C Srinivasan
Articles written in Journal of Chemical Sciences
Volume 93 Issue 2 March 1984 pp 157-164 Organic
C Srinivasan P Kuthalingam A Chellamani S Rajagopal N Arumugam
The kinetics of oxidation of
Volume 97 Issue 5-6 December 1986 pp 555-563 Organic
Mechanism of the oxidation of alkyl aryl and diphenyl sulphoxides by peroxomonosulphate
R Suthakaran P Subramaniam C Srinivasan
Detailed kinetic investigations of the oxidation of methyl phenyl sulphoxide and diphenyl sulphoxide by peroxomonosulphate in aqueous acetic acid medium reveal that the reactions are first-order, both in the sulphoxide and in the oxidant. Studies with substituted phenyl methyl sulphoxides and 4,4′-disubstituted diphenyl sulphoxides show that electron-releasing groups accelerate the rate of oxidation and electron-withdrawing groups retard it. A fair correlation between log k2 and Hammett substituent constants has been observed in the two series. The mechanism proposed involves the rate-determining nucleophilic attack of the sulphoxide sulphur at the outer terminal peroxo oxygen atom of HSO5−.
Volume 100 Issue 1 February 1988 pp 31-37 Organic
The kinetics of oxidation of ortho-substituted phenylmercaptoacetic acids by bromamine T and metaperiodate ion and also the
Volume 102 Issue 3 June 1990 pp 418-462
Abstracts of posters presented at the symposium
Bhaskar G Maiya S M S Chauhan P Bhyrappa V Krishnan P K Bhardwaj Sabyasachi Sarkar Krishna B Pandeya Pavan Mathur Akhil R Chakravarty Birinchi K Das Digambar V Behere Sandeep Modi Samaresh Mitra Sandeep Modi Digambar V Behere Samaresh Mitra Anil Saxena Sandeep Modi Digambar V Behere S Mitra Shyamalava Mazumdar Okhil K Medhi Samaresh Mitra Shyamalava Mazumdar Samaresh Mitra Anup Madan Sandeep Modi Anil Saxena Digamber V Behere S Mitra T Pandiyan M Palaniandavar K L Narayanan H Manohar R Ramaraj C C Thomas S Rajagopal T Rajendra C Srinivasan P Ramamurthy R Roy M C Saha S Panchanan P S Roy C Balagopalakrishna M V Rajasekharan B V Agarwala S Hingorani G A Nagena Gowda Y S Ramaswamy R Halesha N M N Gowda G K N Reddy G C Saxena K L Gupta P Srivastava V D Gupta M Ray R N Mukherjee R N Mohanty K C Dash Ramesh Kapoor S Yadav V Sood P Kapoor B N Anand R Bains Usha K Aggarwal P Garge R Chikate S Padhye J M Savariault P De Loth J P Tuchgues V K Jain M A Vaidya S C Jain S Kalyan Kumar Harkesh B Singh K M Mangaonkar D N Patkar N K Jha Pankaj Sharma S K Date C E Deshpande S D Sathaye S B Deshpande H S Potdar V S Darshane A C Dash R K Nanda N N Das S Gangopadhyay P Banerjee S K Kulshreshtha P S Zacharias N Arulsamy T Ramasami V Subramanian B U Nair M Kanthimathi G Sundararajan V Shivasubramanian R G Bhattacharya S Biswas J Armstrong E M Holt A P Koley
Volume 103 Issue 5 October 1991 pp 637-643 Organic
Mechanism of permanganate ion oxidation of diaryl sulphoxides — A kinetic study
S Rajagopal Geetha Sivasubramanian R Suthakaran C Srinivasan
The oxidation of 4,4′-disubstituted diphenyl sulphoxides by potassium permanganate on Hammett type correlations give a small positive ρ value (0.34). This is in contrast to the oxidation of aryl methyl sulphides (ρ = −1.36) by the permanganate ion. On the basis of rate data a mechanism of nucleophilic attack of MnO4− on the substrate has been proposed.
Volume 104 Issue 1 February 1992 pp 9-13 Inorganic and Analytical
G Allen Gnanaraj S Rajagopal C Srinivasan
The quenching rate constants,
Volume 104 Issue 1 February 1992 pp 67-76 Physical and Theoretical
Kinetics and mechanism of oxidation of N-substituted phenothiazines by chromium(VI)
K Pitchumani V Subramanian P P Jegatheesan C Srinivasan
The kinetics of oxidation of N-acetylphenothiazine (NAPT) by Cr(VI) in 80% acetic acid-20% water (v/v) mixture is first-order each in [NAPT] and [Cr(VI)]. The reaction is catalysed by added acid with a third-order dependence in [HCIO4], Increase in polarity of the solvent medium decreases the rate. The oxidation is insensitive to variations in ionic strength as well as added acrylamide. Oxidations of phenothiazine (PT) and N-methylphenothiazine (NMPT) under similar conditions are found to be very fast. However kinetic investigations with NMPT in an acetic acid-sodium acetate buffer show first-order dependence each in [NMPT] and [Cr(VI)] and a fractional-order dependence in [H+] in the pH range 1.80-3.09. Increase in polarity of the medium increases the rate. In both the cases, the corresponding sulphoxides are identified as oxidation products. Based on the kinetic results, mechanisms for oxidations are proposed.
