JOURNAL OF RESEARCH of the National Bureau of Standards - A. Physics and Chemistry Vol. 72A, No.4, July- August 1968 Periodic Acid, a Novel Oxidant of Polycyclic,
Aromatic Hydrocarbons *
Alexander J. Fatiadi
Institute for Materials Research, National Bureau of Standards, Washington, D.C. 20234
(April 1, 1968)
Certain polycycli c, aromatic hydrocarbons can be oxidized with periodic acid in aprotic solvents co ntaining a small proportion of water. A unique, two·fold character of response to pe riodic acid by these hydrocarbons has been found: (1) producti on of a coupling reaction through a radical in ter mediate [conve rsion of pyre ne into l,l'-b ipyrene, and fluore ne into 1,2-b is(2,2'-bipheny lylene)ethyle neJ or (2) conversion into qui nones by a two-equivalent ox idation mechanis m that does not involve a radical int ermediate [acenaphthene, anthracene, a nthrone , benz[alanthracene, naphthacene, naphthalene, and phenanthrene]. Little or no reacti on was observed whe n oxidation was attempted wi th sodium meta periodate in stead of pe riodi c acid . Electron-s pin resonance revealed no radical intermediate in th e ox id ati on of malonic ac id with either periodic acid or sodium periodate.
Key Words: Aproti c solvents; aromatic hydrocarbons; malonic acid ; periodic acid; pyrene radical; quinones; reacti on mecha ni s m; sodium metape ri odate.
1. Introduction oxidation on solids , on e-electron transfer oxidation , and various other methods .
Recentl y in this laboratory  , I the fate of certain P eriodi c acid (o r its salts) has been used extensively of the polycyclic, aromatic hydrocarbons that have for cleavage of 1,2-glycols, and a-hydroxy-aldehydes been identified as cons tituents of polluted air has been and -ketones [28- 33]. In aprotic solvents containing studied under conditions simulating those that these some water, periodic acid has been used for the oxi substances encounter as air pollutants; that is, (a) in dative hydroxylation of an active methylene group the presence of ultraviolet irradiation, (b) exposure to [34- 36] , for oxidative cleavage of enols and reductones air and s li ght heat, and (c) contact with powdered [37, 38] , and for hydroxylation and further oxidation solids (particulates). Oxidation of many of the hydro of compounds containing an isolated double bond, carbons studied occurs under such conditions. In e.g., cinnamic acid  and cholesterol  . order ·to identify the products, it was necessary to The application of periodic acid alone as an oxidant synthesize possible oxidation products for use as for polycyclic, aromatic hydrocarbons has not hitherto reference materials. been reported [33, 41]. Sodium metaperiodate has, The main object of the present report is to describe however, been used conjointly with s uch diol-forming the usefulness of periodic acid for the oxidation of agents as osmium tetraoxide or ruthe nium tetraoxide pol ycyclic, aromatic hydrocarbons. Numerous reagents . The present study s hows that, wh e n it reacts with certain polycyclic, aromatic compounds, periodic 1 have been used to effect such oxidations, including the Milas reagent , the Fenton reagent  , benzoyl acid has the ability to (1) produce radi cals by abstrac peroxide [4, .5 ] , benzyl radicals  , ph enyl radicals tion of (a) electrons or (b) protons, (2) oxidize a methine  , and oth er free-radical reagents  , lead tetra group at an activated double bond of polycyclic, acetate [9, 10] , ozone [11- 14] , and peroxy acids [I.5 ] aromatic compounds, or (3) oxidize an activated I in cludi ng hydrogen peroxide in acetic acid  , methylene group. i peroxyaceti c acid [17, 18] , and peroxytriAu oroacetic 'T acid [19- 21]. In addition, there are autooxidations 2. Reaction Conditions  , metabolic oxidation  , peroxidase oxidation  , photooxidation using solutions [2.5], photo- 2.1 . Solvent
*Prel illlinary co mmunic ation: Che rn . CO llllllun. 1967, to87. The choice of a solvent in which to oxidize polycyclic,
l Fi gures in urac kets indicate the lit erature refe re nces allhe e nd of this paper. aromatic hydrocarbons with periodic acid appears to
341 be very important. In the present work, glacial acetic compound having the phe ne structure and one active acid was usually the first so lvent investi gated ; some methine group [pyre ne (I)], and (3) compounds having times, propionic acid could be used. In most cases, one or two active methylene groups [anthrone (8 ), oxidations in formi c acid afford lower yie ld s than in acenaphthe ne (15), and flu orene (20)]. Maloni c acid acetic acid. A seri es of aproti c solv e nts, mi scible with (14), which has an acti ve methylene group, was also water and relatively stable in th e presence of periodic ox idized. In addition, the following co ndensed-rin g, acid at elevated temperature, was tri ed. These solvents, polycyclic, aromatic hydrocarbons we re tested: in th e order of their decreasing sta bility to the oxidant biphe nyl , c hrysene, coronene, Au oranthe ne, perylene, are: N,N-dimethylformamide, p-dioxane, acetonitrile, picene, p-terphenyl, and triphenylene. acetone, tetrahydrofuran, methyl s ulfoxide, and acetic anhydride. Methyl s ulfoxid e was used in the oxidation of anthracene with good results, but its application 3. Results and Discussion with other hydrocarbons has not ye t been f'xplored. The stability of N,N-dimethylformamide in the pres 3.1. Effect of Solvent ence of periodic acid has previously bee n indicated  . Such solvents as formamide, 2-methoxyethanol, bis(2·methoxyethyl) ether (di glyme), or 1,2-dimethoxy The effect of various solv ents on the reacti on may ethane are not suitable as the reaction medium, be be seen from the following examples: ox idation of cause of in stability in the presence of periodic acid' phenanthrene (1 0 ) with periodic acid gave a poor at elevated te mperature. When aceti c 'anhydride -.va", yie ld (3-6%) of phenanthre nequinone (II) in N ,N· used .in the oxidation of pyrene with pe riodic acid, dimethylformamide or in glacial acetic acid, but