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The Essential Problems.-Chromic acid and potassium permanganate
have been regularly used as oxidising agents for well over a century both
in volumetric analysis and in degradative organic chemistry, yet even today
knowledge of the mechanisms of their reactions is only fragmentary. I n
organic chemistry few of their reactions are specific, or even quantitative.
The overall valency changes which the respective anions undergo when
they are reduced to stable products (eqns. 1-3) cannot occur except by

A Cr3+



alkaline'5 MnO,

(3-electron change)

. . .


'(5-electron change)

. . .
. . .


(3-electron change)


a series of consecutive changes because quantum restrictions prevent more
than a pair of electrons associated with any one atom from ever behaving
in an identical manner. Again the electron transfers involved in these
complete reductions of chromate and permanganate are not potentiometrically reversible; the redox potentials listed for them are spurious figures
calculated from free-energy changes [AE = ( RT/nF)AG].
Many studies of isotopically labelled ions have shown that electron
transfer between ions of similar atomic structure is fast and reversible
(e.g., eqns. 4, 5),2* 3 whereas reactions clearly involving the rupture of
covalencies (e.g., eqn. 6) * are generally slow, for with them appreciable
activation energy is needed to reach the transition state.







9 (Mn03-0H)-








. (5)
- (6)

C. B. Amphlett, Quart. Rev., 1953, 8, 219; W. F. Libby, J . Phys. Chem., 1952, 56,
863; D. R. Stranks and R. G. Wilkins, Chern. Rev., 1957, 57, 743.
2 A. W. Adamson, ibid., 1951, 55, 93; M. J. Polissar, J . Anzer. Chem. Soc., 1936,
58, 1372; J. A. Happe and D. S. Martin, ibid., 1955, 77, 4212.
W. F. Libby, ibid., 1940, 62, 1930; J. C. Sheppard and A. C. Wahl, ibid., 1953,
75, 5133; 1957, 79, 1020.
4 M . C. R. Symons, J . , 1954, 3676.


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Both electron transfer and covalency breaking processes
are involved
in the sequence of consecutive reactions involved in the stripping of oxygen
from anions of type (M04)n- to give cations Mm+ and it is now clear that
the order in which the successive valency changes occur may differ from
reaction to reaction according to the nature of the substrate that is attacked.
From mechanistic studies of these changes there is, for the inorganic chemist ,
much to be learned concerning the structure and stability of chromium
and manganese ions of intermediate valency level. Here the organic chemist
can give valuable help, because today a considerable body of evidence
concerning the ways in which organic compounds of different structural
type tend to oxidise can be used to forecast probable reaction paths. Again,
only by the use of organic compounds can one readily select oxidations
that are slow enough for kinetic study and the possible detection of transient
intermediates. This Review will therefore deal mainly with oxidations of
organic substances.
Routes of Oxidation of Organic Compounds.-Below pyrolysis temperatures, oxidations are all bimolecular, or concerted, reactions. These can
be classed as ( a ) 1-electron transfers (e.g., 7; Fenton's reaction), or ( b ) 2electron transfers of type S,2 (e.g., 8; epoxidation of an olefin).





4- .CHFW


Ph-CO-0- 4- HO-C%-EHR


. (7)
. ( 8)

Processes ( a ) necessarily generate free radicals and often lead to chain
reactions, with very distinctive kinetics, whilst processes ( b )involve transient
ions and are rarely chain reactions. Thus kinetic studies can often be discriminatory, but may be difficult to interpret when consecutive reactions
are involved. Detection of a free radical by a characteristic reaction, e.g.,
catalysis of vinyl polymerisation or direct combination with oxygen, is
diagnostic of ( a ) , whilst recognition of reactions typical of carbonium ions,
e.g., 1: 2-molecular rearrangement, can point to (b).
Recognising that favoured reactions take the path requiring the least
activation energy, one can, taking solvent conditions into account, forecast
the route of oxidation from structural considerations. 1-Electron transfers
become exothermic and require little activation energy only if the immediately resulting radical is a resonance-stabilised system. Related studies
with several 1-electron abstractors (Ce4+, (Fe(CN), )3-, Cu2+, etc.), of which
the complexed ions of MnIII are typical (p. 296), indicate the general sequence
of oxidisability to be : 1: 4 or 1: 2-dihydric phenols > monohydric phenols >
aldehydes and ketones (as enols), 1: 2-glycols > allylic systems, ethers >
monohydric alcohols, olefins.
Olefins, other than allylic systems, are not easily attacked, except by
very powerful oxidisers such as Co3fY5especially if of catio-enoid type


are entities of high energy
(C:C*C:O or C:C*CN),since radical-ions, =C-C=,
level. Olefins however are easily attacked by electrophilic reagents of
type ( b ) , e.g., peracids or halogens, particularly in solvents such as water
C. E. H. Bawn and J. A. Sharp, J . , 1957, 1866.

it is important to know when. (Cr0. Pollowing Stamm. much of the published evidence for propounding the foregoing generalisations comes from studies of oxidation by means of chromium or manganese compounds that are described more explicitly in the following paragraphs. By inductive reasoning along these lines. Stamm. first postulated by StammJ6 and continuing with further electron-transfer oxidation of dissociated hydroxyl (*O)-. by Oesper.(II) (12) . (13) S y m o n ~using . .~ H2180. Mn. . (Mn04)2-+ + O2 ..+ (OH)’ + (OH)- + 4(Mn04)*-+ (MnOJ2- GO)60)- 4- 2H20 + HO . . : . p. 1938. The Ions of Manganese. (Mn0. New York. To this end it is helpful to consider structurally similar ions of the whole transition group Ti.g. . it being recognised that the stability and structure of any ion in solution depends on the acidity or alkalinity of its environment. tentative oxidation mechanisms can now be inferred with a sufficient degree of success to aid considerably the interpretation of experimental results.4 but in strong alkali i t slowly decomposes to manganate and oxygen. .-The purple permanganate ion (Mn0. 4(Mn04)(Mn0.rsc. trans. Mn2+. In solution it does not exchange oxygen with symmetrically tetrahedral and the anion of a strong acid. . However. “ Newer Methods of Volumetric Analysis Nostrarid & Co.)*OH (Mn0. . t o give cations.)2-. such as hydroxyl or atomic chlorine.lly effected by hydroxyl radicals. as in Aryl-C-. unless the resulting organic radical has a high degree of resonance stabilisation.1039/QR9581200277 Articleremoval Online which can co-ordinate and then react with carbonium ions.has shown that in equation (10) all the oxygen comes from the water and therefore favours a reaction sequence commencing with the electron transfer (11).) anion and a cation X2+ is known. . Inc. With manganese and vanadium each valency between that of a stable (XO. Fe.)- + - + 4(0H)+ (OH).WATERS : OXIDATION BY CHROMIUM AND MANGANESE CORWOUNDS 279 Downloaded by University of Sussex on 17 January 2013 Published on 01 January 1958 on http://pubs. to oxygen (eqns. Cr3+.)- etc. cf. V. ”.OH . .(lo) .View Again of hydrogen from H-C is greatly facilitated by a base-catalysed. 7) needs free radicals of very high energy.) | doi:10. whereas homolytic hydrogen abstraction (e.. and how. he has suggested that oxidations brought about by strongly alkaline permanganate are rea. 11-13). through H02*and (02*)-. and hence suggestions can be made concerning possible structures and properties of chromium ions of the intermediate valencies Crv and CrIV. this removal of oxygen occurs. Valency states of chromium and manganese Since oxidations by chromic acid and permanganate involve the eventual stripping of oxygen from anions. Van . . Co. 284). Cr. . or their H. (H0.). concerted 2-electron movement (9.

