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`PERGAMON PRESS
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`e!)
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`M. M. HIRSCHLER
`Translation Editor
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`A. K. HENN AND I. G. EVANS
`
`Translators
`
`N. M. Emanuel, G. E. Zaikov and Z. K. Maizus
`
`Academy of Sciences of the USSR, Moscow
`
`by
`
`Medium Effects in Radical Reactions
`
`Oxidation of Organic Compounds
`
`any Pergamon journal available on request from your nearest Pergamon office.
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`SENJU EXHIBIT 2120
`INNOPHARMA v. SENJU
`IPR2015-00903
`
`

`
`v
`
`Printed in Great Britain by A. Wheaton & Co. Ltd .. Exeter
`
`logists employed in chemical works and in technical laboratories dealing with
`
`It will also be of interest to engineers and engineering techno(cid:173)
`
`compounds.
`
`field of radical reactions and in particular in the oxidation of organic
`
`The monograph is intended for scientific research workers specialising in the
`
`problems of oxidation processes.
`
`products formed.
`
`valuable oxygen-containing compounds and lowering the amount of secondary
`
`In this manner the reaction may be regulated, increasing the yield of
`
`ted.
`
`of the medium on the rate and course of the oxidation process can be predic(cid:173)
`
`tary reactions (including chain-propagation and termination), the influence
`
`pate. On the basis of a knowledge of the influence of the medium on elemen(cid:173)
`
`on a series of radical reactions, in which stable and alkyl radicals partici(cid:173)
`
`relating to the influence of the medium
`
`Problems are examined
`
`reactions,
`
`of the medium in chain-initiation, branching, propagation and termination
`
`compounds. To begin with, data are gathered and collated, relating to the role
`
`phase states in radical-chain processes involved in the oxidation of organic
`
`This monograph deals with the role of solvents and of the composition of
`
`Preface
`
`First edition 1984
`without permission in writing from the publishers.
`tape, mechanical, photocopying, recording or otherwise,
`form or by any means: electronic, electrostatic, magnetic
`reproduced, stored in a retrieval system or transmitted in any
`All Rights Reserved. No part of this publication may be
`Copyright © 1984 Pergamon Press Ltd.
`
`. )
`
`( 2 1 JUN
`
`~-.
`-----
`
`ISBN 0-08-022067-3
`547' .23
`Ill. Maizus, Z K
`I. Title II. Zaikov, G E
`2. Chemistry, Organic
`1. Oxidation
`Oxidation of organic compounds.
`Emanuel, Nickolai Markovich
`British Library Cataloguing in Publication Data
`
`80-40511
`
`00281.09
`
`D-6242 Kronberg-Taunus, Federal Republic of Germany
`Pergamon Press GmbH, Hammerweg 6,
`
`OF GERMANY
`FEDERAL REPUBLIC
`
`7524() Paris, Cedex 05, France
`Pergamon Press SARL, 24 rue des Ecoles,
`Potts Point, N.S.W. 2011, Australia
`Pergamon Press !Aust.) Pty. Ltd., P.O. Box 544,
`
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`Pergamon Press Canada Ltd., Suite 104,
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`Elmsford, New York 10523, U.S.A.
`Pergamon Press Inc., Maxwell House, Fairview Park,
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`Oxford OX3 OBW, England
`Pergamon Press Ltd., Headington Hill Hall,
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`U.K.
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`Page 2 of 8
`
`

`
`itself does not affect the oxidation reaction).
`
`bicarbonate solution is acidified with perchloric acid (perchloric acid
`
`the reaction, since the inhibitory effect is eliminated if the sodium
`
`It has been shown that it is the bicarbonate ion which in fact inhibits
`
`(*)
`
`(6.43)
`
`x'
`
`+
`
`~OOH
`c
`
`/
`
`HX ___ .... ~ /OH
`
`+
`
`/"'o-o·
`
`~ /OH
`
`a reducing agent and take part in reactions as follows :
`
`cals consists in the fact(68) that it can act both as an oxidising agent and
`The difference between the a-hydroxyl peroxyl radical and other peroxyl radi(cid:173)
`
`concentration of ions in the solution remains unchanged; hence such a
`
`(Fig, 102), Measurements of the electrical conductance have shown that the
`
`rate of inhibition of the reaction remains constant during the experiment
`
`cyclohexanol, reduces the rate of oxidation at 75°C by a factor of 3. The
`
`mol-l i in the oxidation of
`
`5
`
`Thus, sodium bicarbonate introduced at 4 x 10-
`
`by the bicarbonate ion on the radical chain process involved in the oxidation
`
`of cyclohexanol,
`
`of a negat1ve catalyt1c effect
`
`.
