Journal of Scientific and Technical Research (Sharda University, Noida)

Open Access Open Access  Restricted Access Subscription Access
Open Access Open Access Open Access  Restricted Access Restricted Access Subscription Access

Binary Systems of A Hydrophobic Aprotic Ionic Liquid and Water as Catalysts for Michael Addition Reaction


Affiliations
1 Department of Chemistry, University of Dhaka, Dhaka, Bangladesh
2 University Grants Commission of Bangladesh, Sher-E-Banglanagar, Dhaka, Bangladesh
     

   Subscribe/Renew Journal


Binary systems of an Aprotic Ionic Liquid (AIL), 8-hexyl-1,8-diazabicyclo[5.4.0]-undec-7-ene-8-iumhydroxide ([C6DBU]OH) and water were prepared at molar ratio, XAIL ranging from 0 to 1.0. Physicochemical properties of the pure and binary systems of the AIL have been studied in detail by viscosity, Fourier Transform Infrared (FTIR) spectroscopy, and dynamic light scattering measurements and thermogravimetric analysis. The negative deviation of excess viscosity at XAIL < 0.4 indicated the formation of micelle like aggregation and the positive deviation of excess viscosity at XAIL > 0.4 indicated the formation of reverse micelle like aggregation due to the surfactant-like behavior of the long alkyl chain in [C6DBU]OH. The spectral and the particle size analyses show the presence of the confined water at XAIL > 0.4 in the cored structure of the reverse micellar aggregates. The variation of the microstructures in water-rich and ionic liquid (IL)-rich region significantly influenced the kinetics of Michael addition reaction between acetylacetone and 2-cyclohexene-1-one in absence of organic solvents while using [C6DBU]OH and its binary systems with water as catalysts. The reaction was studied by using thin layer chromatographic technique using aluminum plates coated with silica gel as the stationary phase and mixture of chloroform and n-hexane (1:1 by volume) as the eluent. The progress of the addition reaction was monitored by observing the development of spots in the chromatographic plate. The kinetic investigations in the presence of 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU), NaOH, and a DBU based protic IL, [HDBU]OH have also been made and the catalytic performances have been compared. Finally, the role of the [C6DBU]OH and its binary systems with water as catalysts in the mechanism of the Michael addition reaction has been explained in terms of different molecular interactions.

Keywords

Aprotic Ionic Liquid, Average Reaction Rate, Catalyst, Micelle, Reverse Micelle, Michael Addition Reaction, 1, 8-Diazabicyclo[5.4.0]-Undec-7-Ene (DBU).
User
Subscription Login to verify subscription
Notifications
Font Size

  • H. Tokuda, K. Hayamizu, K. Ishii, M. A. B. H. Susan, and M. Watanabe, “Physicochemical properties and structures of room temperature ionic liquids 1. variation of anionic species,” Journal of Physical Chemistry B, vol. 108, no. 42, pp. 16593-16600, 2004.

  • H. Tokuda, K. Hayamizu, K. Ishii, M. A. B. H. Susan, and M. Watanabe, “Physicochemical properties and structures of room temperature ionic liquids. 2. variation of alkyl chain length in imidazolium cation,” Journal of Physical Chemistry B, vol. 109, no. 13, pp. 6103-6110, 2005.

  • H. Tokuda, K. Ishii, M. A. B. H. Susan, S. Tsuzuki, K. Hayamizu, and M. Watanabe, “Physicochemical properties and structures of room-temperature ionic liquids. 3. variation of cationic structures,” Journal of Physical Chemistry B, vol. 110, no. 6, pp. 2833-2839, 2006.

  • M. A. B. H. Susan, A. Noda, S. Mitsushima and M. Watanabe, “Brønsted acid-base ionic liquids and their use as new materials for anhydrous proton conductors,” Chemical Communications, no. 8, pp. 938-939, 2003.

  • D. Singh, V. Singh, and R. L. Gardas, “Volumetric and acoustic properties of a DBU (1, 8-diazobicyclo [5.4.0] undec-7-ene) based protic ionic liquid in water at T=(293.15 to 328.15) K,” Journal of Solution Chemistry, vol. 44, no. 3-4, pp. 634-651, 2015.

  • K. Ahmed, A. Auni, G. Ara, M. M. Rahman, M. Y. A. Mollah, and M. A. B. H. Susan, “Solvatochromic and fluorescence spectroscopic studies on polarity of ionic liquid and ionic liquid-based binary systems,” Journal of Bangladesh Chemical Society, vol. 25, no. 2, pp. 146-158, 2012.

  • M. Marium, M. M. Rahman, M. Y. A. Mollah, and M. A. B. H. Susan, “Molecular level interactions in binary mixtures of 1-ethyl 3-methylimidazolium tetrafluoroborate and water,” RSC Advances, vol. 5, no. 26, pp. 19907-19913, 2015.