a with application of heat, a violent reaction occurred. good yield (45- 55%) in p-dioxane. Anthracene (5 ) affurded a moderate yield (30%) of anthraquinone (6 ) in acetic acid, a good yield (50 to 60%) in acetone or .2.2. Temperature methyl sulfoxide, and an excellent yield (90%) in To initiate oxidation of polycyclic, aromatic hydro N,N-dimethylformamide. Naphthalene (7 ) in p-dioxane carbons with periodic acid, some degree of heating was practi cally unaffected; but, in aceti c acid, showed was found to be necessary. In the conversion of pyrene oxidation in good yield (70%) to '1,4-naphthoquinone (I ) into 1.l'-bipyrene (2) only mild warming (40 to (9 ). Naphthacene (3 ) gave a low yield (10- 15%) of 50 °C) was necessary; however, dimerization of flu orene naphthacenequinone (4 ) when oxidized in p -dioxane (20) into 1,2-bis(2,2'-biphe nylylene)ethylene (24) re or aceti c acid, but an exce ll ent yield (80%) in N,N quired a much hi gher te mperature. The oxidations dimeth ylfo rmamide . Pyrene (I ) was not oxidized in that resulted in quinone formation us ually require 5 N,N-dimethylformamide, p-dioxane, acetone, or to 10 min of heating at 95 to 130 °C to start; then the e thanol, but was oxidized in acetic acid. Fluore ne te mperature must be lowered to 60 to 80 °C to avoid (20) was not affected in N,N-dimethylformamide, vi gorous and some times violent reaction. Usually, the p·dioxane, or acetonitrile, but dimerized in acetic acid. beginning of the oxidation (and the end of the induc· It may be concluded from these experime nts that the tion period) is noted by a change of the reaction solvent participates in th e overall reaction process. medium from colorless to red or brown-red; sometimes, As noted by Ritchie and co-workers  , the effect this is followed by evolution of iodine vapor. of the solvent on reactions in solution is associated with a so-called solve nt reorganizati on, and this factor may make an appreciable contribution to energies of 2.3. Proportion of the Oxidant activation in solution. Furthe rmore, the polarity of the solvent may partake in promotion of the rate Oxidative d im erization of pyrene (I ) to 1,l'·bipyrene of oxidation, by hydrogen bonding in the transition (2 ) was effected with a 1 : 1 mole ratio of periodic acid state. to hydrocarbon. In this reaction, it was possihle to de monstrate stoic hiometric consumption of the per iodic acid. However, in the oxidation of the other hvdro 3.2. General Reactivity of Polycyclic, Aromatic carbons to quinones, approximately 4.2 moles of the Compounds Toward Periodic Acid oxidant were used per mole of hydrocarbon. This proportion was emplo yed on the assumption that, in Results obtained in this study on the acti on of each hydrocarbon molecule, two methine or me thylene periodic acid on a variety of polycyclic, aro matic groups become hydroxylated and then oxidized to the hydrocarbons reveal that linear and angular poly corresponding quinone. cyclic, aromatic hydrocarbons having the acene structure (anthracene, benz[a]anthracene, naph 2.4. Compounds Oxidized thacene, pentaceue, and their analogs)  are the most reactive; next are the condensed·ring aromatic Three kinds of polycyclic, aromatic hydrocarbons compounds having the phene structure (acenaphthe ne, were used in the oxidati ons: (1) compounds having benzo[a]pyrene, pyrene, etc.)  ; and c hrysene and the acene structure with two active methine groups picene are less reactive. Little or no reacti on was [naphthacene (3 ), anthracene (4 ), naphthale ne (7 ), observed with biphenyl, coronene, fluoranthene, benz[a]anthracene (12), and pentacene (17)], (2) a perylene, p-terphenyl, and triphe nyle ne.
342 The stability of perylene and triphenylene toward The mechanism of 1T-electron abstraction and 10 s pe ri odi c acid may partially be explained by an asym of a proton involved in the dimerization of 1 to 2 metric anne lation effect [47, 48], by which a hyd ro resembles the mechanism recently proposed by carbon attains the maximum number of aromati c Cooper and Waters [64, 65] ; this is an outer-sphere sextets and , co nsequentl y, the maximum degree of mechanis m postulated to operate in the oxidation of stabi li ty. Other factors that may influe nce th e reac aromatic hydrocarbons by cobaltic ions. Acetic acid tivity of polyc yelic, aromatic hydrocarbons toward may, by solvation , protect the radicals prior to dimeri periodi c acid are: (1) basicity of the hydrocarbon [49 , zation. As may be seen by examination of a model of 50], (2) presence of a reactive bond or a free-valence dimer 2 , dimerization of the radical cations (Ia) center [51, 52, 53], or a position of hi ghest unpaired probably proceeds by their approaching each other electro n-densiti es [54, 55] or high unpai red spin head-to-head to give a less sterically hindered product. de nsities , (3) ability of periodic acid (as an electro The e.s.r. spectrum of pyrene radical la is shown in phile) to form an association complex with a hydrocar figure 1 (s pectrum A). bon, and (4) the ionization potential of the hydrocarbon I [57 , 58]. Inc reasin g reactivity toward peri odic acid is J 0 .9 L H usually paralleled by a decreasin g ioni zati on potential i GausSI of the hydrocarbon , as fo Jl ows: naphthacene (3 ) > pentacene (17) > pyrene (I ) > anthracene (5 ) > phenanthrene (10) > naphthalene (7 ). This may explain why naphthacene (3 ), having an ionization potential of 6.92 eV. , is most reactive, and naph thalene (7 ), having an ionization potential of 8.60 e V. , is the least reactive in th e seri es. In general, periodic acid preferably attacks a reactive center in stead of a reactive bond of the aromatic rin g in the polycycljc hydrocarbons. For example, anthracene (5 ) is attacked by period ic acid A at the most reactive (para) centers (9,1O-positions), in stead of at the most reactive bond (the 1,2-positions). Phenanthrene (10) is attacked at the 9,1O-positions, which constitute the most reactive bond and are the most reactive ce nters of the hydrocarbon.
