Abstract
Nitrogen six-membered heterocyclic compounds, such as pyrimidines, are of synthetic interest because they constitute an important class of natural and synthetic products. 2-oxo-1,2,3,4-tetrahydropyrimidines are important drugs which have shown broad spectrum activities such as inhibitory against human immunodeficiency virus (HIV) replication, antimitotic, antiproliferative, and cytotoxic activities. Their derivatization involves the oxidation of C(sp3)-H bonds and is a major reaction for making double bonds in synthetic chemistry and biological systems. However, actual methods use toxic solvents or require strictly anhydrous conditions. As a consequence, there is a need for new and environmental benign protocols. Here we present water ultrasound oxidation of the benzylic position in 2-oxo-1,2,3,4-tetrahydropyrimidines and benzylic acid salts, into double bond using heterogeneous oxidizing agents Cu(III) or Ag(III). This method has several advantages such as the use of green solvent, broad substrate scope, excellent yields and less amounts of waste with excellent values of green chemistry metrics.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Bagoji AM, Magdum PA, Nandibewoor ST (2016) Oxidation of acebutolol by copper(III) periodate complex in aqueous alkaline medium: a kinetic and mechanistic approach. J Solut Chem 45:1715–1728. https://doi.org/10.1007/s10953-016-0539-x
Bugarčić Z, Novokmet S, Senić Ž, Bugarčić Ž (2000) A selective conversion of benzilic alcohols to the corresponding carbonyl compounds by means of an Ag(III) Complex. Monatsh Chem 131:799–802. https://doi.org/10.1007/s007060050
Bugarčić Z, Novokmet S, Kostić V (2005) Selective oxidation of some primary and secondary benzylic alcohols to the corresponding carbonyl compounds with a Cu(III) complex. J Serb Chem Soc 70:681–686. https://doi.org/10.2298/JSC0505681B
Canto RFS, Bernardi A, Battastini AMO, Russowsky D, Eifler-Lima VL (2011) Synthesis of dihydropyrimidin-2-one/thione library and cytotoxic activity against the human U138-MG and Rat C6 Glioma cell lines. J Braz Chem Soc 22:1379–1388. https://doi.org/10.1590/S0103-50532011000700025
Casitas A, Ribas X (2013) The role of organometallic copper(III) complexes in homogeneous catalysis. Chem Sci 4:2301–2318. https://doi.org/10.1039/C3SC21818J
Chopra R, Kaur P, Singh K (2015) A probe with aggregation induced emission characteristics for screening of iodide. Dalton Trans 44:16233–16237. https://doi.org/10.1039/C5DT02185E
Climent MJ, Corma A, Iborra S, Mifsud M, Velty A (2010) New one-pot multistep process with multifunctional catalysts: decreasing the E factor in the synthesis of fine chemicals. Green Chem 12:99. https://doi.org/10.1039/B919660A
Dondoni A, Massi A, Minghini E, Sabbatini S, Bertolasi V (2003) Model studies toward the synthesis of dihydropyrimidinyl and pyridyl α-amino acids via three-component Biginelli and Hantzsch cyclocondensations. J Org Chem 68:6172–6183. https://doi.org/10.1021/jo0342830
Donoghue PJ, Tehranchi J, Cramer CJ, Sarangi R, Solomon EI, Tolman WB (2011) Rapid C-H bond activation by a monocopper(III)-hydroxide complex. J Am Chem Soc 133:17602–17605. https://doi.org/10.1021/ja207882h
Duarte RCC, Ribeiro MGTC, Machado AASC (2015) Using green star metrics to optimize the greenness of literature protocols for syntheses. J Chem Educ 92:1024–1034. https://doi.org/10.1021/ed5004096
Gowda JI, Sataraddi SR, Nandibewoor ST (2012) Oxidation of xylitol by a silver(III) periodate complex in the presence of osmium(VIII) as a homogeneous catalyst. Catal Sci Technol 2:2549–2557. https://doi.org/10.1039/C2CY20336G
Janković N, Bugarčić Z, Marković S (2015) Double catalytic effect of (PhNH3)2CuCl4 in a novel, highly efficient synthesis of 2-oxo- and thioxo-1,2,3,4-tetrahydropyrimidines. J Serb Chem Soc 80:1–13. https://doi.org/10.2298/JSC141028011J
