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Mechanistic and Catalytic Behavior of Os for the Chlorpheniramine Maleate and Bromamine-B Redox System

Sonal Singh

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, mechanism

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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.


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