Radical phenyl

The phenyl radical is considered to be one of the most reactive hydrocarbon radicals though the reasons for this high reactivity have not been clear. Three different electronic configurations have been proposed for it. In the first, the electron remains in the s -orbital of the carbon atom at which bond scission has occurred (i.e. it is a or-type radical). In the second, an electron from the ir-system can pair with the unpaired electron to give a lone pair in the p -orbital and leave 5 electrons in the 6-centre 7r-system. In the third, the carbon atom at which scission has occurred becomes divalent and does not participate in the 7r-system this leaves a radical with 5 electrons in a 5-centre w-system. 

Porter and Ward (1965) have obtained the optical absorption spectrum of the phenyl radical by flash photolysis and from an analysis of the wavelength shifts observed for a series of halogenated phenyl radicals they conclude that the ground state of the phenyl radical corresponds to the first structure (i.e. the unpaired electron remains in the sp -orbital). Thus it was of particular interest to obtain the e.s.r. spectrum of the phenyl radical for this would give additional information and help to assign the correct structure (Bennett et al., 1966a). 

Our initial experiments to prepare the radical by the reaction of sodium atoms with phenyl iodide were inconclusive because the resolution was very poor when the parent halide was used as the matrix. Attempts to increase the resolution by using camphane or adamantane as a matrix were unsuccessful as immediately after formation the phenyl radical abstracted hydrogen from the matrix to form benzene and a radical from the matrix. Complete reaction also occurred with matrices of other saturated hydrocarbons which possessed only secondary hydrogens 

The spectrum which consists of a triplet of triplets is attributed to a major hyperfine interaction with the orlAo-protons and a smaller interaction with the meta-protons. The coupling to the jpara-proton is not resolved and must be less than 3 G. The values of the hyperfine coupling constants are listed in Table 1, together with the theoretical values which have been calculated on the assumption that the unpaired electron is located in an sp -hybrid orbital on the valence carbon. The agreement between the predicted and experimental values is reasonable and shows that the unpaired electron remains in the sp -orbital which is in accord with the conclusion obtained from optical spectroscopic measurements. 

Experimental and Theoretical Hyperfine Coupling Constants for the Phenyl Radical 

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The radical phenylation of a large number of mono- and dialkyl-thiazoles has been investigated (393,395,396,399-405, for a general review cf. 398) and analyzed in terms of partial rate factors. As in other instances the alkyl groups slightly activate the substrate in certain positions toward phenyl radicals, but they also induce some steric hindrance to the approach of the aryl radical from the onho positions (Fig. 1-19). 

Benzoyl peroxide has been the most common source of phenyl radicals. But in reaction with thiazoles the benzoyloxy radical abstracts a hydrogen atom from the thiazole nucleus or from a methyl group in the case of methylthiazoles, giving by-products such as dithiazolyls or 2.2 -dithiazolylethane (183). The results obtained with benzoyl peroxide are summarized in Tables III-23, III-24. and III-25. 

In the case of substituted aryl radicals, the results may be slightly different, depending on the polarity of the radicals. With electrophilic radicals the overall reactivity of the thiazole nucleus will decrease and the percentage of 5-substituted isomer (electron-rich position) will increase, in comparison with phenyl radicals. The results are indicated in Table III-28. 

TABLE in-29. VARIATION IN THE PERCENTAGES OF PHENYL 1 SOMERS AND REACTIVITY OF THIAZOLE WITH DIFFERENT PHENYL RADICAL SOURCES (182, 184). 

The thiazolyl radicals are, in comparison to the phenyl radical, electrophilic as shown by isomer ratios obtained in reaction with different aromatic and heteroaromatic compounds. Sources of thiazolyl radicals are few the corresponding peroxide and 2-thiazolylhydrazine (202, 209, 210) (see Table III-34) are convenient reagents, and it is the reaction of an alky] nitrite (jsoamyl) on the corresponding (2-, 4-, or 5-) amine that is most commonly used to produce thiazolyl radicals (203-206). The yields of substituted thiazole are around 40%. These results are summarized in Tables III-35 and IIT36. 