Kaan HY, Ulaganathan V, Rath O, Prokopcová H, Dallinger D, Kappe CO, Kozielski F (2010) Structural basis for inhibition of Eg5 by dihydropyrimidines: stereoselectivity of antimitotic inhibitors enastron, dimethylenastron and fluorastrol. J Med Chem 53:5676–5683. https://doi.org/10.1021/jm100421n
Kappe CO (2000) Recent advances in the biginelli dihydropyrimidine synthesis. New tricks from an old dog. Acc Chem Res 33:879–888. https://doi.org/10.1021/ar000048h
Karade NN, Gampawar SV, Kondre JM, Tiwari GB (2008) A novel combination of (diacetoxyiodo)benzene and tert-butylhydroperoxide for the facile oxidative dehydrogenation of 3,4-dihydropyrimidin-2(1H)-ones. Tetrahedron Lett 49:6698–6700. https://doi.org/10.1016/j.tetlet.2008.09.045
Karade HN, Acharya J, Kaushik MP (2012) An efficient and rapid dehydrogenation of 4-aryl-3,4-dihydropyrimidin-2(1H)-ones (DHPMs) using CAN/HCl. Tetrahedron Lett 53:5541–5543. https://doi.org/10.1016/j.tetlet.2012.08.017
Kim J, Park C, Ok T, So W, Jo M, Seo M, Kim Y, Sohn J-H, Park Y, Ju MK, Kim J, Han SJ, Kim TH, Cechetto J, Nam J, Sommer P, No Z (2012) Discovery of 3,4-dihydropyrimidin-2(1H)-ones with inhibitory activity against HIV-1 replication. Bioorg Med Chem Lett 22:2119–2124. https://doi.org/10.1016/j.bmcl.2011.12.090
Kumar P, Roithová J (2012) Mass spectrometric studies of silver complexes with a pyridine dicarboxamide ligand: interconversion of Ag(I) and Ag(III) oxidation states in the gas phase. Eur J Mass Spectrom 18:457–463. https://doi.org/10.1255/ejms.1195
Kumar A, Kumar P, Ramamurthy (1999) Kinetics of oxidation of glycine and related substrates by diperodatogrgentate(III). Polyhedron 18:773–780. https://doi.org/10.1016/S0277-5387(98)00352-0
Li T, Xie HY, Fu ZF (2012) Micellar electrokinetic chromatography-chemiluminescent detection of biogenic amines using N-(4-aminobutyl)-N-ethylisoluminol as derivatization reagent and trivalent copper chelate as chemiluminescence enhancer. Anal Chim Acta 719:82–86. https://doi.org/10.1016/j.aca.2012.01.016
Liu X-J, Wang W-P, Huo C-D, Wang X-C, Quan Z-J (2017) Palladium-catalyzed dehydrogenation of dihydro-heterocycles using isoprene as the hydrogen acceptors without oxidants. Catal Sci Technol 7:565–569. https://doi.org/10.1039/C6CY02038K
Matador E, Monge D, Fernández R, Lassaletta JM (2016) Solvent-free synthesis of quaternary α-hydroxy α-trifluoromethyl diazenes: the key step of a nucleophilic formylation strategy. Green Chem 18:4042. https://doi.org/10.1039/c6gc00408c
McCann K, Brigham DM, Morrison S, Braley JC (2016) Hexavalent americium recovery using copper(III) periodate. Inorg Chem 55:11971–11978. https://doi.org/10.1021/acs.inorgchem.6b02120
Muškinja J, Janković N, Ratković Z, Bogdanović G, Bugarčić Z (2015) Vanillic aldehydes for the one-pot synthesis of novel 2-oxo-1,2,3,4-tetrahydropyrimidines. Mol Divers 20:591–604. https://doi.org/10.1007/s11030-016-9658-y
Nasr-Esfahani M, Montazerozohori M (2011) Asian J Chem 23:3841–3844
Neves CMB, Simões MMQ, Domingues MRM, Santos ICMS, Neves MGPMS, Paz FAA, Silvaa AMS, Cavaleiro JAS (2012) Novel biomimetic oxidation of lapachol with H2O2 catalysed by a manganese(III) porphyrin complex. RSC Advances 2:7427–7438. https://doi.org/10.1039/C1RA00578B
Patil AD, Kumar NV, Kokke WC, Bean MF, Freyer AJ, De Brosse C, Shing M, Trunch A, Faulkner DJ, Carte B, Breen AL, Hertzberg RP, Johnson RK, Westley JW, Potts CMB (1995) Novel alkaloids from the sponge batzella sp.: inhibitors of HIV gp120-human CD4 binding. J Org Chem 60:1182–1188. https://doi.org/10.1021/jo00110a021
Ribeiro MGTC, Yunes SF, Machado AASC (2014) Reaction scale and green chemistry: microscale or macroscale, which is greener? J Chem Educ 91:1901–1908. https://doi.org/10.1021/acs.jchemed.7b00056
