Abstract
Introduction: The N-heterocyclic compounds have been extensively studied in pharmaceutical industries. Furthermore, syntheses of such compounds employing organo-catalyst have been associated with sustainable technology.
Methods: The synthesis of new, stable ionic liquids and their catalytic applications in one-pot multicomponent Biginelli reaction is presented. The method provides broad substrate scope, yielding the corresponding 3,4-dihydropyrimidin-2(1H)-ones and 3,4-dihydropyrimidin-2(1H)-thiones, in good to excellent yields, respectively.
Results and Conclusion: The developed reactions are associated with certain advantages, short reaction time and sustainable conditions. The protocol has advantages eco-friendly procedure, recovery and reusability of catalyst, which showed consistent activity.
Keywords: Biginelli reaction, multicomponent, Ionic liquid, organocatalyst, dihydropyrimidinones, dihydropyrimidinthiones.
Graphical Abstract
[http://dx.doi.org/10.1002/1521-3773(20000915)39:18<3168::AIDANIE3168> 3.0.CO;2-U] [PMID: 11028061]
b) Hulme, C.; Gore, V. “Multi-component reactions : emerging chemistry in drug discovery” ‘from xylocain to crixivan’. Curr. Med. Chem., 2003, 10(1), 51-80.
[http://dx.doi.org/10.2174/0929867033368600] [PMID: 12570721]
[http://dx.doi.org/10.1021/cr00075a007]
b) Zhu, J.; Bienymé, H., Eds.; Multicomponent Reactions in Organic Synthesis; Wiley-VCH: Weinheim, 2005.
[http://dx.doi.org/10.1002/3527605118]
c) van der Heijden, G.; Ruijter, E.; Orru, R.V.A. Efficiency, diversity and complexity with multicomponent reactions. Synlett, 2013, 24, 666-685.
[http://dx.doi.org/10.1055/s-0032-1318222]
[http://dx.doi.org/10.1002/ejoc.201100661]
[http://dx.doi.org/10.1021/ar000048h] [PMID: 11123887]
[http://dx.doi.org/10.1039/b920821f]
[http://dx.doi.org/10.1126/science.286.5441.971] [PMID: 10542155]
[http://dx.doi.org/10.1016/S0223-5234(00)01189-2] [PMID: 11248403]
[http://dx.doi.org/10.1016/j.ejmech.2006.09.003] [PMID: 17070617]
[http://dx.doi.org/10.1016/j.bmcl.2004.01.039] [PMID: 15026060]
[http://dx.doi.org/10.1021/jm00106a048] [PMID: 1995904]
[http://dx.doi.org/10.1021/jm00095a023] [PMID: 1387168]
[http://dx.doi.org/10.3390/30100001]
[http://dx.doi.org/10.3390/50300227]
[http://dx.doi.org/10.1055/s-2005-865222]
[http://dx.doi.org/10.1016/j.tet.2005.02.059]
b) Adibi, H.; Samimi, H.A.; Beygzadeh, M. Iron(III) trifluoroacetate and trifluoromethanesulfonate: recyclable Lewis acid catalysts for one-pot synthesis of 3,4-dihydropyrimidinones or their sulfur analogues and 1,4-dihydropyridines via solvent-free Biginelli and Hantzsch condensation protocols. Catal. Commun., 2007, 8, 2119-2124.
[http://dx.doi.org/10.1016/j.catcom.2007.04.022]
c) Mondal, J.; Sen, T.; Bhaumik, A. Fe3O4@mesoporous SBA-15: a robust and magnetically recoverable catalyst for one-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones via the Biginelli reaction. Dalton Trans., 2012, 41(20), 6173-6181.
[http://dx.doi.org/10.1039/c2dt30106g] [PMID: 22475989]
d) Seyedi, N. Glycerin and [Iron(III)(salen)]Cl as an efficient catalytic medium for multicomponent reactions. Transition Met. Chem., 2013, 38, 93-103.
