One-Pot Synthesis of Dihydropyrimidinones Using Polyaniline-Bismoclite Complex. A Facile and Reusable Catalyst for the Biginelli Reaction

Abstract

Polyaniline-bismoclite complex was used as an efficient catalyst for the three-component condensation reaction of an aldehyde, β-ketoester, and urea in ethanol to afford the dihydropyrimidinones in excellent yields. Furthermore, after completion of reaction the catalyst could be easily recovered and reused without affecting its activity.

polyaniline-bismoclite - reusable catalyst - dihydropyrimidinones - one-pot condensation - Biginelli reaction

References

<A NAME="RG05804ST-1A">1a</A> Rovnyak GC. Kinball SD. Beyer B. Cucinotta G. Dimarco JD. Gougoutas JZ. Hedberg A. Malley M. McCarthy JP. Zhang R. Moreland S. J. Med. Chem.  1995,  38:  119 

<A NAME="RG05804ST-1B">1b</A> Aswal KS. Rovnyak GC. Kinball SD. Floyd DM. Moreland S. Swanson BN. Gougoutas JZ. Schwartz J. Smillie KM. Mallay MF. J. Med. Chem.  1990,  33:  2629 

<A NAME="RG05804ST-2A">2a</A> Atwal KS. Swanson BN. Unger SE. Floyd DM. Moreland S. Hedberg A. O’Reilly BC. J. Med. Chem.  1991,  34:  806 

<A NAME="RG05804ST-2B">2b</A> Grover GJ. Dzwonczyk S. McMullen DM. Normadinam CS. Sleph PG. Moreland SJ. J. Cardiovasc. Pharmacol.  1995,  26:  289 

<A NAME="RG05804ST-3A">3a</A> Nagarathnam D, Wong WC, Miao SW, Patance MA, and Gluchowski C. inventors; PCT Int. Appl. WO  97 17, 969. 

<A NAME="RG05804ST-3B">3b</A> Sidler DR, Larsen RD, Chartrain M, Ikemoto N, Roberg CM, Taylor CS, Li W, and Bills GF. inventors; PCT Int. WO  99 07, 695. 

<A NAME="RG05804ST-4">4</A> Bruce MA, Pointdexter GS, and Johnson G. inventors; PCT Int. Appl. WO  98 33, 791. 

<A NAME="RG05804ST-5A">5a</A> Overman LE. Rabinowitz MH. Renhowe PA. J. Am. Chem. Soc.  1995,  117:  2657 

<A NAME="RG05804ST-5B">5b</A> Snider B. Shi Z. J. Org. Chem.  1993,  58:  3828 

<A NAME="RG05804ST-6A">6a</A> Snider B. Chen J. Patil AD. Freyer A. Tetrahedron Lett.  1996,  37:  6977 

<A NAME="RG05804ST-6B">6b</A> Patil AD. Kumar NV. Kokke WC. Bean MF. Freyer AJ. De Brosse C. Mai S. Truneh A. Faulkner DJ. Carte B. Breen AL. Hertzberg RP. Johnson RK. Westley JW. Ports BCM. J. Org. Chem.  1995,  6:  1182 

<A NAME="RG05804ST-7">7</A> Biginelli P. Gazz. Chem. Ital.  1893,  23:  360 

<A NAME="RG05804ST-8A">8a</A> Folkers K. Harwood HJ. Johnson TB. J. Am. Chem. Soc.  1932,  54:  3751 

<A NAME="RG05804ST-8B">8b</A> Wipf P. Cunningham A. Tetrahedron Lett.  1995,  36:  7819 

<A NAME="RG05804ST-8C">8c</A> Folkers K. Johnson TB. J. Am. Chem. Soc.  1934,  1180 

<A NAME="RG05804ST-9">9</A> ZrCl₄: Reddy ChV. Mahesh M. Raju PVK. Babu TR. Reddy VVN. Tetrahedron Lett.  2002,  43:  2657 

<A NAME="RG05804ST-10A">10a</A> InBr₃: Fu NY. Yuan YF. Cao Z. Wang SW. Wang JT. Peppe C. Tetrahedron  2002,  58:  4801 

<A NAME="RG05804ST-10B">10b</A> InCl₃: Ranu BC. Hajra A. Jana U. J. Org. Chem.  2000,  65:  6270 