Rousseaux S, Vrancken E, Campagne J-M (2012) Chiral aryl–copper(III) electrophiles: new opportunities in catalytic enantioselective arylations and domino processes. Angew Chem Int Ed 51:10934–10935. https://doi.org/10.1002/anie.201205805
Russowsky D, Canto RFS, Sanches SAA, D’Oca MGM, de Fátima A, Pilli RA, Kohn LK, Antônio MA, de Carvalho JE (2006) Synthesis and differential antiproliferative activity of Biginelli compounds against cancer cell lines: monastrol, oxo-monastrol and oxygenated analogues. Bioorg Chem 34:173–182. https://doi.org/10.1016/j.bioorg.2006.04.003
Sandhu S, Sandhu JS (2012) Past, present and future of the Biginelli reaction: a critical perspective. Arkivoc i:66–133
Sari O, Roy V, Métifiot M, Marchand C, Pommier Y, Bourg S, Bonnet P, Schinazi RF, Agrofoglio LA (2015) Synthesis of dihydropyrimidine α, γ-diketobutanoic acid derivatives targeting HIV integrase. Eur J Med Chem 104:127–138. https://doi.org/10.1016/j.ejmech.2015.09.015
Shanmugam P, Perumal P (2006) Regioselective dehydrogenation of 3,4-dihydropyrimidin-2(1H)-ones mediated by ceric ammonium nitrate. Tetrahedron 62:9726–9734. https://doi.org/10.1016/j.tet.2006.07.063
Shanmugam P, Perumal PTV (2007) An unusual oxidation–dealkylation of 3,4-dihydropyrimidin-2(1H)-ones mediated by Co(NO3)2·6H2O/K2S2O8 in aqueous acetonitrile. Tetrahedron 63:666–672. https://doi.org/10.1016/j.tet.2006.11.010
Sharma V, Chitranshi N, Agarwal AK (2014) Significance and biological importance of pyrimidine in the microbial world. Inter J Med Chem. https://doi.org/10.1155/2014/202784
Sheldon RA (2016) Green chemistry and resource efficiency: towards a green economy. Green Chem 18:3180. https://doi.org/10.1039/C6GC90040B
Sheldon RA (2017) The E factor 25 years on: the rise of green chemistry and sustainability. Green Chem 19:18–43. https://doi.org/10.1039/C6GC02157C
Svanfelt J, Kronberg L (2011) Synthesis of substituted diphenylamines and carbazoles: phototransformation products of diclofenac. Environ Chem Lett 9:141–144. https://doi.org/10.1007/s10311-009-0259-1
Vikse KL, Chen P (2015) Elementary reactions at organocopper(III): A gas-phase and theoretical study. Organometallics 34: 1294–1300. https://doi.org/10.1021/acs.organomet.5b00038
Weiss M, Bringmann T, Groger H (2010) Towards a greener synthesis of (S)-3-aminobutanoic acid: process development and environmental assessment. Green Chem 12:1580. https://doi.org/10.1039/C002721A
Yadav P, Sankar M (2014) Synthesis, spectroscopic and electrochemical studies of phosphoryl and carbomethoxyphenyl substituted corroles, and their anion detection properties. Dalton Trans 43:14680–14688. https://doi.org/10.1039/C4DT01853B
Yao B, Liu Y, Zhao L, Wang D-X, Wang M-X (2014a) Designing a Cu(II)–ArCu(II)–ArCu(III)–Cu(I) Catalytic Cycle: Cu(II)-catalyzed oxidative arene C-H bond azidation with air as an oxidant under ambient conditions. J Org Chem 79:11139–11145. https://doi.org/10.1021/jo502115a
Yao H, Zhang M, Zeng W, Zeng X, Zhang Z (2014b) A novel chemiluminescence assay of mitoxantrone based on diperiodatocuprate(III) oxidation. Spectrochim Acta, Part A 117:645–650. https://doi.org/10.1016/j.saa.2013.07.061
Acknowledgements
The authors are grateful to the Ministry of Education, Science and Technological Development of the Republic of Serbia for financial support (Grant 172011).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Gavrilović, M., Janković, N., Joksović, L. et al. Water ultrasound-assisted oxidation of 2-oxo-1,2,3,4-tetrahydropyrimidines and benzylic acid salts. Environ Chem Lett 16, 1501–1506 (2018). https://doi.org/10.1007/s10311-018-0766-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10311-018-0766-z