Chapter 7 - Arene Reactions - Arene Hydrogenation

CHAPTER 7 ARENE REACTIONS
CHAPTER 7 OBJECTIVES
INTRODUCTION ELECTROPHILIC AROMATIC SUBSTITUTION PALLADIUM-CATALYZED REACTIONS Arene-Olefin Coupling Arene-Arene Coupling Oxidative Substitution Oxidative Carbonylation COPPER-CATALYZED OXIDATIONS Decarboxylation Phenol Coupling COUPLING REACTIONS OF ARYL HALIDES ARENE HYDROGENATION IFP Process Allyl Cobalt Catalysts Partial Hydrogenation of Benzene AROMATIC INTERMEDIATES FOR SPECIALTY CHEMICALS Metal Ion-Directed Ortho Substitution
Professor Bassam El Ali 2
INTRODUCTION
Benzene and its derivatives form a broad range of itcomplexes and -aryl derivatives with transition metal ions. These arene and aryl complexes are intermediates in many catalytic reactions that have potential application in industry and in laboratory syntheses. Some palladium(II)-catalyzed reactions accomplish substitutions or couplings of arenes that are difficult to effect by conventional methods, but these have found little industrial use.
Professor Bassam El Ali
INTRODUCTION
Copper complexes catalyze some unique reactions that are used on a moderate scale. Ziegler catalysts related to those used in olefin polymerization have become important in the hydrogenation of benzene. A variety of soluble catalysts are used in synthesis of specialty chemicals, especially in the venerable dyes industry.
ELECTROPHILIC AROMATIC SUBSTITUTION

One major limitation on use of the metal-catalyzed reactions is that classical organic methods for electrophilic aromatic substitution work so well. Many large-scale arene reactions (Figure 7.1) are catalyzed by simple Lewis or Bronstd acids. The primary interaction of the acid is with the attacking reagent rather than with aromatic substrate.

One In chlorination, for example, FeCl3 reacts with chlorine to form a polarized complex which behaves as though free Cl+ were formed.
This activated reagent attacks benzene to replace H with Cl. Similar mechanisms generate incipient NO2 from nitric acid or C2H5 from ethylene. The Monsanto process for AlCl3-ethylation of benzene as a route to styrene has been described.
Figure 7.1 Some important industrial processes based on electrophilic substitution reactions of benzene.

