F* sin uat o pe Ceg 78 Ma 2 30 7-17 From Dara Pht ink 15,2200, yh. 2P-2. ‘iY pre 91 kos Ra CHEMICAL KINETICS ‘AND CATALYSIS Kinetics of Oxidation of Aniline, p-Aminobenzoic Acid, and p-Nitroaniline by 2,6-Dichloroquinone-4-Chloro-Imide! R. Venkata Nadh. B, Syama Sundar, and P, S, Radhakrishnamurti Department of Chemistry, Nagarjuna University, Nogarjunanagar, India Received January 25, 1999 Abstract—The kinetics of the oxidation of aniline, p-aminabenaoi acid, and p-nitroaniline by 2,6-dichloro- {quinone-4-chloro-imide was studied in aqueous acetic acid. The reaction was found o be consecutive: the first Stage was oxidation by HOCI (te hydrolytic product obtained from 2,6-diehloroquinone-4-chloro-imide), and the second stage was oxidation of aniline by 2,6-dichloroquinone. The reactions were found tobe first order in the oxidant and fist order in the substrate. The reaction was independent of (H"] in the range studied using HCIO, for p-aminobenzoic acid and p-ntvoanline. A slight inverse dependence on {H*] was observed with anlin, for which changes in pH resulie in reaction acceleration. The reactions were not susceptibleto changes. in pH as observed in the acetic acid-sodium acetate buffer media inthe case of p-aminobenzoic acid and ‘Paitroaniline, The primary products were the corresponding hydrazobenzenes, which finally yielded azoben- ‘ene, A suitable mechanism was postulated to explain the results, Recently, the kinetics of the oxidation of the thio- cyanate ion by 2,6-dichloroquinone-4-chloro-imide has been reported [1]. This communication deals with the oxidation of aniline, p-aminobenzoic acid, and 4 soaniline by this new oxidizing agent. EXPERIMENTAL 26-Dichloroquinone-4chloro-imide: a Fluka (purum grade) sample was used to make the stock solution in lacial acetic acid. Aniline, p-aminobenzoic acid, and prnitroaniline were recrystallized, All other chemicals, {cide solvents used in theae investigations were of ant: lytical reagent grade. Kinenic method: aliquots of the reaction mixture were analyzed by the iodometric method. The react ‘mixture containing 2,6-dichloroquinone-4-chloro-imide (5.0 mb) was pipetted out at various intervals of time into a mixture of a iodate-free potassium iodide solu- tion containing dilute sulphuric.acid (2 N) in a carbon dioxide atmosphere. The liberated iodine was titrated against the standard thiosulfate solution to the disep- pearance of the blue starch-iodine end point. RESULTS AND DISCUSSION ‘The following facts emerge from the kinetic data: The Aniline-2,6-Dichloroquinone-4-Chloro-Imide System (1)In 100% acetic acid, the reaction is exclusively the ‘oxidation of aniline by 2,6-dichloroquinone-4-chloro- "Fis aril was sobmited bythe authors in English imide, This implies tht the N halo compound dos not undergo hydrolysis in this medium and the reaction is ‘only oxidation of aniline by unhydrolyzed 2,6-dichloro- ‘quinone-4-chloro-imide. Boric acid does not accelerate the rate ofthe reaction. (2) In aqueous acetic acid, the reaction involves two steps: (a) oxidation of aniline by the product of hydrolysis ‘f 2,6-dichloroquinone-4-chloro-imide, whicti is HOCI; (©) concurrent oxidation of aniline by 2,6-dichloro- p-benzoguinone, the other hydrolytic product of 2,6- p-aminobenzoic acid > prnitroaniline, Tre plot of lope versus is vitualy linear, indica ing thatthe electron deactivating groups decrease reaction rate. It has been