2 substitution a t the manganese centre (eqn. 4710. R. Scholder. 2. . 659. R. stable only in alkali. D. J. Waters. Pode and W. lo A. 3373. The sky-blue - 3(Mn04)2- + 4H' (MnO4I2- + (OH)-= 2(Mn04)(MnOJ3- 4. Reaction (15) can explain its route of formation. E. Waters. Waterstradt.CrO.MnO. C. Carrington. for Symons has found that alkaline manganate in isotopic water. obtainable as a sparingly-soluble salt. Carrington and M. K. 281.. (Mn04)2-. Whereas dilute aqueous (alkaline) solutions of hypomanganate can be prepared. Schonland. This has been visualised as an X. D. Carrington. 1953. for. . absorption spectra. slowly exchanges oxgyen with the water. | doi:10. J. Charge transfer between manganate and permanganate (eqn. K. like Ti(OH). 1956.1039/QR9581200277 View Article Onlinefor more active anions (*O)-. and H$hO4 are probably of the same order as those of H. 14) in more acid solution.. Wiberg has been able to prepare l80-labelled permanganate and therewith trace the route of the oxygen atoms in several of the oxidation reactions of permanganate solutions. H. F. would be far too weak an acid to exist in any solution as (MIIO. By using this equilibration. Y.*.This is t o be expected. 435.MnO. (with MnIV) and permanganites XMnO. Symons. 1946. S. D. Symons. (with Mnv) are known only as solid products of alkali fusion of manganese dioxide. R. and H3VO4.. Lux. C. H2180. The dissociation constants of H. 2H..' The green manganate ion. and thermodynamic properties of ions (Mn04)n. and subsequently the disproportionation of manganate (eqn. H.~ of metastable solutions of (Mn04)2and (Mno. Electronic structures. . 6). anions decrease markedly in the order (Mn04)-> (Mn04)2-> (Mr~o. R. J. a compound Mn(OH).and (HMn0.have been studied by Symons and his colleagues. 10 These ions undoubtedly undergo displacement reactions involving hydroxyl. 1956.) 3-.)~-. for oxidation A.MnO..280 QUARTERLY REVIEWS Downloaded by University of Sussex on 17 January 2013 Published on 01 January 1958 on http://pubs. manganites.)~-and would immediately be dehydrated to an insoluble product. 14). 1954. Fischer and.rsc. 1. 3373. 1956.lo9 l1 The oxidising powers of the MnO. J. J.and hydrated manganese dioxide can be explained as occurring by electron transfer in this way. and M. J. X. 1957. Schonland. A.). by fusing together at red heat potassium permanganate and sodium hydroxide. J. . C. 2.. Symons. . Naturforschung. for solutions less than N in hydroxyl ion slowly disproportionate (eqn. 5) is fast and permanganate appears to convert hypomanganate very rapidly into r n a n g ~ ~ n a t eDisproportionation . l1 A. A.OM . and it can well be therefore that the disproportionations of compounds of Mnvl and Mnv involve the ions ( stable (Mn04).. and M. Drummond and W. 292) for the separation of transient (MnO. f + . Chem.MnO.) anions in several oxidations. D. 234. (15) hypomanganate ion. anorg. is even less stable and disproportionates similarly in solutions less than SN in hydroxyl ion..O (14) . 277. However this simple theory cannot suffice those permanganate oxidations that can be effected rapidly in weak alkali.)2-. (MnO.)3. However there is now strong evidence (see p.

1039/QR9581200277 WATERS : OXIDATION BY CHROMIUM AND MANGANESE COMPOUNDS 281 View Article Online involves electron gain. . The complexed ions. but for this starch-iodide solutions can be used. A.Downloaded by University of Sussex on 17 January 2013 Published on 01 January 1958 on http://pubs. . l5 H. . l5 The reactions of MnIII complexes are therefore similar to those of free Mn3+ but the redox potential of MnIII-MnII solutions naturally depends on the nature and concentration of the complexing agent. 1935. 1952. Tervalent manganese gives a cherry-red cation. Ubbelohde. Again. .). 142. . for example. 12 l3 . for dissolution of hydrated manganese dioxide requires very much stronger acid than that which can completely prevent oxidation of manganous salts by permanganate.14 Their colours are not sufficiently intense to provide direct end-points. The first See Ann. . usually written as (17).(17) Mn3+ .. . and the tendency of such substances to be dehydrated to insoluble materials. 49. this can be associated with the symmetry of electrically neutral MIV(OK).2 Several suggestions as to the mechanism of the Guyard reaction have been propounded. P. .)2- + + 2H20 . 16a. pyrophosphate. R. 1952. I. in concentrated (> 9 ~ sulphuric ) acid. 1943. is + 2(Mn04)' + 3Mn2+ (Mn04)- + Mn2+ + 5Mn02 4(0H)' e (Mn0. J. Although manganese dioxide is a well-known oxidising agent. . + 4H+ . With the metals from vanadium to iron the quadrivalent state marks the transition between stability as oxyanions and as cations.(18) not truly a reversible equilibrium. Rev. Mn3+. FeIII. 16b) but MnIII can be stabilisecl in solutions of much lower acidity by chelating agents. For the simple Mn3+-Mn2+system this has the very high value of 1. J. {Mn(H2P20. yet no homogeneous oxidations involving MnIV are known . 170.. Eng. M. 1605. are structurally similar to the octahedral co-ordination compounds of CrIII. Chem.g. . 1953. e. 1 4 I.)3-. . 15. Taube. (160) (166) tionates (eqns. 50. .rsc.13 At lower acidities this cation rapidly dispropor2Mn3+ Mn4+ + + 2H20 + - Mn2+ Mn4+ MnO.. . as. 50.15 v. . . long used in the presence of sulphuric or other mineral acids. This Guyard reaction. which has to be effected by electron movement contrary to the charge on the anion. Watters. Ind. all of which depend on postulates concerning the structures of transient manganese ions of intermediate valency. 47. isotope exchange does not seem t o occur between permanganate ions and manganous ions in the absence of a precipitate or colloid of manganese dioxide. Chem. . Kolthoff and J.. the fairly specific heterogeneous oxidations that can be effected by activated manganese dioxide in aprotic solvents l 2 cannot yet be related to reactions of dissolved manganese compounds. .org | doi:10. .. In neutral or weakly acid solutions Mn2+ is oxidised by permanganate to manganese dioxide. Anal. and ColI1 and have easily-displaced ligands. 8. Reports. Such solutions of MnIII are useful volumetric reagents.

14 Somehow the rapid reduction of (MnO.. (C5H.20 Since strong acids enhance the oxidising powers of CrV1it has been suggested that cations such as (HCrO.N. Novick.. Ber. following the procedure for making K. Its solutions in very strong alkali rapidly absorb oxygen and immediately disproportionate on dilution with water.. They will oxidise neutral solutions of iodide. K . Westheimer and A. + Downloaded by University of Sussex on 17 January 2013 Published on 01 January 1958 on http://pubs. R.. 202. I n the presence of pyrophosphate for example manganous salts can be quantitatively titrated (electrometrically) at pH 6 to the MnIII stage with aqueous permanganate. J. .are both powerful oxidisers. Adamson. is devoid of oxidising power and it has been established that (Cr207)2-is a much weaker oxidiser than (HCrO. Neuss and W.)-(Mn0. the chlorochromate anion. Chem. J . Westheimer. Quadrivalent chromium is known in CrF. particularly valuable since they can be used in orga. and are a t once decomposed by water.e.H. . 2o Mn3+in an acid solution must be possible by a route that does not involve formation of any significant amount of Mn(OH). 55..282 QUARTERLY REVIEWS Article Online stage is probably the reversible electron transfer (18)..HCrOCl. F. Bailey and M. with removal of Mn4+ as hydrated manganeEe dioxide. Weinland and Fiederer 2 2 had prepared a series of salts.l0 Mn3+-Mn2+ = 1. C. Alkaline chromate. 1952.)..17 The Ions of Chromium.)-.. . AdamsonY16F..(I91 This vitiates any chance of using l 8 0 in studies of the mechanism of chromic acid oxidations.CrQ4 by alkali fusion. 16) to follow. Tompkins. 1951. too. = 3.)2- f HzO . (Cr04)2-. i.N = pyridine). such as Rb2CrOC15 and C.-Chromic acid is a fairly strong acid ( K .1039/QR9581200277 + 2(HCr04)- (Cr20. I n more concentrated solutions the dehydration ( 19) occurs extensively. . or (ii) if a selective complexing agent has been added t o lower the concentration of free Mn3+to a requisite extent. = 0.. '74. 500. .51 v shows that oxidation of Mn2+can proceed significantly only (i)if the acidity is low enough for the subsequent disproportionation of Mn3+ (eqn.)2. . 4387. is much less active than (Cr03-OH)-. . 2 2 R. W. H. 455 and later notes.MnO. H.= 0. Riemann.)-. behaving stoicheiometrically as if they contained CrV. F. The dioxide. J . 21 N.nic solvents. 38. D.)-.. | doi:10. and E.+).2 x l8 andin dilute aqueous solution largely exists as (HCr0. Abel. CrO. I n this way. Faraday SOC. CrQ2C12. Truns. 19 F. W.rsc. 1943.. one can explain the solubility of chromium trioxide in acetic acid. 39. This is conceivable if compounds of Mnv and MnIV have amphoteric character and can form cations analogous t o V02+ and V02+. Chem. 11. J . Weinland and M. Chem. 293. SOC. 131. C. Symons. J. 2235. HSO. 4042. Such ions have been postulated by A. that appear to contain the anion (CrvOCl. l7 18 .lS Though the anhydride. Earlier. Cohen and F. Phys. 80. 56. 1906. E. 16 A. SOC. Amer. (Cr0.. C.6 v. Tompkins.1934. (Mn0. Mo?zutsh. View Reference to the published redox potentials. CrO..1942. J. Abel. . . Chem. and the acid chloride. Phys. Amer.Cl)-.)+ can exist (cf. 1957.. I n 1957 Bailey and Symons 21 prepared green K. 1949.18. and CrCl. whereas neutral K2Cr2Q7does not do so.