The palladium-catalyzed reactions seem to involve electrophilic attack of Pd on the aromatic ring. The resulted arylpalladium compounds react by conventional organometallic mechanisms like those observed for olefins. -complex involving one double bond is believed to be transformed to a -aryl complex via electrophilic metallation or oxidative addition processes:
PALLADIUM-CATALYZED REACTIONS
Palladium(II) salts, especially the acetate, catalyze many oxidative substitution reactions of benzene and other aromatic hydrocarbons. These reactions are not used commercially, but have been studied as potential processes for manufacture of styrene, phenol, and substituted biphenyls. Like the olefin reactions, the arene reactions are very sensitive to reaction conditions. A change in acetate concentration in the benzene Pd(OAc)2 reaction makes biphenyl the major product.
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Arene-Olefin Coupling
When styrene and Pd(OAc)2 are heated in benzene that contains acetic acid, trans-stilbene is a major product:
The phenyl groups in the stilbene comes from benzene. The reaction is catalytic when it is conducted under oxygen pressure. Similarly, ethylene can be phenylated catalytically to form styrene, stilbene, and higher derivatives.
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The arene-olefin coupling reactions do not give high yields of a single product. Arene-arene coupling is not observed in the presence of olefin, but addition of acetic acid to the C=C bond occurs. The styrene-PdCl2 complex in benzene/acetic acid that contains sodium acetate gives -phenylethyl acetate in addition to stilbene and a little -acetoxystyrene.
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This lack of selectivity has reduced the appeal of the benzene-ethylene reaction as a potential industrial process for styrene production. The mechanism of arene-olefin coupling is unclear. Two very plausible proposals appear in the literature. Both involve metallation of the benzene ring by a Pd2+ electrophile as a key step.
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It seems likely that the electrophile coordinates to the face of the ring (perhaps off-center) and displaces a proton as illustrated for toluene:
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The formation of the -aryl derivative appears to be a common step in arene-olefin coupling, arene-arene coupling, and arene acetoxylation. The para specificity observed with toluene in some of these reactions can be interpreted as evidence for attack by a bulky electrophile.
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The coupling proceeds through coordination of the olefin to the Ar-Pd compound to give a complex 1. Figure 7.2 shows two conventional mechanisms for formation of styrene from an ethylene complex. In the upper pathway ethylene inserts into the Ar-Pd bond to form a -phenethyl complex 2. Hydrogen elimination by transfer to the metal gives styrene and an unstable Pd-H species which decomposes to palladium metal. Alternatively (lower equation), the ethylene is metallated to form a -vinyl derivative 3.
Figure 7.2. Two pathways for styrene synthesis from an ethylene complex of an arylpalladium compound..
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This compound then undergoes reductive elimination of the two organic ligands to form the styrene directly. There is good precedent for both pathways. Preformed -vinyl complexes react with benzene to form styrenes as in the lower pathway. On the other hand, preformed -phenylpalladium compounds react with olefins to form similar products.
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In a related reaction that may be useful in organic synthesis, aryl halides and olefins react to form styrenes. For example, o-bromotoluene and ethylene react at 125C and 9 atmospheres pressure to form omethylstyrene in 86% yield.
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A palladium complex formed in situ from palladium acetate and triphenyl is used as a catalyst rather than a reagent. It appears that the reaction proceeds via an arylpalladium complex formed by oxidative addition of aryl bromide to a palladium(0) complex. Once the aryl-Pd bond is formed, coordination, insertion, and coupling of the olefin proceed as shown in Figure 7.2.
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Arene-Arene Coupling
Benzene, palladium chloride, and sodium acetate in acetic acid react to form biphenyl in high yield.
This reaction uses the palladium salt as a stoichiometric oxidant, but the reaction becomes catalytic in palladium when it is carried out under oxygen pressure.
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The stoichiometric coupling to form biphenyl is ordinarily accompanied by phenyl acetate formation, but acetoxylation is almost completely suppressed by 50 atmospheres oxygen pressure. Heteropolymolybdate ions serve as catalysts to couple the palladium and O2 redox systems. With a Pd(OAc)2/Hg(OAc)2/H5(Mo10V2PO40) catalyst, toluene is converted to dimethylbiphenyls with good rates and yields at 1.5 atmospheres pressure and 5090C.
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The oxidative coupling occurs with a variety of aromatic compounds. Much of the industrial interest in this reaction lay in its potential use to couple toluene to 4,4-dimethylbiphenyl and o-xylene to 3,4,3,4-tetramethylbiphenyl. These compounds are possible precursors of biphenyldi- and tetracarboxylic acids, which yield polyamides and polyimides with interesting physical properties.
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Ube Industries makes Upirex, a high-performance polyimide, from the tetracarboxylic acid obtained by oxidative coupling of dimethyl phthalate to the tetraester:
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Neat dimethyl phthalate is treated with a palladium(II) chelate, copper(II) acetate and oxygen. The reaction may be conducted at atmospheric pressure. With the 1,10-phenanthroline complex of Pd(OAc)2, 93-94% selectivity to the desired isomer is obtained at approximately 10% conversion. When the reaction is carried out under more severe conditions (160-180C, 10 atmospheres pressure) to get commercially acceptable reaction rates, the selectivity is about 82% at 9% conversion.
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As in the palladium-catalyzed arene-olefin coupling, it seems likely that a -arene-palladium compound 4 forms in the initial reaction of benzene with a palladium (2+) salt, but the subsequent C-C bond formation mechanism is. unclear. Kinetic studies suggest formation of intermediate phenylpalladium 5 and diphenylpalladium 6 intermediates which lead to coupling by reductive elimination of two C-Pd bonds (upper sequence in Figure 7.3).
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Oxidative Substitution
Figure 7.3. Alternative pathways for arene-arene coupling.