Volume 104 Issue 4 August 1992 pp 525-532 Physical and Theoretical
R Ramaraja V Gomathi Sankareswari C Srinivasan
Montmorillonite-and cellulose-adsorbed 3,6-diaminoacridine are prepared. The adsorption isotherm studies show that while 3,6-diaminoacridine molecules are adsorbed in the interlayer spaces of the montmorillonite clay, the dye molecules are adsorbed on the surface of cellulose. Quenching studies reveal that the Al3+ ions of the aluminosilicate layers of the clay also quench the excited state emission of the adsorbed 3,6-diaminoacridine.
Volume 104 Issue 6 December 1992 pp 762-790
J Basu K K Rohatgi-Mukherjee S Chatterjee S Sarkar S N Bhattacharyya G K Dasmahapatra Thomas Wolff Gunther Von Bunau S N Dhawan Dipankar Sen Subhash Ch Bera S C Gupta N S Yadav Manabendra Sahu Manjubikash Saha V Masilamani D Sastikumar Pradipta Kumar Behera Ashok Kumar Mishra S Muthusamy V T Ramakrishnan P Ramamurthy S Sampath R Narayan M C Durai Manickam C Srinivasan K Pitchumani M Roja S Rajagopal Reba Ray Samaresh Mukherjee A Samanta E Natarajan S Selvaraj P Natarajan S S Talwar K Viswanathan P Natarajan Aruna Dhathathreyan K S Dhathathreyan Basanti Biswal Pill-Soon Song S Das M Muneer A Haridas V B Manilal R Jayakumar T Ramasami M Julliard M Chanon P N Joshi U C Biswal C L Joshy E Purushothaman Bhaskar G Maiya S Ganesan B Nagarajan V Narayanan Prasanna Mohanty V Shubin S D S Murthy N V Karapetyan R Ramaraj K V Gobi V Gomathi Sankareswari S Ranganayaki K Bahadur Sajal Kumar H R Sonawane D G Kulkarni N R Ayyangar N Sukumar T V Venkitachalam A S Rao S I Ali Harpal Kaur V Anbalagan T S Srivastava Awadhesh Kumar P K Chowdhury K V S Rama Rao J P Mittal N Balasubramanian S Balasubramanian G B Dutt S Doraiswamy Bidyut Kumar Manna K K Rohatgi-Mukherjee A Chandra B Bagchi S Arunachalam J R Devadason T Dhanasekaran K Joseph Prabahar Lizamma Mathew V Ramakrishnan J Rajaram V R S Rao P Narayanan V N Sivasankara Pillai K I Priyadarsini T Rajendran M Palaniandavar M Kaneko A Kira M S Sidhu Arti Chopra Barinder Gill Thomas Baby V P N Nampoori
Volume 106 Issue 3 June 1994 pp 645-653
Nonadiabaticity in the photoinduced electron transfer reactions of metal complexes
S Rajagopal C Srinivasan G Allen Gnanaraj
The rate of electron transfer (ET) in a variety of chemical and biological processes is influenced by factors like the free energy change (†G), the donor-acceptor electronic coupling and the medium. The effect of donor-acceptor electronic coupling on the rate of photoinduced intermolecular electron transfer is considered by taking Ru(II) and Cr(III) metal complexes in the excited state as electron acceptors and organic compounds as electron donors. The electronic coupling between the donor and acceptors depends strongly on donor-acceptor distance. The electron transfer distance is varied by introducing alkyl groups of different sizes either on the bipyridine ligand of the metal complex or on the quencher. The semiclassical theory of electron transfer expresses kET as the product of a nuclear and an electronic transmission coefficient (
Volume 115 Issue 4 August 2003 pp 273-280
Regioselective photoamination of 4-nitroveratrole upon cyclodextrin complexation
M C Durai Manickam K Pitchumani C Srinivasan
Photoamination of 4-nitroveratrole in cyclodextrins with the nucleophiles ammonia, methylamine and hexylamine provides a new route to regioselectivity. This method gives a displaced product para to the nitro group as the predominant product, in contrast to the solution reaction wherein the meta-displaced product predominates. This is due to the change in the mechanistic shift from
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