An Efficient and Mild Procedure for the Preparation of Aldonic Acids via Oxidation of D-Sucrose by Employing N-Bromophthalimide Oxidant and Micellar System

Y. Katre; M. Singh; A. K. Singh

doi:10.3139/113.110107

Published by De Gruyter April 5, 2013

An Efficient and Mild Procedure for the Preparation of Aldonic Acids via Oxidation of D-Sucrose by Employing N-Bromophthalimide Oxidant and Micellar System

Ein effizientes und mildes Verfahren zur Herstellung von Aldonsäuren durch Oxidation von Saccharose unter Verwendung von N-Bromphthalimid und micellaren Systemen

Y. Katre , M. Singh and A. K. Singh

From the journal Tenside Surfactants Detergents

https://doi.org/10.3139/113.110107

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Abstract

The oxidation reactions of D-sucrose have been carried out with N-bromophthalimide in the presence of micellar aggregates at 45°C. The kinetics revealed first order dependence on N-bromophthalimide (NBP) and fractional order dependence on D-sucrose. Variation of mercuric acetate concentration has an insignificant effect on reaction rate. The stoichiometric ratio of NBP:D-sucrose was 1:2 and the oxidation product was aldonic acid confirmed by FeCl₃–HCl test. The influence of salts on the reaction rate has also been studied. Phthalimide (NHP) and sulfuric acid (H₂SO₄) inhibit the rate. Thermodynamic and activation parameters have been evaluated and a mechanism consistent with the kinetic data has been proposed. Cetyltrimethylammonium bromide (CTAB) and TritonX-100 (TX-100) catalyze the reaction, while sodium dodecyl sulfate (SDS) inhibits the rate of reaction. The applicability of Berezin's model was tested to explain the observed micellar effects. The rate constants (k_M) and binding constants (K_S + K_O) have been evaluated.

Kurzfassung

Die Oxidationsreaktion von Saccharose wurde mit N-Bromphthalimid in Anwesenheit von micellaren Aggregaten bei 45°C durchgeführt. Die Kinetik zeigte ein Verhalten 1. Ordnung von N-Bromphthalimid (NBP) und eine gebrochene Ordnung von Saccharose. Die Veränderung der Quecksilberacetatkonzentration hat einen unwesentlichen Einfluss auf die Reaktionsrate. Das stöchometrische Verhältnis von NBP:Saccharose war 1:2. Das Oxidationsprodukt Aldonsäure wurde durch den FeCl₃–HCl-Test bestätigt. Der Einfluss von Salzen auf die Reaktionsgeschwindigkeit wurde ebenfalls untersucht. Phthalimid (NHP) und Schwefelsäure hemmen die Reaktionsgeschwindigkeit. Die Thermodynamik- und die Aktivierungsparameter wurden ermittelt und ein Mechanismus für eine konsistente Deutung der Daten vorgeschlagen. Cetyltrimethylammoniumbromid (CTAB) und TritonX-100 (TX-100) beschleunigen die Reaktion, während Natriumdodecylsulfat (SDS) die Reaktionsgeschwindigkeit verringert. Die Anwendbarkeit des Berezin Modells für die Erklärung der mizellaren Effekte wurde geprüft. Die Geschwindigkeitskonstante k_M und die Bindungskonstanten (K_S + K_O) wurden ermittelt.

Key words:: Micellar catalysis; critical micellar concentration; kinetics; D-sucrose; Berezin's model

Stichwörter:: Mizellare Katalyse; kritische Mizellkonzentration; Kinetik; D-Sucrose; Berezin-Model

^∗ Dr. Yokraj Katre, Department of Chemistry, Kalyan Post Graduate College, Bhilai Nagar, Durg, (C.G.) – 490006, India, Tel.: 0788-2391124, 91-98261-89766, Fax: 0788-2226338. E-Mail: yokrajkatre@gmail.com

Dr. Yokraj Katre received his M. Sc. in 1977 from Sagar University, India, and his M. Phil. in 1985 and Ph.D. in 1988 from Vikram University, Ujjain, India, under the guidance of Dr. S. K. Solanki. He participated in 8th International conference of Surfactants and presented a paper at the University of Florida, Gainesville, in 1990. He has been an assistant professor of chemistry in Kalyan P. G. College, Bhilai, since 1978. He continues his research related to micellar kinetics. He has completed three research projects (two UGC and one CCOST). He has attended 233^rd ACS conference in Chicago in 2007, attended 12^th Asian Chemical Congress in Kuala Lumpur, Maleysia in 2007. He has published more than 36 research papers in different international journals. Under his guidance four students have been awarded their Ph. D. degree. At present he is Prof. & Head, Department of Chemistry, Kalyan Post Graduate College, Bhilai, C. G., INDIA.

