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Synlett 2009(6): 917-920  
DOI: 10.1055/s-0028-1087960
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Indium Trichloride Catalyzed One-Pot Synthesis of New (2-Amino-3-cyano-4H-chromen-4-yl) Phosphonic Acid Diethyl Ester

Parthasarathy Jayashree, Gnanamani Shanthi, Paramasivan T. Perumal*
Organic Chemistry Division, Central Leather Research Institute, Adyar, Chennai 600020, India
Fax: +91(44)24911589; e-Mail: ptperumal@gmail.com;
Further Information

Publication History

Received 12 December 2008
Publication Date:
16 March 2009 (online)

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Abstract

A one-pot synthesis of new (2-amino-3-cyano-4H-chromen-4-yl) phosphonic acid diethyl ester was achieved in good yields by indium trichloride catalyzed three-component reaction of salicylaldehyde and malononitrile with triethyl phosphite.

Key words

chromenes - salicylaldehyde - triethyl phosphite - malononitrile - three-component

    References and Notes

  • 1a Allen MC. Fuhrer W. Tuck B. Wade R. Wood JM. J. Med. Chem.  1989,  32:  1652 
    Google Scholar
  • 1b Patel DV. Rielly-Gauvin K. Ryono DE. Tetrahedron Lett.  1990,  31:  5587 
    Google Scholar
  • 1c Stowasser B. Budt KH. Li JQ. Peyman A. Ruppert D. Tetrahedron Lett.  1992,  33:  6625 
    Google Scholar
  • 2 Kafarski P. Lejczak B. Phosphorus, Sulfur Silicon Relat. Elem.  1991,  63:  1993 
    Google Scholar
  • 3a Baylis EK. Campbell CD. Dingwall JG. J. Chem. Soc., Perkin Trans. 1  1984,  2845 
    Google Scholar
  • 3b Atherton FR. Hassal CH. Lambert RW. J. Med. Chem.  1986,  29:  29 
    Google Scholar
  • 4 Maryanoff BE. Reitz AB. Chem. Rev.  1989,  89:  863 
    CrossrefGoogle Scholar
  • 5a Engel R. Chem. Rev.  1977,  77:  349 
    Google Scholar
  • 5b Hiratake J. Oda J. Biosci. Biotechnol. Biochem.  1997,  61:  211 
    Google Scholar
  • 5c Schug KA. Lindner W. Chem. Rev.  2005,  105:  67 
    Google Scholar
  • 5d Moonen K. Laureyn I. Stevens CV. Chem. Rev.  2004,  104:  6177 
    Google Scholar
  • 5e Palacios F. Alonso C. De Los Santos JM. Curr. Org. Chem.  2004,  8:  1481 
    Google Scholar
  • 6 Hafez EA. Elnagdi MH. Elagamey AGA.
    El-Taweel     FMAA. Heterocycles  1987,  26:  903 
    CrossrefGoogle Scholar
  • 7 Hiramoto J. Nasuhara A. Michiloshi K. Kato T. Kikugawa K. Mutat. Res.  1997,  395:  47 
    CrossrefGoogle Scholar
  • 8 Bianchi G. Tava A. Agric. Biol. Chem.  1987,  51:  2001 
    CrossrefGoogle Scholar
  • 9a Elagamey AGA. El-Taweel FMAA. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem.  1990,  29:  885 
    Google Scholar
  • 9b Bloxham J. Dell CP. Smith CW. Heterocycles  1994,  38:  399 
    Google Scholar
  • 10a Dömling A. Curr. Opin. Chem. Biol.  2000,  4:  318 
    Google Scholar
  • 10b Dömling A. Curr. Opin. Chem. Biol.  2002,  6:  306 
    Google Scholar
  • 10c Ugi I. Werner B. Dömling A. Molecules  2003,  8:  53 
    Google Scholar
  • 10d Weber L. Drug Discovery Today  2002,  7:  143 
    Google Scholar
  • 10e Orru RVA. Greef M. Synthesis  2003,  1471 
    Google Scholar
  • 10f Bienayme H. Hulme C. Oddon G. Schmitt P. Chem. Eur. J.  2000,  6:  3321 
    Google Scholar
  • 10g Dömling A. Chem. Rev.  2006,  106:  17 
    Google Scholar
  • 10h Zhu J. Bienayme H. Multicomponent Reactions   Wiley-VCH; Weinheim: 2005. 
    Google Scholar
  • 11a Frost CG. Chauhan KK. J. Chem. Soc., Perkin Trans. 1  2000,  3015 
    Google Scholar
  • 11b Fringuelli F. Piermatti O. Pizzo F. Vaccaro L. Curr. Org. Chem.  2003,  7:  7 
    Google Scholar
  • 11c Frost CG. Hartley JP. Mini-Rev. Org. Chem.  2004,  1:  1 
    Google Scholar
  • 12a Shanthi G. Perumal PT. Synlett  2008,  2791 
    Google Scholar
  • 12b Shanthi G. Perumal PT. Tetrahedron Lett.  2007,  48:  6785 
    Google Scholar
  • 12c Shanthi G. Perumal PT. Tetrahedron Lett.  2008,  49:  7139 
    Google Scholar
  • 12d Shanthi G. Subbulakshmi G. Perumal PT. Tetrahedron  2007,  63:  2057 
    Google Scholar
  • 12e Babu G. Nagarajan R. Natarajan R. Perumal PT. Synthesis  2000,  661 
    Google Scholar
  • 12f Babu G. Perumal PT. Aldrichimica Acta  2000,  33:  16 
    Google Scholar
  • 12g Babu G. Perumal PT. Tetrahedron  1998,  54:  1627 
    Google Scholar
  • 12h Babu G. Perumal PT. Tetrahedron Lett.  1997,  38:  5025 
    Google Scholar
  • 15 Bhuyan PJ. Deb ML. Tetrahedron Lett.  2005,  46:  6453 
    CrossrefGoogle Scholar
13

