A Kinetic Study on the Synthesis of N-arylation of Indole Under Synergetic Effect of Multi-Site Phase Transfer Catalysis System

Author(s): Manickam Sathiyaraj, Perumal Venkatesh*

Journal Name: Current Organocatalysis

Volume 7 , Issue 2 , 2020

Become EABM
Become Reviewer

Graphical Abstract:


Abstract:

Background: Phase transfer catalysis technique is recognized as an attractive method for synthesizing several organic compounds under heterogeneous reaction.

Methods: In this study, the effect of Multi-site Phase-Transfer Catalyst (MPTC) was tested during the synthesis of 1-(4-nitrophenyl)-1-indole from 1-chloro-4-nitrobenzene (CNB) and indole in a heterogeneous solid-liquid condition using sodium hydroxide at 50°C.

Results: In a synergetic condition, in the presence of MPTC the conversion of 1-chloro-4- nitrobenzeneyield was increased, which is proved the efficacy of this catalyst. In addition, the rate of this reaction was also enhanced by the change in volume of water.

Conclusion: The apparent reaction rate was found to be of pseudo-first-order kinetics. MPTC is a promising tool for many organic reactions. Therefore, increase the rate constant can be achieved by various parameters, such as temperature, MPTC, sodium hydroxide, and stirring speed.

Keywords: 1-(4-nitrophenyl)-1-indole, 1-chloro-4-nitrobenzene, indole, kinetics, MPTC, solid-liquid reaction.