Miss Minu Singh received her M. Sc. in organic chemistry in 2006 from Bhilai Mahila Mahavidyalaya, Bhilai, India. She has completed her Ph. D. from Kalyan Post Graduate College, Bhilai, India, in the area of micellar oxidation kinetics, under the supervision of Dr. Y. R. Katre. She has published six research papers in different international journals. At present she is assistant professor in Kalyan Post Graduate College, Bhilai, C. G., INDIA.

Dr. Ajaya Kumar Singh received his M. Sc. In inorganic chemistry from Poorvanchal University, Jaunpur, India, and his D. Phil. in physical chemistry in 2002 from the University of Allahabad, India, under the supervision of Dr. Ashok Kumar Singh. He was selected as an assistant professor of chemistry at Government Science College, Mungeli, Bilaspur, through M. P. Public Service Commission, Indore in 1994. He was awarded a Teacher Research Fellowship to complete his research work in 2000–2002. He is currently associate professor of chemistry at Government V. Y. T. P. G. Autonomous College, Durg, India, where he continues his research work, which is mainly related to transition metal ion-catalyzed oxidation kinetics as well as micellar oxidation kinetics. He is the author of more than 35 papers related to this field. Two students awarded their Ph. D. degree under his guidance.

References

1. Sala, L. F., Cirelli, A. and Lederkremer, R.: J. Chem. Soc. Perkin Trans.2 (1977) 685.Search in Google Scholar

2. Gupta, M., Saha, S. and Banerjee, P.: J. Chem. Soc. Perkin Trans.2 (1988) 1781.Search in Google Scholar

3. (a) Sala, L. F., Signorella, S. R., Rizzotto, M., Frascaroli, M. I. and Gandolfo, F.: Can. J. Chem.70 (1992) 2046. (b) Signorella, S. R., Rizzotto, M., Daier, V., Frascaroli, M. I., Palopoli, C., Martino, D., Bousseksou A. and Sala, L. F.: J. Chem. Soc. Dalton Trans. 1607 (1996). 10.1139/v92-258Search in Google Scholar

4. Pottenger, C. R. and Johnson, D. C.: J. Polym. Sci. Part A8 (1968) 301.Search in Google Scholar

5. Singh, S. V., Saxena, O. C. and Singh, M. P.: J. Am. Chem. Soc.92 (1970) 537. 10.1021/ja00706a020Search in Google Scholar

6. Isbell, H. S. and Frush, H. L.: Carbohydr. Res.28 (1973) 295. 10.1016/S0008-6215(00)82784-6Search in Google Scholar

7. Mehrotra, R. N. and Amis, E. S.: J. Org. Chem.39 (1974) 1788. 10.1021/jo00925a053Search in Google Scholar

8. Sen Gupta, K. K., Sen Gupta, S. and Basu, S. N.: Carbohydr. Res.71 (1979) 75. 10.1016/S0008-6215(00)86062-0Search in Google Scholar

9. (a) Sen Gupta, K. K. and Basu, S. N.: Carbohydr. Res.72 (1979) 139. (b) Sen Gupta, K. K. and Basu, S. N.,: Carbohydr. Res. 80 (1980) 223. (c) Sen Gupta, K. K. and Basu, S. N.,: Carbohydr. Res. 86 (1980) 7. 10.1016/S0008-6215(00)83929-4Search in Google Scholar

10. Sen Gupta, K. K., Basu, S. N. and Sen Gupta, S.: Carbohydr. Res.97 (1981) 1. 10.1016/S0008-6215(00)80520-0Search in Google Scholar

11. Virtanen, P. O. I. and Kurkisuo, S.: Carbohydr. Res.138 (1985) 215. 10.1016/0008-6215(85)85105-3Search in Google Scholar

12. Gennis, R. B.: Biomembranes. Molecular Structure and Function, Springer-Verlag, New York, 1989, p. 20.10.1007/978-1-4757-2065-5Search in Google Scholar

13. Darnell, J., Lodish, H. and Baltimore, D.: Molecular Cell Biology, Scientific American Books. New York, 1990, p. 491.Search in Google Scholar

14. Alberts, B., Bray, D., Lewis, J., Raff, M., Roberts, K. and Watson, J. D.: Molecular Biology of the Cell, Garland Publishing. New York, 1994, p. 477.Search in Google Scholar

15. Fendler, J. H.: Membrane Mimetic Chemistry, Wiley, New York, 1982.Search in Google Scholar

16. Buurma, N. J., Serena, P., Blandamer, M. J. and Engberts, J. B. F. N.: J. Org. Chem.69 (2004) 3899. 10.1021/jo049959lSearch in Google Scholar PubMed

17. Khazaei, A. and Ghorbani-Vaghei, R.: Tetrahedron Lett.44 (2003) 7525. 10.1016/j.tetlet.2003.08.003Search in Google Scholar

18. Khazaei, A. and Ghorbani-Vaghei, R.: Tetrahedron Lett.43 (2002) 3073. 10.1016/S0040-4039(02)00344-1Search in Google Scholar