<A NAME="RG05804ST-11">11</A> BiCl₃: Ramalinga K. Vijyalakshimi P. Kaimal TNB. Synlett  2001,  863 

<A NAME="RG05804ST-12">12</A> LiClO₄: Yadav JS. Reddy BVS. Srinivas R. Venugopal C. Ramalingam T. Synthesis  2001,  1341 

<A NAME="RG05804ST-13">13</A> BF₃·OEt₂: Hu EH. Sidler DR. Dolling U.-H. J. Org. Chem.  1998,  63:  3454 

<A NAME="RG05804ST-14">14</A> La(OTf)₃: Ma Y. Qian C. Wang L. Yang M. J. Org. Chem.  2000,  65:  3864 

<A NAME="RG05804ST-15">15</A> Bi(OTf)₃: Adapa SR. Alam MM. Varala R. Synlett  2003,  67 

<A NAME="RG05804ST-16">16</A> Cu(OTf)₂: Paraskar AS. Dewkar GK. Sudalai A. Tetrahedron Lett.  2003,  44:  3305 

<A NAME="RG05804ST-17">17</A> Xia M., Wang YG. Tetrahedron Lett.  2002,  43:  7703 

<A NAME="RG05804ST-18">18</A> Salehi P. Dabiri M. Ali Zolfigol M. Fard MAB. Heterocycles  2003,  60:  2435 

<A NAME="RG05804ST-19">19</A> Yadav JS. Reddy BVS. Sridhar P. Reddy JSS. Nagaiah K. Lingaiah N. Saiprasad PS. Eur. J. Org. Chem.  2004,  552 

<A NAME="RG05804ST-20A">20a</A> Kappe CO. J. Org. Chem.  1997,  62:  7201 

<A NAME="RG05804ST-20B">20b</A> Kappe CO. Eur. J. Med. Chem.  2000,  35:  1043 

<A NAME="RG05804ST-21">21</A> Eynde JJV. Audiart N. Canonne V. Michel S. Haverbeke YV. Kappe CO. Heterocycles  1997,  45:  1967 

<A NAME="RG05804ST-22A">22a</A> Kappe CO. Tetrahedron  1993,  49:  6937 ; and references cited therein

<A NAME="RG05804ST-22B">22b</A> Mayer TU. Kapoor TM. Haggarty S. King RW. Schreiber SL. Mitchison TJ. Science  1999,  286:  971 

<A NAME="RG05804ST-22C">22c</A> Kappe CO. Shishkin OV. Uray G. Verdino P. Tetrahedron  2000,  56:  1859 

<A NAME="RG05804ST-23">23</A>

(a) Typical Procedure for the Preparation of Polyaniline-Bismoclite Complex (i)Preparation of polyaniline-sulfate salt: In a typical experiment, 10 mL of aniline was added to an aqueous solution (700 mL) containing H₂SO₄ (30 mL) in a 2 L-round-bottomed flask. The solution was kept under constant stirring at 5-10 °C. To this solution, sodium persulfate (23.8 g) in water (250 mL) was added during 15-20 min. The reaction was allowed to continue for 4 h. The precipitated polyaniline-sulfate salt was filtered, washed with water (5 L) followed by acetone (500 mL). (ii) Preparation of polyaniline base: The obtained polyaniline-sulfate salt was dispersed in an aqueous solution of NaOH (1 L, 1 N) and stirred for 12 h at ambient temperature. The solution was filtered and washed several times with water to remove the excess NaOH. The product (polyaniline base) was dried at 100 °C until a constant mass was reached. (iii) Preparation of polyaniline-bismoclite complex: Polyaniline base (5 g) prepared by the above method was added to acetone (500 mL) containing 0.1 M of BiCl₃. The solution was stirred for 4 h under an N₂ atmosphere at ambient temperature. The solution was filtered and washed with acetone (1 L). The powder was dried at 100 °C until a constant mass was reached.
(b) Properties of PANI-BC complex The PANI-BC complex possesses useful properties,
(i) number of dopant groups(bismoclite) per aniline unit in the polymer chain, i.e., x = 0.38; (ii) amount of bismoclite present in polyaniline salt (51.5%); (iii) conductivity (0.004 S/cm); (iv) pellet density (1.85 g/cm³) and particle size from SEM analysis (0.8-3 µm with core shell morphology).