Arenes react with palladium (2+) salts in the presence of anionic nucleophiles to form substitution products. The most studied reaction is acetoxylation.
The acetoxylation was of interest as a potential phenol synthesis because phenyl acetate is easily hydrolyzed to phenol and acetic acid.
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An analogous oxidation of phenyl acetate has been studied us a route to the acetates of catechol, resorcinol, and hydroquinone. The acetoxylation of benzene can be made catalytic in palladium by addition of inorganic oxidants such as K2Cr2O7, but it is repressed by oxygen. The best results are from the use of a heterogeneous catalyst, as in the closely analogous vinyl acetate synthesis.
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Nearly quantitative yields of phenyl acetate and phenol are obtained by passing benzene and acetic acid vapors in a dilute oxygen stream over a supported palladium metal catalyst at 130-190C. Palladium(II) trifluoroacetate reacts readily with electron-rich arenes such as anisole and toluene to form trifluoroacetoxy derivatives with preference for ortho and para substitution. The reaction can be made catalytic in palladium by use of K2S2O8 as a cooxidant, just as was done earlier in acetoxylations with Pd(OAc)2 in acetic acid. The reaction is moderately fast and clean with a range of arene substituents from CH3 to CO2CH3.
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In the acetoxylation, meta products predominate even with toluene, for which electrophilic attack by Pd2+ might be expected to give ortho and para isomers. A possible explanation for this phenomenon and for the delicate balance between substitution and coupling involves competitive reactions of an arene -complex 4 as in arene-arene coupling. An alternative explanation is that the palladation of arenes to form -arylpalladium species like 5 in Figure 7.3 is simply a nonselective aromatic substitution.
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Oxidative Carbonylation
The reaction of palladium(II) salts with CO and an arene is a potentially interesting synthesis of arylcarboxylic acid derivatives. Carbonylation of arylmercury and arylthallium compounds in the presence of palladium acetate-, metalmetal exchange forms an arylpalladium complex which carbonylates readily.
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The acylpalladium species formed reacts with alcohols to give esters. Carboxylation of toluene by this route because the metallation is highly para-specific. Both the mercury and thallium reactions yield over 90% methyl para-toluate, an intermediate in terephthalic acid synthesis for polyester manufacture. Difficulties in reoxidizing the reduced metal salts have inhibited industrial use of this chemistry.
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For laboratory syntheses of benzoic acid derivatives, a closely related carbonylation of aryl halides may be useful. Palladium complexes such as PdBr2(PPh3)2 catalyze the reaction of bromobenzene with CO and butanol under mild conditions (100C, 1 atmosphere):
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With bromo- and iodoarenes, yields are high and many kinds of functional groups are tolerated by the catalyst. The mechanism of the reaction is not clearly established. It seems likely that the palladium(II) complex is reduced by CO or the alcohol. The resulting zero-valent complex reacts with the aryl halide to form an arylpalladium complex:
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COPPER-CATALYZED OXIDATIONS
Copper(II) salts catalyze several synthetically useful oxidations of aromatic compounds. An oxidative decarboxylation of benzoic acid yields phenol. Oxidative coupling of 2,6-disubstituted phenols produces polymers. These reactions differ in mechanism from the analogous oxidative substitution and coupling reactions with palladium catalysts. The palladium-catalyzed oxidations seem to involve organometallic intermediates like the olefin oxidations. The copper-catalyzed reactions are commonly described as free-radical processes, although organocopper intermediates may be present.
Decarboxylation
Copper salts catalyze both decarboxylation and oxidative decarboxylation of benzoic acid and its derivatives:
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Decarboxylation
The simple decarboxylation is often used in organic synthesis and the oxidative decarboxylation has been used commercially for manufacture of phenol. In both reactions, a copper(I) salt catalyzes CO2 elimination but, in the oxidative process, copper(II) also plays an important part.
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Decarboxylation
The simple decarboxylation is very clean with arene carboxylic acids. When cuprous benzoate is heated above 200C in a high-boiling solvent such as quinoline, benzene is formed in 99% yield. The salt need not be preformed, but can be prepared in situ by reaction with CuO2CCH3, CuO2CCF2, or an arylcopper(I) complex. The copper(I) compound may be used in catalytic quantities and is quite tolerant of other functional groups.
Decarboxylation
For example, 0.1 equivalent of [CuC6F5]4 catalyzes the decarboxylation of an indolecarboxylic acid in high yield:
Copper(II) benzoate, in contrast to the Cu(I) salt, undergoes oxidative decarboxylation. This reaction is the basis for phenol syntheses developed by Dow and by Lummus.
Decarboxylation
Steam and air are blown through a solution of copper(II) and magnesium salts in molten benzoic acid at 230-240C. Carbon dioxide evolves rapidly and phenol distills from the mixture in about 80% yield. One particularly interesting feature of the oxidative decarboxylation is that the phenolic hydroxyl group occupies a position ortho to that of the original carboxyl group. For example, p-toluic acid yields m-cresol. Similarly, 1-14C-benzoic acid gives 2-14C-phenol.
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Decarboxylation
The origin of the ortho placement of the entering substituent comes from study of the stoichiometric pyrolysis of copper(II) benzoate. Heating this salt in mineral oil at 250C produces a mixture of copper(I) salts and some free benzoic acid:
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Decarboxylation
The ortho-benzoatobenzoate and the salicylate salts almost certainly result from intramolecular attack on an ortho-C-H of the benzene ring. The attack is usually described as the result of two one-electron transfers:
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Decarboxylation
This formulation of the mechanism is based on attack of the ortho position by an incipient benzoate radical. The arenium radical 7 thus formed is oxidized by a second copper(II) ion to produce the observed copper(I) o-benzoatobenzoate 8 (X = PhCO2). No organocopper intermediates are involved in this description of the reaction. The catalytic phenol synthesis is a combination of several reactions as shown in Figure 7.4.
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Decarboxylation
The first is the pyrolysis of copper(II) benzoate. The copper(I) o-benzoatobenzoate decarboxylates rapidly at 230-250C to form pl benzoate. This ester is hydrolyzed under the phenol synthesis conditions to give phenol and benzoic acid. The copper(I) salts are reoxidized by air to regenerate copper(II) benzoate.
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Decarboxylation
Figure 7.4. Reactions involved in phenol synthesis by oxidative decarboxylation of benzoic acid.
Phenol Coupling
The oxidation of phenols by air in the presence of copper(I) salts call take several different pathways as shown in Figure 7.5. Phenol itself is oxidized by oxygen top-benzoquinone in 80% yield in a reaction catalyzed by copper(I) chloride in acetonitrile. When a pyridine complex of copper(I) chloride is used in methanol solution, a major product is the monomethyl ester of cis,cis-muconic acid 10.
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Phenol Coupling
The same product is obtained from 1,2-dihydroxybenzene. Probably both oxidations involve o-benzoquinone 9 as an intermediate prior to ring cleavage. The copper(I)-catalyzed oxidations of phenols show considerable ortho-para specificity. When the ortho positions are blocked by alkyl or halo substituents, reaction occurs at the para position, even with the CuCl/pyridine complex as a catalyst. The With very bulky ortho substituents such as tert-butyl, two phenol molecules couple to form the quinoid dimer 12 shown in Figure 7.5.
Phenol Coupling
Figure 7.5. Oxidation of phenols by copper(I) chloride/amine/oxygen.