45. Chem. Chern. as would be expected for an oxyanion.ctions such as (20).. Soc. 1958. (HCr04)-. 23 24 28 A. 6.1039/QR9581200277 WATERS : OXIDATION BY CHROMIUM AND MANGANESE COMPOUNDS 283 Online is thought to result from many chromic acid oxidations andView has Article been isolated as a brown powder that immediately decomposes in ~ a t e r . However the main evidence for transitory Crv and CrIV ions comes from the study of chromic acid oxidations of organic compounds.. Mn2+) did not occur. 2 ~ By analogy with vanadium it can be suggested that CrO. . H. I n reactions such as (21) only one equivalent of the second component is oxidised per chromate ion. 1949. and by analogy with the chemistry of manganese (eqn. two equivalents of the second component can.g. The strong reducer Cr2+ will not be considered in this Review. vanadium and manganese. Oxidations of alcohols. Analogies between chromium and the two adjacent elements. 62.t 2H3As03 f Mn2++ 6H+ 2Cr3' 4. (23 I n rea. A. 18) reaction (22) can be postulated as a rapid equilibrium. Rev. 74. in the limit.. He pointed out that transient ions having intermediate valency states must be postulated to explain the occurrence of induced oxidations. + + Chromic acid oxidations -inorganic reactions The mechanism of chromic acid oxidation was reviewed in 1949 by F. Taube. Leo and F. 4383.2H3As04 M n 0 2 4H20 (21) + + . Fe2+. VO. Phys. Westheimer. e.. VO+. V2+. a later reaction being rate-controlling.Downloaded by University of Sussex on 17 January 2013 Published on 01 January 1958 on http://pubs. 419. F. such as (20) and (21) under conditions in which direct oxidation of the second oxidisable component (I-. Chem. the ion of Crv resembling that of hypomanganate. 4H20 (at pH 3) (20) 2(HCr04).+. Thus the redox potential for the CrV1-Crv equilibrium must be similar to that of the FeIII-FeII system. .)Fe2++ 2 I7H'Cr3+ Fe3+ I. Ce3+. this being consistent with a cation (Cr4+ I. Westheimer. | doi:10. Ogard and H. as recent work has verified. J. 1952. H. or of vanadate. Arner. be oxidised per mole of chromic acid. He considers that CrTVcan oxidise iodide to iodine. Westheimer 24 has inferred that CrIV must be a stronger oxidising agent than MnTI1 (this has had some recent confirmation 25) and yet a powerful reducing agent. Ti3+. . this is indicative of oxidation through quinquevalent chromium. Westheimer 24 who had previously shown19 that the only active oxidising species in acidic aqueous solution is the acid chromate ion. are helpful in formulating hypotheses concerning mechanisms of reduction of chromate to C F . should be basic rather than acidic. This indicates that the reaction proceeds through quadrivalent chromium (reaction 23).rsc.2l It may be noted that the inorganic reactions proceeding through Crv are those in which the primary reducing agent is an ion that can provide one eZectron. J. Kinetic study of the oxidation of ferrous ion by chromic acid indicates that the initial step is rapid and reversible. E. + + -+ + + (HCrO.+Cr3+ 1 0 ) whilst Crv oxidises iodide to hypoiodite.

in the presence of manganous salts one equivalent of manganese dioxide can be obtained for every two equivalents of isopropyl alcohol oxidised. Samuel. AS" - crm Cr" + 4. I. D.1039/QR9581200277 CrV + (l-$Asq)- - CrIV 2~rV.Cr04)2-.Cr04. . acid-catalysed esterification of the alcohol preceded the slower oxidation. Xoc. which he wrote as a concerted base-catalysed process giving quadrimlent chromium ((HCr0. 37. 26. acyl-oxygen bond fission. by comparing the rates of oxidation of H-CMe. i. Xoc. such as aromatic aldehydes.CrO2-OH:+ H20 H30++ CM%=O t H. Nicolaides.. . . and probably many other types of organic compound. Chromic acid oxidations -organic reactions (i) Oxidation of Alcohols. .Article (23)Online . .*OH. . reversible. R. i .] that would rapidly oxidise Mn2+. Amer.. Diisopropyl chromate. 71. Yoffe.e. H. 28 M. I n 1943 Westheimer and Novick l9 established that the oxidation of isopropyl alcohol resembles reaction (21) . A n a l . Zeiss and C.-This reaction has been studied in great detail. . 25.-] and on [H+I2(in moderately dilute acids) is consistent with an acid-catalysed esterification involving un-ionised H. Amer. 26 27 . (26) . are of this character and it may be noted that all these reactions involve t'he rupture of a covalency. reaction ( 2 5 ) presumably being similar in type to reaction (23) as would be expected of an ion (H. . Chem. 3603. Ghenz. and A. Oppenauer and H. His reaction mechanism (eqns. as a fast reaction. . H. . . . . Westheimer and N. J . . 246.*OH and D-CMe.-butyl chromate having been introduced by Oppenauer and Oberrauch 27 as a specific oxidiser for alcohols. established that the H(D)-C bond of the alcohol is broken in the rate-determining stage of the oxidation. Matthews. . Kinetic analysis of oxidations of type (21) indicates however that both the valency levels of CrV1and CrVare probably involved in t.O: + 2H' + HO-CMe2-H + H-CMe. H.). 1949. nO-Cr02-OHZ H-CM5O. . V. View . . . argentina.CrO. Quim. Chromate esters are now well known. tert. (27) .. .(H. (29 hydroxy-acids. which can be extracted by benzene from F.or CrO. Dependence of the oxidation rate on [HCrO. 1949. (24 AS^ .org | doi:10. 1956.he absence of the second oxidisable component and Westheimer has therefore postulated. 78. 1954. e . .284 QUARTERLY REVIEWS (HCr04)- + Crv' + Downloaded by University of Sussex on 17 January 2013 Published on 01 January 1958 on http://pubs. D.As04)- . Oberrauch. - (HCr04)- H. Anbar. Westheimer and Nicolaides.. of an electron-pair bond. 27) has been so widely applied as a model for other oxidations that it merits further consideration. N. Dostrovsky. 1694. I n 1949. . . It has been shown 23 that this reagent acts by rapid trans-esterification with primary and secondary alcohols : this esterification and its reverse 28 usually involve electron-pair displacements at the chromium atom.26 Westheimer 24 therefore concluded that a rapid. J. the re-oxidation of CrIV and the 2-electron reduction of Crv (reactions 24 and 25). J . . Asoc.rsc. . but was usually destroyed by reaction (24).

Chena. as would be expected for a base-catalysed fission of a C-H bond as shown in equation (27). 1735.g. H.)+ or (HCrO. 1058.23 This decomposition is catalysed by pyridine. However. since solvents have a very great effect on the reaction velocity.. giving the cation shown in equation (27). 1666. Krupicka. slightly more Crvl than that required for CrIV). are exact models for all reactions of chromic acid.30that could easily be mistaken for chromium compounds of valency intermediate between CrV1 and C P .29 since stoicheiometrically a reaction of rate dependent on the product [Ester of CrV1][H20][H+]is equivalent to the measured rate which depends on the product [H. T. 1957.). 3 2 J. 80. undissociated chromic-chromate complexes such as CrlI1(HCrO. Czech. I n 86.*OH.CrO.CrO. However Graham and Westheimer question the above argument . They concede however that in very strong acid a cyclic process such as (28) may operate. E.whilst chloride markedly retards reaction by formation of the more stable chlorochromate ion. R. Listy. | doi:10.CrO. 1949.][Alcohol][H+] and no extra water molecule...5% acetic acid the rate of oxidation of isopropyl alcohol is 2500 times as fast as in water. 1958. Chem. Chem. and Ind. 599. (H. or to the formation of a highly reactive acetyl-chromic anhydride. Soc. a t low acidities and a.1039/QR9581200277 WATERS : OXIDATION BY CHROMIUM AND MANGANESE COMPOUNDS 285 Article Online chromic acid-isopropyl alcohol mixtures. 31 J.CrO. involving molecular H..2O I n glacial acetic acid chromic acid oxidations exhibit autoretardation. 1320. 1948. J.CrO. protonated species.*CO*O*CrO. J. 1668. R.. For oxidations in strongly acid aqueous solutions Westheimer has suggested that proton addition to the acid chromate ester. a t higher acidities. 20. 52. ~by 2 showing that the logarithm of the oxidation rate is linearly dependent on Hammett's acidity function H.CrO. (Cl*CrO3)-.. decomposes underView anhydrous conditions in the latter solvent by a first-order reaction. 3030.)+. Slack and W. A.rsc. Comm.. favours the electron switch from the water molecule that acts as base catalyst.)(O*CO*CH.. The effect of phosphoric acid is similar. Chem. Coll. CH.. RoEek and J. argue that a molecule of water need not be required as catalyst and suggest that the oxidation proceeds by a bimolecular cyclic electron switch as in reaction (28). . RoEek and K r ~ p i c k a . 1955. one can question whether neutral chromate esters. RoEek and Krupicka consider that the cyclic mechanism explains more satisfactorily than the catalysed mechanism the relative rates of oxidation G.29 a difference that can be ascribed to solvent displacement of the ionisation of H.. owing to the formation of brown. RoEek. These however may be broken up by the addition of an acid stronger than H. 29 30 . water and acetates being retarders that favour this complex formation. depositing a brown powder containing CrV1and CrlI1 in the ratio 42 : 58 ( L e . Graham and F. e. Westheimer. Waters.l but more complex on account of its stepwise dissociation. sulphuric acid which markedly accelerates oxidations.Downloaded by University of Sussex on 17 January 2013 Published on 01 January 1958 on http://pubs.