observed that, in 100% acetic ci, the oxidation of aniline by 2,6-dichloroquitone- ‘chioco-imide (A) itself occurs. = In the aqueous system, two processes occur: () oxidation of aniline by HOCI and (2) oxidation of aniline by 2,6-dichloroquinone. ‘The kinetic rates of the second reaction are dis- tinetly much lower than the kinetic rates ofthe first pro- cess of the oxidation of aniline and p-aminobenzoic acid. In the ease of p-nitroaniline, the reactions are Songly rerded. The frst oxidation stage rate slightly higher than the rate of.the second stage. The ‘tends are clear in all cases. But the degree ofa decrease inthe rate is much lesser in the case of p-nitroaniline. It ‘may be appropriate to say that, when the ebatae is ‘very much deactivated (6 being +0.778) as in the case of p-nitroanilin, the kinetic rates observed with HOCL ‘and 2,6-dichloroquinone do not clearly indicate the df= ferent cepa ofthe two diverse oxidizing species, namely, HOCI and 2,6-dichloro- though ib toads re cece With ane and pain: benzoic acid, the difference’ in the rates clearly brings ‘ut te diferent capacities ofthe two oxidizing species, the first step of oxidation by HOC! being faster than the second step of oxidation by 2,6-dichloro-p-benzo- «quinone (B). RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY Vel. 75, uNE 177 \ ‘Table 4. Oxidation of p-nitroailine by >/-dichloroquinone- a ona Mir'= a0" pat ou aa] ee coor | ca, [A oop 5 0.0005 M 47 1.00 oe 0.001 M. 1s 1.28 smu | ist | te retmaine | ons | an | oe cos | ur | to ne ze | tr | om 10% om 0.69 ~ oe | ao | ts wamenn | oa | ta | om com [aa | ox teapawe ae | ur | San Ere | eee eae oe woo, | oomsu | ose | az sons [-et_| es Eemnpaee ‘THE MECHANISM OF REACTION In a nof-aqueous medium: ° " ° a Dene WT ee: we oe Pe i78, \VENKATA NADH et al NH—HN OO In an aqueous medium: ° ° a cl a. 1 +H,0 == +HOCI, @ N-cl N-H Le. (exobenzene) mo Our o* 1 5 ont ° 9 a. 1 cl cl +0 == +N, se a we) NH + HX — NHAX, Ni nu? © CobLgNH + CHE, BE HN - NHC Hy +H CaHNH-NHCQHs HOS Cyt N=NC Hy, (azobenzene) ae OH 0, © on @ QO + CeHaNH® + Cqttrl, = coerce) %, (CaHGNH-NHC Hy —— 2 on CHEN=NCAy, ‘The side reaction that occurs in the aqueous system is as follows: “fro Qa ein 8 ° oe Om o: ee NH, ‘The above mechanistic sequences explain the for- mation of products both in aqueous and non-aqueous media. The reaction route involves electron transfer at the rate-determining step giving RNH*, which, at the fat age, ves hydrazohenzene, Finally ben- zene is converted into azobenzene atthe final stage. The ‘bed p value of ~3.25 is evidence for such a rate- dete.inining step invoiving an ionic path is. This nega- tive p value suggests that the electron. withdrawing groups retard the process. REFERENCES 1. Neeraj, V. Venkata Nadh, R., Syama Sundar, B. Radhakishnamur, PS, Oxdn, Commun, (in press). (ndosnitine) 2 Scudi, 1.V,, Bastedo, W.A., and Webb, TJ. Chem., 1940, vol. 136, p. 399. 3, Robinson, MT. J: Phys. Chem., 1957, vol 60, p. 120. 4, Pausacker, K.H. and Riggs, N.V. J. Chem. Soc, 1953, 1p. 1989; 1984, p.3122. 5, Pausacker, KH. and Scroggie, .G.,J. Chem. Soc, 1954, 4003. 6, Radhakrishnamurt, PS. and Prasada Rao, M.D, Indian J.Chem, Sect. B, 1976, vol. 14, p. 790. 7. Radhakrishnamurt, PS. and Pati, S.N., Indian J. Chem, Sect. A: Inog., Bio-inorg., Phys, Theor. Anal. Chem, 1980, vol. 19, p. 980, 1. Biol. RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY* Vol. 75 No.2 2001 ' i I