a . Oxidation of Pyrene With Periodic Acid (I : I Mole Ratio) Treatment of pyrene (I ) with periodic ,acid (1: 1 mole ratio) in aqueous acetic acid has been shown  to give 1,1' -bipyrene (2 ) in a yield of over 70 percent. The fo rmation of the radical intermediate postulated  in the coupling reaction has now been verified by electron-spin resonance measurement, and the pyrene radical (l a) has been observed at room temperature. Thus, oxidati ve dimerization of I to 2 FIGU RE] . (A) The electron-spin resonance spectrum of pyrene radical la prepared by treatment of pyrene (in acetic acid) probably proceeds through intermediate Ia as de with periodic acid, H, JO ,; (in water) at room temperature, picted. Abstrac tion of a 1T-elec tron by a molecule of g = 2.0041. (8) Anthracene (i n N,N-dimethylformamide) on periodic acid fro m an aromatic nucleus would produce treatment with periodic acid in water. Sample 8 seen under the pyrene radical la; dimerization to the stable comparable conditions. No radicals were observed, and the upper limit of radical concentration is at most '/ ,ooot h of l,l'-bipyrene (2) would follow the loss of one proton that in sample A. [60- 62]. The overall oxidation process of I to dimer 2 involves the loss of two protons. In its ability to The absence of the hyperfine structure for the pyrene abstract an electron from the aromatic ring, the radical cation (Ia), as compared to the seven-line acceptor (periodic acid). functions like organic per spectrum of the equivalent [54, 66] pyre ne anion r adical oxides, which generally abstract electrons from donor (splitting constant 1.09 gauss)  may be explained molecules . on the basis of a probable interaction of the 1T-elec tron radical (Ia) originally formed with oxygen, to give a relatively stable pyrene peroxide (sigma) radical of type 24; this reaction is probably in competition with the dimerization of Ia to 2. The oxygen was probably r ~ - e supplied by periodic acid, because dilution and de ~-H'IO. oxygenation (by bubbling nitrogen into the diluted I solution) produced a similar one-line e.s.r. spectrum. It is known that dissolved oxygen can cause line 10 broade ning in the e.s.r. s pectrum by spin-spin inte r-
343 acti on (di pole interaction); the spectrum can also be similar to that described for pyrene, a number of other narrowed to one lin e by exchange inte racti on between polycycli c, aromatic hydrocarbons were treated with the rad iral and the hydrocarbon. this reagent. Although it was found that many of these hydrocarbons are indeed affected by periodic acid, b. Oxidation of Pyrene With Periodic Acid (1 :4 Mole Ratio) the reac ti on that occurs is oxidation to quinones Treatment of pyrene (1) with periodic acid (1: 4 in stead of coupling. molar ratio) at 95°C ini ti ally affords green-yellow 2 which, on further stirring (30 min), changes to lustrous, d. Oxidation of Naphthacene (3) brown crystals. The resulting crystalline compound is A solution of naphthacene (3 ) in N,N-dimethylform probably an addition complex between 2 , iodine, iodi c amide was oxi dized with aqueous periodic acid in a acid , or periodic acid ; but the structure of the com 1 : 4 mole rati o, to give 80 to 85 percent of naphtha pound is not yet known. The product cannot be re cenequinone (4 ). In a similar way, a series of other crystallized without loss of iodine. Analysis of the hydrocarbons have been converted into quinones, as unknown indicated the presence of up to 59 percent described in the experimental part. iodine; titration of a solution of the unknown in N,N-dimethylformamide with sodium thiosulfate in o acidic solution, and with arsenite in basic solution, con firm ed t he presence of iodll1 e and iodate. T he prod aq , DMF o:r¢© uct loses iodine on bein g heated at 230 °C/0.05 mm , to o yi eld crude 2 (identihed by thin-layer chromatography) 3 4 in addition to an unknown iodo compound. The same result was observed when the unknown was heated e. Oxidation of An th ra c e~ e (S) with a 30 percent aqueous solution of sodium hydrogen In order to determine whether these reactions with sulfite. Recrystallization of the unknown compound periodic acid involve a free-radical mechanism, the 'from boiling, glacial aceti c acid gave a very s mall ' oxidation of anthracene (5) was examined in the yield of the new compound as light-brown crys tals; presence of inhibitors and radical-capture agents its infrared spectrum showed two bands, at 5.75 [70, 71]. (nonconjugated C=O) and at 6.1 J-Lm (conjugated Equimolar proportions (0.01 mole) of anthracene C= O). (5 ) and (a) acrylamide, (b) methyl methacrylate, (c) c. Oxidation of Polycyclic, Aromatic Hydrocarbons to Quinones; acrylonitrile, or (d) 2,5-di-tert-a mylhydroquinone were Possible Reaction Mechanisms stirred at 75 °C with periodic acid (0.04 mole) in 25: 4 As reported by Bunton , periodic acid in aqueous (v/v) acetonitrile -water (145 m1) for 45 min; in each solution exi sts as an equilibrium between the free case, a hi gh yield of anthraquinone (6 ) was obtained. acid and its various anions. When an aqueo us solution and practically no polymerization of reagents a, b, or c was observed. In the experiment with d, some yellow 2,5-di-tert-amylbenzoquinone crystallized out when the filtrate was cooled. Thus , the se experiments gave no evidence of radical participation in the oxidation of peri odic acid is mixed with an excess of aceti c acid of 5 to 6 , a conclusion confirmed by e.s.f. monitoring (or other water-mi scible solvent used in the reacti on), of the oxidation path in the range from 0 to 100 °C in the equilibrium is shifted to the left (undissociated aqueous N,N-dimethylformamide or aqueous aceti c ac id ). Hence, under the reacti on conditions described, acid. As may be seen from figure 1, the e.s.f. spectrum pe ri odic ac id can func ti on as the free acid and as the B for oxidation of 5 shows no radical; whereas, the monoanion ; these two forms will be used here in dis dimerization of 1 , as discussed earlier, proceeds cussing possible reacti on mecha ni sms for the oxidation through a radical intermediate (s pectrum A). of a variety of polycyclic , aromatic hydrocarbons to qUIn ones. f. Oxida tion of Naphthalene (7); Mechanism for Oxidation of a n It is assumed that, in the oxidation of polycyclic, Act ive Center and a Methine Group aromatic hydrocarbons having a reactive center and As suggested in the previous communication  , a methine group, the properties of which can be com the first step in the mechanism of the oxidation of pared to the nucleophilic character of the olefini c naphthalene may involv e association between periodic group , the attacking species is free periodic acid acid (an electrophile) and the free-valence center of (a n electrophile); whereas, in the oxidation of poly th e aromatic rin g [51- 53}, or with a position hav in g cyclic, aroma ti c hydrocarbons having an active the highest unpaired electron densities ; these methyle ne group, which is more acidic than the possibilities are in agreeme nt with the basicity of the methine group, the attacking species is probably polycyclic, aromatic hydroc arbons [49, 50]. the monoanion of periodic acid (a supplier of active The reaction path for the oxidation of polycyclic, hydroxyl groups); thus, the oxidizing species involv ed aromatic hydrocarbons to quinones by peri odic acid depends on the nature of the hydrocarbon employed. may be contrasted with that of oxidation with chromic To determine whether periodic acid wo uld serve as acid, for which an intermediate (resulting from electro -a general reagent for effecting coupling reactions philic addition) as the initial step in oxidation of 344 HO OH + \/ ~ QJ'(/I(~"0- H5I06 OH ~ ~ • + 00 ~~ H2O H H +
7 70 7b
~ 1H2 O
OH 0 H OH
