A new catalyst for the synthesis of 2-substituted perimidinescatalysed by FePO4
Journal of Taibah University for Science xxx(2016)xxx–xxx
Available online at https://www.sodocs.net/doc/e99913236.html,
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A new catalyst for the synthesis of2-substituted perimidines
catalysed by FePO4
F.K.Behbahani?,Fatemeh M.Golchin
Department of Chemistry,Karaj Branch,Islamic Azad University,Karaj,Iran
Received10July2015;received in revised form22September2015;accepted18October2015
Abstract
The reaction of1,8-diaminonaphthalene with aromatic aldehydes gave2-substituted perimidines in the presence of FePO4as a versatile,green and reusable catalyst at room temperature.
?2015The Authors.Production and hosting by Elsevier B.V.on behalf of Taibah University.This is an open access article under the CC BY-NC-ND license(https://www.sodocs.net/doc/e99913236.html,/licenses/by-nc-nd/4.0/).
Keywords:Synthesis;2-Aryl-2,3-dihydro-1H-perimidines;Catalyst;FePO4
1.Introduction
Multinuclear N-heterocyclic compounds,such as per-
imidines,are of wide interest because they exhibit a
diverse range of biological activities[1].Due to their bio-
logical activities,there are several preparative methods
for the synthesis of perimidines[2–7].The most com-
monly method for the preparation of perimidines is the
condensation reaction of1,8-diaminonaphthalene with
a carbonyl group,which requires a special reagent or
force reaction conditions.However,because of the con-
tinuing interest in this?eld,investigation into simple
methods for the synthesis of perimidines is impor-
tant.Recently,the use of an inorganic solid acid in
?Corresponding author.Tel.:+9802634418145;
fax:+9802634418156.
E-mail address:Farahnazkargar@https://www.sodocs.net/doc/e99913236.html,(F.K.Behbahani).
Peer review under responsibility of Taibah
University.
https://www.sodocs.net/doc/e99913236.html,/10.1016/j.jtusci.2015.10.004
1658-3655?2015The Authors.Production and hosting by Elsevier B.V.on behalf of Taibah University.This is an open access article under the CC BY-NC-ND license(https://www.sodocs.net/doc/e99913236.html,/licenses/by-nc-nd/4.0/).
organic synthesis has become more popular[8–12].In
addition to the cases mentioned above,FePO4is an inex-
pensive,safe and available reagent[13]that has also
been employed for the selective oxidation of CH4to
CH3OH[14]and benzene to phenol[15],one-pot syn-
thesis of dihydropyrimidinones and thiones[16],one-pot
three component synthesis of2,4,5-trisubstituted imid-
azoles[17],synthesis of1,2,4,5-tetraarylated imidazoles
[18],acetylation of alcohols and phenols with acetic
anhydride[19],synthesis of bis(indolyl)methanes[20],
synthesis of1,2-disubstituted benzimidazoles[21]and
synthesis of2-disubstituted benzimidazoles[22].In
addition,a part of our programme is aimed at develop-
ing selective and environmental friendly methodologies
for the preparation of?ne chemicals[17–21];due
to the versatile biological properties of perimidines
and as a continuation of our studies on the synthe-
sis of heterocyclic compounds,we report a clean and
simple synthetic method for the preparation of perim-
idines using FePO4as an ef?cient catalyst,which was
employed as green catalyst for the reaction between1,8-
diaminonaphthalene and aromatic aldehydes at ambient
temperature.The attractive features of this procedure are
2F.K.Behbahani,F.M.Golchin/Journal of Taibah University for Science xxx(2016)xxx–xxx
O H
NH2NH2
Ethanol HN NH
H
+FePO4
R
R
1a-h h-a3
2
Scheme1.Synthesis of2-substituted perimidines using FePO4.
a good conversion and reusability of the catalyst and an easy work up(Scheme1).
2.Results and discussion
Initially,to ascertain a suitable condition,the reac-tion of1,8-diaminonaphthalene with benzaldehyde in the presence of FePO4was performed in various solvents, such as water,ethanol,acetonitrile and dimethylsulphox-ide.Ethanol was found to be the most effective solvent for this reaction.The results are shown in Table1.
To establish the optimum amount of the catalyst needed for this reaction,various ratios of FePO4were examined using benzaldehyde(1.0mmol)and1,8-diaminonaphthalene(1.0mmol)at room temperature as a model reaction(Table1).Any desired products were not obtained in the absence of the catalyst over 24h,and the best yields were obtained with10mol% of FePO4in12h.Thus,the catalyst is an essential component for the synthesis of2-phenyl-2,3-dihydro-1H-perimidine(Table2).
To generalize the model reaction,the reactions were performed at room temperature for the time indicated in Table3by taking a1:1molar ratio mixture of 1,8-diaminonaphthalene and the aromatic aldehyde in the presence of FePO4in ethanol to give2,3-dihydro-1H-perimidines in suitable yields.As observed from the results presented in Table3,aromatic aldehydes containing both electron-withdrawing groups(NO2, Cl)and electron-donating groups(Me,OH)reacted
Table1
Optimization of the varying solvents for the synthesis of2-phenyl-2,3-dihydro-1H-perimidine.
