Main Article Content
Abstract
Benzyl chloride, benzyl bromide and their para substituted derivatives were selectively oxidized to corresponding benzaldehydes by acidified monochromate in toluene and ethyl acetate with the help of phase transfer catalysts like tetrabutylphosphonium bromide (TBPB), tetrabutylammonium bromide (TBAB), tetrabutylammonium hydrogen sulphate (TBAHS), cetyltrimethylammonium bromide (CTMAB) and tricaprylmethylammonium chloride (TCMC). The reaction was carried out by simple magnetic stirring for about 2 h at 60 ºC. The products were recrystallized and analyzed by infrared and UV-visible spectral techniques. Benzaldehyde and substituted benzaldehydes were formed in good yield (> 90%) on oxidation of benzyl chlorides and benzyl bromides. The reaction is proved to be highly selective due to the absence of acids or any other products during the reaction. All the phase transfer catalysts were highly effective in bringing out the reaction in both the solvents. This is highly significant as the oxidation reaction will not occur in non-polar solvents without the presence of phase transfer catalysts.
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References
- K.B. Wiberg, Oxidation in Organic Chemistry, Academic Press: London and New York (1965).
- S. Paterson, Alcohol oxidation: Reaction, Effects and Applications, Nova Science Publishers, Inc., New York (2018).
- S. Dash, S. Patel and B.K. Mishra, Oxidation by Permanganate: Synthetic and Mechanistic Aspects, Tetrahedron, 65, 707 (2009); https://doi.org/10.1016/j.tet.2008.10.038
- K. Bijudas, Kinetics and Mechanism of the Selective Oxidation of Benzyl Alcohols by Acidified Dichromate in Aqueous Acetic Acid Medium, Orient. J. Chem., 30, 1391 (2014); https://doi.org/10.13005/ojc/300360
- Z. Hu, L. Ma, J. Xie, H. Du, W.W.Y. Lam and T.-C. Lau, Ruthenium-Catalyzed Oxidation of Alcohols by Bromate in Water, New J. Chem., 37, 1707 (2013); https://doi.org/10.1039/c3nj00102d
- D. Dey and M.K. Mahanti, Kinetics of Oxidation of Substituted Benzyl Alcohols by Quinolinium Dichromate, J. Org. Chem., 55, 5848 (1990); https://doi.org/10.1021/jo00310a015
- P.D. Sharma, P. Panchariya, P. Purohit and P.K. Sharma, Structure-Reactivity Correlation in the Oxidation of Substituted Benzyl Alcohols by Imidazolium Fluorochromate, Eur. Chem. Bull., 2, 816 (2013); https://doi.org/10.17628/ECB.2013.2.816
- T. Mallat and A. Baiker, Reactions in “sacrificial” solvents, Catal. Sci. Technol., 1, 1572 (2011); https://doi.org/10.1039/c1cy00207d
- E.V. Dehmlow and S.S. Dehmlow, Phase Transfer Catalysis, VCH, Weinheim: Germany (1993).
- Y. Sasson and R. Neumann, Handbook of Phase Transfer Catalysis, Kluwer Academic Publishers; Dordrecht (1993).
- C.M. Starks and C.L. Liotta, Phase-Transfer Catalysis, In: Fundamentals I.: Phase Transfer Catalysis, Principles and Techniques, Academic Press, New York (1978).
- M. Makosza, Phase-Transfer Catalysis. A General Green Methodology in Organic Synthesis, Pure Appl. Chem., 72, 1399 (2000); https://doi.org/10.1351/pac200072071399
- G. Ilia, S. Iliescu and A. Popa, Polymer-Supported Phase Transfer Catalysts in Green Organic Syntheses, Curr. Green Chem., 2, 264 (2015); https://doi.org/10.2174/2213346102999150306112846
- R.A. Jones, Quaternary Ammonium Salts, Their Use in Phase-Transfer Catalysed Reactions, Academic Press, New York (2001).
- S.E. Denmark, N.D. Gould, L.M. Wolf, Synthesis of Catalyst Libraries and Evaluation of Catalyst Activity, A Systematic Investigation of Quaternary Ammonium Ions as Asymmetric Phase-Transfer Catalysts. Synthesis of Catalyst Libraries and Evaluation of Catalyst Activity, J. Org. Chem., 76, 4260 (2011); https://doi.org/10.1021/jo2005445
- K.V. Ponmuthu, D. Kumaraguru, J.B. Arockiam, S. Velu, M. Sepperumal and S. Ayyanar, New Quaternary Phosphonium Salt as Multi-Site Phase-Transfer Catalyst for Various Alkylation Reactions, Res. Chem. Intermed., 42, 8345 (2016); https://doi.org/10.1007/s11164-016-2600-1
- D. Pletcher and S.J.D. Tait, The Oxidation of Alcohols and Aromatic Hydrocarbons by Dichromate in Two Phase Systems, J. Chem. Soc. Perkin Trans. 2, 788 (1978); https://doi.org/10.1039/P29790000788
- K. Bijudas and T.D. Radhakrishnan Nair, Selective Oxidation of Benzyl Alcohol with Monochromate in Non-polar Solvents, Indian J. Chem., 43A, 1216 (2004).