Radicals derived from monocyclic substituted aromatic hydrocarbons and having the free valence at a ring atom (numbered 1) are named phenyl (for benzene as parent, since benzyl is used for the radical C5H5CH2—), cumenyl, mesityl, tolyl, and xylyl. All other radicals are named as substituted phenyl radicals. For radicals having a single free valence in the side chain, these trivial names are retained ... 

The extent of decarboxylation primarily depends on temperature, pressure, and the stabihty of the incipient R- radical. The more stable the R- radical, the faster and more extensive the decarboxylation. With many diacyl peroxides, decarboxylation and oxygen—oxygen bond scission occur simultaneously in the transition state. Acyloxy radicals are known to form initially only from diacetyl peroxide and from dibenzoyl peroxides (because of the relative instabihties of the corresponding methyl and phenyl radicals formed upon decarboxylation). Diacyl peroxides derived from non-a-branched carboxyhc acids, eg, dilauroyl peroxide, may also initially form acyloxy radical pairs however, these acyloxy radicals decarboxylate very rapidly and the initiating radicals are expected to be alkyl radicals. Diacyl peroxides are also susceptible to induced decompositions ... 

It is estimated that thiophene reacts with phenyl radicals approximately three times as fast as benzene. Intramolecular radical attack on furan and thiophene rings occurs when oxime derivatives of type (112) are treated with persulfate (8UCS(Pt)984). It has been found that intramolecular homolytic alkylation occurs with equal facility at the 2- and 3-positions of the thiophene nucleus whereas intermolecular homolytic substitution occurs mainly at position 2. 

Phenyl radicals attack azoles unselectively to form a mixture of phenylated products. Relative rates and partial rate factors are given in Table 7. The phenyl radicals may be prepared from the usual precursors PhN(NO)COMe, Pb(OCOPh)4, (PhC02)2 or PhI(OCOPh)2. Substituted phenyl radicals react similarly. 

Benzoyl peroxide is the source of the phenyl radicals, except for the first entry, where it is nitrosoacetanilide. 

Unsymmetrical azo compounds must be used to generate phenyl radicals because azobenzene is very stable thermally. Phenylazotiiphenylmethane decomposes readily because of the stabihty of the triphenylmethyl radical ... 

Part B of Table 12.2 gives some addition reaction rates. Comparison of entries 19 and 20 shows that the phenyl radical is much more reactive toward addition than the benzy 1 radical. Comparison of entries 22 and 23 shows that methyl radicals are less reactive than phenyl radicals in additions to an aromatic ring. Note that additions to aromatic rings are much slower than additions to alkenes. 

The same is true for decarbonylation of acyl radicals. The rates of decarbonylation have been measured over a very wide range of structural types. There is a very strong dependence of the rate on the stability of the radical that results from decarbonylation. For example, rates for decarbonylations giving tertiary benzylic radicals are on the order of 10 s whereas the benzoyl radical decarbonylates to phenyl radical with a rate on the order of 1 s . ... 

Some fraction of the benzoyl radicals may lose carbon dioxide to give phenyl radicals, which also initiate polymerization [43]. The nature of the initial inter-... 

Radicals of the alkanes are referred to as alkyl radicals. There are two other important radicals they are the vinyl radical, which is produced when a hydrogen atom is removed from ethylene, and the phenyl radical, which results when a... 

Arylations have been used to prepare pentafluorophenylbenzene, but the overall reliabihty of these methods is quesQoiiable In particular, if phenyl radicals... 

When cobaltous chloride is added instead of cuprous chloride, a 20% yield of the conjugate addition product and a 40% yield of compound 29 are obtained from 7. The isolation of some biphenyl indicates the probable presence of phenyl radicals. 

Dimesitylimidazolium chloride with chromocene gives the carbene 32 (R = C1) (990M529). With phenylmagnesium chloride, 32 (R = C1) gives 32 (R = Ph), the product of substitution of the chloride ligand by phenyl radical. In chloroform, 32 (R = C1) gives the chromium(III) species 33. In contrast,... 