Entry Solvent(5ml)Yield%a 1Ethanol95
2Water/ethanol(30/70)90
3Acetonitrile70
4DMSO70
a Condition:Benzaldehyde(1.0mmol),1,8-diaminonaphthalene
(1.0mmol)and FePO4(10mol%)at room temperature.Table2
Optimization of the catalyst amount for the synthesis of2-phenyl-2,3-dihydro-1H-perimidine.
Entry Catalyst(mol%)Yield%a 10–2160 3580 41095
a Condition:Benzaldehyde(1.0mmol),1,8-diaminonaphthalene, ethanol(5ml),ethanol and FePO4at room temperature.
smoothly to produce high product yields.Aromatic aldehydes with electron-withdrawing groups showed an increased reaction rate(Table3).A reasonable path-way for the formation of2-substituted perimidines in the presence of FePO4is disclosed in Scheme2. Nucleophilic attack of1,8-diaminonaphthalene2to FePO4-activated aldehyde1afforded intermediate3 following intermediate4.In situ dehydration of com-pound4and intramolecular nucleophilic attack of the second amino group to FePO4-activated imine interme-diate5obtained intermediate6to produce the desired compound7.
3.Conclusion
In conclusion,we developed a simple,rapid,ef?cient and green method based on the use of a heteroge-neous and reusable catalyst accompanied by the use of ethanol as a solvent due to its low cost,environmen-tally friendly nature and convenient synthetic method for the synthesis of biologically important perimidines catalyzed by FePO4.The reaction conditions are mild, and the reaction gives excellent product yields.In addi-tion,to show the advantages of using FePO4as a solid catalyst in the synthesis of2-phenyl-2,3-dihydro-1H-perimidine,our protocol was compared with previously reported methods(Table4).From the results given in Table4,the advantages of this work are evident regarding the good yield,easy separation and reusability of the catalyst.
4.Experimental
Mps were measured by using the capillary tube method with an electro thermal9200apparatus.The IR spectra were recorded using a Perkin Elmer FT-IR spectrometer scanning between4000and400cm?1. 1H NMR and13C NMR spectra were obtained on a
Bruker DRX-500MHz in CDC13.Analytical TLC of
F.K.Behbahani,F.M.Golchin/Journal of Taibah University for Science xxx(2016)xxx–xxx3 Table3
Synthesis of2-substituted perimidines using FePO4.
Entry Aldehyde Product Time(h)Yield%M.P.(?C)
Found Reported[ref.]
1
O
H
1a
HN
HN
3a
1580%160–161163[11,23]
2
O
H
O2N
1b
HN
HN
O2N
3b
7.090%188–190190[23,10]
3
O
H
NO2
1c
HN
HN
2
3c
8.085%158–160160[23,9]
4
O
H
1d
HN
HN
3d
1280%100–101103[12]
5
O
H
1e
HN
HN
3e
1578%160–161163[10,11]
6
O
H
Cl
1f
HN
HN
Cl
3f
1085%116–118116[9,13]
7
O
H
HO
1g
HN
HN
HO
3g
1680%188–189189[9,10]
4
F .K.Behbahani,F .M.Golchin /Journal of Taibah University for Science xxx (2016)xxx–xxx
Table 3(Continued )Entry
Aldehyde
Product
Time (h)
Yield %
M.P.(?C)
Found
Reported [ref.]
8
O
H Cl
Cl
1h HN
HN
Cl Cl
3h
10
80%
158–160
160[10,9]
Table 4
Synthesis of 2-phenyl-2,3-dihydro-1H -perimidine catalyzed by various catalysts.
Entry
Catalyst
Solvent
Time
Yield%
Ref.1CuY-zeolite
EtOH
25min/RT 81[24]2Fe 3O 4/SiO 2/(CH 2)3N +Me 3Br 3core–shell nanoparticles No solvent 12min/80?C 93[25]3AcOH
EtOH 24h/RT 52[26]4Ytterbium(III)tri?uoromethanesulphonate MeCN 24h/RT 88[27]5I 2
EtOH 40min/RT 84[28]6NaY zeolite
EtOH 45–50h/RT 70[23]7Cu(NO 3)2·2H 2O EtOH 10min/RT 83[29]
8
FePO 4
EtOH
12h/RT
80
This work
NH
HN
2O
R
2
3
5
6
7
Scheme 2.Proposed mechanism of the FePO 4-catalysed synthesis of 2-substituted perimidines.
all reactions was performed on Merck precoated plates (silica gel 60F-254on aluminium).
4.1.General procedure for preparation of 2-arylperimidines
To a solution of 1,8-diaminonaphthalene (1mmol)and aromatic aldehyde (1mmol)in ethanol (5ml),
FePO 4(10mol%,0.01g)was added.The mixture was stirred at room temperature for appropriate times (Table 1).After the completion of the reaction,the cata-lyst was separated by ?ltration,ethanol was evaporated and the solid product was observed.
4.2.Recycling of the catalyst
After the completion of the reaction,hot ethanol (10ml)was added to the reaction mixture,and then,the catalyst was separated by ?ltration.The precipitate was washed with hot ethanol and then air dried for the catalyst recovery study.The catalyst was reused for the synthesis of 2-phenyl-2,3-dihydro-1H -perimidine three times (80,80,78)%.
Appendix A.Supplementary data
Supplementary data associated with this article can be found,in the online version,at doi:10.1016/j.jtusci.2015.10.004.
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