H5I06 H5I06 4 4 Q) mo,'",o 000 H OH ~OH 9 7d 7c
alkenes and polycyclic, aromatic hydrocarbons has' oxidation of te tralin (19) to the hydrope roxide, which been postulated [78, 79]. For example, the mechanis m may involve a chain-radical inte rmediate, has been for the ox idation of naphthalene (7 ) to l,4-naphtho reported [72, 73]. quinone (9) apparently proceeds by a two-equivale nt It is believed that oxidation of a nthrone (8 ) to oxidation_ This reaction involves electrophilic attack a nthraquinone (6 ) proceeds by a push-pull mechanism, of periodic acid, as shown in 7 a; with the formation as de pi cted in sche me A; a monoanion of pe riodic of inte rmediate 7b_ Collapse of 7b by loss of iodi c acid functions here as an active hydroxylating species; acid, and addition of water to the cationic center of the dihydro inte rm ediate 8d is probably the n oxidized 7b, affords the 1,4-dihydro-l,4-diol (7c), which is further to a nthraquinone (6). The attack by a mono then rapidly ox idized by pe riodic acid to dione 9 in anion of periodic acid on a methyl e ne group of 8 is 70 percent yield_ The transformation of 7b to 7 c is a type of in sertion of a li gand oxygen atom into a ? supported by the fact that only the mono negativ ely C-H bond; this may possibly be the way in which charged ion of periodic acid decomposes, and that the active oxygen of periodic acid is transferred; an the undissociated or dinegatively charged intermediate alternative way, postulating the in sertion of an un is inert to oxidative decomposition [80, 81,82,83]_ The bound oxygen atom, was s uggested by Bunton . last step in thi s sequence of reac tions is supported The insertion mechanism in the ozone oxidation of by the observation that 1,4-naphthalenediol (7 d) is flu orene or anthrone has recently been proposed . oxidized with periodic acid to dione 9 in a yield of ::J 80 percent. The suggested mechanism for the oxidation of 7 3.3. Oxidation of Malonic Acid (14) to 9 is another possible way in which periodic acid can transfer its oxygen atom to an aromatic moiety_ Oxidation of malonic acid (14) with periodic acid Hence, the behavior of periodic acid toward polycyclic, or sodium period ate has been thoroughly studied aromatic hydrocarbons has a unique, two-fold charac [35, 75], and the products 14b and 14c, which may ter; it can (1) produce coupling products through a arise from intermediate 14a, have been isolated and ('" radical inte rmediate, or (2) convert them into quinones, + apparently by a two-equivalent oxidation mechanism COOH COOH CO 2 C OOH that does not involve a radical intermediate_ I I I + HIO:1 + 2H 2 0 g. Oxidation af Anthrone (8); Mechanisms for the Oxidation of an HCH HsIO(; HC- OH  14b COOH 1 Active Methylene Group I ~ I ~ 14c l The oxidation of anthrone (8 ) with periodic acid COOH COOH was also investigated. This compound has a be nzilic 14 14a type of me thylene group, similar to the methyle ne group of tetralin (19), for whi c h a chain-radical id entified [35 , 75]. Assuming that products 14b and r intermediate, analogous to 8a and supposedly initiated 14c arise from 14, as reported [35, 75], this oxidative by treatment of 19 with chromic acid or pe riodic cleavage reaction has been checked for possible par acid, has been postulated . However, e..s . r. monitor ticipation of free radicals. By means of e.s. r. measure I ing of the reaction mixture obtained on treatme nt of ments, hydroxylation of malonic acid (14) with pe ri odi c " anthrone (8) with periodic acid showed no radicals, acid and sodium periodate was examined in water; r thus excluding scheme B, whi c h would proceed monitoring of the reaction path (at 0 to 60 °C) did not through a radical intermediate (8a). S imilar auto- reveal free radicals, in agreement with an earlier ob-
299- 54 7 0 6B - 5 345
- ~ R 0 0= OH J2L ~ + ; /OH 10, + H20 §H ~ I'OH o 0-
8 8d 6 SCH EME A
0 0 0 0 ) " " " H+ " ~ ~ ~ ~Hs I06 q:© ~. ~H 8 8a 8b 8e
0 0 "  " + HIO, + 2 H O ~ (I()l) 2 ~ 0" 8d 6 SC HEME B servation  obtained by chemical evidence (no H polymerization of acrylonitrile). - It is also believed that the reported [35, 75] hydrox ylation of an active methylene group in malonic acid (14) and its derivatives by periodic acid ·or sodium periodate in aqueous solution also proceeds by a ligand push-pull mechanism, similar to that described for anthrone (8) (see sec. 3.8), although direct transfer of an oxygen atom by periodate to the active methylene group of malonic acid (electrophilic oxidation) has also been proposed . However, x-ray irradiation of crystals of malonic acid (14) produces radicals having an unpaired electron centered on a methylene carbon atom [76, 77]. FIGURE 2. The e.S.r. spectrum of fluorene radical, prepared Finally, hydroxylation of an active methylene group by treatment of fluorene (in acetic acid) with periodic acid, of an acyclic compound (such as malonic acid and its H, IO" (in water) at room temperature, g = 2.0036 ± 0.0002. derivatives) can be effected by periodic acid and of hydrocarbon 23 can be explained on the basis of sodium periodate, whereas the hydroxylation (and the relative reactivity of radical 21, which apparently oxidation) of an active methylene group in polycyclic, quickly absorbs oxygen (either from the air, or from aromatic hydrocarbons can be effected only by periodic the oxidant) to gi ve the stable fluorene radical (24). , acid, and no oxidation has been observed with sodium This is then easily converted into the stable fluorene " periodate. hydroperoxide (25). Thus, the radical 21 may alter 3.4. Oxidative Coupling of Fluorene (20); Mechanism natively interact with oxygen prior to dimerization; of Oxidation of an Extremely Active Methylene Group fluo~ e ne (20), as known, re~ c ts with molecular oxygen to gIve a stable hydro peroxIde (25). Moreover, a pos Fluorene (20) has an unusually active methylene sible interaction of radicals 21 and 24 can also con group , and consequently, it is an extremely reac tribute to lowering of the yield of the product. The ,.., tive hydrocarbon. Treatment with periodic acid (1: 2 above reaction is, therefore, a second example we mole ratio) in warm aqueous acetic acid produced a have found of oxidative dimerization which proceeds coupling product, 1 ,2·bis(2,2' -biphenylylene)ethylene through a radical intermediate. (23), in about 10 percent yield. E.s.r. monitoring of Radical 21 has probably lost its hyperfine structure the oxidation reaction at room tem perature revealed on contact with oxygen, and the hydroperoxide radical the presence of a radical (moderate intensity), as shown 24 is probably responsible for the broad, one-line e.s.r. , in figure 2_ A plausible reaction mechanism that can spectrum that is actually observed (see fig. 2). explain the formation of the coupling product (23) is 4. Experimental Procedures shown here; periodic acid anion abstracts a hydrogen 4.1 . Spectral Measurements atom from a meth ylene group in 20 with formation of a radical (21); di merization of 21 gives hydrocar Infrared absorption spectra of compounds were bon 22; elimination of two protons produces the recorded with Perkin-Elmer Model 137 and Model orange-red 23. Only traces of fluoren-9-one (26) 257 spectrophotometers.2 E.s.r. spectra were recorded could be identified in the reaction mixture (thin-layer j 2 Certain comme rcial in struments are identified in this paper in order to specify adequately 1 chromatography); this mixture was not analyzed for the ex perimental procedure. In no case does such identification imply recommendation or e nd or~e m e nt by the National Bureau of S tandards. nor does il imply Ihal Ihe equipment its fluorene hydroperoxide (25) content. The low yield identified is necessaril y the best available for the purpose.
