Mechanistic and Catalytic Behavior of Os for the Chlorpheniramine Maleate and Bromamine-B Redox System
Abstract
Chlorpheniramine maleate (CPM) is an important antihistamine agent. To the best of our knowledge there is no report in the literature about the oxidation of CPM with halogen + 1 oxidant from the stand point of its kinetics and mechanistic chemistry. Hence, a systematic kinetics and mechanistic study on the oxidation of CPM with bromamine-B (BAB) in the presence of NaOH and Os(VIII) catalyst has been carried out at 303 K. The reaction exhibits a first-order dependence of rate on [BAB]o and [Os(VIII)]. The order with respect to [CPM]o is zero, whereas it is fractional on [NaOH]. Activation parameters were evaluated. The stoichiometry of the reaction is 1:1 and the oxidation products were identified as (4- chlorophenyl)(pyridine-2-yl)methanol and 2-(dimethylamino)acetaldehyde from GC-MS analysis. The Os(VIII) catalyzed reaction is about four-fold faster than the uncatalyzed reaction. Based on the experimental results, possible reaction mechanism and kinetic model have been proposed. Keywords: chlorpheniramine maleate, bromamine-B, oxidation-kinetics, Os(VIII) catalysis, mechanismReferences
British Pharmacopoeia. 1980; 1: 105p.
Celma C., Allue J.A., Prunonosa J., et
al. Simultaneous determination of
paracetamol and chlorpheniramine in
human plasma by liquid
chromatography–tandem mass
spectrometry, J Chromatogr A. 2000;
(1): 77–86p.
Fried K.M., Young A.E., Usdin Yasuda
S., et al. The enantioselective
determination of chlorpheniramine and
its major metabolites in human plasma
using chiral chromatography on a βcyclodextrin
chiral stationary phase and
Mechanistic and Catalytic Behavior of Os Singh
IJEM (2016) 14-29 © JournalsPub 2016. All Rights Reserved Page 28
mass spectrometric detection, J Pharm
Biomed Anal. 2002; 27(3): 479–88p.
Song H., Zhang Z., Wang F.
Electrochemiluminescent determination
of chlorphenamine maleate based on Ru
(bpy)2+
immobilized in a
nano‐titania/nafion membrane.
Electroanalysis. 2006; 18(18): 1838–
p.
Samadi-Maybodi A., Nejad-Darzi
S.K.H., Ilkhani H. A new sensor for
determination of paracetamol,
phenylephrine hydrochloride and
chlorpheniramine maleate in
pharmaceutical samples using nickel
phosphate nanoparticles modified
carbon past electrode, Anal Bioanal
Electrochem. 2011; 3(2): 134–45p.
Savanur A.P., Lamani S.D.,
Nandibewoor S.T., et al. Mechanistic
investigations of uncatalysed and
Os(VIII) catalysed oxidation of
chloropheniramine an antihistamine
drug by diperiodatoargentate (III)
complex in aqueous alkaline medium: a
comparative kinetic approach, J Chem
Pharm Res. 2011; 3(6): 1061–88p.
Khudaish E.A., Al-Hinaai M., AlHarthy
S., et al. Electrochemical
oxidation of chlorpheniramine at
polytryamine film doped with
ruthenium (II) complex: measurement,
kinetic and thermodynamic studies,
Electrcochim Acta. 2014; 135: 319–
p.
Campbell M.M., Johnson G.
Chloramine T and related N-halogenoN-metallo
reagents, Chem Rev. 1978;
(1); 65–87p.
Banerji K.K., Jayaram B.,
Mahadevappa D.S. Mechanistic aspects
of oxidations by N-metallo-Nhaloarylsulphonamides,
J Sci Ind Res.
; 46(2); 65–76p.
Armesto X.L., García M.V., Santaballa
J.A. Aqueous chemistry of N-halocompounds,
Chem Soc Rev. 1998;
(6): 453–60p.
Kolvari E., Ghorbani-Choghamarani
A., Salehi P., et al. Application of Nhalo
reagents in organic synthesis, J
Iran Chem Soc. 2007; 4(2); 126–74p.
Jagadeesh R.V., Puttaswamy.
Chloramine-T, Second Update; -
Electronic Encyclopedia of Reagents
for Organic Synthesis. John Wiley &
Sons Ltd. http:/Onlinelibrary. 2013.
Puttaswamy Mahadevappa D.S.,
Rangappa K.S. Oxidation of indigo
carmine by N-haloarenesulfonamidates:
a kinetic study, Bull Chem Soc Jpn.
; 62(10), 3343–48p.
Nirmala V., Vinod K.N., Puttaswamy.
Os (VIII)-Catalyzed oxidation of some
aliphatic ketones by sodium Nchlorobenzenesulfonamide
(Chloramine-B) in the presence of
sodium hydroxide: kinetic mechanistic
chemistry, Synth React Inorg Met-Org
Nano-Met Chem. 2011; 41(6); 644–
p.
Puttaswamy, Jagadeesh R.V.
Ruthenium(III)-catalyzed mechanistic
investigation of oxidation of an azo dye
by sodium N-haloarenesulfonamidates
in acid medium: a comparative
spectrophotometric kinetic study, Appl
Catal A: Gen. 2005; 292: 259–71p.