. This hypothesis assumes that the esterification equilibrium (26) is not markedly affected by steric conditions. Experientia. has suggested that for cyclic (e g. ibid. in view of later evidence of acid and base catalysts of glycol fission by lead tetra-acetate.(30) H+ .. Sagor.. a concerted electron-pair mechanism may be more plausible. 23. 1958. 316.1039/QR9581200277 286 QUARTERLY REVIEWS View Article Online of para-substituted l-phenylethanols. found by Kwart and Francis 33 to followthe order MeO. mainly to a ket0ne.. Westheimer. Belv. Mosher and E. 38.. This phenomenon has been investigated more closely by Hampton. 39 J. it is of zero order with respect t o chromic acid and seems to involve the slow formation of an olefin which is then rapidly oxidised. S. 306. 73.C*COPh. Leo. Whitmore. J . . which yields benzaldehyde and tert. Harnpton. Soc. D. W. Chromic acid will also effect glycol fission. Though of first order with respect to the alcohol. Oxidation of tertiary alcohols is more difficult than that of primary or secondary alcohols but can be effected in the presence of sulphuric acid. F. and valuable for structural diagnosis. Barton's conclusion is not quantitatively correct 35 and the cyclic mechanism (28) is in much better accord with observations..34 accepting the validity of Westheimer's mechanism. 70. + I . Slack and Waters 37 isolated an intermediate containing two atoms of chromium per pinacol molecule. Chem.> C1. J . Chem. but this is sharply reduced by adding Mn2+ or Ce3+ ions to remove any CrlV OH Ph-FH-CMe. Slack a n d W. Eschenmosor.> H. CrV' -+ - + Ph-$H-CMe.. 594. R. .> Me. Compounds of CrV cannot however entirely be neglected in considering steps in alcohol oxidation. . Francis. Amer. 1956.C-CHPh*OH. Mosher and his collaborators 3* noted that some C-C bond cleavage occurs during chromic acid oxidations of alcohols of type R.C*CHR'*OH. + *CM% Crm 4- Ph-C#=O HzO t CrV Ph-$H-CMe3 0.Downloaded by University of Sussex on 17 January 2013 Published on 01 January 1958 on http://pubs. Barton. H. A. and Westheimer 39 for a-tert.> Me&. 38 W. This they supposed to decompose to give CrV: however. Leo.. ibid. 1951. 2544. 1302.-butylbenzyl alcohol Me. 1955. and F. J . J. Chim. 77. 1955. SOC. 33 34 . . 71. 4970. electron-donating substituents favouring oxidation. Waters. Mosher and F. Though qualitatively true. 6. 3 5 J.~6 Esters of tertiary alcohols appear t o be oxidised in a similar way.(29) . (31) H. 1529. 0. Acta. H. Czech. 78. 1948. 36 M7. A. .-butyl alcohol as well as pivalophenone. 3 7 R. steroid) secondary alcohols molecules with accessible (equatorial) hydrogen atoms should be oxidised more readily than their hindered epimers (with axial H).rsc. Artier. and from the reaction between pinacol and chromyl chloride. W.-. 4907. . RoEek. 1949. . Langerak. 1950. J. 1956. Chem. 833. Me. -CMe3 + HOOCMe. Cornna. Soc. '78. 286. Barton. Schreiber and A. | doi:10. Kwart and P. Coll. Chenz. 1949.> NO. Up to 67% of C-C cleavage may occur.

A. G./lc. SOC.) accelerate the oxidation. . .Wenkert and B. ( b ) Trans. = 4.0 both [PhCHO] and [HCr04-] and in the acid range 0.g. . naturally.3) as required by the mechanism Ph-CHO i-M+ i Ph&-OH YH ihCr04)- PH Ph-F' ti Fast Ph-C+&-Cr02-!H A H . NO. as would be expected for the shift of the equilibrium of reaction (32) in formation of cations (Ar*CH*OH)+.g. 3022. Deuterium labelling. 4 1 W . Chem.rsc. has been regarded as indicative of free-radical formation. (32) PH + H+ + (Cr 02)+ OH- Ph-C=O (33) Electron-attracting groups (e. (ii) Oxidation of Aromatic Aldehydes. as with isopropyl alcohol oxidation.1958.C*CDPh*OH. Mill. 75. 1953.1946. 5605.. 42E. it has been shown that the addition of nianganous or cerous ions reduces the oxidation rate by 30-40% by eliminating secondary reactions due to Cr1v. Xoc. Faraday SOC. B. .. With benzaldehyde. . Amer. e. if it is granted that reaction (24) may be reversible. J .1039/QR9581200277 WATERS OXIDATION BY CHROMIUM AND MANGANESE COMPOUNDS 287 View Article Online CrIV intermediate as soon as it is formed. .29~40 The oxidation of benzaldehyde is of first order with respect t. and effects of substituents have magnitudes according with Hammett's a function. 211. 1151. (a) J. M. 1946. . but a very complex mixture of products can result from controlled reactions with limited amounts of oxidant. . 184.42 I n cyclic systems axial attack of the chromic acid is thought to occur. . but a sequence of l-electron changes such as (29)-(31) cannot altogether be excluded. Wiberg and T. Oxidations of aliphatic aldehydes have not received detailed study. J. Mosher and D. It is significant that aliphatic aldehydes are oxidised less easily than the corresponding primary alc0hols. 80.018-0*3~ the logarithm of the rate constant varies linearly with the Hammett function H. Arner.41 However it is now thought that the oxygen absorption may be caused either by direct reactions of CrIVor CrV compounds with or by traces of organic free radicals formed by reactions between CrIV and organic molecules. 297) to give mixtures of a-hydroxy-ketones and a@-unsaturatedketones. .-Chromic acid oxidation of olefins eventually leads to carbon-carbon fission a t the olefinic link with formation of ketones and carboxylic acids. 4 0 K . Waters. Preiss. Comparison with PhCDO shows that the rate-determining stage involves H-C cleavage (E. by use of Me. Jackson. It has been suggested therefore that the C-C cleavage is an oxidation involving Crv [formed from CrlV by reaction (24)]. . but may well occur by a different mechanism.Downloaded by University of Sussex on 17 January 2013 Published on 01 January 1958 on http://pubs.29 Oxygen greatly increases the oxidation rate.~3 (iii) Oxidation of 0lefins... ibid... p. .40 Uptake of oxygen is quite common in oxidations of organic compounds by chromic acid and.indicates that chromic acid itself does not effect C-C fission..-This is now well understood. . Chem. | doi:10. 4 3 W. 1958. 80. . because oxidations of aliphatic ketones are thought t o occur by way of their enols (cf..