346 0 HO, '" /OH H -- 2 .-- ,~, HO :;" : 'OH 0- 1",01 g~\ ~~ 20 22 O2
0 t /OH --. + I .- 10; + H2O --HYDROPEROXIDE I 'OH (STABLE) ~=§ 0- ©OOH 0 - 0 - 23 24 25 wit h a Varian Model 4500 EPR Spectrometer with mixture was treated with water (50 ml), and cooled, to JOO-kHz fie ld modulation; the samples were placed yield naphthacenequinone (4), 1.0-1.1g (80- 85% ), rin a Varian Model V- 4548 aqueous-solution sample mp 278 to 281°C. Sublimation at 200 °C/0.05 mm cell. gave li ght-yellow needles, mp 288 to 290 °C, iden tical with an authentic sample [86, 87] by mixture, 4 _2_ Purification of Quinones mp, infrared spectrum, and thin-layer chromatog raphy on sili ca gel G (250-ILm layer ,S X 20 cm j:!;lass Final purification of crude quinones was performed plate) with 8: 1: 1 (v/v) benzene-N,N-dimethyl by column chromatography (s ili ca gel, 100- 200 mesh, formamide - acetic acid (solvent A), 60 min, Rf acetic acid or benzene - acetic acid as eluant), by a 0.70 ± 0.02. On spraying with ca. l.5M sulfuric acid technique described elsewhere _ in methanol (spray A) and heating (120 °C for 2 min), th e yellow spot (thin-layer chromatogram), having a 4_3 _ Treatment of Pyrene (1) With Periodic Acid (1 : 1 strong green Auorescence, changed to olive-brown. .Mole Ratio) 4 .6 . Oxidation of Anthracene (5) to Anthraquinone (6) Treatment ()f pyrene (1) (0.1 mole in aceti c acid) with periodic acid (0.1 mole in water) yielded a couplin g A solution of anthracene (5) (3.56 g, 0.02 mole) in. ) product, 1,l '-bipyrene (2) in over 70 percent yield; the N,N-dimeth ylformamide (50 ml) was stirred with an prod uct was isolated according to the publis hed pro aqueous solution of periodic acid (18.5 g, 40 ml, 0.08 cedure r59]. mole) at 95 °C for 8 min, and then at 80 °C for 30 min. The rather dark reaction mixture was then cooled to 4.4. Treatment of Pyrene (1) With Periodic Acid about 5 °C; light-yellow needles of anthraquinone (6 ) (1 : 4 Mole Katio) crystallized out and were filtered off. The product was washed with methanol, and dried; yield 3.6-3.7 g A so lu tion of pyrene (1 ), (2. 02 g, 0.01 mole) in glacial (86-89%), mp 280 to 282 °C; di lution of the filtrate with aceti c acid (50 ml) was stirred with an aqueous solution water yielded an additional crop (0.2-0.3 g), bringing of periodic acid (9 .2 g, 5 ml , 0.04 mole) at 50°C for 2 the total yield to 91- 95 percent. min and th en at 95 °C for 30 min; the grayish green 2 A sample purified by sublimation at 220 °C/0.05 that originally crystallized out graduall y changed to a mm, and recrystallized from glacial aceti c acid, brown-red so li d_ The product was filt ered off, washed melted at 285 to 286°C, lit  mp 281 to 282°C: thin with glacial acetic acid (2 X 10 ml), and dried in a vac- layer chromatograph y on sili ca gel G (solvent A), 60 (' uum desiccator; yield 8.2-8.5 g, mp 245 to 250°C min, Rf 0.67± 0.02. On a thin-layer chromatogram, I (with evolution of iodine). quinone 6 gave a scarcely visible spot; sprayin g (spray A sample was hed with water, and dried to constant A) and heating (120 °C) produced a strong yell ow spot wei ght at room temperature, was analyzed. Found: having a pink Au orescence. C, 28.3; H , 1.23; I , 50.9. 4.7_ Oxidation of Naphthalene (7) to A sample was hed with glacial acetic acid, and dried 1 ,4-Naphthoquinone (9) at 25 °C/O. l mm [or 4 hr, was analyzed. Found: C, 18.6; ? H, 0.8; I, 59.0_ A solu tion of naphthalene (7) (2.56 g, 0.02 mole) in 4.5. Oxidation of Naphthacene (3) to Naphthacene glacial aceti c acid (75 ml) was stirred wi th an aqueous quinone (4) solution of periodic acid (18.5 g, 15 mI, 0.08 mole) at 110 °C for 8 min and then at 80 °C for 30 min. The reac A solution of naphthacene (3 ) (1.15 g, 0.005 mole) tion mixture was cooled, poured into about 250 ml of in N,N-dimethyIIormamide (100 ml) was stirred with ice-cold water, and kept at room temperature for an aqueous solution of periodic acid (4.6 g, 5 ml, 0.02 several bours. The yellow, powdery 1,4- naphthoquinone mole) at 120 °C for 8 mi n and th en (to lessen the vig (9) was filt ered off, washed with water, and dried; orous reaction) at 80 °C for 30 min. The reacti on yield 2.0- 2.3 g (67-72%)_ The product was purified by
347 column chromatography on silica gel with 2: 1 (v/v) sample recrystallized from methanol (charcoal), acetic acid - benzene as eluant to remove impurities melted at 168 to 170°C; lit mp 166°C ,169 to 170 °C (solvent A), RJ 0.90 ± 0.01 , RJ 0.83 ± 0.01 , RJ O.54 ± 0.02, ; thin-layer chromatography on silica gel G (solvent and RJ 0.48 ± 0.02 (probably due to 1,2-naphthoqui· A), 60 min, RJ 0.83 ± 0.02. The yellow spot (pink none). A sample recrystallized from ether and then fluorescence) of 13, on spraying (spray A) and heating, from glacial acetic acid melted at 124 to 125 °C, darkened only very slowly. lit  mp 125 °C; thin·layer chromatography on silica ge l G (solvent A), 60 min, RJ 0.66 ± 0.02. The 4.11 . Oxidation of Acenaphthene (15) to ye ll ow s pot of 9 on a thin·layer chromatogram turns Acenaphthenequinone (16) pink·brown on exposure to ultraviolet light. A solution of acenaphthene (15) (1.54 g, 0.01 mole) 4.8. Oxidation of Anthrone (8) to Anthraquinone (6 ) in glacial acetic