[http://dx.doi.org/10.1007/s11243-012-9665-5]
[http://dx.doi.org/10.1016/S0040-4039(03)00619-1]
[http://dx.doi.org/10.3390/molecules14020763] [PMID: 19223824]
[http://dx.doi.org/10.1016/j.catcom.2004.06.007]
[http://dx.doi.org/10.1080/17518250802342527]
[http://dx.doi.org/10.1021/jo0205199] [PMID: 12530887]
[http://dx.doi.org/10.3390/11080649] [PMID: 17971737]
[http://dx.doi.org/10.1016/S0040-4039(02)00280-0]
[http://dx.doi.org/10.1021/jo000711f] [PMID: 10987976]
[http://dx.doi.org/10.1016/S0022-328X(03)00139-6]
[http://dx.doi.org/10.1016/j.molcata.2004.02.025]
[http://dx.doi.org/10.3389/fchem.2018.00376] [PMID: 30211156]
[http://dx.doi.org/10.1055/s-2001-14587]
[http://dx.doi.org/10.1016/j.tetlet.2009.01.103]
[http://dx.doi.org/10.1016/S0040-4039(01)01728-2]
[http://dx.doi.org/10.1016/S0040-4039(00)01645-2]
[http://dx.doi.org/10.1002/cjoc.20020200505]
[http://dx.doi.org/10.1021/jo9919052] [PMID: 10864778]
[http://dx.doi.org/10.1016/j.apcata.2005.11.001]
b) Sharghi, H.; Jokar, M. Al2O3/MeSO3H: A novel and recyclable catalyst for one-pot synthesis of 3,4-dihydropyrimidinones or their sulfur derivatives in Biginelli condensation. Synth. Commun., 2009, 39, 958-979.
[http://dx.doi.org/10.1080/00397910802444258]
[http://dx.doi.org/10.1021/jo802585b] [PMID: 19301883]
[http://dx.doi.org/10.1590/S0103-50532004000200002]
[http://dx.doi.org/10.1016/S0040-4039(01)01603-3]
[http://dx.doi.org/10.1039/C3NJ01618H]
[http://dx.doi.org/10.1016/j.molstruc.2014.02.035]
[http://dx.doi.org/10.1515/gps-2016-0149]
[http://dx.doi.org/10.1002/cjoc.20020200711]
[http://dx.doi.org/10.1055/s-2002-20956]
[http://dx.doi.org/10.1016/j.molcata.2012.12.005]
[http://dx.doi.org/10.1016/j.molcata.2014.08.025]
[http://dx.doi.org/10.1055/s-2005-869899]
[http://dx.doi.org/10.1039/C9NJ02139F]
[http://dx.doi.org/10.1002/ejoc.200300559]
[http://dx.doi.org/10.1016/j.tetlet.2005.07.021]
[http://dx.doi.org/10.1016/j.tetlet.2007.06.005]
[http://dx.doi.org/10.3184/030823402103172563]
[http://dx.doi.org/10.1016/j.catcom.2013.08.006]
[http://dx.doi.org/10.1016/S1872-2067(10)60263-X]
[http://dx.doi.org/10.1016/j.arabjc.2014.08.008]
[http://dx.doi.org/10.1039/c3ra43014f]
[http://dx.doi.org/10.1016/S1872-2067(12)60759-1]
[http://dx.doi.org/10.1007/s10562-011-0639-6]
b) Rani, V.R.; Srinivas, N.; Kishan, M.R.; Kulkarni, S.J.; Raghavan, K.V. Zeolite-catalyzed cyclocondensation reaction for the selective synthesis of 3,4-dihydropyrimidin-2(1H)-ones. Green Chem., 2001, 3, 305-306.
[http://dx.doi.org/10.1039/b107612b]
c) Kang, L.; Jin, D.; Cai, Y. Silica-supported ionic liquid Si[SbSipim][PF6]: An efficient catalyst for the synthesis of 3,4-dihydropyrimidine-2-(1H)-ones. Synth. Commun., 2013, 43, 1896-1901.
[http://dx.doi.org/10.1080/00397911.2012.678462]
[http://dx.doi.org/10.1007/s12039-018-1467-7]
[http://dx.doi.org/10.1016/j.tetlet.2011.12.134]
b) Rajack, A.; Yuvaraju, K.; Praveen, C.; Murthy, Y.L.N. A facile synthesis of 3,4-dihydropyrimidinones/thiones and novel N-dihydro pyrimidinone-decahydroacridine-1,8-diones catalyzed by cellulose sulfuric acid. J. Mol. Catal. Chem., 2013, 370, 197-204.
[http://dx.doi.org/10.1016/j.molcata.2013.01.003]
c) Ahmed, N.; Siddiqui, Z.N. Sulphated silica tungstic acid as a highly efficient and recyclable solid acid catalyst for the synthesis of tetrahydropyrimidines and dihydropyrimidines. J. Mol. Catal. Chem., 2014, 387, 45-56.