Hickinbottom and his collaborators. Amer.. this in fact was one of the main bugbears of early interpretations of oxidative degradations of terpenes. 5. 1360. L. Wood.4400. Peters. From Hickinbottom's studies the nature of the main initial reaction is now evident. under comparable conditions of acidity. 1957. pinacolinic rearrangement products are often formed. 1954. and in any case it does not represent the main oxidation route..49 Representation as (35). G. C.1039/QR9581200277 View Article Online The systematic studies of products by W.1948. J. Xoc.. Davis and W. has been regarded as an indication of some homolytic attack on the methylene group.. 1733. G . 48 M.~~ I n natural-product research this has been used for diagnosis of the -C=C-CH. Ginsberg and R. Peters. . J . or of some polar product easily converted into one of the latter " . SOC. ~Moreover ~ pinacolinic products cannot be formed from 1 : 2-diols nearly as rapidly as the latter are oxidised. ibid. F. . Pedlow. 1941. and D. M. A. 1951. H. Hogg. J . giving a carbonium ion and not necessarily a cyclic intermediate such as (111). both with chromic acid in aqueous sulphuric acid and with chromium trioxide in acetic anhydride. Chem. 79. r R2E-CHRiO-%r-O0 -!%R. 1 : 2-Diol formation is certainly a secondary reaction for epoxides can be isolated in high yields from olefins by the use of chromium n R.C=CHR' + fO=$r=Oi 0 .satis44 45 W. J.'-Oti + (HCr'"03)- (34) (1) trioxide in acetic anhydride diluted with carbon d i ~ u l p h i d e . Pappo. Szmuszkovicz. Whitmore and G. .. and earlier papers of the series.E-CHR. I). D. 516. J . Even the epoxides cannot be the initial products for they can be oxidised by chromic-sulphuric acid mixtures more rapidly than they can be hydrolysed or isomerised by sulphuric acid of the same c o n c e n t r a t i ~ n .org | doi:10. allylic oxidation is a frequent side reaction . Even if this hypothesis is correct the reaction may be due to CrIVrather than Crvl. J. 2205.288 QUARTERLY REVIEWS Downloaded by University of Sussex on 17 January 2013 Published on 01 January 1958 on http://pubs. like oxygen uptake during the oxidation. . *and ~ cyclohexene 37 yo of ~ycZohex-2-enone. have led to the conclusion that aliphatic olefins give mixtures that " can easily be explained by the initial formation of an epoxide. 63. Wood. Chem. 3352.. 70. Hickinbottom. R. M. 1958. Zwanzig. 758. J9 H. Hickinbottom. I). W. J . W. 1: 2-diol. it is electron-pair donation by the olefin to O=Cr. 1955. Zeiss and F. thus 1-phenylcycZohexene gives up to 25% of 3-phenylcycZohex-2e n ~ n e . 4 6 D.system and. to C-C bond fission products. 4 7 F. 4 4 ~ 45 As the above example shows. J. Hickinbottom. J.R. Amer. and D.rsc. ~ ~ For aqueous chromic acid the oxidation is of first order with respect t o both the olefin and chromic acid. giving a product that with water promptly yields the conjugate acid of an epoxide (I)4 5 48 ~ (reaction 34). Fieser and J. With alicyclic compounds.

This.HO-CH-C=C-C=O I I l l I CH=C-C-C=O HY) HO-Cr 0. . Long. J. Chem..Crq I I I (HCrOJ- l - l O=C-C=C. J.@unsaturated ket0nes. This indicates that chromyl chloride acts as an electrophilic reagent. 1952. Soc. 293). C6Hlo(Cr02C12)2. (1 v) O=Cr-CL Mechanism (35) can be extended to oxidations of conjugated dienes. which easily yield unsaturated 1 : 4-diketones or ketolsy50and also to oxidation with double-bond shift of .WATERS : OXIDATION BY CHROMIUM AND MANGANESR COMPOUNDS 289 Downloaded by University of Sussex on 17 January 2013 Published on 01 January 1958 on http://pubs. of course. such as a-CH.. Cristol and K. Arner.~1reactions often encountered with terpenes and steroids possessing structures that could not yield cyclic C P intermediates : $ 1 1 1 CH=C-C=CH I I I - + H. R*CH=CH. 72. the effect of the latter being proportional 50 51 J. . H. R*CHCl*CH. all subsequent stages can be adequately represented as passing via (I). R.-0-CrO-C1) + (cf. is the site of homolytic oxidation and possibilities of 1-electron transfer have been considered by Slack and Waters. J. Barton. 11) for which various cyclic mesomeric or non-classical structures such as (IV) must be written so as to explain the eventual trans-combination of the chloride ion. J. 3751.C=O F. 451. 52 S. R. Elks. Holness. Thomas. groups of aromatic side-chains. H. 1954. adding by an oxygen atom to the n-electrons of the double bond giving a carbonium cation (R*CH*CH. Overton. .-This requires vigorous conditions and preferentially occurs a t tertiary C-H groups or similar sites of reactivity. whilst olefins. Rosenfelder.30 Oxidations of hydrocarbons a. | doi:10. (iv) Oxidation of Saturated Hydrocarbons.C1. K.1039/QR9581200277 View Article Online factorily explains the difference between chromic acid oxidation and the attack on olefins of osmium tetroxide or potassium permanganate ( retarded by bases and catalysed by acids. and W.Hydrolysis gives 30-40% of trans-2-chlorocycZohexano1.*OH. D. and then much more slowly to form a brown solid.~2 I n carbon tetrachloride solution cyclohexene reacts rapidly to give C6H. G. and G. M.Cr0.. 1950. Evans. H. R. Eiler. .rsc. 4353. k I I l l -t 'CH-C=C-CH-OH c (36) I I l l HO-CH-C=C-CH-OH I l l $H-C=C-C=O __t OH (HCrOJ- .48 RCH-CH. (37) H+ The initial lead for the formulation of mechanisms (34) and (35) for chromic acid oxidations of olefins came from a study by Cristol and Eiler of the addition of chromyl chloride to 0lefins. N.. J ... by similar treatment yield chlorohydrins. J.

thus seems to be indicated: For such a mechanism steric factors should be important: in H-C bridgehead molecules.C=CH*Me. which usefully afford protection against subsequent oxidation. the isolation of easily-oxidised primary or secondary alcohols or their esters would clearly be impracticable. 54 55 . RoEek.53 This indicates attack by a cation. 1958. Chem...C-H and Et. Soc. W. &tard.. Enough has been said about the Guyard reaction (p.Downloaded by University of Sussex on 17 January 2013 Published on 01 January 1958 on http://pubs. M. Bradley. Hobbs and B. 1509.. C. It is suggested that they should be formulated as salts. such as anthracene and phenanthrene.-Though benzene is resistant to oxidation. Qualitatively. under the conditions that have to be used. Chim. Coll. Sager and A. 58.. Sager and Bradley54have shown that the rate-determining stage ruptures the C-H(D) bond. 1519. Amer. Undoubtedly the Btard reaction55 of chromyl chloride has a similar mechanism.. Phys..C-OH is an early product and conclude that it is not formed from the free cation Et. F. 1187.)+.56 Chromic acid oxidations of CH. e. assin hydrolysis of chromate esters. SOC. They find that the alcohol Et.) +. F. such as camphane which yields e ~ i c a m p h o r oxidative . J .org | doi:10. Chem. and it is significant that the Rtard complexes which generally contain two molecules of chromyl chloride per molecule of hydrocarbon are formed by direct addition and not by elimination of hydrogen chloride. Rev. Ladbury and C. 1957.-The 53 J.C-D.~~ attack is transferred t o a CH. Permanganate oxidations literature of oxidation by permanganate was reviewed in 1958 by Ladbury and C~llis. 403. Again. Chem. polycyclic aromatic and heterocyclic hydrocarbons. 5 7 J.1039/QR9581200277 290 QUARTERLY REVIEWS ViewBy Article Online comparing to H. (HCrO. Houston. the rates of oxidation of Et. group. 22. Cullis. are easily oxidised to quinones. Czech. 1954. 76.. W. 1881.1956.g. The oxidation may occur in stages but. 281) t o make i t clear that it is only when the selection of experimental conditions allows of oxidation of Mn2+and of the equilibration (16) that permanganate be- General Features. J .~VConsequently the following pages aim a t giving a broad picture of reaction mechanisms and show the very limited extent to which similarities can be traced between the chemistry of chromium and manganese. A concerted electrophilic substitution followed by cleavage of an O-Cr link. Ann. 78. 22. (v) Oxidations of Aromatic Hydrocarbons.rsc.C+ since this would promptly yield the much too easily oxidised olefin Et. the order of reactivity of these compounds is that of their electron availability and this is wholly consistent with attack by a cation such as (HCrO. chromic acid easily destroys ring systems containing electron-donating substituents such as OH or NH. Comm. Amer. 5 6 C. 218. Chem. groups give high yields of ketones: oxidations in acetic anhydride usually give their diacetyl derivatiGes >C(OAc).. 1354.