Ananda S., Demappa T., Made Gowda
N.M. Oxidation of primary amines by
bromamine-B catalyzed by
Osmium(VIII) in alkaline medium: a
kinetic and mechanistic study, Int J
Chem Kinetics. 1997; 29: 737–44p.
Puttaswamy, Nirmala V. Kinetics and
mechanism of Ruthenium (III) and
Osmium (VIII) catalyzed oxidation of
dopamine with bromamine-B in acid
and alkaline media, Stud Surf Sci Catal.
; 133: 535–40p.
Puttaswamy, Sukhdev A., Shubha J.P.
Palladium (II)-catalyzed oxidation of
tranexamic acid by bromamine-B in
alkaline medium and uncatalyzed
reaction in acid medium: A study of
kinetic and mechanistic chemistry, J
Mol Catal A: Chem. 2010; 332(1): 113–
p.
Kamble D.L., Nandibewoor S.T.
Osmium (VIII)/ruthenium (III) catalysis
of periodate oxidation of acetaldehyde
in aqueous alkaline medium, J Phys
Org Chem. 1998; 11(3): 171–6p.
Jagadeesh R.V., Puttaswamy. Ru (III),
Os (VIII), Pd (II) and Pt (IV) catalysed
oxidation of glycyl–glycine by sodium
N‐chloro‐p‐toluenesulfonamide:
comparative mechanistic aspects and
kinetic modelling, J Phys Org Chem.
; 21(10): 844–58p.
Rani D.G., Pushparaj F.J.M., Alphonse
I., et al. Kinetics and mechanism of
oxidation of 4-oxoacids by
hexacyanoferrate (III) catalysed by Os
(VIII), Indian J Chem, Sect B. 2002;
(10): 2153–59p.
Puttaswamy, Nirmala V. Ruthenium
(III)-and osmium (VIII)-catalyzed
oxidation of 2-thiouracil by
bromamine-B in acid and alkaline
media: a kinetic and mechanistic study,
Transition Met Chem. 2003; 28(4):
–17p.
Vinod K.N., Puttaswamy, Ninge
Gowda K.N. Mechanistic aspects for
the oxidation of sunset yellow dye by
chloramine-T in presence of perchloric
acid and in sodium hydroxide medium
catalyzed by Os (VIII): a
spectrophotometric kinetic approach,
Inorg Chim Acta. 2009; 362(6): 2044–
p.
Mahadevappa D.S., Ahmed M.S.
Dibromamine-B as a new redox titrant
in non-aqueous or partially aqueous
media, Talanta.1979; 26(7): 590–97p.
Morris J.C., Salazar J.A., Wineman
M.A. Equilibrium studies on N-chloro
compounds. I. The ionization constant
of N-chloro-p-toluenesulfonamide1, J
Am Chem Soc. 1948; 70(6): 2036–41p.
Akerlof G. Dielectric constants of some
organic solvent-water mixtures at
various temperatures, J Am Chem Soc.
; 54(11): 4125–30p.
Bishop E., Jennings V.J. Titrimetric
analysis with chloramine-T-I: the status
of chloramine-T as a titrimetric reagent,
Talanta. 1958; 1(3): 197–99p.
Murthy A.R.V., Rao B.S. Oxidation of
chloramine-T. Part-II. Redox potential
of chloramine-T-sulfonamide system,
Proc Indian Acad Sci. 1952; 35, 69–
p.
Hardy F.F., Johnston J.P. The
interaction of N-bromo-Nsodiobenzenesulphonamide
(bromamine B) with p-nitrophenoxide
ion, J Chem Soc, Perkin Trans 2. 1973;
: 742–46p.
Higuchi T., Hussain A. Mechanism of
chlorination of cresol by chloramine-T.
Mediation by dichloramine-T, J Chem
Soc B: Phys Org. 1967; 549–52p.
Griffith W.P. The Chemistry of Rare
Platinum Metals. New York:
Interscience; 1967.
Mackay K.M. Introduction to Modern
Inorganic Chemistry. 4th Edn. PrenticeHall,
Englewood Cliffs, New Jersey;
Cotton F.A., Wilkinson G., Gaus P.L.
Transition elements, Basic Inorg Chem.
Mayell J.S. Oxidation of olefins by
ferricyanide using osmium tetroxide
catalyst, Ind Eng Chem Prod Res Dev.
; 7(2): 129–36p.
Laidler K.J. Chemical Kinetics. New
Delhi: Tata McGraw Hill; 1995.
Benson S.W. The Foundations of
Chemical Kinetics. New York: McGraw
Hill; 1960.
Frost A.A., Pearson R.G. Kinetics and
Mechanism. 2nd Edn, New York:
Wiley; 1961.
Laidler K.J., Eyring H. The effect of
solvents on reaction rates, Ann N Y
Acad Sci. 1940; 39(1): 303–6p.
Amis E.S. Solvent Effects on Reaction
Rates and Mechanisms. NewYork:
Academic Press; 1966.
Reihardt C. Solvent and Solvent Effects
in Organic Chemistry. 3rd Edn. New
York: Wiley; 2003.