  • M. S. Miran, T. Yasuda, M. A. B. H. Susan, K. Dokko, and M. Watanabe, “Binary protic ionic liquid mixtures as a proton conductor: High fuel cell reaction activity and facile proton transport,” Journal of Physical Chemistry C, vol. 118, no. 48, pp. 27631-27639, 2014.

  • P. Attri, P. M. Reddy, and P. Venkatesu, A. Kumar, T. Hofman, “Measurements and molecular interactions for N,N-dimethylformamide with ionic liquid mixed solvents”, Journal of Physical Chemistry B, vol. 114, no. 18, pp. 6126-6133, 2010.

  • Q. G. Zhang, N. N. Wang, and Z. W. Yu, “The hydrogen bonding interaction between the ionic liquid 1-ethyl-3-methylimidazolium ethyl sulfate and water,” Journal of Physical Chemistry B, vol. 114, no. 14, pp. 4747-4754, 2010.

  • J. S. Yadav, B. V. S. Reddy, A. K. Basak, and A. V. Narsaiah, “Aza-Michael reactions in ionic liquids. A facile synthesis of β-amino compounds,” Chemistry Letters, vol. 32, no. 11, pp. 988-989, 2003.

  • B. C. Ranu, and S. Banerjee, “Ionic liquid as catalyst and reaction medium. The dramatic influence of a taskspecific ionic liquid, [bmIm] OH, in Michael addition of active methylene compounds to conjugated ketones, carboxylic esters, and nitriles,” Organic Letters, vol. 7, no. 14, pp. 3049-3052, July 2005.

  • B. C. Ranu, S. Banerjee, and R. Jana, “Ionic liquid as catalyst and solvent: The remarkable effect of a basic ionic liquid, [bmIm]OH on Michael addition and alkylation of active methylene compounds,” Tetrahedron, vol. 63, no. 3, pp. 776-782, 2007.

  • J. Nowicki, M. Muszynski and J-P. Mikkola, “Ionic liquids derived from organo super bases: En route to superionic liquids”, RSC Advances, vol. 6, no. 11, pp. 9194-9208, 2016.

  • G. Ara, “Ionic liquids and their binary systems with molecular solvents as catalyst and reaction medium for organic synthesis,” A dissertation submitted to University of Dhaka, Bangladesh for PhD degree, 2017.

  • K. C. Lethesh, S. N. Shah, and M. I. A. Mutalib, “Synthesis, characterization, and thermophysical Properties of 1,8-diazobicyclo[5.4.0]undec-7-ene based thiocyanateionic liquids,” Journal of Chemical and Engineering Data, vol. 59, no. 7, pp. 1788-1195, 2014.

  • Z. Wang, Z. Li, Y. Jin, W. Liub, L. Jiang, and Q. Zhang, “Organic superbase derived ionic liquids based on the TFSI anion: Synthesis, characterization, and electro-chemical properties,” New Journal of Chemistry, vol. 41, no. 12, pp. 5091-5097, 2017.

  • H. X. Zeng; Z. P. Li, and H. Q. Wang, “Physical chemistry property of water/TX-100/hexanol/octane reverse micro-emulsion,” Acta Physico-Chimica Sinica, vol. 15, no. 1, pp. 522-527, 1999.

  • T. K. Jain, M. Varshney, and A. Maitra, “Structural studies of aerosol OT reverse micellar aggregates by FT-IR spectroscopy,” Journal of Physical Chemistry A, vol. 93, no. 21, pp. 7409-7416, 1989.

  • M. Kumbhakar, T. Goel, T. Mukherjee, and H. Pal, “Role of micellar size and hydration on solvation dynamics: A temperature dependent study in triton-X-100 and brij-35 micelles,” Journal of Physical Chemistry B, vol. 108, no. 50, pp. 19246-19254, 2004.

  • J. Workman Jr. and L. Weyer, “Practical guide and spectral atlas for interpretive near-infrared spectroscopy,” CRC Press, Florida, (2nded.), 2012.

  • L. Cammarata, S. G. Kazarian, P. A. Salter, and T. Welton, “Molecular states of water in room temperature ionic liquids,” Physical Chemistry Chemical Physics, vol. 3, no. 23, pp. 5192-5200, 2001.

  • L. Zhang, Z. Xu, Y. Wang, and H. Li, “Prediction of the solvation and structural properties of ionic liquids in water by two-dimensional correlation spectroscopy,” Journal of Physical Chemistry B, vol. 112, no. 20, pp. 6411-6419, 2008.

  • D. Fulvio, S. Guglielmino, T. Favone, and M. E. Palumbo, “Near-infrared laboratory spectra of H2O trapped in N2, CH4, and CO: Hints for trans-neptunian objects’ observations,” Astronomy & Astrophysics, vol. 511, no. 62, pp. 1-9, 2010.