435. 47. J . Drummond and W. both of these can be investigated experimentally. Drummond and W. (MnO. according to whether they yielded dissolved blue (Mn0. 56. However the quantitative conversion of (Mn0. SOC. considered separately below (p. in which the blue anion (&b~o. showed that whilst (M~IO. 1407. Y. 1955. Chem. often giving oxalate as the end-product. 791.ions.into BaMnO. F.59 Consequently the mechanisms of oxidations effected by manganic salts.. I n minera'l acid solution where oxidation of Mi2+to Mi3+can occur easily the manganic ions have a higher redox potential than (MnO. under these conditions does not indicate invariable 1-electron abstraction. A.ion is directly involved there are two distinct paths.. yet its reactions could be divided into two (Mn04)-. W. 2. e. J.). Following Stamm. was not a specific oxidiser for particular organic groups. 2571. M.-Oxidations by electron transfer can be studied only in alkaline solutions in which the anions (Mn04)2-and (Mn04)3. 61 A. who introduced alkaline permanganate as a volumetric reagent and used baryta to prevent bulk reduction beyond the manganate stage (BaMnO. occurring by oxidations of aldehydes and ketones through their enol anions. Cullis. Ladbury and C. J. 555. are of particular relevance to the understanding of the modes of action of solutions of permanganate in mineral acid. 4186.are reasonably stable.g who studied oxidations effected by sodium manganate in 10N-potassium hydroxide. 59 J. 2850. Of aliphatic compounds only ethers. These are tabulated. This is the case with those permanganate oxidations which exhibit autocatalysis. Chem. For oxidations in which the (Mn0. Modes of Electron Transfer to (MnO.. . . 296). F. A significant feature of these oxidations was the repeated stepwise degradation of hydrocarbon chains. By adding fluoride or pyrophosphate to remove free M n 2 + and Mn3+ these oxidations can be inhibited almost completely.). angew. a visible product or immediately gave brown hydrated manganese dioxide (MnIV). H. 1953.58 Side-chain oxidation of aromatic hydrocarbons seems to be largely. Stamm. Waters.)~has a reasonably long life.)e --+ (MIIO.)~-. Waters.)".1934.60. J. Drummond and Waters 61 verified that organic compounds of many types were rapidly and extensively attacked by cold alkaline permanganate. (a)mere electron | doi:10. of this type. Lamer and D. 1934.. Y o s t . and ( b ) direct oxygen transfer. so many substrates are then oxidised by manganic cations and not directly by the permanganate.). tertiary alcohols (excluding 1: 2-diols). since the immediate electron transfer (39) destroys any evidence for the transient existence of a Mnv valency leveLg + Later work by Pode and Waters. though not exclusively. A. Amer. 6o H.1039/QR9581200277 WATERS : OXIDATION BY CHROMIUM AND MANGANESE COMPOUNDS 291 Viewthis Article Online comes a 5-electron acceptor. is very insoluble).g.Downloaded by University of Sussex on 17 January 2013 Published on 01 January 1958 on http://pubs..anions. Y. 579. the best known examples of which are the oxidations of hydrogen peroxide and of oxalic and malonic acids. and the anions of saturated acids resisted attack. A.)~-.)3. 1954.

. only the compounds of Group A . 1956. J. Group B.)2. olefins.and (O. aldehyde oxidation. There may of course be oxidations in which the mechanistic course depends on the pH of the environment and it does seem as if. and the rapid oxidations of 1: 2-diols. 3176.8 a-Hydroxy-acids.lose electrons directly with (Mn04)-. undergo autoxidation that can be catalysed by cupric salts (eqn. Downloaded by University of Sussex on 17 January 2013 Published on 01 January 1958 on http://pubs. thus aldehydes could not be tested. HSO. A. all the types of molecule that are attacked by alkaline permanganate. Though it is possible to formulate oxidations of Group B as 2-electron transfers. e. Rigby.8 Ketones.).. . phenols. 40) and radical dimers of sulphur comCu2+ + (HS03)- e Cu+. are oxidised by both (MnO. 2452. It is significant however that whilst manganate can attack. I n contrast.06. are easily oxidised by undoubted 1-electron-abstracting ions such as Mn3f or [Fe(CN)6]3-. (Mn04)2-.. 64 HowG2 S.292 QUARTERLY REVIEWS View Article Online Classification of oxidations effected by alkaline manganate Group A .by mere I-electron abstraction. Baer and G.into | doi:10.)3-.rsc.:). ketonic acids. Waters.-(i) Permanganate oxidation of oZeJins. c 3 H.and (Mn0. + . even amongst organic reactions. p. Substances oxidised by direct conversion of (Mn0. Substances oxidised by l-electron transfer (MnvI +Mnv). sulphite. but not those of Group B.)3-. 4312. which are rapidly attacked by manganate .. .1039/QR9581200277 Hydrogen peroxide. but in alkali both (H0.9. Arsenite. The scope of this survey was naturally limited by considerations of solubility and stability in strong alkali .* thiosulphate. .S. . 297). Other analogies support the general conclusion that substances of Group A . 1953. the direct electron transfer process occurs only in reactions between two ions (cf. Land and W.62 I n acid permanganate (free H202)it needs trace catalysis by Mn3+. probably a matter of relative redox potentials. which yield (MnOJ3. 1957. alkaline manganate has been shown to exhibit the same stereospecificity of attack. J.from (Mn04)2-.*). . Na. may however react by l-electron transfer. though much more slowly. formic acid. Na2S.. the evidence given below shows that most of them involve oxygen transfer as the prime reason for the valency change of the manganese. R. 6 3 Phosphites and hypophosphites. J. it may be recalled.S.g. Thus the stepwise l-electron transfer is the invariable course of oxidation of hydrogen peroxide to oxygen..)2. oxidises only to (AsO*)~-and is not directly attacked by M n 3 + .06. 64 W. Other noteworthy experimental features are the stability of phenoxide anions t o (MnO.. It is well known that dilute aqueous permanganate very rapidly oxidises olefins to cis-1 : 2-diols. More recently. Oxidations known to involve Oxygen Transfer. unsaturated acids. Stein. and (&tno. Alcohols.(40) pounds. Sulphites. as established for example with Ce3+. a're well known.

and then. by bimolecular attack of hydroxyl anion on the manganese + f-y "d" '0cis-Diol (VII) 0 I HC-YOH B ~ I * 9~ H . Xoc. 127.Downloaded by University of Sussex on 17 January 2013 Published on 01 January 1958 on http://pubs. 1957. 522. Acyloin production is thought to involve oxidation of the Mnv ester (VI) by permanganate anion to (VII). An alternative attack of a base on G. 2822.1039/QR9581200277 WATERS : OXIDATION BY CHROMIUM AND MANGANESE COMPOUNDS 293 View Article if Online ever a careful selection of experimental conditions is imperative good yields of diol are required. 27. 6 7 I<. Chern. 48. 284). Mottram. 'O R. 1925. J.. N. c8 G. Arner. 40. Criegee.R' is a t once formed 65 whereas in decidedly alkaline solution (pH 12 or over). is further oxidised only slowly. J ... Phys. SOC.rsc. B.. similar t o that operating in chromic acid oxidation of secondary alcohols (p. Lapworth and | doi:10. have been able t o establish that in the oxidation of oleate up to 1-5(i.which then by a concerted base-catalysed process.70 Only recently has clear support for this hypothesis come from the work of Wiberg and Saegebarth 6 7 who. + (HM&J- +(H@ centre. virtually 2) atoms of oxygen can be transferred from perrnanganate anions to each olefin molecule.. King. both of which hydrolyse between the manganese and the oxygen atoms. Saegebarth. 553. To explain cis-hydroxylation the formation of a primary cyclic adduct (V) containing MnV. Annalen.67 Again glycol fission and Wagner rearrangement can both occur as side reactions. by using l*O-labelled permanganate under favourable conditions for diol formation. Wagner. Thus the intermediate (V) must have two C-0-Mn bonds. G5 T . To explain the formation of either the 1 : 2-diol or the acyloin. 1921.1895. 1936. chirn. when once formed.66 Organic co-solvents (acetone or alcohol) favour diol formation. O9 J. 6 6 A . '79. Boeseken. 1788.. 1628. even in the presence of an excess of permanganate. 219.suggested by Wagner 68 and then Boeseken. 1928. J . Chena.Gg has long been favoured. J. containing MnV1. particularly since from spatially similar osmium tetroxide the analogous cyclic intermediates have been isolated. A.C 0 - HC-%H I * ~ ~ ~ O ?=O (Vll) Acyloin. Rec. Traw. the diol predominates and. Wiberg and K. 1936. 683. to hypomanganate and the cis-diol (41). gives the acyloin and MnIV. 75. Russ. Wiberg and Saegebarth suggest that the cyclic intermediate rapidly hydrolyses t o (VI). By rapid addition of permanganate to a neutral solution of an olefin an acyloin R*CH(0H)CO.