Phenyl radicals can be generated by the thermal decomposition of lead tctrabcnzoate, phenyl iodosobenzoate, and diphenyliodonium hydroxide,- - and by the electrolysis of benzoic acid.- These methods have been employed in the arylation of aromatic compounds, including heterocycles. A method of promise which has not been applied to the arylation of heterocycles is the formation of aryl radicals by the photolysis of aromatic iodides at 2537... 

The results are consistent with the rate-determining step being addition of the aryl radical to the aromatic ring, Eq. (9). Support for this mechanism is derived from the results of three other studies (a) When A -nitrosoacetanilide is decomposed in pyridine, the benzene formed by abstraction of hydrogen from pyridine by phenyl radical accounts for only 1 part in 120 of the reaction leading to phenyl-pyridines. (b) 9,9, 10,lCK-Tetrahydro-10,10 -diphenyl-9,9 -bianthryl is formed in the reaction between phenyl radicals and anthracene, probably by the addition mechanism in Eq. (11). Adducts are also formed in the reactions of benzyl radicals with anthracene- and acridine. ... 

The quantitative phenylation of pyridine has been studied by two groups of workers. Dannley and Gregg showed that 2-, 3-, and 4-phenylpyridine are formed in relative amounts 58 28 14 in the phenylation of pyridine with dibenzoyl peroxide, as estimated by infrared spectrophotometry. Hey and his co-workers obtained the ratios shown in Table I for the phenylation of pyridine using four different sources of phenyl radicals. ... 

The close similarity in the isomer ratios obtained from different sources of the phenyl radical suggests that the mechanism of aryla-tion is independent of the nature of the reagent which generates the radical. This principle has been used in reverse in that the constancy of isomer ratios has been cited as evidence that the decomposition of lead tetrabenzoate gives free phenyl radicals. 

The reactivity of pyridine relative to that of benzene has been measured using the competitive technique developed by Ingold and his schoool for corresponding studies of electrophilic aromatic substitution. The validity of the method applied to free-radical reactions has been discussed. Three sources of the phenyl radical have been used the results obtained are set out in Table II. 

In many cases, however, the ortho isomer is the predominant product, and it is the meta para ratio which is close to the statistical value, in reactions both on benzenoid compounds and on pyri-dine. " There has been no satisfactory explanation of this feature of the reaction. One theory, which lacks verification, is that the radical first forms a complex with the aromatic compound at the position of greatest electron density that this is invariably cither the substituent or the position ortho to the substituent, depending on whether the substituent is electron-attracting or -releasing and that when the preliminary complex collapses to the tr-complex, the new bond is most likely to be formed at the ortho position.For heterocyclic compounds such as pyridine it is possible that the phenyl radical complexes with the nitrogen atom and that a simple electronic reorganization forms the tj-complex at the 2-position. 

There is an early report that thiophene reacts at the 3-position in phenylation with benzenediazonium chloride and aluminum trichloride, but in the Gomberg reaction thiophene has been found to substitute mainly at the 2-position both with p-tolyl and with p-chloro-phenyl radicals.Bcnzothiazole is phenylated at the 2-position in low yield by dibenzoyl peroxide a small quantity of the 4-isomcr is also obtained. ... 

Qualitatively, the results shown in Tables IV and V indicate that the methyl radical, just as the phenyl radical, substitutes pyridine preferentially in the 2- and 4-positions. The absence of the 3-isomer in these reactions is probably a result of the method of analysis... 

It is difficult to treat the effect of a heteroatom on the localization energies of aromatic systems, but Brown has derived molecular orbital parameters from which he has shown that the rates of attack of the phenyl radical at the three positions of pyridine relatively to benzene agree within 10% with the experimental results. He and his co-workers have shown that the formation of 1-bromoisoquinoline on free-radical bromination of isoquinoline is in agreement with predictions from localization energies for physically reasonable values of the Coulomb parameters, but the observed orientation of the phcnylation of quinoline cannot be correlated with localization ener-... 