acid (40 ml) was stirred with an aqueous solution of periodic acid (9.2 g, 6 ml, 0.04 mole) at A solution of anthrone  (8) (1.95 g, 0.02 mole) in no °C by the procedure described in section 4.6. glacial acetic acid (50 ml) was stirred with an aqueous Dilution with ice·water yielded a yellow, crystalline solution of periodic acid (9.2 g, 5 ml, 0.04 mole) at powder of 16, 1.2-1.3 g (66- 72%). The crude product 90 °C by the procedure described in section 4.6. The was purified by column chromatography on silica gel ~ yield of anthraquinone (6 ) was 1.97 g (94%). with 3: 1 (v/v) benzene- ace tic acid. A sample recrys tallized from glacial acetic acid gave yellow needles, 4.9. Oxida tion of Phe nanth rene (1 0) to mp 260 to 261°C, lit mp 261 °C ; thin·layer chro Phenanthreneq uinone (11) matography on silica gel G, solvent A, 60 min, RJ 0.44±0.02. A solution of phenanthrene (10) (3.56 g, 0.02 mole) in redistilled p-dioxane (50 ml) was stirred with an 4 .12. Oxidation of Pentacene (17) to 6, 13-Pentacene - ~ aqueous solution of periodic acid (18.6 g, 20 ml, 0.08 quinone (1 8 ) mole) at 95°C for 5 to 7 min (or to the point where the clear, yellow solution just turned brown-red), and then A solution of pentacene (1 7) (0.28 g, 0.001 mole) at room te mperature for 30 min. The reaction mixture in N ,N-dimethylformamide (75 ml) was stirred with an was treated with water (20 ml), and stirred for 30 min aqueous solution of periodic acid (0.92 g, 2 ml, 0.004 in an ice-bath. The orange, crystalline product was mole) at 135 °C for 5 min, and then at 60 °C for 30 min. filtered off, washed with 10 ml of 1 : 1 (v/v) cold, aqueous The reaction mixture was treated with water (35 ml), ethanol, and dried in the air. The thoroughly dry, and cooled, to yield 18, 0.250- 0.267 g (81- 87%), orange product was stirred with cold benzene (20 ml), mp 382 to 384°C. Sublimation at 250 °C/0.05 mm, the suspension was filtered, and the solid was dried; followed by recrystallization from 1: 1 (v/v) N,N- I yield of c rude phenanthrenequinone (II) 1.6- 1.8 g; dimethylformamide - ethanol, gave light· yellow nee concentration and cooling of the filtrate yielded an dles, mp 393 to 395°C, lit mp 370 to 371 °C ; 394 °C additional crop (0.3 g); total yield, 1.9-2.3 g (45-55%), ; thin-layer chromatography on silica gel G (solvent mp 201 to 203°C. A), 60 min, RJ 0.78 ± 0.01. The yellow spot (pink A sample recrystallized from benzene, and then fluorescence), on spraying (spray A) and heating, from glacial acetic acid, melted at 205 to 207 °C, lit turned cherry-red. < mp 205°C  , 198 °C ; thin-layer chromatography on silica gel G, (solvent A), 60 min, RJ 0.60 ± 0.01. On 4 .13. Oxidative Dimerization of Fluorene (20) to spraying (spray A) and heating, the orange-yellow spot 1 ,2-Bis(2 ,2 '-biphenyly lene)ethylene (23) changed to olive-brown. A solution of fluorene (20) (1.66 g, 0.01 mole) in 4. 10. Oxidation of Benz[ a ]anthracene (12) to glacial acetic acid (50 ml) was stirred with an aqueous Benz[a]anthracene-7,12-dione (13) solution of periodic acid (5.7 g, 0.025 mole,S ml) at no °C for 15 min; the solution slowly turned orange· A solution of benz[a]anthracene (12) (2 .3 g, 0.01 red, and a precipitate (iodic acid) appeared. The mole) in N,N-dimethylformamide (40 ml) was stirred reaction mixture was treated with water (5 ml), stirred with an aqueous solution of periodic acid (9.2 g, 5 ml, for an additional 15 min at 105 to no °C and then at 0.04 mole) at 100 °C for 10 min, and then at 85 °C for room temperature (20 min), cooled (visible crystalliza 30 min. The reaction mixture was then diluted with tion of the orange solid), and treated with an excess j water (50 ml), and cooled in an ice·bath; yellow, pow of cold water with stirring. The orange solid (some- " dery 13 was filtered off, washed with water, and dried; times mixed with a syrup) was separated by filtration yield 1.9- 2.9 g (70- 78%). A good yield of the product (or decantation), dissolved in warm glacial acetic acid was also obtained when acetic acid (50 ml, no 0c) (50 ml), and passed through a column of silica gel 'I was used as the solvent. (glacial acetic acid as eluant). Rechromatography of The crude product was purified by column chro the orange band, and repeated recrystallization from matography on silica gel with 1: 1 (v/v) acetic acid warm glacial acetic acid, gave orange-red crystals benzene to remove impurities (sol vent A); RJ O.53 ± 0.02 of 23,0.16- 0.18 g (9.6-10.8%) mp 185 to 187 °C, lit ~ and RJ 0.44 ± 0.02 (s trong green fluorescence). A mp 182 to 183 °C ; 187 to 188 °C [98, 99]; thin-layer I l______348 chromatography on silica gel G with 4:3:3 (v/v)  Roitt, I. M., and Waters, W. A., J. Chern. Soc. 1952, 2695. heptane - ethyl acetate - glacial acetic acid, 60 min,  Davies, D. I., Hey, D. H., and Williams, C. H. , J. Chern. Soc. 1958 ,1878. Rf 0.91 ± 0.01. When the reaction was conducted at  Beckwith, A. L. J., and Waters, W. A., J. Chern. Soc. 1957, 55 to 60 °C for 5 hr, the reaction mixture contained , 1001. in addition to compound 2 3, a trace amount of Auoren-  Norman, R. O. c., and Waters, W. A. , J. Chern. Soc. 1958 , 9-one; solvent A, 60 min, R 0.82 ± 0.0l. 167. f [8J Norman, R. O. c., Thompson, C. A., and Waters, W. A., Hydrocarbon 23 belongs to the class of fulvalenes J. Chern. Soc. 1958, 175. ; and alternative methods (and mechanisms) for  Fieser, L. F., and Putman, S. 1'., ]. Am. Chern. Soc. 69, preparation of 23 have recently been re vi e wed [100). 