73 showed that both (MnO. Stafford. I n very alkaline solution. C. A similar mechanism to (43) was earlier suggested by Merz. phys. Chem.oxidised formate anions and gave the first indication of the transient existence of blue (&tr~O. B. G. . The electron transfer stage of oxidation of (VI) to (VII) is introduced to avoid postulating reduction of manganese below the valency level of &Iv. but this like the hydrolysis of (VI) presumably needs free hydroxyl anions. 1951. 73 J. Holluta.itution of PhCDO for Ph*CHO decreases the reaction velocity 7-fold. 7 4 F.and possibly hydroxyl radicals has been tentatively proposed. Chem. 78. Wiberg and R.O * Ar-$. (42) + Ar-$20 + (Mnvo3)-. (*O-Mnq)- OH Fast H. . and for oxidation of alcohols by permanganate.. Wiberg and R. (ii) Oxidation of aromatic aldehydes.71 It is a bimolecular reaction showing general acid catalysis and has been assigned the following mechanism (42. 1786. indicating a rough reaction order of [Ar*CHOJ[MnO. 32 and 33).Downloaded by University of Sussex on 17 January 2013 Published on 01 January 1958 on http://pubs.). 276. 489. Amer. Chem.. Xoc. Stewart.)--c CO.43)is exactly similar to that operating in oxidation of aromatic aldehydes by chromic acid (eqns. J . I n neutral or weakly alkaline solution the reaction is approximately bimolecular. J . B. 2. .1941. . J . showing that electron-attracting substituents by preventing the formation of the organic catior. 1214.1956. (43) OH drawn for relative oxidation rates of substituted aromatic aldehydes. The scheme (42. 1922. 75 so that the initial reaction is one between two similarly charged ions: (HCq) . shows a primary salt effect. Formic acid is more easily oxidised by strongly alkaline than by acid permanganate and is scarcely attacked by manganic cations. they thought however that in this case a valency change from &Iv to MnII was concerned. Stewart.'~. 638. .rsc. A. 1955. A Hammett plot can be + Ar-CHO t (H30)+ =i?Ar-ZH-OH Fast H H -1 Ar-5' + I. (iii) Formic acid oxidation.-][OH-]h. + (MnOJ- + (OH)' . . J. in 1922.MnO. 201. For this a free-radical chain mechanism involving the anion Ar*CH(0H)-O. Waters. 37. This has also been proved to involve oxygen transfer from manganese to carbon in neutral or acid media.1039/QR9581200277 294 QUARTERLY REVIEWS View Article Online the hydroxyl hydrogen of (VII) can lead to glycol fission.74.+ (MnO. . Trans. Early work of Holluta. . Tompkins.and (Mn04)2. and is not dependent upon PH. . 102. a more complex mechanism is involved since (i) the deuterium effect decreases and (ii) the overall rate rises only about %fold per unit change of pH. . SOC. Ht .. . Merz. (44) K. and W.. 32. when manganate results. 7'9. 101. 34. 7 5 K. Amer. An alternative route of diol formation is of course hydrolysis of ester (VII) by 0-Mn bond fission. in reaction (42) decrease the rate of | doi:10.)~-. 43) because subst. OH . .%O-. Stafford. 71 72 . Furaday SOC. This is more complicated.

4) has been noted by Wiberg and Stewart who also showed.. 79. but this does not explain the selectiveness of attack on a y-C-H group.Hin preparative yields. 2129. .org | doi:10. SOC. . A concerted -&3h. Stewart. (iv) Oxidations of tertiary C-H in aliphatic acids R2CH*[CH2]. Amer. whereas formic acid is oxidised less easily than formate. (11 )I.6) but no oxygen transfer.73 To avoid this argument they suggest the partly-bonded transition state (IX). -O-C.. Symons. C. 0 . Though most saturated carboxylic acids asreinert to cold alkaline permanganate. 5 ~alkali ) equally effective oxidation occurs.). = 6. and optically active carboxylic acids give racemic products./k. but with complete retention of optical activity.-ji (IX ) Q- -0-C=O*t Slaw Ht + (Mn03)- . (46) hydride-ion removal (46) would explain these observations.WATERS : OXIDATION BY CHROMIUM AND MANGANESE COMPOUNDS 295 Downloaded by University of Sussex on 17 January 2013 Published on 01 January 1958 on http://pubs. solutions. whereas with manganate in dilute (ca. Kenyon and Symons.rsc. Kenyon and Symons suggest that the strongly alkaline permanganate may remove a hydrogen atom via hydroxyl radicals [formed as in eqn. . that there is a definite (18-300/0) transfer of lSO to the resultant carbon dioxide. 3057. With permanganate in concentrated (>5 ~alkali ) the yields can reach 70--90%. = 7. as in eqn. 3580.1039/QR9581200277 View Article Online A deuterium effect ( k H / k . followed by a slow concerted rearrangement involving both C-H and O-Mn links. The latter reaction must therefore be a hydride removal involving an Mnvl to MnIV valency change and the transient formation of an optically inverted y-lactone. J . + (H-O-Mn03)-. (45) (MnO.*C0. J. 76 77 R. (43). 1953. suggested for chromic acid oxidation of saturated hydrocarbons. second-order reaction in which there is a clear deuterium effect (k.from which hydrogenbonding to the whole (MnO. Kenyon and M. .*C02H.75 This could be explained by a reversible addition to a carbonyl bond. Chem. but they regard t'his as improbable. .77 found that acids of the general structure given above can be converted into hydroxy-acids R2C(OH)*[CH2]. This is a base-catalysed. A structure similar to (IX) has been proposed by Stewart to explain the mechanism of permanganate oxidation of diphenylmethanol76 in dilute alkali. The sequence (47) can be compared with mechanism (38). J . . as in sequence (45).1957. though it does not suffice in the case of formic acid. since the 0 1 7-8:MnO.) can be thought t o promote the chemical change. R. or manganate . by using labelled permanganate.-H n + O=Mnqu - O=Cph.anion would be expected to add to un-ionised formic acid (with a fairly definite C=O bond) more rapidly than to formate anion.

Y. have been prepared and | doi:10. many complex manganics salts. 1958.6l I n general. J. Bull... Waters. dependent on pH. of the organic free radicals generated by the initial stages of MnlI1 oxidations. 62. though they must be far less stable than anions of form (MnO.296 QUARTERLY REVIEWS View Article Online Downloaded by University of Sussex on 17 January 2013 Published on 01 January 1958 on http://pubs..g. G. 70. 81 H. I.82 The distinctive features of several of these ozidations.1 to 1. 1939.)%-. Drummond and W. J .81 On account of the resistance towards oxidation of vinyl cyanide and methyl methacrylate the induced polymerisation of these monomers can be used to establish the presence.15 The various manganic pyrophosphates. (Mn03)2-. Chem.2 v. + 3(OH)- A point of general interest to be noted from inspection of these oxygen transfers is that they show that both manganite. Soc. Chein. often a t rates suitable for kinetic study. 2836. Nichols. A.lcoholsand olefins are not attacked though ally1 and crotyl alcohols can be oxidised very slowly. 2129. oxalates. The redoxpotential measurements of Watters and Kolthoff 8O give values. Amer. J.1039/QR9581200277 H20 + (HMnOJ3- - MnO.7~Since most chelating agents form much more stable complexes with tervalent than with bivalent cations. + L. 1953. though the sulphate.)3}3. (MnO.O. France. monohydric a. which have been examined by Waters and his collaborators. Cartledge and P. SOC. malonic and oxalic acids. e. A.79 and pyrophosphates. cc-hydroxyacids.)--. malonates. probably in the form of a complex ion. Land and W. Domange. 594.chim. Towards organic compounds manganic pyrophosphate is quite a selective oxidant : it attacks aliphatic aldehydes and ketones. 78 7g . 3057. Kolthoff.P. to (Mn(H. showing that manganic pyrophosphate is decidedly a more potent oxidiser than ferric salts but inferior to ceric salts.. yield stable solutions at acidities down to pH 6 and are clearly the most suitable of these complexes for use in oxidation studies. are noted below. and phenols.rsc. and permanganite.anions must be entities capable of transient existence.). 1940. J. is stable in sulphuric acid of over 60% ~oncentration. Oxidations involving manganic ions On account of the disproportionation (16) free manganic cations cannot exist in significant concentration in aqueous solution.according to the degree of ionisation of the pyrophosphate groups. 6. H. Waters. Wetters and I. Amer. SOC.P20. 2455. M. ranging from Mn(H. and something of the nature. Most of these have rapidly displaceable ligands. in the range 1. 8 2 A. 8o J.1948. M. 1: 2-diols..

