A green, highly efficient, and eco-friendly protocol for Knoevenagel–Michael addition reaction is reported in Chickpea leaf exudates (CLE) as a naturally sourced biosurfactant. The reactions between dimedone/4-hydroxycoumarins and a variety of aryl aldehydes were carried out in presence of CLE to afford diketodiols/biscoumarins. The synthetic pathway complies with several key requirements of green chemistry principles such as the employment of natural feedstock as green reaction media, ambient temperature, atom economy along with natural biosurfactant type Bronsted acids, and recyclable and biodegradable catalyst which led to a 28-fold increase in molar efficiency versus industrial standard protocols. Its dynamic phase is confirmed by the optical microscopy technique and critical micelle concentration measurement. The notable advantages of the present protocol were simple work-up procedure, high yield within short reaction time, easy separation of products, avoiding tedious column chromatography thus making the protocol environmentally friendly, sustainable, and economical.
This is a preview of subscription content, access via your institution.
Buy single article
Instant access to the full article PDF.
Price excludes VAT (USA)
Tax calculation will be finalised during checkout.
P. Tundo, P.T. Anastas, Green Chemistry: Theory and Practice, 1st edn. (Oxford University Press, Oxford, 1998)
H.C. James, J.M. Duncan, Handbook of Green Chemistry and Technology (Wiley-Blackwell Publishing, Hoboken, 2002), p. 564
G. Yanlong, Green Chem. 14, 2091 (2012)
L. Chao, T.A. Paul, Chem. Soc. Rev. 41, 1413 (2012)
B.R. Dhevalapally, J. Org. Chem. 72(14), 5056 (2007)
M.B. Arias, M.T. Albarran, I.P. Martinez, F.M. Martinez, G. Espinosa, E. Molins, E. Espinosa, J. Chem. Crystallogr. 29, 759 (1999)
P. Shanmugasundaram, K.J. Prabahar, V.T. Ramakrishnan, J. Heterocycl. Chem. 30, 1003 (1993)
S.T. Morbale, S.D. Jadhav, M.B. Deshmukh, S.S. Patil, RSC Adv. 5, 84610 (2015)
S.T. Morbale, S.K. Shinde, S.A. Damate, M.B. Deshmukh, S.S. Patil, Lett. Org. Chem. 15, 57 (2018)
H.V. Chavan, B.P. Bandgar, ACS Sustain. Chem. Eng. 1, 929 (2013)
B.M. Patil, S.K. Shinde, A.A. Jagdale, S.D. Jadhav, S.S. Patil, Res. Chem. Intermed. 47, 4369 (2021)
K.M. Khan, G.M. Maharvi, M.T.H. Khan, A.J. Shaikh, S. Perveen, S. Begum, M.I. Choudhary, Bioorg. Med. Chem. 14, 344 (2006)
G.M. Maharvi, S. Ali, N. Riaz, N. Afza, A. Malik, M. Ashraf, M. Lateef, J. Enzyme. Inhib. Med. Chem. 23, 62 (2008)
R. Zhang, T. Futagoishi, M. Murata, A. Wakamiya, Y. Murata, J. Am. Chem. Soc. 136, 8193 (2014)
I. Manolov, C.M. Moessmer, N. Danchev, Eur. J. Med. Chem. 41, 882 (2006)
S.S. Li, Z. Gao, X. Feng, S.M. Hecht, J. Nat. Prod. 9, 1608 (2004)
K.M. Khan, S. Iqbal, M.A. Lodhi, G.M. Maharvi, Z. Ullah, M.I. Choudhary, A.U. Rahman, S. Perveen, Bioorg. Med. Chem. 12, 1963 (2004)
S. Han, F.F. Zhang, H.Y. Qian, L.L. Chen, J.B. Pu, X. Xie, J.J. Chen, J. Med. Chem. 58, 5751 (2015)
N. Srividya, P. Ramamurthy, P. Shanmugasundaram, V.T. Ramakrishnan, J. Org. Chem. 61, 5083 (1996)
H.S.P. Rao, V.S. Tangeti, J. Chem. Sci. 125, 777 (2013)
J.M. Khurana, K. Vij, J. Chem. Sci. 124, 907 (2012)