`
`.
`
`(67 68)
`
`'
`
`In part~cula~ examples exist
`
`.
`
`compounds,
`
`and also inhibit radical chain processes of oxidation of a number of organic
`
`It is now evident that ions can participate in chain-propagation reactions
`
`influence the mode of homolytic decomposition of a hydroperoxide.
`
`rolytic decomposition of ROOH and only recently was it shown that they could
`
`hydroperoxides: it had been observed as a rule that ions influence the hete(cid:173)
`
`introduced (Table 79).
`
`r8le of ions consisted in changing the rates and mode of decomposition of
`
`radical is formed and no inhibition is observed when bicarbonate ions are
`
`/ ~o-o'
`"" /H
`
`c
`
`is oxidised, a
`
`12
`
`a
`6
`
`When c
`
`/~oo·
`~/OH
`
`c
`
`hydroxy-peroxyl radicals
`
`oxidation in aqueous solutions of electrolyte (acids, alkalis, salts) the
`
`cently, it was assumed (see Chapter 5) that when organic compounds undergo
`in the presence of solvents has not been very widely investigated, Until re(cid:173)
`
`reactions in the radical chain processes of the oxidation of organic compounds
`
`may take place in solvents with high dielectric constants. The r8le of ionic
`
`which was not tackled was the possible occurrence of other processes which
`
`In doing this, however, a problem
`
`tions of this chapter and in Chapter 5.
`
`chain-propagation and chain-termination was examined in the preceding sec-
`
`constants of the reactiops and on the mechanism of the elementary steps of
`
`The influence of both specific solvation and unspecific solvation on the rate
`
`THE ROLE OF IONIC REACTIONS IN THE ELEMENTARY PROCESSES OF
`
`6.7
`
`CHAIN-PROPAGATION AND CHAIN-TERMINATION
`
`Inhibition of oxidation by bicarbonate ions is observed only in the case of
`
`consumed(*).
`
`0.1
`
`1.3 ±
`
`1.1 ± 0.1
`1.4 ± 0,1
`
`0.1
`
`1.3
`
`1. 5 ± 0.11
`
`the substance (negative catalyst) which terminates the chain is not itself
`
`of negative homogeneous catalysis in a radical chain-reaction, during which
`
`inhibition by bicarbonate ions of the oxidation of cyclohexanol is an example
`
`The constancy of the inhibition rate over a prolonged period implies that
`
`during inhibition as opposed to, for example, the case of amines or phenols.
`
`compound can be considered an ideal inhibitor because it is not consumed
`
`385
`
`Specific Solvation
`
`0,0655
`
`1.097
`
`1.4
`
`Molar ratio of cyclohexane : heptane
`
`of cyclohexane and heptane
`
`concentration
`
`on the relative
`
`sec eye o
`k
`H
`
`H
`
`;k
`
`1
`
`Dependence of
`
`TABLE 78
`
`Oxidation of Organic Compounds
`
`384
`
`55
`
`85
`
`(oC)
`
`T
`
`Page 3 of 8
`
`

`
`no1 on the concentration of water in the presence and absence of sodium
`
`of negative catalyst. The dependence of the rate of oxidation of cyc1ohexa(cid:173)
`
`ble, in principle, to inhibit any desired number of chains from one particle
`
`The twofold reactive capacity of the a-hydroxyperoxyl radical makes it possi(cid:173)
`
`74,3% II -
`
`0.15 mol
`
`-
`
`94.3$ II -5.7% H
`
`5,0% iso-C
`
`-
`
`89,3% II-5,7% H
`
`20.0% 1
`
`-
`
`74.3% II-5, 7 H
`
`0 -
`
`2
`H
`
`84,3% II
`
`89,3% II
`
`94,3% II-5, 7% H
`
`91% 1-9% H20
`
`System
`
`12
`
`2
`
`[H,OJ (vol %)
`
`4
`
`60
`
`time (min)
`
`40
`
`20
`
`0
`
`Q
`,.,
`
`~
`
`<I
`" 0
`E
`-'
`
`Temperature 75°C
`
`-1
`
`£
`
`-1
`
`mol
`
`= 3 x
`
`2. bicarbonate concentration
`
`present;
`
`1. no sodium bicarbonate
`
`cyclohexanone,
`
`the rate of oxidation of
`
`The influence of water on
`
`Fig. 103
`
`mol £-l s-1
`
`7
`
`~n
`W. h= 6,9 x 10-
`
`Temperature 75°C
`
`= 4 x 10-5 mol-l .e_-l
`
`2.