1038 (1947).  Criegee, R. , in Oxidation in Organic Chemistry, K. B. Wiberg a . Attempted Oxidation of Biphenyl, Coronene, Fluoranthene, Pe ry (Ed.) (Academi c Press, New Yo rk, N.Y., 1965) p. 277. lene, p-Terphenyl, and Triphenylene  Ba il ey, P. S. , C hem. Rev. 5,925 (1958).  Copeland, P. C., Dean , R. E. , and McNeil, D., ]. Chem. Soc. A solution of the hydrocarbon (0.001 to 0.01 mol e) in 1961,1232. acetic acid or 1: 1 (v/v) acetic acid -N,N-dimethyl  Moriconi , E. J. , and Taranko, L. B., J . Org. Che rn . 28, 1831 formamide was stirred with aqueous periodic acid (1963). (0.004 to 0.04 mole) at 100 to 140° for 5 min , and then  Battersbee, J. E., and Bailey, P. S., J . Org. Chern. 32, 3899 ( at 60 to 80° for 30 min. Treatm ent of th e reaction mix (1967).  Van Duuren, B. L., Bekersky, J ., and Lefar, M., J. Org. C hern. ture with water regenerated the starting compound, 29,686 (1964). sometimes contaminated with iodine (thin-layer  Arnold, R. 1'. , and Larson, R., J. Org. Chem. 5, 250 (1940). chromatography).  Ogata, Y. , Kotake, M., and Aoki , K., Chern. Ind. (London) 1965,1903.  Ogata, Y. , Kotake, M., and Aoki, K. , Chem.Ind. (London) 4.14 Oxidation of Pyrene (1), Anthracene (5), and 1965,1904. Malonic Acid (14) in E.S .R. Cell  Chambers, R. D., Coggin, P. , and Musgrave, W. K. R. , J . C hem. Soc. 1959, 1804. a . Pyrene (1)  Waring, A. J ., and Hart, H. , J. Am. Chem. Soc. 86,1454 (1964).  Bu ehl er, C. A., and Hart, H., J. Am. C hem. Soc. 85, 2177 An aliquot (0.4 ml) of pyrene (0.02 M, in glacial (1963). acetic acid) was pipeted into a cell and mixed with  Treibs, W., and Thormer, J., Chern. Be r. 94,1925 (1961). one drop of cold , aqueous periodic acid (0.5 M) at room  Boyland, E., and Solomon, J. B., Biochem. J. 59,518 (1955).  Clark, C. T. , Downing, R. D., and Martin, J. B., J. Org. Chem. temperature. The e.s.r. s pectrum was immediately 27,4701 (1962). recorded, and showed the prese nce of free radicals.  Bowen, E. J. , Advan. Photochem. 1,23 (1963).  Fried, J., and Schumm, D. E., J. Am. Chem. Soc. 89, 5508 b. Anthracene (5) (1967).  Tipson, R. S., Oxidation of polycyclic, aromatic hydrocarbons, An aliquot (0.4 ml) of anthracene (0.2 M, in N,N NBS Mono. 87, Washington, D.C. , 1965. dimethylformamide) was cooled to about 0 °e, intro  Bobbitt, J . M., Advan. Carbohydrate Chem. 11 , 1 (1956). duced into the cell, and mixed with two drops of cold ,  J ackson, E. L. , Org. Reactions 2, 341 (1941).  Dyer, J. R., Methods Bioche m. Anal. 3 ,11 (1956). aqueous periodic acid (0.5 M); the e.s.r. spectrum was  Cuthrie, R. D., Advan. Carbohydrate Che m. 16, 105 (1961). scanned from 0 to 60°, and showed no radicals. Another [321 Bunton, C. A., in ref. 10, p. 367. sample of anthracene (0.01 M, in acetic acid) was  Sklarz, B. , Quart. Rev. (London) 21, 3 (1967). scanned from 20 to 60 °C, and showed no radicals;  Wolfrom, M. L., and Bobbitt, J. M., J. Am. Chem. Soc. 78, heating of the cell (boiling-water bath) and scanlllng 2840 (1956).  Bose, J. L., Foster, A. N. , and Stephens, R. W., J. Chern. Soc. of the spectrum did not reveal free radicals. 1959,3314.  Symons, M. C. R., J. Chem. Soc. 1955, 2794. c. Malonic Acid (14)  Hesse, C., and Mix, K., Chem. Ber. 92,2427 (1959).  Schwarz, J. C. P., Chem. Ind. (London) 1955,1588. An aliquot (0.4 ml) of malonic acid (0.3 M, in water)  Chatterjee, A., and Marjumdar, S. c., Anal. Chern. 28,878 was mixed in the cell with two drops of aqueous periodic (1956). acid (0.5 M) at room temperature; the e.s.r. spectrum  Craber, R. P., Snoddy, C. S., Jr., Arnold, H. B., and We ndler, did not reveal any radicals; warming (hot-water bath) N. L. , J. Org. Che rn. 21, 1517 (1956).  Hudson, B. C., and Barker, R., J. Org. C he m. 32,2101 (1967). or cooling (ice-bath) of the cell and scanning of (he  Obe rend er, F. C. , and Dixon , J . A. , J . Org. Chem. 24, 1226 spectrum did not reveal any radicals. (1959). The oxidation was also repeated with aqueous  Fatiadi, A. J ., Carbohyd. Res. 1,489 (1966). sodium periodate solution; the result was negative.  Ritc hi e, C. D., Skinner, C. A., and Badding, V. C., J . Am . Chem. Soc. 89, 2063 (1967).  Clar, E., Polycyclic Hydrocarbons, Vo l. 1, p. 50 (Academic Press, New York, N.Y., 1964). The author thanks C. F. Kokoszka and N. Adams  Ref. 45, p. 56. for the e.s.r. measure ments.  Ref. 45, p. 77.  Ref. 45, p. 84.  Mackor, E. L. , and van der Waals, J. H., Trans. Faraday Soc. 5. References 66 (1958).  Streitwieser, A., Jr., and Hammons, J. H. , Progr. Ph ys. Org. I Chern. 3,4 (1965). [I] Fatiadi, A. J., Environ. Sci. Tech. 7,580 (1967).  Brown, R. D. , J. Chern. Soc. 1950 , 691 , 3249. >  Cook, J . W., and Schoental, R. , ]. C hern. Soc. 1948,170.  Dewar, M. J . S., J. Am. Chem. Soc. 74,3357 (1952).  Wallace, J. C., Hydrogen Peroxide in Organic Chemistry,  Pull man, B., and Pu ll man, A., P rogr. Org. Chem. 4, 31 (1958). (Dupont Monograph), p. 67.  Carrington, A., Quart. Rev. (London) 17,67 (1963).