B. Maleki, M. Raei, H. Alinezhad, R. Tayebee, A. Sedropoushan, Org. Prep. Proced. Inter. 50, 288 (2018)
V.K. Rao, M.M. Kumar, A. Kumar, Indian J. Chem. 50B, 1128 (2011)
Y. Ren, B. Yang, X. Liao, RSC Adv. 6, 22034 (2016)
B.M. Sapkal, P.K. Labhane, J.R. Satam, Res. Chem. Intermed. 43, 4967 (2017)
S.S. Ganesan, J. Kothandapani, A. Ganesan, Lett. Org. Chem. 11, 9 (2014)
J.K. Rajput, G. Kaur, Catal. Sci. Technol. 4, 142 (2014)
M. Tajbakhsh, M. Heidary, R. Hosseinzadeh, Res. Chem. Intermed. 42, 1425 (2015)
A. Ilangovan, S. Muralidharan, P. Sakthivel, S. Malayappasamy, S. Karuppusamy, M.P. Kaushik, Tetrahedron Lett. 54, 491 (2013)
S. Kantevari, R. Bantu, L. Nagarapu, J. Mole. Cat. A: Chem. 269, 53 (2007)
B. Pawar, V. Shinde, A. Chaskar, Green Sus. Chem. 3, 56 (2013)
J. Albadi, A. Mansournezhad, S. Salehnasab, Res. Chem. Intermed. 41, 5713 (2014)
J.M. Khurana, S. Kumar, Tetrahedron Lett. 50, 4125 (2009)
J.M. Khurana, S. Kumar, Monatsh Chem. 141, 561 (2010)
R. Karimian, F. Piri, A.A. Safari, S.J. Davarpanah, J. Nano. Chem. 3, 52 (2013)
K. Tabatabaeian, H. Heidari, A. Khorshidi, M. Mamaghani, N.O. Mahmoodi, J. Serbian Chem. Soc. 77, 407 (2012)
Z.N. Siddiqui, F. Farooq, Catal. Sci. Technol. 1, 810 (2011)
M. Kidwai, V. Bansal, P. Mothsra, S. Saxena, R.K. Somvanshi, S. Dey, T.P. Singh, J. Mole. Cat. A: Chem. 268, 76 (2007)
S.R. Mali, S.K. Shinde, S.A. Damte, S.S. Patil, R. Soc. Open Sci. 5, 170333 (2018)
R.C. Patil, S.A. Damate, D.N. Zambare, S.S. Patil, New J. Chem. 45, 9152 (2021)
P.W. Chia, B.S. Lim, F.S.J. Yong, S.C. Poh, S.Y. Kan, Environ. Chem. Lett. 16, 1493 (2018)
D. Das, Tetrahedron Lett. 61, 152298 (2020)
D. Sarmah, K.K. Borah, U. Bora, Sustain. Chem. Pharm. 24, 100551 (2021)
K. Venkateswarlu, Environ. Chem. Lett. 19, 3887 (2021)
M. Sarmah, M. Mondal, U. Bora, ChemistrySelect 2, 5180 (2017)
R.C. Patil, U.P. Patil, A.A. Jagdale, S.K. Shinde, S.S. Patil, Res. Chem. Intermed. 46, 3527 (2020)
R.C. Patil, S.K. Shinde, U.P. Patil, A.T. Birajdar, S.S. Patil, Res. Chem. Intermed. 47, 1675 (2021)
R.C. Patil, A.A. Jagdale, U.P. Patil, J.S. Ghodake, S.S. Mali, C.K. Hong, S.S. Patil, Catal. Lett. 151, 3617 (2021)
A. Ilangovan, S. Malayappasamy, S. Muralidharan, S. Maruthamuthu, Chem. Cent. J. 5, 81 (2011)
K. Nikoofar, F.M. Yielzoleh, J. Saudi Chem. Soc. 22, 715 (2018)
S. Ogo, Y. Takebe, K. Uehara, T. Yamazaki, H. Nakai, Y. Watanabe, S. Fukuzumi, Organometallics 25, 331 (2006)
One of the authors Rupesh C. Patil is grateful to SARTHI, Pune (Government of Maharashtra) for the award of CMSRF-2019 fellowship [CIN-U74999PN2018NPL177394, dated 11th Sept. 2019]. The authors are also thankful to Shivaji University, Kolhapur and Indian Institute of Chemical Technology (IICT), Hyderabad, for spectral analysis.
Conflicts of interest
There are no conflicts interests to declare.
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Below is the link to the electronic supplementary material.
About this article
Cite this article
Patil, R.C., Zambare, D.N., Damate, S.A. et al. Chickpea leaf exudates (CLE) mediated Knoevenagel–Michael reactions for the synthesis of diketodiols and biscoumarins. Res Chem Intermed 48, 2181–2198 (2022). https://doi.org/10.1007/s11164-022-04707-8