`1. without additive;
`9 vol % of water.
`hexanol in the presence of
`
`in the oxidation of cyclo(cid:173)
`
`the absorption of oxygen
`
`Kinetic curves relating to
`
`Fig. 102
`
`(6.44)
`
`+ 02
`
`+ HX
`
`x· -
`
`+
`
`~o-o·
`c
`
`/
`
`~/OH
`
`Oxidation of Organic Compounds
`
`386
`
`1,00
`
`3,00
`
`0,61
`
`2,92
`
`0,58
`
`3.84
`
`0.42
`
`7.70
`
`0.55
`
`5.72
`
`0.64
`
`4.74
`
`0,95
`
`3,3
`
`0,21
`
`8,52
`
`0
`W/W
`
`(mol £
`)
`-1
`0
`W X 10-6
`
`""o-o·
`
`/
`
`~/OH
`
`~o-o·
`c
`
`/
`
`""o-o·
`c
`
`~/OH
`""-o-o·
`
`~ /OII
`/
`
`/~-o·
`"""~
`
`c
`
`~o-o·
`c
`
`/
`"" /H
`
`/
`"""/H
`/ ~o-o·
`""" /H
`
`""-o-o·
`c
`
`c
`
`""-o-o·
`c
`
`"'o-o·
`c
`
`c
`
`""o-o'
`c
`
`~ /OH
`
`/
`""-/H
`/
`"" /H
`/ "'o-o·
`""' /H
`/
`
`0H
`
`9
`H
`4
`
`20,0% tert-C
`
`0
`
`2
`
`5,7% H
`
`H202
`
`0
`
`2
`
`0H
`2o
`
`7
`H
`3
`
`0
`
`2
`
`10,0% 1
`
`5, 7%
`
`5.0% I
`
`5, 7%
`
`0
`
`2
`
`Structure of peroxyl radicals
`
`[!laco;J
`compounds, Temperature 75°C
`
`1,4 X
`
`and Cyclohexanone (11), and mixture of these
`
`Oxidation of Aqueous Solutions of Cyclohexanol (1)
`
`The Influence of Sodium Bicarbonate on the
`
`TABLE 79
`
`387
`
`Solvation
`
`Page 4 of 8
`
`

`
`(6.48)
`
`2
`+ HO'
`
`3
`
`HC0
`
`___ ,...
`
`H202
`
`+
`
`co3•
`
`this is most probably connected with the reaction
`
`then k7k8k9
`
`,
`
`-1(69)
`
`is 2,1 x 10 ~mol s
`
`-1
`
`5
`
`-1
`
`s
`
`-1
`
`mol
`
`and kt
`
`-1
`
`= 8,75 mol ~
`
`5 ~
`
`1.8 X 10
`
`k7k8;k9kt [RH]
`
`(6,LXXV)
`
`(6,LXXIV)
`
`(6 .47)
`
`+ HCOj
`
`/
`OH ~ /
`
`c
`
`+ HC03 (6,46)
`
`)c==o +
`
`(6,45)
`
`+ co3
`
`/~OOH
`"" /OH
`
`c
`
`(kt + k7k8
`
`kakt
`
`kls [!Ico3l
`
`1 +
`
`0
`
`9 [an]
`
`k
`
`k9 -
`
`co3
`
`+
`
`' co3
`
`k7
`
`HC03 -
`
`+
`
`"'o-o·
`c
`
`at 75 C
`
`o
`
`389
`
`-1 -!