[1]
Rasmussen, J.K.; Smith, H.K. Phase transfer free radical reactions: The crown ether potassium peroxy disulphate initiator system. J. Am. Chem. Soc., 1981, 103, 730-736.
[http://dx.doi.org/10.1021/ja00393a069]
[2]
Wang, M.L.; Hsieh, Y.M. Kinetic study of dichlorocyclopropanation of 4-vinyl-1- cyclohexene by a novel multisite phase transfer catalyst. J. Mol. Catal. Chem., 2004, 210, 59-68.
[http://dx.doi.org/10.1016/j.molcata.2003.09.025]
[3]
Yang, H.M.; Lin, C.L. Phase transfer catalyzed benzylation of sodium benzoate using aliquate 336 as catalyst in liquid-liquid system. J. Mol. Catal. Chem., 2003, 206, 67-76.
[http://dx.doi.org/10.1016/S1381-1169(03)00446-1]
[4]
Makosza, M.; Fedorynski, M. Phase transfer catalysis – basic principles, mechanism and specific features. Curr. Catal., 2012, 57, 79-87.
[http://dx.doi.org/10.2174/2211544711201020079]
[5]
Yadav, G.D. Insight into green phase - transfer catalysis. Top. Catal., 2004, 29, 145-161.
[http://dx.doi.org/10.1023/B:TOCA.0000029797.93561.cd]
[6]
Dehmlow, E.V.; Dehmlow, S.S. Phase Transfer Catalysis, Monographs in Modern Chemistry; Verlag Chemie: Weinheim, Germany, 1983.
[7]
Sasson. Y.; Neumann, R. Handbook of Phase Transfer Catalysis; Chapman & Hall: New York, 1997.
[8]
Jarrousse, J.J. The influence of quatemary ammonium chloride on the reaction of labile hydrogen compounds and chlorine-substituted chlorine derivatives. C. R. Hebd. Seances Acad. Sci. Ser., 1951, C232, 1424-1434.
[9]
Wang, M.L.; Lee, Z.F. Reaction of 4,4-bis (chloromethyl)-1,10-biphenyl and phenol in two-phase medium via phase-transfer catalysis. J. Mol. Catal. Chem., 2006, 264, 19-127.
[10]
Hsiao, H.C.; Kao, S.M.; Weng, H.S. Synthesis of n-butyl phenyl ether by tri-liquid- phase catalysis using poly(ethylene glycol)-600 as a catalyst. 1. Analysis of factors affecting the formation of a third liquid phase. Ind. Eng. Chem. Res., 2001, 39, 2772-2778.
[http://dx.doi.org/10.1021/ie990824t]
[11]
Mason, D.; Magdassi, S.; Sasson, Y. Role of a third liquid phase in phase-transfer catalysis. J. Org. Chem., 1991, 56, 7229-7232.
[http://dx.doi.org/10.1021/jo00026a010]
[12]
Abimannan, P.; Rajendran, V. Kinetic study for the synthesis of 1-nitro-4-(prop-2- yn yloxy) benzene in solid-liquid PTC condition. Curr. Catal., 2016, 5, 44-50.
[http://dx.doi.org/10.2174/2211544705666160202002843]
[13]
Selvaraj, V.; Rajendran, V. Preparation of 1,3-bis(allyloxy)benzene under a new multi-site phase-transfer catalyst combined with ultrasonication--a kinetic study. Ultrason. Sonochem., 2013, 20(5), 1236-1244.
[http://dx.doi.org/10.1016/j.ultsonch.2013.02.011] [PMID: 23545104]
[14]
Murugan, E.; Gopinath, P. Catalytic activity of novel soluble multi-site phase transfer catalyst in dichlorocarbene addition of pinene. J. Mol. Catal. Chem., 2008, 294, 68-73.
[http://dx.doi.org/10.1016/j.molcata.2008.08.004]
[15]
Murugan, E.; Tamizharasu, G. New soluble multi-site phase transfer catalysts and their catalysis for dichlorocarbene addition to citronellal assisted by ultrasound—A kinetic study. J. Mol. Catal. Chem., 2012, 363, 81-89.
[http://dx.doi.org/10.1016/j.molcata.2012.05.020]
[16]
Ali, H.E. Cycloalkylation reaction of fatty amines with a a-dihaloalkanes role of bis-quaternary ammonium salts as phase-transfer catalysts. Catal. Commun., 2007, 8, 855-860.
[http://dx.doi.org/10.1016/j.catcom.2006.09.013]
[17]
Vivekanand, P.A.; Balakrishnan, T. Superior catalytic efficiency of a new multisite phase transfer catalyst in the C-alkylation of dimedone – a kinetic study. Catal. Commun., 2009, 10, 1371-1375.
[http://dx.doi.org/10.1016/j.catcom.2009.02.022]
[18]
Loganathan, S.; Rajendran, V. Ultrasound assisted polymerization of N-vinyl imidazole under phase-transfer catalysis condition--a kinetic study. Ultrason. Sonochem., 2013, 20(1), 308-313.
[http://dx.doi.org/10.1016/j.ultsonch.2012.07.004] [PMID: 22922071]
[19]
Harikumar, K.; Rajendran, V. Ultrasound assisted the preparation of 1-butoxy-4-nitrobenzene under a new multi-site phase-transfer catalyst--kinetic study. Ultrason. Sonochem., 2014, 21(1), 208-215.
[http://dx.doi.org/10.1016/j.ultsonch.2013.07.016] [PMID: 23948491]
[20]
Idoux, J.P.; Wysocki, R.; Young, S.; Turcot, J.; Ohlman, C.; Leonard, R. Polymer-supported “multi-site” phase transfer catalysts. Synth. Commun., 1983, 13, 39-144.
[http://dx.doi.org/10.1080/00397918308061972]
[21]
Balakkrishnan, T.; Jayachandran, J.P. Multisite phase-transfer catalyst for organic transformations. ACS Symp. Ser., 1997, 659, 277-292.
[http://dx.doi.org/10.1021/bk-1997-0659.ch021]
[22]
Devulapelli, V.G.; Weng, H.S. Synthesis of cinnamyl acetate by solid–liquid phase transfer catalysis: Kinetic study with a batch reactor. Catal. Commun., 2009, 10, 1638-1642.
[http://dx.doi.org/10.1016/j.catcom.2009.04.032]
[23]
Selvaraj, V.; Harikumar, K.; Sathiyaraj, M.; Rajendran, V. Kinetic investigation of nitroarylation of pyrrole with 1-chloro-4-nitrobenzene using a new multi-site phase- transfer catalyst under ultrasonic condition. Chem. Sci. J., 2015, 6, 1-8.
[24]
Wang, M.L.; Chen, C.J. Kinetic study of synthesizing 1-(3- phenylpropyl)pyrrolidine- 2,5-dione under solid-liquid phase-transfer catalytic conditions assisted by ultrasonic irradiation. Org. Process Res. Dev., 2010, 14, 737-745.
[http://dx.doi.org/10.1021/op900332c]
[25]
Yadav, G.D.; Jadhav, Y.B. Kinetics and modeling of liquid–liquid phase transfer catalysed synthesis of p-chlorophenyl acetonitrile: role of co-catalyst in intensification of rates and selectivity. J. Mol. Catal. Chem., 2003, 192, 41-52.
[http://dx.doi.org/10.1016/S1381-1169(02)00419-3]
[26]
Selvaraj, V.; Rajendran, V. Propargylation of indene-1,3-dione under a new phase-transfer catalyst combined with ultrasonication--a kinetic study. Ultrason. Sonochem., 2014, 21(2), 612-619.
[http://dx.doi.org/10.1016/j.ultsonch.2013.09.013] [PMID: 24134829]


open access plus

Rights & PermissionsPrintExport Cite as

Article Details

VOLUME: 7
ISSUE: 2
Year: 2020
Page: [89 - 95]
Pages: 7
DOI: 10.2174/2213337206666190701140914

Article Metrics

PDF: 16
HTML: 2