(2-Amino-3-cyano-4 H -chromen-4-yl) Phosphonic Acid Diethyl Ester (4a, Table 1, Entry 1); Typical Procedure
To a stirred mixture of salicylaldehyde (1 mmol) and malononitrile (1 mmol) in EtOH, triethyl phosphite, and InCl3 (20 mol%) was added. The reaction mixture was stirred at r.t. for the appropriate time (Table  [¹] ). After complete conversion as indicated by TLC, the mixture was poured into ice and extracted with EtOAc. The organic extracts were washed with brine solution, dried over Na2SO4, and concentrated under vacuum to yield pure product 4a.

14

(2-Amino-3-cyano-4 H -chromen-4-yl) Phosphonic Acid Diethyl Ester (4a, Table 1, Entry 1)
White solid; mp 140-142 ˚C. IR (KBr): νmax = 3349, 3167, 2189, 1648, 1422, 1233, 1030 cm-¹. ¹H NMR (500 MHz, DMSO-d 6): δ = 1.09 (t, 3 H, J = 6.9 Hz), 1.14 (t, 3 H, J = 6.85 Hz), 3.87 (m, 4 H), 4.04 (d, 1 H, ² J PH = 17.6 Hz), 6.97 (d, 1 H, J = 8.4 Hz), 7.10 (t, 1 H, J = 6.85 Hz), 7.14 (br s, 2 H, NH2, D2O exchangeable), 7.22 (m, 2 H). ¹³C NMR (75 MHz, DMSO-d 6): δ = 16.1, 16.2, 34.5 (d, ¹ J CP = 144.0 Hz), 47.3 (d, ² J CP = 7.5 Hz), 62.1 (d, ² J CP = 7.5 Hz), 62.2 (d, ² J CP = 6.75 Hz), 115.9, 117.7, 120.1, 124.2, 128.8, 129.4, 149.9, 162.6. ³¹P NMR (202.5 MHz, DMSO-d 6): δ = 23.17. MS: m/z = 308 [M+]. Anal. Calcd (%) for C14H17N2O4P: C, 54.55; H, 5.56; N, 9.09. Found: C, 54.50; H, 5.52; N, 9.03.
(2-Amino-6-bromo-3-cyano-4 H -chromene-4-yl) Phosphonic Acid Diethyl Ester (4f, Table 1, Entry 6)
White solid; mp 180-182 ˚C. IR (KBr): νmax = 3353, 3156, 2190, 1655, 1417, 1241, 1040 cm-¹. ¹H NMR (300 MHz, DMSO-d 6): δ = 1.13 (m, 6 H), 3.91 (m, 4 H), 4.17 (d, 1 H, ² J PH = 18.0 Hz), 6.99 (d, 1 H, J = 8.7 Hz), 7.26 (br s, 2 H, NH2, D2O exchangeable), 7.44 (m, 2 H). ¹³C NMR (75 MHz, DMSO-d 6): δ = 16.1, 16.2, 34.1 (d, ¹ J CP = 144.0 Hz), 47.0 (d, ² J CP = 7.5 Hz), 62.2 (d, ² J CP = 7.5 Hz), 62.4 (d, ² J CP = 7.5 Hz), 115.6, 118.1, 119.8, 120.4, 131.4, 131.8, 149.2, 162.3. ³¹P NMR (202.5 MHz, DMSO-d 6): δ = 22.64. MS: m/z = 387 [M+], 389 [M + 2]. Anal. Calcd (%) for C14H16BrN2O4P: C, 43.43; H, 4.17; N, 7.24. Found: C, 43.38; H, 4.11; N, 7.20.