`
`s
`
`1>
`
`-2
`
`and b == ~PTLRHJ== 1.0 x 10 mol2 ~
`
`r, ,,
`
`Solvation
`
`5 ~
`
`Addition of hydrogen peroxide weakens the inhibitory effect of sodium bicar(cid:173)
`
`bonate;
`
`3,3 X
`
`Since
`
`a
`
`(6,LXXIII)
`
`(6,LXXII)
`
`) i'
`b~
`
`(1 + a
`
`1
`
`-.Jr-1inh
`
`w
`
`0
`w
`
`in which W is the rate of oxidation in the absence of sodium bicarbonate,
`
`0
`
`From tqese equations
`
`(6.LXXI)
`
`1 +a [!!co;J
`
`W=
`
`w2
`
`w2
`
`or
`
`and the concentration of bicarbonate ion by the following empirical
`
`The rate of oxidation of cyclohexane is related to the rate of inhibition
`
`expression :
`
`the following expression is obtained for fairly low concentrations
`
`12
`
`)
`
`CHC03 l x 105 (mol [1
`4
`
`0
`
`k7 Q·!Co;J
`
`Assuming
`
`c / "'H
`/~-o· +
`
`·~/OH
`
`~/OH
`
`/
`
`~/OH
`
`scheme
`
`~
`
`)(
`
`"' 0
`E
`0
`~
`'.,
`
`~
`' No
`~
`N
`
`mol
`
`6,9 x
`
`65°C,
`
`1 and 4. 75°C and 2 and 3,
`bicarbonate concentration~3•4)
`~;w2 with increasing sodium
`water, and the variation of
`
`in the presence of 9 vol%
`
`oxidation of cyclohexanone
`
`concentration on the rate of
`
`Effect of sodium bicarbonate
`
`Fig. 104
`
`of oxidation (Fig, 104).
`
`The kinetic relations which were obtained are in good agreement with the
`
`increase in bicarbonate ion concentration results in a reduction in the rate
`
`(see Fig. 104).
`
`1,8 x 10
`
`a
`
`to the increased degree of dissociation of the bicarbonate into ions. The
`
`bitory effect of sodium bicarbonate also increases. This is evidently due
`
`bicarbonate (Fig, 103) shows that, with increasing water content, the inhi(cid:173)
`
`Oxidation of Or~anic Compounds
`
`388
`
`Page 5 of 8
`
`

`
`solutions the reaction involves the following mechanism :
`
`)that in basic
`
`73
`
`For example, in the case of triphenylmethane, it was shown(
`
`lar form of the substance into the corresponding ionic form.
`
`In such a case, the r6le of the medium is to convert the molecu(cid:173)
`
`compounds,
`
`The ionic forms are often more reactive than the molecular forms of such
`
`8
`
`pH
`
`6
`
`4
`
`0
`0
`
`0
`
`400
`
`[NoOHl < 10' (g eqwv l-')
`
`ll:
`4 2
`" E
`
`-!..,
`ill)
`
`6
`
`I ·~.~
`
`0
`
`4
`
`a
`~
`
`3::
`
`)(
`
`Q
`E -
`.,
`0
`;:_.
`~ ,.,
`
`' N~
`":~:
`
`24
`
`Temperature 75°C,
`
`s
`-1
`
`-1
`
`mol .Q,
`
`"' 5,6 X
`
`ph ate buffer,
`
`function of pH of the phos-
`10 val% water, plotted as a
`hexanol in the presence of
`Rate of oxidation of cyclo-
`
`Fig. 106
`
`Temperature 75°C
`
`.Q,-ls-1
`
`6.9 x 10 mol
`
`-7
`change in [}!aOH]
`2. change in w:;w2
`(!Ja (OH)
`function of changes in
`increasing U<aoH], • ~ W as a
`1, change in W with
`
`with
`
`21.
`
`presence of 9 val% water.
`
`ide concentration in the
`function of sodium hydrox(cid:173)
`
`cyclohexanol plotted as a
`Rate of oxidation of
`
`Fig. 105
`
`diarylcarbinols, etc~71-83)
`tion of complex organic molecules such as diarylmethanes, triarylmethanes,
`
`The pi! of the medium has a particularly marked effect on the rate of oxida(cid:173)
`
`reactions 6,45-6,47),
`the capacity of the Hco; ion to react with the hydroxy peroxyl radicals (see
`bonic acid, and, as was shown above, inhibition is governed in this case by
`
`l
`
`weaker, the weaker the base. This does not apply, however, to salts of car(cid:173)
`
`would be expected that the degree of inhibition should be proportionately
`
`27 rapidly dissociates, From what has been stated here it
`
`The ion-radical o
`
`(6.49)
`
`"\ /C=O
`
`+
`
`0
`
`2
`H
`
`+
`
`2
`0 :
`
`+ OH-
`
`/. "'o-o·
`
`~/OH
`
`c
`
`inactive form (see reaction 6,49)(70):
`This inhibition is due to conversion of the hydroxy peroxyl radical into an
`
`•
`
`than 6. 0 a marked reduction in the rate of reaction is observed (Fig.
`
`depend on the pH of the medium at low p!I values, but when the pH is higher
`
`, i.e. the
`
`.