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Phenol Coupling
From a technological viewpoint, the most important oxidation in this class is that of 2,6-xylenol. This oxidation produces a para-phenylene oxide polymer 11 by coupling an oxygen of one phenol molecule to the para carbon of another. This aromatic polyether is a high melting plastic which is very resistant to heat and to water. It has found wide use as an engineering thermoplastic under the trade name PPO.
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Phenol Coupling
An even more rigid and higher melting material is obtained by the analogous oxidation of 2,6diphenylphenol. The all-aromatic character of this material imparts outstanding thermal stability. The oxidation of 2,6-xylenol is easy. In a semiworks experiment that may simulate commercial practice, 2,6-xylenol is reacted with oxygen in toluene at 40C in the presence of copper(II) chloride, dibutylamine, NaBr, and a quaternary ammonium dispersing agent.
Phenol Coupling
A high molecular weight polymer is formed in about 80 minutes. The polymerization process is reversible in the presence of catalyst. The catalyst is deactivated with a chelating agent or with HCl in order to stabilize the polymer. The latter approach is used in a laboratory synthesis of poly(2,6-dimethyl- 1,4-phenylene ether).
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Phenol Coupling
The course of the oxidation is sensitive to the amine:copper ratio in the catalyst. High ratios of amine to copper produce the polyphenylene oxide polymer. However, at low ratios, the major product is a quinoid dimer 13.
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Phenol Coupling
This product resembles the dimer 12 obtained from 2,6di-tert (Figure7.5). The basis for the divergence in the reaction pathway seems to lie in the interaction of the phenol with the catalytic copper complex. The reaction of copper(I) chloride with oxygen in pyridine gives a polymeric copper(II) oxide, [Cu(py)xO]n. In methanol that contains pyridine, the oxidation gives a copper(II) methoxide, [CuCl(OMe)(py)x].
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Phenol Coupling
This methoxide reacts with phenols to give phenolates which undergo the observed coupling processes.
Without excess pyridine, the preformed complex gives mainly quinoid dimer. It seems likely that the copper(II) phenolate gives rise to a phenolate radical which is still associated with a copper(I) ion:
Phenol Coupling
The O-Cu association inhibits O-C interactions between two radicals but leaves a clear path for C-C coupling of the para-quinoid form to give the observed dimer 13.
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Phenol Coupling
The simplest chain-growth mechanism is coupling of a monomeric phenolate radical with a similar radical 14 generated from a polymer chain (Figure 7.6). Addition of the polymeric radical to the pant position of a monomeric radical forms a coupling product 15 with a cyclohexadienone end group. Tautomerization of the end group to a phenol structure yields the enlarged polymer. The phenol end group can react with copper(II) again to form another polymeric radical that can undergo chain growth by a similar mechanism.
Phenol Coupling
Figure 7.6. A chain-growth step in the copper-catalyzed oxidative polymerization of 2,6-xylenol.

Phenol Coupling
In all the phenol oxidation processes shown in Figure 7.5. It seems likely that a copper(II) species is the actual oxidant even though a copper(I) salt is often the preferred catalyst precursor. The role of copper(II) as a one-electron oxidant can also be filled by a cobalt or manganese complex that bears a tightly bound chelating ligand.
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Phenol Coupling
In particular, the cobalt complex 16 known as Salcomine or cobalt(salen) is very efficient for the oxidation of phenols top-benzoquinones.
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COUPLING REACTIONS OF ARYL HALIDES

Many reactions of halobenzenes are catalyzed by soluble transition metal complexes. The Ar-X bond is notoriously sluggish toward direct substitution even by powerful nucleophiles such as RS. Traditionally such nucleophilic substitutions have been catalyzed by copper salts, as in the ammonolysis of pchlorobenzotrifluoride to form p-aminobenzotrifluoride, an important industrial intermediate.
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A more broadly useful synthesis tool is the coupling of aryl halides with organometallic compounds such as Grignard reagents. The coupling catalysts or reagents usually are complexes of copper or nickel although many other metals are active. These coupling reactions have bee reviewed extensively.
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Salts and complexes of Fe, Co Ni, Pd, and Cu catalyze the reactions of halobenzenes with Grignard reagents to form alkylbenzenes and biphenyls:
This reaction does not proceed well in the absence of the transition metal compound, but it becomes rapid when the proper catalyst is present. Alkyllithinm, zinc, and aluminum compounds can often be substituted for the Grignard reagent.

