SeO₂-Mediated Oxidation of 1,3-Diazabuta-1,3-dienes: A Single-Pot Synthesis of Functionalized 4-Hydroxyimidazoles

Abstract

A single-pot novel synthesis of variedly substituted 4-hydroxyimidazoles by SeO₂-mediated oxidation of 1-aryl-2-phen­yl/thiomethyl/secondary amino-4-N,N-dimethylamino-4-methyl-1,3-diazabuta-1,3-dienes is reported.

functionalized imidazoles - selenium dioxide - 1,3-di­azabuta-1,3-dienes

References and Notes

<A NAME="RD06506ST-1A">1a</A> Lednicer D. Mitscher LA. In Organic Chemistry of Drug Synthesis   Vol. 1:  Wiley Interscience; New York: 1977.  p.226 

<A NAME="RD06506ST-1B">1b</A> Bure F. Kulhanek J. Tetrahedron: Asymmetry  2005,  16:  1347 

<A NAME="RD06506ST-1C">1c</A> Loksha YM. El-Barbary AA. El-Badawi MA. Nielsen C. Pedersen EB. Bioorg. Med. Chem.  2005,  13:  4209 

<A NAME="RD06506ST-1D">1d</A> Kumar R. Lown JW. Eur. J. Med. Chem.  2005,  40:  641 

<A NAME="RD06506ST-2A">2a</A> Benner SA. Heeb NV. Tetrahedron Lett.  1994,  35:  3045 

<A NAME="RD06506ST-2B">2b</A> Somayaji V. Skorey KI. Brown RS. Ball RG. J. Org. Chem.  1986,  51:  4866 

<A NAME="RD06506ST-3">3</A> Knapp S. Albaneze J. Schugar HJ. J. Org. Chem.  1983,  58:  997 

<A NAME="RD06506ST-4A">4a</A> Laufer S. Wagner G. Kotschenreuther D. Angew. Chem. Int. Ed.  2002,  41:  2290 

<A NAME="RD06506ST-4B">4b</A> Zhang C. Sarshar S. Moran EJ. Krane S. Rodarte JC. Benbatoul KD. Dixon R. Mjalli AMM. Bioorg. Med. Chem.  2000,  10:  2603 

<A NAME="RD06506ST-5">5</A> For recent reviews, see ‘Histamine H3 Receptor’: Menge WMPB. Timmerman H. Pharmacochem. Lib.  1998,  30:  145 

<A NAME="RD06506ST-6A">6a</A> Sezen B. Sames D. J. Am. Chem. Soc.  2003,  125:  5274 

<A NAME="RD06506ST-6B">6b</A> Tan KL. Bergman RG. Ellman JA. J. Am. Chem. Soc.  2002,  124:  13964 

<A NAME="RD06506ST-6C">6c</A> Sisko J. Kassick AJ. Mellinger M. Filan JJ. Allen A. Olsen MA. J. Org. Chem.  2000,  65:  1516 

<A NAME="RD06506ST-6D">6d</A> Groarke M. McKervey MA. Nieuwenhuyzen M. Tetrahedron Lett.  2000,  41:  1275 

<A NAME="RD06506ST-7">7</A> Guillemet M. Robert A. Baudy-Floc’h M. Tetrahedron Lett.  1995,  36:  547 ; and references cited therein

<A NAME="RD06506ST-8A">8a</A> Little TL. Webber SE. J. Org. Chem.  1994,  59:  7299 

<A NAME="RD06506ST-8B">8b</A> Teuber HJ. Emmerich G. Tetrahedron Lett.  1971,  18:  1459 

<A NAME="RD06506ST-8C">8c</A> Sorrell TN. Allen WE. J. Org. Chem.  1994,  59:  1589 

<A NAME="RD06506ST-8D">8d</A> Eissenstat MA. Weaver JD. J. Org. Chem.  1993,  58:  3387 

<A NAME="RD06506ST-9">9</A> Jayakumar S. Mahajan MP. Tetrahedron  2002,  58:  2899 

<A NAME="RD06506ST-10A">10a</A> Jayakumar S. Ishar MPS. Mahajan MP. Tetrahedron  2002,  58:  379 

<A NAME="RD06506ST-10B">10b</A> Kumar V. Mohan C. Gupta M. Mahajan MP. Tetrahedron  2004,  61:  3533 

<A NAME="RD06506ST-10C">10c</A> Mohan C. Kumar V. Mahajan MP. Tetrahedron Lett.  2004,  45:  6075 

<A NAME="RD06506ST-10D">10d</A> Marwaha A. Singh P. Mahajan MP. Velumurugan D. Tetrahedron Lett.  2004,  45:  8945 

<A NAME="RD06506ST-11">11</A> Nishi M. Tanimoto S. Okano M. Oda R. Yuki Gosei Kagaku Kyokai Shi  1969,  27:  754 ; Chem. Abstr. 1969, 71, 101438v

<A NAME="RD06506ST-12">12</A>

2,3-Diphenyl-3H-imidazol-4-ol (2a): mp 159-160 °C. Anal. Calcd for C₁₅H₁₂N₂O (%): C, 76.25; H, 5.12; N, 11.86. Found C, 76.12; H, 5.03; N, 12.08. ¹H NMR (300 MHz): δ = 7.28 (m, 1 H, ArH), 7.45-7.90 (m, 8 H, ArH), 7.96-8.00 (m, 3 H, 2 ArH + OH exchangeable with D₂O). ¹³C NMR (75.4 MHz): δ = 119.8, 120.1, 124.5, 127.0, 128.8, 129.0, 129.3, 131.8, 134.5, 143.2, 145.8. MS: m/z = 236 [M⁺].
3-Phenyl-2-piperidin-1-yl-3H-imidazol-4-ol (2b): mp 143-144 °C. Anal. Calcd for C₁₄H₁₇N₃O: C, 69.11; H, 7.04; N, 17.27. Found: C, 69.25; H, 6.96; N, 17.21. ¹H NMR (300 MHz): δ = 1.65-1.69 (m, 6 H, -CH₂CH₂CH₂-), 3.54-3.58 (m, 4 H, -CH₂NCH₂-), 7.05-7.14 (m, 4 H, ArH), 7.22-7.27 (m, 2 H, ArH), 10.72 (s, 1 H, OH exchangeable with D₂O). ¹³C NMR (75.4 MHz): δ = 25.2 (-CH₂), 26.0 (-CH₂CH₂-), 44.4 (-CH₂NCH₂-), 118.0, 126.5, 128.2, 129.1, 134.2, 142.2, 146.2. MS: m/z = 243.
(1,2-Diphenyl-1H-imidazol-4-yl)dimethylamine (10a): mp 116-118 °C. Anal. Calcd. for C₁₇H₁₇N₃: C, 77.54; H, 6.51; N, 15.96. Found: C, 77.42; H, 6.38; N, 16.20. ¹H NMR (300 MHz): δ = 3.1 [s, 6 H, -N(CH₃)₂], 7.18-7.48 (m, 11 H, ArH). ¹³C (75.4 MHz): δ = 44.0 [-N(CH₃)₂], 121.2, 122.8, 123.0, 124.8, 126.2, 128.1, 128.7, 131.0, 132.7, 136.2, 148.3. MS: m/z 263 [M⁺].