349  Streit wieser, A., Jr., Molecular Orbital Theory for Organic [75) Huebner, C. F. , Ames, S. R., and Bubl, E. c. , J. Am. Chern. Chemists, p. 324 (John Wiley & Sons, Inc., New York, N.Y., Soc. 68, 1621 (1946). 1961).  McConnell, H. M., HeUer, c., Cole, T., and Fessenden, R. W., <  Bolton, J. R., Carrington, J., and McLachlan, A. D., Mol. J. Am. Chern. Soc. 82, 766 (1960). I Phys. 5, 31 (1962).  Cole, T., and Heller, C., J. Chern. Phys. 34, 1085 (1961). [57) Kiser, R. W., Tables of Ionization Potentials (United States [78) Wiberg, K. B., in ref. 10, pp. 138, 142. Atomic Energy Com mi ssion, 1960) pp. 53,54. [79) Waters, W. A., Mechanisms of Oxidation of Organic Corn· [58) Streitwieser, A., Jr., Progr. Phys. Org. Chem. 1, 1 (1963). pounds, p. 110 (John Wiley & Sons, Inc., New York, N.Y.,  F'atiadi. A. J., J. Org. Chem. 32,2903 (1967). 1964). (60) Lewis,1. c., and Singer, L. S., J. Chem. Phys. 43,2712 (1965).  Buist, G. J., Bunton, C. A., and Mil es, ]. H., J. Chern. Soc. (61) Wilk, M., Bez, W., and Rochlitz, J., Tetrahedron 22, 2599 1957,4567. . (1966). [81) Buist, G. J., and Bunton, C. A., J. Chern. Soc. 1954, 1406.  Reynolds, W. L., and Lumry, R. W., Mechanisms of Electron [82) Bunton, C. A., in ref. 10, p. 381. Transfer, p. 68 (The Ronald Press Co., New York, N.Y., [83) Bunton, C. A., and Hellyer, J., J. Am. Chern. Soc. 89,6252 1966). (1967). [63) Ref. 3, p. 99. [84) Ciar, E., Polycyclic Hydrocarbons, Vol. 2 (Academic Press, [64) Cooper, T. A., and Waters, W. A., J. Chem. Soc. (B) 1967, New York, N.Y., 1960). 687. [85) Fatiadi, A. J., J. Chromatog. 20, 319 (1965). [65) Cooper, T. A., and Waters, W. A., J. Chem. Soc. (B) 1967,455. [86) Moriconi, E. ]., O'Connor, W. F., and Taranko, L. B. , Arch. [66) Ingram, D. ]. E., Spectroscopy at Radio and Microwave Biochern. Biophys. 38,283 (1959). Frequencies, p. 370, 2d ed. (Plenum Press, New York, N.Y. , [87) Fieser, L. F. , J. Am. Chern. Soc. 53, 2336 (1931). 1967). [88) Groves, C. E., Ann. 167,357 (1873). [67) Hoijtink, G. J., Townsend, J., and Weissman, S. I., J. Chern. [89) Meyer, K. H., Ann. 379,38 (1911). Phys. 34, 507 (1961). [90) Graebe, c., Ann. 167, 131 (1873).  Bunton, C. A., in ref. 10, p. 370. [91) Fittig, R., and Ostermayer, E., Ann . 167, 361 (1873).  Edwards, J. 0., in Peroxide Reaction Mechanisms, p. 77, [92) Graebe, C., Ann. 340, 259 (1905). J. O. Edwards (Ed.) (Interscience Publishers, New York, (93) Moriconi, E. ]., O'Connor, W. F., and Wallenberger, F. T., N.Y., 1962). J. Am. Chem. Soc. 81,6466 (1959).  Walling, c., Free Radicals in Solution, pp. 162, 430 (John [94) Weast, R. c., and Selby, S. M.. Handbook of Clwllli stry and " Wiley & Sons, Inc., New York, N.Y., 1957). Physics, p. C75 (C hemi cal Rubber Pub. Co., Cleveland, I [71) Bevington, J. c., Radical Polymerization, chap. 7 (Academic Ohio, 1961). Press, New York, N.Y., 1951). [95) Clar, C., and John, F., Ber. 62,3021 (1929). [72) Stewart, R., Oxidation Mechanisms, p. 61 (W. A. Benjamin, [96) Ried, W. , and Anthofer, F., Angew. Chern. 65, 601 (1953). Inc., New York, N.Y., 1964).  de la Harpe, c., and van Dorp, W. A., Ber. 8, 1048 (1875). (73) Pryor, W. A., Free Radicals, p. 288 (McGraw. Hill Book Co., [98) Graebe, c., Ber. 25, 3146 (1892). New York, N.Y., 1966). [99) Graebe, c., and von Mantz, B., Ann. 290, 238 (J896). [74) Bunton, C. A., in ref. 10, p. 391. [100) Bergmann, E. D., Chern. Rev. 68,41 (1968).