A careful study of the phenylation of quinoxaline with benzoyl peroxide, various benzenediazonium salts, and A -nitrosoacetanilide indicates that the 2-position is most reactive to phenyl radicals and that the 5-position is more reactive than the 6. The yields of 2-, 5-, and 6-phenylquinoxaline are in the ratio of 40 10 1, Benzoyl peroxide and A—nitrosoacetanilide are the most effective phenylating reagents. 

An arenediazonium ion 1 in aqueous alkaline solution is in equilibrium with the corresponding diazohydroxide 4 The latter can upon deprotonation react with diazonium ion 1, to give the so-called anhydride 5. An intermediate product 5 can decompose to a phenyl radical 6 and the phenyldiazoxy radical 7, and molecular nitrogen. Evidence for an intermediate diazoanhydride 5 came from crossover experiments " ... 

The very reactive phenyl radical reacts with the aromatic substrate 2, present in the reaction mixture. Subsequent loss of a hydrogen radical, which then combines with 7 to give 4, yields a biaryl coupling product e.g. the unsymmetrical biphenyl derivative 3 ... 

The initiating radicals are assumed to be SCN, ONO or N3 free radicals. Tris oxalate-ferrate-amine anion salt complexes have been studied as photoinitiators (A = 436 nm) of acrylamide polymer [48]. In this initiating system it is proposed that the CO2 radical anion found in the primary photolytic process reacts with iodonium salt (usually diphenyl iodonium chloride salt) by an electron transfer mechanism to give photoactive initiating phenyl radicals by the following reaction machanism ... 

Triphenylsulfonium tetrafluoroborate [(C6Hs)3 S" BF4 ] is used instead of diphenyl iodonium chloride to give phenyl radical as the initiating species. Potassium [tris(oxalato) cobaltate) (III)] with diphenyl iodonium chloride also has been used as the photoinitiator of acryl-... 

Peroxide initiators may also undergo primary radical transfer to produce unsaturated end groups, which may result in a less stable polymer. In the case of benzoyl peroxide, an additional possibility is initiation by phenyl radicals to give a polymer with terminal phenyl groups [Eq. (17)] ... 

Meanwhile, it was found by Asai and colleagues [48] that tetraphenylphosphonium salts having such anions as Cl, Br , and Bp4 work as photoinitiators for radical polymerization. Based on the initiation effects of changing counteranions, they proposed that a one-electron transfer mechanism is reasonable in these initiation reactions. However, in the case of tetraphenylphosphonium tetrafluoroborate, it cannot be ruled out that direct homolysis of the p-phenyl bond gives the phenyl radical as the initiating species since BF4 is not an easily pho-tooxidizable anion [49]. Therefore, it was assumed that a similar photoexcitable moiety exists in both tetraphenyl phosphonium salts and triphenylphosphonium ylide, which can be written as the following resonance hybrid [17] (Scheme 21) ... 

The proposed mechanism is based on the basis of the fact that ylides (Scheme 23 and Scheme 24) undergo bond fission between the phosphorus atom and the phenyl group in TPPY as reported by Nagao et al. [51] and between the sulfur atom and the phenyl group in POSY as observed in triphenylsulfonium salts [52-55] when they are irradiated by a high-pressure mercury lamp. The phenyl radicals thus produced participate in the initiation of polymerization. 

Giese and Kretzschmar7j found the rate of addition of hexenyl radicals to methyl acrylate increased 2-fold between aqueous tetrahydrofuran and aqueous ethanol, Salikhov and Fischer74 reported that the rate constant for /-butyl radical addition to acrylonitrile increased 3.6-fold between tetradecane and acetonitrile. Bednarek et al75 found that the relative reactivity of S vs MMA towards phenyl radicals was ca 20% greater in ketone solvents than it was in aromatic solvents. 

For reactions with S, specificity is found to decrease in the series cyanoisopropyl mcthyl Fbutoxy>phcnyl>bcnzoyloxy. Cyanoisopropyl (Scheme 3.3),7 f-bntoxy and methyl radicals give exclusively tail addition. Phenyl radicals afford tail addition and ca l% aromatic substitution. Benzoyloxy radicals give tail addition, head addition, and aromatic substitution (Scheme 3.4). ... 

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