Nickel complexes have received the broadest study in this reaction. The most effective catalysts are NiCl2(PR3)2 complexes although the yields vary with the nature of the phosphine and of the Grignard reagent. Generally, highest yields are obtained with complexes of chelating phosphines such as Ph2P(CH2)3PPh2 (DPPP).
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For example, o-dichlorobenzene reacts with nbutylmagnesium bromide in the presence of NiCl2(DPPP) to form o-dibutylbenzene in about 80% yield.
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This product would be difficult to prepare by conventional organic syntheses. Similar yields are obtained with a wide range of n-alkyl and aryl Grignard reagents. However, with sterically hindered aryl Grignard reagents such as 2,4,6-trimethyl-phenylmagnesium bromide, the nonchelate complex NiCl2(PR3)2 is most effective.
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The ligand effect is illustrated in the coupling of (CH3)2CHMgCl and chlorobenzene with various NiCl2L2 complexes.
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The chelating phosphine ligand DPPP gives almost entirely the simple coupling product. However, the methyl chelate ligand leads to extensive isomerization. The triphenylphosphine complex produces extensive reduction of the chlorobenzene to benzene. These seemingly anomalous results can be accommodated by a mechanism proposed for the coupling reaction. The mechanism is illustrated in Figure 7.7.
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As in the stoichiometric coupling described above, a nickel(0) complex is a key intermediate and provides entry to the catalyst cycle. Oxidative addition of chlorobenzene to NiL2 gives a phenyl complex 17. A metathetical reaction of the Grignard reagent gives a complex 18 containing both -aryl and -alkyl ligands. In the normal coupling process, reductive elimination of the two organic ligands from nickel gives isopropylbenzene and NiL2 to complete the catalytic cycle.
Figure 7.7 A sirnplitied mechanism for the coupling of chlorobenzene and isopropyl niagnesium (L = R3P)
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However, when the phosphine ligands are small or weakly bound, other reactions can occur. -Hydrogen elimination from the isopropyl ligand forms a hydrido olefin complex:
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As indicated in the equation, the hydrido complex is in equilibrium with both n- and i-propyl compounds. If isomerization of the alkyl group is faster than reductive elimination of the alkyl and aryl ligands, npropylbenzene is the major product. Reductive elimination of the Ni-H and Ni-Ph bonds in the hydrido complex gives benzene.
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The reaction pathways described above account for the observed products simply, but they do not represent a detailed mechanism. They fail to account for the observations that oxidizing agents such as O2 and ArBr accelerate the coupling reaction and electron acceptors such as nitroarenes inhibit it. The accelerating effect of simple oxidizing and alkylating agents is probably due to depletion of the phosphine ligand which, in turn, opens coordination sites on the metal ion.
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A more important effect, however, is probably access to odd electron species such as Ni(I) and Ni(III) that accelerate the reductive elimination process. Mechanisms that involve free radicals or one-electron transfers have been suggested for catalysts based on Fe, Co, and Cu complexes. As with nickel, phosphine complexes of palladium catalyze coupling of halobenzenes with organomagnesium and zinc reagents.
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The high yields and mild conditions of these reactions often justify the use of the precious metal catalysts. The reaction pathways seem similar to those of nickel. Zero-valent complexes such as Pd(PPh3)4 are quite effective, but the more stable PdCl2(PPh3)2 or Pd(Ar)(I)(PPh3)2 complexes are more convenient for most purposes.
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ARENE HYDROGENATION
Hydrogenation of aromatic compounds with soluble catalysts has received concerted scientific scrutiny only in recent years. Homogeneous catalysts for the hydrogenation of arenes have been known since the early 1950s, but they have received little attention because heterogeneous catalysts are extraordinarily effective for this reaction.
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ARENE HYDROGENATION
For the organic laboratory, Adams catalyst (brown PtO2) hydrogenates aromatics at 25C and 3 atmospheres pressure. In commercial practice, palladium-on-carbon or high surface area nickel catalysts are used to hydrogenate benzene to cyclohexane on a very large scale.
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ARENE HYDROGENATION
In recent years, however, two major developments in industrial benzene hydrogenation have occurred.
A seemingly soluble nickel catalyst developed by the Institute Franais du Ptrole (IFP) has been applied extensively in Europe for hydrogenation of benzene to cyclohexane. The selectivity of ruthenium catalysts for hydrogenation of benzene to cyclohexane has been increased to the point that industrial use is likely. The potentially practical catalysts are heterogeneous, but soluble ruthenium complexes provide useful models for the chemistry.
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ARENE HYDROGENATION
IFP Process
Benzene is hydrogenated to cyclohexane on a scale of millions of tons per year to provide the feedstock for making adipic acid, a major intermediate in production of nylon. The process is customarily carried out with a Raney nickel heterogeneous catalyst, but the conventional technology is being displaced by IFPs soluble nickel catalyst. Apparently the mechanical and thermal advantages of working with a soluble catalyst rather than a slurry compensate the problems of catalyst separation and recycle that usually handicap homogeneous catalysts. In this instance, the volatility of cyclohexane facilitates separation of the product from the catalyst.
ARENE HYDROGENATION
IFP Process
It has been known for many years that the Ziegler olefin polymerization catalysts catalyze the hydrogenation of arenes. Complexes prepared by reaction of triethylaluminum with a cobalt or nickel salt catalyze the hydrogenation of benzene and its derivatives. For example, benzene is reduced to cyclohexane rapidly and quantitatively at 150-190C and about 75 atmospheres pressure with Al(C2H5)3 and Ni(2ethylhexanoate)2 as the catalyst.
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ARENE HYDROGENATION
IFP Process
Similarly, a combination of Co(2-ethylhexanoate)2 and excess alkylaluminum compound reduces the xylenes to dimethylcyclohexanes. The cis-dimethylcyclohexanes are favored over trans by about 2:1, consistent with a predominant cis addition of hydrogen. A significant problem with the simple Ziegler systems is the instability of the soluble catalysts. It appears that IFP has solved this problem with careful control of reaction conditions, control of the Al:Ni ratio, and, possibly, use of adjutants to stabilize the soluble nickel species.
