3
in excellent yields. Among the 23 examples, 8 compounds (3f,
3g, 3h, 3i, 3p, 3r, 3s, 3p) are novel perimidines. Due to the
potential importance of the perimidines in biological and material
science, the newly developed green methodology will be
efficacious to chemists and industrialists.
Acknowledgment
NAH thanks the Council of Scientific and Industrial
Scheme 2: Multi-gram scale reaction of 1,8-diamino
naphthalene with benzaldehyde
Research (CSIR), New Delhi-India for
a
research
fellowship. GA and SR thank the Kerala State Council for
Science Technology and Environment (KSCSTE),
Trivandrum, India for a research grant (Order No.
341/2013/KSCSTE dated 15.03.2013) and research
fellowship respectively.
We propose a mechanism for the transformation which
involves the initial formation of an imine at one of the amino
groups of 1,8-diamino naphthalene by reacting with the aldehyde
eliminating a molecule of water. The imine then undergoes a
nucleophilic attack by the other amino group furnishing the
required dihydro perimidine product (Scheme 3). The
hydrophobic interaction between water and reactants bring the
reactant molecules closer thereby increasing the reaction rate.
Also the hydrogen bonding between water molecule and nitrogen
atom of imine increases the electrophilicity of the adjacent
carbon and thereby favours the nucleophilic attack by free amino
group. According to the molecular mechanism of “on water”
reactions proposed by Jung and Marcus, approximately 25% of
water molecules have free OH groups at the interface and can
form potential H-bonding with the substrate.19 Such available H-
bonds in water clusters can act as a catalyst and enhance the
reaction rate. However the exact reason behind this “on water”
effect is still ambiguous.15, 19
References and notes
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of Chemistry; 2014; (c) Jamsheena, V.; Shilpa, G; Saranya, J.;
Harry, N. A.; Lankalapalli,
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Tetrahedron 2011, 67, 5168-5175.
Scheme 3: Proposed mechanism for the synthesis of 2,3-
dihydro-1H-perimidines on water.
13. Mobinikhaledi, A.; Fard, B.; Sasani, F.; Amrollahi, M. A.
Bulgarian Chem. Commun. 2013, 45, 353.
Conclusion
14. (a) Butler, R. N.; Coyne, A. G. Chem. Rev., 2010, 110, 6302-6337
(b) Chanda, A.; Fokin, V. V. Chem. Rev. 2009, 109, 725-748
15. Narayan, S.; Muldoon, J.; Finn, M.G.; Fokin, V.V.; Kolb, H.C.;
Sharpless, K.B. Angew. Chem Int Ed. 2005, 44, 3275-3279.
16. Breslow, R. Acc. Chem. Res. 2004, 37, 471-478.
17. Klijn, J. E.; Engberts, J. B. F. N. Nature, 2005, 435, 746-747.
18. Butler, R. N.; Coyne, A. G. Org. Biomol. Chem. 2016, 14, 9945-
9960.
We have developed a novel eco-friendly on water protocol for
the synthesis of 2,3-dihydro-1H-perimidines by the reaction of
aldehydes with 1,8-diamino naphthalene. The reaction proceeded
without any catalyst, at room temperature, in 30 minutes time.
Moderate to excellent yields of the products were obtained with
heterocyclic, aromatic and aliphatic aldehydes. The multi-gram
scale reaction was also found to be successful giving the product
19. Jung, Y.; Marcus, R. A. J. Am. Chem. Soc. 2007, 129,5492-5502
Graphical Abstract