19. Khazaei, A., Zolfigol, M. A. and Rostami, A.: Synthesis2959 (2004).10.1055/s-2004-834919Search in Google Scholar

20. Khazaei, A., Ghorbani-Vaghei, R. and Tajbakhsh, M.: Tetrahedron Lett.42 (2001) 5099. 10.1016/S0040-4039(01)00897-8Search in Google Scholar

21. Azarifar, D., Zolfigol, M. A. and Maleki, B.: Synthesis1744 (2004).Search in Google Scholar

22. Zolfigol, M. A., Ghaemi, E., Madrakian, E. and Choghamarani, A. G.: Mendeleev Commun.16(1) (2006) 41. 10.1070/MC2006v016n01ABEH002116Search in Google Scholar

23. Ramachandrappa, R., Puttswamy, Mayanna S. M. and Gowda, N. M. M.: Int. J. Chem. Kinet.30 (6) (1997) 407. 10.1002/(SICI)1097-4601(1998)30:6<407::AID-KIN2>3.0.CO;2-WSearch in Google Scholar

24. Park, M.-S. and Choi, C.-U.: Arch. Pharmacal Res.16 (2) (1993) 152. 10.1007/BF03036864Search in Google Scholar

25. Sengupta, P. K. and Pramanik, A. R.: Eur. Polym. J.30 (4) (1994) 421. 10.1016/0014-3057(94)90038-8Search in Google Scholar

26. El-Brashy, A., Belal, F., Walash, M. I. and Rizk, M.: Pharmacy World Sci. 10(2) (1988) 90.Search in Google Scholar

27. Barakat, M. Z. and Abdel-Wahab, M. F.: Anal. Chem.26 (1954) 1973. 10.1021/ac60096a035Search in Google Scholar

28. (a) Sengupta, K. K., Begum, B. A. and Pal, B. B.: Carbohydr. Res.309 (1998) 303. (b) Abdel-Akher, M. and Smith, F.,: J. Am. Chem. Soc. 73 (1951) 5859. 10.1016/S0008-6215(98)00136-0Search in Google Scholar

29. Kumar, A. and Mehrotra, R. N.: J. Org. Chem.40 (1975) 1248. 10.1021/jo00897a014Search in Google Scholar

30. Sengupta, K. K., Begum, B. A. and Pal, B. B.: Carbohydr. Res.315 (1999) 70. 10.1016/S0008-6215(98)00329-2Search in Google Scholar

31. Sala, L. F., Signorella, S. R., Rizotto, M., Frascaroli, M. I. and Gondolfo, F.: Can. J. Chem.70 (1992) 2046. 10.1139/v92-258Search in Google Scholar

32. Feigl, F.: Spot Tests in Organic Analysis, 5^th edn., Elsevier publishing Co.; Amsterdam, 1956, p. 358.Search in Google Scholar

33. Cordes, E. H.: Pure & Appl. Chem.50 (1978) 617. 10.1351/pac197850070617Search in Google Scholar

34. Pramauro, E. and Prevot, A. B.: Pure & Appl. Chem.67 (1995) 551. 10.1351/pac199567040551Search in Google Scholar

35. Sokolowski, A., Kazimiera, A. W., Urszula, K., Rutkowski, B. and Syper, L.: Physicochem. Problems Mineral Processing36 (2002) 51.Search in Google Scholar

36. Huibers, P. D. T., Lobanov, V. S., Katritzky, A. R., Shah, D. O. and Karelson, M.: J. Colloid. Interf. Sci.187 (1997) 113. 10.1006/jcis.1996.4680Search in Google Scholar PubMed

37. Mukherjee, P. and Mysels, K. J.: Critical Micelle Concentration of Aqueous Surfactant Systems; NSRDS-NBS36; Superintendent of Documents. Washington, DC, 1971.10.6028/NBS.NSRDS.36Search in Google Scholar

38. Amis, E. S.: Solvent effects on reaction rates and mechanism; Eds.,: Academic Press. New York, NY, 1966.Search in Google Scholar

39. Ray, A. and Nemethy, G.: J. Am. Chem. Soc.93 (1971) 6787. 10.1021/ja00754a014Search in Google Scholar PubMed

40. Perlin, A. S.: Can. J. Chem.42 (1964) 2365. 10.1139/v64-348Search in Google Scholar

41. Jabber, S. F. A. and Rao, V. S.: Ind. J. Chem.33A (1994) 69.Search in Google Scholar

42. Berezin, I. V., Martinek, K. and Yatsimirskii, A. K.: Russ. Chem. Rev. (Engl. Transl.)42 (1973) 787. 10.1070/RC1973v042n10ABEH002744Search in Google Scholar

Received: 2010-02-10

Published Online: 2013-04-05

Published in Print: 2011-01-01

An Efficient and Mild Procedure for the Preparation of Aldonic Acids via Oxidation of D-Sucrose by Employing N-Bromophthalimide Oxidant and Micellar System

Abstract

Kurzfassung

References

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