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ARENE HYDROGENATION
IFP Process
In a typical patent example, benzene is hydrogenated to cyclohexane at 155C and 10 atmospheres hydrogen pressure with a catalyst prepared from a mixture of nickel and zinc octanoates and excess triethylaluminum (Al:Ni = 4.2). The catalysts, even though they are prepared from highly moisture-sensitive organometallic compounds, tolerate the presence of hydroxyl groups in the material to be hydrogenated, for example, Bisphenol A:
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ARENE HYDROGENATION
IFP Process
The nature of the Ziegler-type catalysts is poorly defined. The reaction of Al(C2H5)3 with either a cobalt or nickel salt gives a dark brown or black solution. In the case of nickel, the mixture is neither pyrophoric nor paramagnetic and does not yield solids on ultracentrifugation. It seems likely that the solutions contain metal hydride or alkyl species that are stabilized by coordination to aluminum.
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ARENE HYDROGENATION
IFP Process
A model catalyst system produced by interaction of NiCl2(PEt3)2 with Al2Me3Cl3 at -40C was characterized by EXAPS. Many species were present, but the average structure corresponded to:
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ARENE HYDROGENATION
IFP Process
Relatively stable catalysts are obtained by the reaction of triethylaluminum with cobalt(II) acetylacetonate in the presence of tributylphosphine. This catalyst system effects cohydrogenation of olefins and arenes under mild conditions. At 30C and 1,5 atmospheres hydrogen pressure, styrene and benzene are hydrogenated to form primarily ethylbenzene and cyclohexane. Hydrogenation of the olefin is much faster than reduction of the arenes.
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ARENE HYDROGENATION
Allyl Cobalt Catalysts
The -allyl complex Co(C3H5)(P(OMe)3)3 hydrogenates benzene to cyclohexane at room temperature and atmospheric pressure. The hydrogenation is slow but very stereoselective. When D2 is the reducing agent, all-cis-cyclohexane-d is formed in over 95% yield at low conversion. Similarly, naphthalene and anthracene give the cisperhydro derivatives. In contrast to the Ziegler systems, benzene is hydrogenated more rapidly than naphthalene and anthracene with the allyl catalyst.
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ARENE HYDROGENATION
With alkylbenzenes, the rates fall in the order: benzene> toluene > xylenes > mesitylene> durene Little or no cyclohexene is produced from benzene under ordinary conditions. The major drawbacks of tins catalyst axe the low hydrogenation rate and the limited catalyst life. A catalyst derived from reaction of RhCl3 and a quaternary ammonium salt [(C8H17)3NCH3]+Cl- produces results very similar to those obtained with the allyl cobalt catalyst except that it is more stable and functions in the presence of water.
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ARENE HYDROGENATION
It seems likely that the whole family of soluble cobalt and nickel catalysts function by a mechanism like that sketched in Figure 7.8. The precursor complex designated "Co" reacts with hydrogen to form a dihydride complex, "CoH2" which may be stabilized by Lewis acidic ligands in the case of the IFP catalyst. In the allyl cobalt series, such dihydrides have been observed spectroscopically. In the interaction of benzene with the CoH2 species, the benzene ligand is probably complexed through a single double bond.
ARENE HYDROGENATION
Addition of a Co-H bond to this C=C bond gives a cyclohexadienyl complex. Transfer of a second Co-H gives 1,3-cyclohexadiene, which is still coordinated to the cobalt. In the normal operation of the catalyst, it probably remains coordinated to the metal for two more H addition cycles that ultimately yield cyclohexane. The overall process is very similar to the hydrogenation of an olefin by Wilkinson's catalyst.
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ARENE HYDROGENATION
Figure 7.8 Catalytic cycle for hydrogenation of one double bond in benzene.
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ARENE HYDROGENATION
Partial Hydrogenation of Benzene
The hydrogenation of benzene to cyclohexene has been a major target of industrial research because the oxidation of cyclohexene to adipic acid may proceed more cleanly than the current cyclohexane oxidation. Most of the research has centered on ruthenium and its complexes because this metal seems to hydrogenate benzene in preference to cyclohexene.
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ARENE HYDROGENATION
When used in the presence of aqueous NaOH, ruthenium- on-magnesia gives about 50% cyclohexene at moderate conversion of benzene. Recently issued patents and papers point the way to even greater selectivity with aqueous slurries of metallic ruthenium catalysts.
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ARENE HYDROGENATION
While industrial cyclohexene production will probably use heterogeneous catalysts, research on soluble ruthenium and osmium catalysts may be instructive in understanding the operation of the metallic catalysts. Bis(hexamethylbenzene) ruthenium(0) hydrogenates benzene rapidly at 90C and 2-3 atmospheres pressure. The reaction resembles that catalyzed by ruthenium metal in that substantial amounts of cyclohexene are formed (40-55% dimethylcyclohexenes from the xylenes).
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ARENE HYDROGENATION
The bis(hexamethylbenzene) ruthenium catalyst differs in several respects from the allyl cobalt catalysts discussed above, but is said to operate by a similar mechanism. It differs in giving cyclohexene as a substantial product and in producing extensive H/D exchange when D2 is the reducing agent. When xylene is treated with D2, deuterium appears in the methyl groups of the unreduced xylene.
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ARENE HYDROGENATION
In addition, the hexamethylbenzene ligands of recovered catalyst undergo methyl H/D exchange. It was proposed that this exchange occurred via a benzyl intermediate. The bis(hexamethylbenzene)ruthenium(0) is interesting in that one ligand is symmetrically complexed (6) but the other is coordinated through only two C=C bonds (4).
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ARENE HYDROGENATION
Recent research on the hydrogenation of arene complexes of osmium sheds new light on the selective hydrogenation process. Osmium like ruthenium, binds arenes tightly even when only one or two localized C=C bonds are coordinated to the metal. 2-Arene complexes such as the anisole complex 19 have been characterized crystallographically.
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ARENE HYDROGENATION
When this complex is hydrogenated with a heterogeneous rhodium catalyst, the two noncoordinated double bonds are reduced and a methoxycyclohexene complex 20 is isolated:
100
AROMATIC INTERMEDIATES FOR SPECIALTY CHEMICALS