`
`rate is related to the pH of the medium, The rate of the process does not
`tion of phosphates and is. determined by the ratio [!IPo!-J I [!I2
`of these salts, the rate of reaction is independent of the total concentra(cid:173)
`
`4
`
`PO
`
`In the presence of mixtures
`does not affect the rate of oxidation,
`
`4
`
`Po
`
`2
`
`has a marked inhibitory effect.
`
`whereas Na
`It is interesting to note that KH
`
`4
`
`HP0
`
`2
`
`process is completely blocked (Fig. 105) at sufficiently high concentration
`
`increased, the rate of oxidation of alcohol is reduced so that the oxidation
`
`cations in the form of chlorides, When the concentration of hydroxyl ions is
`
`do not influence the rate of reaction as is demonstrated by introducing metal
`
`of hydroxyl ions.
`
`also remain virtually unconsumed and are ideal negative catalysts. Cations
`4
`of [_oH-]/Winh(and also to that of [Hco; ]/Wirn). Inorganic bases and Na
`
`HP0
`
`2
`
`.cyclohexanol, The inhibition time is very long in comparison to the value
`gen phosphate(69)also inhibit the initiation reaction in the oxidation of
`Inorganic bases such as sodium hydroxide, barium hydroxide and sodium hydro(cid:173)
`
`tion,
`which reduces the proportion of co3 ion radicals participating in the reac(cid:173)
`
`391
`
`Specific Solvation
`
`Oxidation of Organic Compounds
`
`390
`
`Page 6 of 8
`
`

`
`):
`
`75
`
`The ionised form also interacts with oxygen<
`
`sible ionisation of dihydroanthracene under the influence of the hydroxyl ion.
`
`One of the possible mechanisms of the oxidation process involves the rever(cid:173)
`
`The catalytic effect of basic solutions was also examined for the oxidation
`
`(84)
`
`of 9,10-dihydroanthracenes and other compounds of the anthracene series.
`
`diphenylmethane in one minute
`(**) The number of moles of o2 absorbed by one mole of
`
`diphenylmethane during the period of reaction.
`(*) The number of moles of 02 absorbed by one mole of
`
`(6. 59)
`
`(6.58)
`
`(6. 57)
`
`(6.56)
`
`(6. 55)
`
`(6. 5 ~)
`
`CO + OH-
`
`2
`
`3
`
`SOCH
`
`2
`
`C(OH)CH
`
`CO
`
`2
`
`3
`
`cH
`
`3
`
`so
`
`3
`
`cuo-+ CH
`
`cHoo-
`
`2
`
`CH-;
`
`2.9
`
`l.l
`
`LO
`
`0.37
`
`0.15
`
`0,02
`
`0
`
`2,7
`
`1.1
`
`2,7
`
`1.0
`
`1.4
`
`Hexamethylphosphamide
`
`COK in
`
`3
`
`)
`3
`
`2-ol
`Hexamethylphosphamide/2-methylpropan-
`
`(80:20)
`
`(6. 53)
`
`rr'
`
`Dimethylsulphoxide/2-methylpropan-2-ol (80:20)
`
`Dimethylformamide/2-methylpropan-2-ol (80:20)
`
`Pyridine/2-methylpropan-2-ol (80:20)
`
`Pyridine
`
`(6,52)
`
`2-Methylpropan-2-ol
`
`):
`
`74
`
`initiation(**)
`
`coefficient(*)
`
`Stoichoimetric Rate of
`
`Solvent
`
`cH, which requires
`
`3
`
`749 mm Hg
`
`TABLE 80
`
`(6,51)
`
`(6. 50)
`
`0.2 mol
`(!.r 2
`cH2
`]
`Oxidation of Diphenylmethane in Different Solvents.
`
`02
`
`Temperature 27 ± 2°C; P
`
`;
`
`COK] =
`
`3
`
`)
`
`3
`
`0,1 mol Q. -l; [<cH
`
`393
`
`Specific Solvation
`
`tiation for dipenylmethane in various conditions.
`
`cate the values of the rates of initiation and of the rate constants of ini(cid:173)
`
`by the rate of ionisation of the organic substances, Tables 80 and 81 indi(cid:173)
`compounds in a number of solvents~71•72) The rate of oxidation is limited
`in the processes of the oxidation of diphenylmethane, fluorene and other
`
`The rates of chain-initiation (the ionisation rate constant) were measured
`
`2
`
`2
`
`2
`
`cHoo--Ar
`3 -
`SOCH3 -Ar
`+ 02 -
`ko
`"
`k.