- D.C.M. Albanese, F. Foschi and M. Penso, Sustainable Oxidations under Phase-Transfer Catalysis Conditions, Org. Process Res. Dev., 20, 129 (2016); https://doi.org/10.1021/acs.oprd.5b00385
- A.C. Ranveer, S.V. Ranade and C.K. Mistry, Selective Oxidation of Lauryl Alcohol to Lauraldehyde under Liquid-Liquid Phase Transfer Catalysis (LL-PTC) with Potassium Chromate as the Oxidizing Agent, Iran. J. Chem. Chem. Eng., 37, 89 (2018).
- K. Bijudas, P. Bashpa, V.P. Bipin, L. Nair, A.P. Priya, M. Aswathi, C. Krishnendu and P. Lisha, Selective Synthesis of Benzaldehydes by Hypochlorite Oxidation of Benzyl Alcohols under Phase Transfer Catalysis, Bull. Chem. React. Eng. Catal., 10, 38 (2015); https://doi.org/10.9767/bcrec.10.1.7189.38-42
- A.N. Ajjou and A. Rahman, Green Organic Solvent-Free Oxidation of Alkylarenes with tert-Butyl Hydroperoxide Catalyzed by Water-Soluble Copper Complex, Open Chem., 18, 165 (2020); https://doi.org/10.1515/chem-2020-0018
- G.D. Yadav and B.V. Haldavanekar, Mechanistic and Kinetic Investigation of Liquid-Liquid Phase Transfer Catalyzed Oxidation of Benzyl Chloride to Benzaldehyde, J. Phys. Chem. A, 101, 36 (1997); https://doi.org/10.1021/jp961678x
- Q. Liu, M. Lu, F. Sun, J. Li and Y. Zhao, Oxidation of Benzyl Halides to Aldehydes and Ketones with Potassium Nitrate Catalyzed by Phase-Transfer Catalyst in Aqueous Media, Synth. Commun., 38, 4188 (2008); https://doi.org/10.1080/00397910802323080
- G.D. Yadav, P.H. Mehta and B.V. Haldavanekar, Capsule Membrane Phase Transfer Catalysis: Selective Alkaline Hydrolysis and Oxidation of Benzyl Chloride to Benzyl Alcohol and Benzaldehyde, Stud. Surf. Sci. Catal., 78, 503 (1993); https://doi.org/10.1016/S0167-2991(08)63359-5
- A.I. Vogel, Text Book of Practical Organic Chemistry, Longman: London (1967).
- D.D. Perrin, W.L. Armarego and D.R. Perrin, Purification of Organic Compounds, Oxford: Pergamon Press (1966).
References
K.B. Wiberg, Oxidation in Organic Chemistry, Academic Press: London and New York (1965).
S. Paterson, Alcohol oxidation: Reaction, Effects and Applications, Nova Science Publishers, Inc., New York (2018).
S. Dash, S. Patel and B.K. Mishra, Oxidation by Permanganate: Synthetic and Mechanistic Aspects, Tetrahedron, 65, 707 (2009); https://doi.org/10.1016/j.tet.2008.10.038
K. Bijudas, Kinetics and Mechanism of the Selective Oxidation of Benzyl Alcohols by Acidified Dichromate in Aqueous Acetic Acid Medium, Orient. J. Chem., 30, 1391 (2014); https://doi.org/10.13005/ojc/300360
Z. Hu, L. Ma, J. Xie, H. Du, W.W.Y. Lam and T.-C. Lau, Ruthenium-Catalyzed Oxidation of Alcohols by Bromate in Water, New J. Chem., 37, 1707 (2013); https://doi.org/10.1039/c3nj00102d
D. Dey and M.K. Mahanti, Kinetics of Oxidation of Substituted Benzyl Alcohols by Quinolinium Dichromate, J. Org. Chem., 55, 5848 (1990); https://doi.org/10.1021/jo00310a015
P.D. Sharma, P. Panchariya, P. Purohit and P.K. Sharma, Structure-Reactivity Correlation in the Oxidation of Substituted Benzyl Alcohols by Imidazolium Fluorochromate, Eur. Chem. Bull., 2, 816 (2013); https://doi.org/10.17628/ECB.2013.2.816
T. Mallat and A. Baiker, Reactions in “sacrificial” solvents, Catal. Sci. Technol., 1, 1572 (2011); https://doi.org/10.1039/c1cy00207d
E.V. Dehmlow and S.S. Dehmlow, Phase Transfer Catalysis, VCH, Weinheim: Germany (1993).