some homogeneous catalytic reactions that are used to produce specialty chemicals on a scale of less than 5000 tons per year (in North America). These reactions are particularly important in the production of dyes, colored pigments, and agrochemicals.
102
34

Metal Ion-Directed Ortho Substitution
One especially valuable property of metal ions is to steer an electrophile or a nucleophile to a position ortho to a substituent on a benzene ring. This effect is seen with widely varying metal ions from (Al+3, Zr+4) to d10 (Hg+2). This family 0f reactions embraces a wide range of mechanisms, but it is generally assumed that the metal ion coordinates to an electron-donating substituent such as -OH or NH2.

This effect is illustrated in Figure 7.9, which outlines a speculative mechanism for the ortho-ethylation of aniline. Aluminum alkyls react with aniline to form the trianilide, which contains Al-N bonds. In the postulated mechanism, interaction of filled orbitals of an ethylene molecule with a vacant p-orbital on aluminum guides the olefin into a location in which a series of electron pair migrations 21 create a new CC bond ortho to the nitrogen substituent on the benzene ring.

Subsequent aminolysis of the Al-C bond in 22 leads to regeneration of an aluminum anilide and formation of intermediate 23, which subsequently tautomerizes to orthoethylaniline. While the postulated mechanism accounts for the observed products, it is tempting to propose an alternative in which the aluminum ion migrates from the nitrogen of the anilide to the ortho position on the benzene ring. Insertion of ethylene into the ortho C-Al bond, a welldocumented reaction, would yield 22, which then proceeds as shown in Figure 7.9 to give ortho-ethylaniline.
35

Figure

Whatever the mechanism, the ortho-ethylation of anilines has become an important industrial process for the manufacture of the widely used herbicides, Lasso and Dual. A critical intermediate for the production of Lasso is 2,6-diethylaniline, which is produced by reaction of aniline with ethylene in the presence of aluminum trianilide. The catalyst can be generated in situ by reaction of triethylaluminum or activated aluminum turnings with excess aniline.

