, 4.95; S, 11.36. 2-(3-Bromophenyl)-5-nitrothiophene (7): mp 76-79 °C (from EtOH). IR (KBr): ν = 1534 (NO2), 1470 (NO2) cm-1. 1H NMR (250 MHz, DMSO-d 6): δ = 8.16 (d, J = 5.0 Hz, 1 H, H3-Thioph), 8.07-8.05 (m, 1 H), 7.82-7.79 (m, 1 H), 7.75 (d, J = 5.0 Hz, H4-Thioph), 7.68-7.64 (m, 1 H), 7.44 (t, 1 H). 13C NMR (62.9 MHz, DMSO-d 6): δ = 150.06, 133.65, 132.81, 131.48, 131.08, 128.57, 125.34, 125.08, 122.74, 122.72. Anal. Calcd for C10H6BrNO2S (284.13): C, 42.27; H, 2.13; Br, 28.12; N, 4.93; S, 11.29. Found: C, 42.22; H, 2.16; Br, 28.08; N, 4.89; S, 11.25. 2-Nitro-4,5-dihydronaphtho[1,2b]thiophene (8): mp 114-116 °C (from EtOH). IR (KBr): ν = 1531 (NO2), 1326 (NO2) cm-1. 1H NMR (250 MHz, DMSO-d 6): δ = 8.09 (s, 1 H, H3-Thioph), 7.55 (d, J = 7.5 Hz, 1 H), 7.37-7.32 (m, 3 H), 2.96-2.93 (m, 2 H, CH2), 2.87-2.84 (m, 2 H, CH2). 13C NMR (62.9 MHz, DMSO-d 6): δ = 147.75, 143.91, 137.50, 136.20, 130.63, 130.03, 128.64, 128.49, 127.52, 123.99, 27.43, 22.78. Anal. Calcd for C12H9NO2S (231.27): C, 62.32; H, 3.92; N, 6.06; S, 13.87. Found: C, 62.40; H, 3.99; N, 6.10; S, 13.84.