Y. Sasson and R. Neumann, Handbook of Phase Transfer Catalysis, Kluwer Academic Publishers; Dordrecht (1993).
C.M. Starks and C.L. Liotta, Phase-Transfer Catalysis, In: Fundamentals I.: Phase Transfer Catalysis, Principles and Techniques, Academic Press, New York (1978).
M. Makosza, Phase-Transfer Catalysis. A General Green Methodology in Organic Synthesis, Pure Appl. Chem., 72, 1399 (2000); https://doi.org/10.1351/pac200072071399
G. Ilia, S. Iliescu and A. Popa, Polymer-Supported Phase Transfer Catalysts in Green Organic Syntheses, Curr. Green Chem., 2, 264 (2015); https://doi.org/10.2174/2213346102999150306112846
R.A. Jones, Quaternary Ammonium Salts, Their Use in Phase-Transfer Catalysed Reactions, Academic Press, New York (2001).
S.E. Denmark, N.D. Gould, L.M. Wolf, Synthesis of Catalyst Libraries and Evaluation of Catalyst Activity, A Systematic Investigation of Quaternary Ammonium Ions as Asymmetric Phase-Transfer Catalysts. Synthesis of Catalyst Libraries and Evaluation of Catalyst Activity, J. Org. Chem., 76, 4260 (2011); https://doi.org/10.1021/jo2005445
K.V. Ponmuthu, D. Kumaraguru, J.B. Arockiam, S. Velu, M. Sepperumal and S. Ayyanar, New Quaternary Phosphonium Salt as Multi-Site Phase-Transfer Catalyst for Various Alkylation Reactions, Res. Chem. Intermed., 42, 8345 (2016); https://doi.org/10.1007/s11164-016-2600-1
D. Pletcher and S.J.D. Tait, The Oxidation of Alcohols and Aromatic Hydrocarbons by Dichromate in Two Phase Systems, J. Chem. Soc. Perkin Trans. 2, 788 (1978); https://doi.org/10.1039/P29790000788
K. Bijudas and T.D. Radhakrishnan Nair, Selective Oxidation of Benzyl Alcohol with Monochromate in Non-polar Solvents, Indian J. Chem., 43A, 1216 (2004).
D.C.M. Albanese, F. Foschi and M. Penso, Sustainable Oxidations under Phase-Transfer Catalysis Conditions, Org. Process Res. Dev., 20, 129 (2016); https://doi.org/10.1021/acs.oprd.5b00385
A.C. Ranveer, S.V. Ranade and C.K. Mistry, Selective Oxidation of Lauryl Alcohol to Lauraldehyde under Liquid-Liquid Phase Transfer Catalysis (LL-PTC) with Potassium Chromate as the Oxidizing Agent, Iran. J. Chem. Chem. Eng., 37, 89 (2018).
K. Bijudas, P. Bashpa, V.P. Bipin, L. Nair, A.P. Priya, M. Aswathi, C. Krishnendu and P. Lisha, Selective Synthesis of Benzaldehydes by Hypochlorite Oxidation of Benzyl Alcohols under Phase Transfer Catalysis, Bull. Chem. React. Eng. Catal., 10, 38 (2015); https://doi.org/10.9767/bcrec.10.1.7189.38-42
A.N. Ajjou and A. Rahman, Green Organic Solvent-Free Oxidation of Alkylarenes with tert-Butyl Hydroperoxide Catalyzed by Water-Soluble Copper Complex, Open Chem., 18, 165 (2020); https://doi.org/10.1515/chem-2020-0018
G.D. Yadav and B.V. Haldavanekar, Mechanistic and Kinetic Investigation of Liquid-Liquid Phase Transfer Catalyzed Oxidation of Benzyl Chloride to Benzaldehyde, J. Phys. Chem. A, 101, 36 (1997); https://doi.org/10.1021/jp961678x
Q. Liu, M. Lu, F. Sun, J. Li and Y. Zhao, Oxidation of Benzyl Halides to Aldehydes and Ketones with Potassium Nitrate Catalyzed by Phase-Transfer Catalyst in Aqueous Media, Synth. Commun., 38, 4188 (2008); https://doi.org/10.1080/00397910802323080
G.D. Yadav, P.H. Mehta and B.V. Haldavanekar, Capsule Membrane Phase Transfer Catalysis: Selective Alkaline Hydrolysis and Oxidation of Benzyl Chloride to Benzyl Alcohol and Benzaldehyde, Stud. Surf. Sci. Catal., 78, 503 (1993); https://doi.org/10.1016/S0167-2991(08)63359-5
A.I. Vogel, Text Book of Practical Organic Chemistry, Longman: London (1967).
D.D. Perrin, W.L. Armarego and D.R. Perrin, Purification of Organic Compounds, Oxford: Pergamon Press (1966).