`
`Ar
`
`-B
`---=-Ar
`B-,02
`
`SOCH
`
`CIIO-
`
`2
`
`3
`
`2
`
`Ar
`
`co + CH
`
`2
`
`Ar
`
`Ar
`
`3
`
`+ CH
`
`CHOO-
`
`2
`
`Ar
`
`Ar
`
`Ar
`
`-
`
`COK
`
`3
`)
`3
`
`cH7
`
`2
`
`Ar
`
`(CH
`
`2 +
`
`CH
`
`2
`
`Ar
`
`(71,72):
`DMSO and in 2-methylpropan-2-ol can be represented by the following scheme
`
`The mechanism of oxidation of diphenylmethane in the presence of (CH
`
`CH' +
`
`2
`
`Ar
`
`rr
`
`+
`
`Ar2CH
`
`CH' by the reaction
`
`2
`
`CH-into Ar
`
`2
`
`dation and converts Ar
`
`tron-acceptors of the nitroaromatic type of substances (rr) accelerates oxi(cid:173)
`
`then undergoes further oxidation. The addition of various elec(cid:173)
`
`CH-
`
`2
`
`The Ar
`
`+
`
`Ar2cH2
`
`The initial step in the oxidation of fluorene in 2-methylpropan-2-ol or in
`
`dimethyl sulphoxide is the dissociation equilibrium(
`
`a fast reaction for addition of o2
`The limiting step in the process is the ionisation of Ar
`
`,
`
`COO -
`
`3
`
`Ar
`
`fast
`
`02
`
`+
`
`ArC:
`
`c:
`
`-
`
`3
`
`Ar
`
`slow
`
`B -
`
`+
`
`CH
`
`3
`
`Ar
`
`Oxidation of Organic Compounds
`
`392
`
`Page 7 of 8
`
`

`
`[<C6H5) ~l (!>oc (CH3) 31 O
`
`dt
`
`d [o2l
`
`(**) Dideuterophenylmethane.
`
`(*) Calculated by the formula
`
`0.015
`0,075
`0,070
`0.105
`0,089
`
`0.12
`0,092
`0,087
`
`0,18
`0,18
`0,15
`
`0,23
`0,20
`0,20
`0,20
`0,20
`
`Temperature 24,5°C
`
`0.23
`0.23
`0,23
`
`Temperature 25,5°C
`
`0,20
`0,20
`0.05
`
`Temperature 31,5°C
`
`0.10(**)
`0,10
`0.10
`0,064
`0,064
`
`0.10
`0,10
`0,05
`
`0.017
`0.064
`0.025
`
`(.Q, mor1 s-1)
`
`(mol r1)
`[!>oc cca3) 3]
`
`(mol t-1)
`[<C6H5) 2CH~] 0
`
`tert.butylate. (*)
`
`in the Presence of Various Amounts of Potassium
`
`Diphenyl Sulphoxide/2-methylpropan-2-ol (80 : 20)
`
`methane Undergoing Oxidation in a Mixture of
`
`Rate Constants for the Ionisation of Diphenyl(cid:173)
`
`TABLE 81
`
`(6.69)
`
`(6.68)
`
`(6.67)
`
`(6.66)
`
`(6.65)
`
`(6,64)
`
`(6,63)
`
`(6 0 62)
`
`(6.61)
`
`HOOROOH -anthraquinone + 2H20
`'ROOH + H-R -'R' + HOO: + H-R'
`'OOROOH + H-R-H -HOOOROOH + H-R'
`
`___,.. anthracene
`
`'R'
`
`-
`
`2 -'OOROOH
`H-Roo' -'ROOH
`H-R' + 02 __ .,.. H-Roo·
`H-R: + 02 --H-R' + 0_2
`
`'ROOH + 0
`
`0
`
`2
`
`H-R-H +OH-~ H-R: + H
`
`-
`
`neral representation(84>:
`This reaction scheme can be represented in the following form, in a more ge(cid:173)
`
`and subsequently an anthraquinone,
`
`@
`
`HOO
`
`H
`
`cond hydrogen atom, to fbrm an intermediate product :
`It is possib:).e that oxidation also takes place, at the same time, at the se-
`
`~ H
`~
`
`+ OH-
`
`H
`
`(6.60)
`
`o
`
`2
`H
`
`H
`
`H
`
`..
`
`+ H20
`
`H
`
`H
`
`@Q0~~
`
`~ H
`
`OH---
`
`H
`
`H j H
`
`a:
`
`/
`
`395
`
`Specific Solvation
`
`Oxidation of Organic Compounds
`
`394
`
`Page 8 of 8