  • H. Wang, J. Wang, and L. Zhang, “Temperature dependence of the microstructure of 1-butyl-3-methylimidazolium tetrafluoroborate in aqueous solution,” Vibrational Spectroscopy, vol. 68, pp. 20-28, 2013.

  • S. Rivera-Rubero, and S. Baldelli, “Influence of water on the surface of hydrophilic and hydrophobic room-temperature ionic liquids,” Journal of the America Chemical Society, vol. 126, no. 38, pp. 11788-11789, 2004.

  • Koddermann, C. Wertz, A. Heintz, and R. Ludwig, “The association of water in ionic liquids: A reliable measure of polarity,” Angewandte Chemie, International Edition, vol. 45, no. 22, pp. 3697-3702, 2006.

  • A. Downard, M. J. Earle, C. Hardacre, S. E. J. McMath, M. Nieuwenhuyzen, and S. J. Teat, “Structural studies of crystalline 1-alkyl-3-methylimidazolium chloride salts,” Chemistry of Materials, vol. 16, no. 1, pp. 43-48, 2004.

  • A. Mele, C. D. Tran, and S. H. De Paoli Lacerda, “The structure of a room temperature ionic liquid with and without trace amounts of water: The role of C-H---O and C-H---F interactions in 1-n-butyl-3-methylimidazolium tetrafluoroborate,” Angewandte Chemie, International Edition, vol. 115, no. 36, pp. 4500-4502, 2003.

  • Y. Wang, H. Li, and S. Han, “A theoretical investigation of the interactions between water molecules and ionic liquids,” Journal of Physical Chemistry B, vol. 110, no. 48, pp. 24646-24651, 2006.

  • C. F. Poole, “Chromatographic and spectroscopic methods for the determination of solvent properties of room temperature ionic liquids,” Journal of Chromatography A, vol. 1037, no. 1-2, pp. 49-82, 2004.

  • S. Aznarez, M. de Ruiz Holgado, and E. L. Arancibia, “Viscosities of mixtures of 2-alkanols with tetraethyleneglycol dimethyl ether at different temperatures,” Journal of Molecular Liquids, vol. 124, no. 1, pp. 78-83, 2006.


Abstract Views: 553

PDF Views: 0




  • Binary Systems of A Hydrophobic Aprotic Ionic Liquid and Water as Catalysts for Michael Addition Reaction

Abstract Views: 553  |  PDF Views: 0

Authors

Gulshan Ara
Department of Chemistry, University of Dhaka, Dhaka, Bangladesh
Mominul Islam
Department of Chemistry, University of Dhaka, Dhaka, Bangladesh
M. Muhibur Rahman
Department of Chemistry, University of Dhaka, Dhaka, Bangladesh
Yousuf A. Mollah
University Grants Commission of Bangladesh, Sher-E-Banglanagar, Dhaka, Bangladesh
Abu Bin Hasan Susan
Department of Chemistry, University of Dhaka, Dhaka, Bangladesh

Abstract


Binary systems of an Aprotic Ionic Liquid (AIL), 8-hexyl-1,8-diazabicyclo[5.4.0]-undec-7-ene-8-iumhydroxide ([C6DBU]OH) and water were prepared at molar ratio, XAIL ranging from 0 to 1.0. Physicochemical properties of the pure and binary systems of the AIL have been studied in detail by viscosity, Fourier Transform Infrared (FTIR) spectroscopy, and dynamic light scattering measurements and thermogravimetric analysis. The negative deviation of excess viscosity at XAIL < 0.4 indicated the formation of micelle like aggregation and the positive deviation of excess viscosity at XAIL > 0.4 indicated the formation of reverse micelle like aggregation due to the surfactant-like behavior of the long alkyl chain in [C6DBU]OH. The spectral and the particle size analyses show the presence of the confined water at XAIL > 0.4 in the cored structure of the reverse micellar aggregates. The variation of the microstructures in water-rich and ionic liquid (IL)-rich region significantly influenced the kinetics of Michael addition reaction between acetylacetone and 2-cyclohexene-1-one in absence of organic solvents while using [C6DBU]OH and its binary systems with water as catalysts. The reaction was studied by using thin layer chromatographic technique using aluminum plates coated with silica gel as the stationary phase and mixture of chloroform and n-hexane (1:1 by volume) as the eluent. The progress of the addition reaction was monitored by observing the development of spots in the chromatographic plate. The kinetic investigations in the presence of 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU), NaOH, and a DBU based protic IL, [HDBU]OH have also been made and the catalytic performances have been compared. Finally, the role of the [C6DBU]OH and its binary systems with water as catalysts in the mechanism of the Michael addition reaction has been explained in terms of different molecular interactions.

Keywords


Aprotic Ionic Liquid, Average Reaction Rate, Catalyst, Micelle, Reverse Micelle, Michael Addition Reaction, 1, 8-Diazabicyclo[5.4.0]-Undec-7-Ene (DBU).

References