WATERS : OXIDATION BY CHROMIUM AND MANGANESE COMPOUNDS 297 Downloaded by University of Sussex on 17 January 2013 Published on 01 January 1958 on http://pubs. It is noticeable that chloral hydrate. 217. and these are easily oxidised further. (49) .g* disproportionate rapidly. + Mn3+ R-CH=CRiO.CHR-CR/=CH-OH (51) . 83 84 . for the oxidation step (eqn.. . + Mn2+ + H+ . 1955. also oxidise at rates independent of the MnIII concentration. in these cases oxidation through a 1 : 4-conjugated enol hydrate (54) is ~ u g g e s t e d . . but of less than first order with respect to pinacol. these have several points of interest.CH=CR'(W) . (52) R-iki-CRk . ~ ~ Specific Oxidation of 1:2=Diols. a-methylacraldehyde. . Thus t.CH=CR!OH t (BH)' Mn3' R.. (53) . A. which cannot form normal enols.. .CH=C&O* + Mn3+ - R. with liberation of carbon dioxide. R. . or. . 8 5 Idem. formaldehyde. resonancestabilised radical that can then lose a second electron from the a-carbon atom. - R. Waters. J. (48) (Immediate) + RCHiER'(0H) .1039/QR9581200277 View Article Oxidation of Aldehydes and Ketones. 497. ~This ~ can be hydroxylated in the a-position.CH=CR?CH=o 2 HO.-These regularly seem t oOnline occur through the enols or enolate ions. J .~3 With ketones the same features emerge only at high MnII | doi:10. J. which can be brought about by several 1-electron-abstracting agents. the actual relationship being 85 of the form . 6: + R. Levesley and W.-c Mn2++ R. 3119. 50) becomes measurable a t low concentration^. as in the case of cyclohexanone oxidation.CH(OH)-CRLO + R. .t (BH)' + FtCH=CF(OH)(M~~sureaable). since this would leave a mesomeric. Idem.&-CR&O H p - + RCH=CRLO' + R. Waters.w=CR<O. are not easily oxidised 8 3 (reactions 51-53). . .-Leading t o quantitative carbon-carbon bond fission. Y. 1953. A.^^ R-Cl-$COR'+ (H30)+ 6: RCH&R'(OH)+ H20 . 1955. - (50) a-Hydroxy-aldehydes or ketones are the first detectable molecular oxidation products.d[MnIII]/dt cc a[Pinacol]/(b [Pinacol]) This has been explained by suggesting that the pinacol must first (reversibly) displace a chelated pyrophosphate group from attachment to the manganese atom before the electron switch (55) can occur. With pinacol the initial oxidat'ion rate is of first order with respect to total MnIII. Drummond and W.86as also does + A.rsc. It has been suggested therefore that the true oxidation step is the removal from an enolate anion of an electron. .he oxidation rates of propionaldehyde and butyraldehyde are of zero order with respect to MnIII and of first order with respect to both aldehyde and hydrogen i0n. Some a-hydroxy-acids seem to oxidise similarly. (54) However ncraldehyde. as in equations (52) and (53). . and formic acid. . and further oxidation can then occur as for a typical 1 : 2-diol. 440. 86 (Miss) P. which cannot yield enols. 1953.&-CR'=O . Pyruvic acid however is oxidised quantitatively to acetic acid by a process related to that of a-hydroxy-acid oxidation and not by e n o l i s a t i ~ n . and crotonaldehyde. J.

Waters. 61).rsc. is profoundly affected by the presence of oxygen. the relative rates of attack are not the same as for their oxidations by lead tetra-acetate or periodic acid and the reaction order with respect to is not the same in all cases. | doi:10. the initial-rate measurements showing that the critical first oxidation step [simplified in eqns. For instance the radical *CMe. for the oxidation of oxalate by manganic 87 89 (Miss) P. in which the two carboxyl groups are so powerfully electron-attracting that there is a marked tendency to further electron gain a t the tervalent carbon centre. Y. like many others.OH. This induced oxidation.and benzyl-malonic acids.H). . . .298 QUARTERLY REVIEWS Downloaded by University of Sussex on 17 January 2013 Published on 01 January 1958 on http://pubs. 840. Moreover it is specifically affected by manganous cations. cannot directly oxidise monohydric alcohols or ethers. for it can effect the oxidations of methyl and ethyl alcohols. ~reduce ~ mercuric ions to mercurous ions. which unlike organic free radicals are merely electron abstractors. N. A. (59) an oxidiser. liberated during the oxidation of pinacol (eqn. An interesting example of this induced reduction by a transient mdical is afforded by oxalic acid (60. (57) . . 55):82or in other W ~ Y S can . HO*CH2-H + -= *CH(C02H)* Mn2++ H t -4- Mn2' --t sCH(CO~H)~. . and A.87 Evidently the stereochemistry of glycol fission by 1-electron abstraction needs further study. and probably many other organic compounds (reaction 59). Malonic acid affords another case in which oxidation by MnlI1 occurs through a chelate complex. . as equation ( 5 7 ) implies. can also reduce MnIII it is. HOCHi + H2C(C02H). J . 1956. even in the presence of manganic salts or other oxidising agents. 1949. for manganic salts themselves. .H). which is not observed with ethyl. Wright. Mn3+ Mn3+ + H2C(qH)2 + . 1954. . 2456. A. Levesley.88 This oxidation.1039/QR9581200277 View Article Online pyruvic acid (56). Though the radical *CH(CO. J . for in fact the great majority of carbon radicals are reducing agents. Few organic free radicals as yet have been shown to exhibit this oxidising power. . J.and trans-glycols are examined. to which the initial organic free radicals are sensitive. J . A. S. (58) . Merz and W. 15. + +CH(CO. Waters. (57) and (58) by neglecting the fact that only a manganic-malonate complex reacts] is reversible. is thought to be due to the electronic structure of the radical *CH(CO.H). When isomeric cyclic cis. Drummond and W. Here one has a novel form of induced oxidation.H). . . .CH(Co. W. ethers.

The important permanganate-oxalic acid reaction. . . J. (65) . P.. 63. .org | doi:10. .1941. . . Weiss. H. . .~O Mn3+ (C20$’-+ Downloaded by University of Sussex on 17 January 2013 Published on 01 January 1958 on http://pubs.H)~CO. Detailed treatment of effects of oxygen would require discussion of mechanisms of reactioiis between organic hydroperoxides and metallic ions . . . Discuss. R-0. has been investigated and discussed so frequently57 that it needs but brief mention here. .H). Cartledge. but it has been reviewed frequently in view of its great technical importance in hydrocarbon chemistry. this cannot be summarised here. . + (Mn04)*.CH(CO. A similar catalysis involving the radical *CH(CO.Sl and that the autocatalytic nature of the overall oxidation is largely due to the rapidity with which the (GO. Anzer. + *O-O.radical-ion can attack permanganate itself (62).Cq)- ’ . . 1947. which often changes the whole course of the reaction subsequent t o the initial production of an organic free radical.CH(CC~. . + HO-CH(CO~H)~ 3% *CH(OH)CO.0. Bell and 0. 9 l R . . Paraday Soc. . (66) 90 J. complexing of these with oxalate groups being important. + CO. . Thus whereas under nitrogen the oxidation of malonic acid takes the course ~ ( c c p )+ . . Chem. for instance. J. Lidwell.. 1935. . operates in the oxidation of malonic acid by acid permanganate. . .)- - C02+ Mn2+ CO. M. + 3C02 proceeding through oxalic acid to complete oxidation to carbon dioxide.H). (60) . . . .H with loss of carbon dioxide a t the stage of tartronic acid and eventual production of a molecule of formic acid. here of the 0. X3+ + x2+ - 7 - (R-0-0:)- R+ 4.. G. + H*CO. 188.WATERS : OXIDATION BY CHXOMIUM AND MANGANESE COMPOUNDS pyrophosphate can promote the reduction of mercuric this being a radical-catalysed chain rea~tion. . 2.1039/QR9581200277 (C02)- + Hg2+ cCC2). SOC. (63) . An important aspect of oxidations involving manganic ions is the influence of oxygen. . + + x2+ R-O-O-H R-0. 299 View Article Online chloride by oxalate. . . (64) X 3 + .H). .H --c CO. . (R-0:)- + + + X3+ x2+ (:OH)- + X3+ + . (61) - (62) Oxygen uptake by radicals is of course another instance of induced reduction. . 1303.rsc. .CH(CO.+ Hg+ C02 + (.. except that it should be pointed out that the initial attack on oxalic acid is effected by manganic ions. . the reaction in the presence of oxygen seems to have the course . . It is sufficient to note that reactions of the types (63)-(66) (where X is a metal of variable R-0-0. molecule. . . Induced reductions and oxidations of this type are undoubtedly involved in quite a number of the oxidations that can be brought about by means of potassium permanganate in mineral acid solution.).t (Mn0. . . + (COZH). f X’ R-0-0.

taking note of the present interest of quantum chemists in structures of compounds of the heavier elements.1039/QR9581200277 300 QUARTERLY REVIEWS Article valency). . the favoured processes dependingView upon theOnline redox potentials of the ions concerned in the particular environment of the reacting system. Indeed all kinetic work on oxidations involving ions of the transition elements in which cognisance has not been taken of the possible intervention of oxygen effects should be viewed with some scepticism. Oxygen undoubtedly affects the course of many oxidations in which acid or alkaline permanganate is the reagent. it can be seen that the systematic understanding of the reactions of both chromic acid and permanganate is beginning to emerge.rsc. some substantiated in good detail but many still remaining as tentative hypotheses. one can hope for theoretical help in the elucidation of many of these problems. The major gap in experimental knowledge now concerns the inorganic chemistry rather than the organic chemistry of oxidation processes. Mnvl. and MnIV in acid media. from other studies.41b but its presence has rarely been taken into account or searched for experimentally. for | doi:10. Mnv. Of the above reactions (63) and (64) are involved in the oxidation of hydrogen peroxide by manganic salts and also in the permanganatehydrogen peroxide reaction. Conclusions Though this Review presents a wide range of reaction mechanisms. Crlv.Downloaded by University of Sussex on 17 January 2013 Published on 01 January 1958 on http://pubs. one can only make tentative suggestions concerning the structures and properties of the unstable ions of CrV. can all occur. However. it is possible to adduce relevant evidence concerning the natures of transient organic ions and free radicals.