[http://dx.doi.org/10.1016/j.molcata.2014.02.019]
d) Kolvari, E.; Koukabi, N.; Armandpour, O. A simple and efficient synthesis of 3,4-dihydropyrimidin-2-(1H)-ones via Biginelli reaction catalyzed by nanomagnetic-supported sulfonic acid. Tetrahedron, 2014, 70, 1383-1386.
[http://dx.doi.org/10.1016/j.tet.2013.10.085]
[http://dx.doi.org/10.1016/S1350-4177(03)00092-0] [PMID: 12726946]
[http://dx.doi.org/10.1039/b102565c]
[http://dx.doi.org/10.1016/j.cclet.2007.04.002]
[http://dx.doi.org/10.1055/s-0036-1591900]
[http://dx.doi.org/10.3390/app6120431]
[http://dx.doi.org/10.1039/C9SC00704K] [PMID: 31160956]
b) Dunn, P.J. The importance of green chemistry in process research and development. Chem. Soc. Rev., 2012, 41(4), 1452-1461.
[http://dx.doi.org/10.1039/C1CS15041C] [PMID: 21562677]
[http://dx.doi.org/10.1016/j.catcom.2012.03.003]
b) Safari, J.; Zarnegar, Z. Brønsted acidic ionic liquid based magnetic nanoparticles: a new promoter for the Biginelli synthesis of 3,4-dihydropyrimidin-2(1H)-ones/thiones. New J. Chem., 2014, 38, 358-365.
[http://dx.doi.org/10.1039/C3NJ01065A]
c) Srivastava, R. Assessment of the catalytic activities of novel Brönsted acidic ionic liquid catalysts. Catal. Lett., 2010, 139, 17-25.
[http://dx.doi.org/10.1007/s10562-010-0404-2]
d) Hallett, J.P.; Welton, T. Room-temperature ionic liquids: solvents for synthesis and catalysis. 2. Chem. Rev., 2011, 111(5), 3508-3576.
[http://dx.doi.org/10.1021/cr1003248] [PMID: 21469639c]
[http://dx.doi.org/10.1016/S0040-4039(01)01139-X]
[http://dx.doi.org/10.1021/cs400291t]
[http://dx.doi.org/10.3390/molecules20033811] [PMID: 25730389]
[http://dx.doi.org/10.1007/s12039-012-0278-5]
[http://dx.doi.org/10.1007/s10562-004-3451-8]
[http://dx.doi.org/10.1080/17518250903252260]
[http://dx.doi.org/10.1039/c2ra22037g]
[http://dx.doi.org/10.1080/00397911.2010.501471]
[http://dx.doi.org/10.1021/jo4003932] [PMID: 23530931]
[http://dx.doi.org/10.1016/j.molcata.2013.10.026]
[http://dx.doi.org/10.1016/j.tetlet.2007.04.130]
[http://dx.doi.org/10.1016/j.bmcl.2014.04.099] [PMID: 24835627]
[http://dx.doi.org/10.1246/cl.2004.1168]
[http://dx.doi.org/10.1016/j.tetlet.2006.06.015]
[http://dx.doi.org/10.1016/j.bmcl.2006.12.068] [PMID: 17490874]
[http://dx.doi.org/10.1002/adsc.200900597]
[http://dx.doi.org/10.1016/j.tetlet.2011.08.175]
[http://dx.doi.org/10.2174/1570179414666161229162243]
[http://dx.doi.org/10.1021/acs.joc.5b00407] [PMID: 26066623]
[http://dx.doi.org/10.1007/s10562-014-1312-7]
b) Nagarajan, S.; Shaikh, T.M.; Kandasamy, E. An ionic liquid catalyzed reusable protocol for one-pot synthesis of 2,3-dihydroquinazolin-4(1H)-one under mild conditions. New J. Chem., 2015, 39, 9693-9699.
[http://dx.doi.org/10.1039/C5NJ01545F]
c) Nagarajan, S.; Shaikh, T.M.; Kandasamy, E. Synthesis of 1-alkyl triazolium triflate room temperature ionic liquids and their catalytic studies in multi-component Biginelli reaction. J. Chem. Sci., 2015, 127, 1539-1545.
[http://dx.doi.org/10.1007/s12039-015-0919-6]
d) Kandasamy, E.; Nagarajan, S.; Shaikh, T.M. Knoevenagel reaction catalyzed by a reusable Bronsted acid based on 1-alkyl-1,2,4-triazolium tetrafluoroborate. Lett. Org. Chem., 2018, 15, 133-138.
[http://dx.doi.org/10.2174/1570178614666171017164516]