The solution of aluminum trianilide in aniline is heated with ethylene at 300-400C and 30-65 atmospheres pressure. Distillation of the reaction mixture gives over 90% 2,6diethylaniline and leaves a residue of aluminum trianilide, which can be used as a catalyst for a subsequent reaction batch. A similar process is used to convert o-toluidine to 2-ethyl-6methylaniline, a key for production of Dual. The solution of aluminum trianilide in aniline is heated with ethylene at 300-400C and 30-65 atmospheres pressure.
36

Distillation of the reaction mixture gives over 90% 2,6diethylaniline and leaves a residue of aluminum trianilide, which can be used as a catalyst for a subsequent reaction batch. A similar process is used to convert o-toluidine to 2-ethyl-6methylaniline, a key for production of Dual.
109

Chemistry closely analogous to that of aniline ethylation is used to produce 2,6-di-t-butylphenol which is widely used in formulating antioxidants and ultraviolet stabilizers for polymers. The reaction of isobutene with phenol in the presence of a protonic acid catalyst ordinarily gives a mixture of t-butyl phenyl ether and para-t-butylphenol along with minor quantities of ortho-t-butylphenol. The course of the reaction changes dramatically when aluminum phenoxide is used as the catalyst.

No significant quantity of the para-t-butylphenol is formed. The reaction can be driven through the use of excess isobutene to produce largely 2,4,6-tri-t-butylphenol which is also useful as a component of stabilizing formulations for polymers. In recent years, another ortho substitution of phenol has received attention as a potential process for making agrichemical intermediates.
111
37

Many of Du Ponts sulfonylurea herbicides, such as chlorosulfuron, are characterized by strong species selectivity in controlling weeds (in addition to their innocuous relationship to life forms other than plants).
112

The selectivity for particular plant species is determined both by the nature of the nitrogen heterocycle at one end of the molecule and the substituents on the arene at the other end. It is often desirable to introduce a substituent ortho to the sulfonyl group on the benzene ring.
113

One approach to placing a hydroxyl group and a sulfur side by side on a benzene ring is the orthoalkylthiolation of phenol. The acid-catalyzed reaction of phenol with dialkyldisulfides generally gives a mixture of ortho and para substituted products:
114
38

It has been observed that aluminum phenoxide catalyzes the alkylthiolation of phenol with greater ortho selectivity than that attained with simple Bronstd or Lewis acid catalysts. For example, an aluminum phenoxide solution, prepared by in situ reaction of aluminum powder with excess phenol, reacts with dimethyl disulfide at 123170C to produce 2-(methylthio)phenol in 40% yield after distillation.
115

The crude reaction mixture contains the ortho- and para-methylthiophenols and two bis(thiophenols) in a ratio of 17:7:3:1. More recently it has been reported that zirconium phenoxide is effective in catalyzing the ortho methylthiolation of phenol.
116

With both the aluminum and zirconium catalysts, it is plausible to suggest that the metal ion steers the dialkyl disulfide reagent to the ortho position on the phenol ring through an assemblage such as:
117
39

Another ortho-substitution process of industrial importance is the mercury(II) catalyzed sulfonation of anthraquinone to produce antraquinone-1-sulfonic acid. This acid is a major intermediate in making anthraquinone dyes, the second largest class of texthe dyes. The effect of Hg2+ ion as a catalyst in this process is dramatic.
118

The uncatalyzed reaction of anthraquinone with oleum containing 45% SO3 at 150C produced the 2-sulfonic acid almost exclusively. When the reaction is carried out in the presence of a small amount of a mercuric salt, the product is primarily anthraquinone-1-sulfonic acid.
119

Continued reaction leads to introduction of a second sulfonic acid group. The second group is directed to an ortho position (5 or 8) of the other benzenoid ring. In mercury- catalyzed reactions such as these, it is likely that the first step is mercuration of the arene ring to form a C-Hg bond. Subsequent reaction of the aryl-Hg function with another reagent (e.g., SO3) places the incoming substituent at the site of the initial attack by mercuric ion.
40

In the anthraquinone example, it is possible that precoordination of the metal ion to the carbonyl group directs the Hg2+ to attack the nearest C-H function. The Hg2+ sulfonation of anthraquinone is valuable industrially because the SO3H group in the 1-sulfonic acid is displaceable by OH- and NO2- to form the 1-hydroxy and l-nitroanthraquinones. The latter can be hydrogenated to 1-aminoanthraquinone, a versathe dye precursor.
121

The 1,5-anthraquinonedisulfonic acid can be converted similarly to 1,5-diaminoanthraquinone. This intermediate was used in making the now-obsolete dye, Vat Yellow 3 (1,5-dibenzamidoanthraquinone). Despite the chemical selectivity conveyed by mercury(II) catalysis, the use of this technology has declined due to health and safety problems related to the extreme toxicity of mercury(II) compounds.
122

Other less toxic metals have been explored in seeking alternative catalysts. Palladium(II) salts, which are often involved in ortho metallation chemistry are reported to catalyze specific asulfonation of anthraquinone. The reaction conditions are somewhat different from those used with mercury(II) catalysts. Both palladium(II) sulfate in tetramethylene sulfone and palladium(II) acetate in liquid SO2 catalyze the sulfonation of anthraquinone by SO3 to form anthraquinone-1-sulfonic acid.
41
42

Chapter 7 - Arene Reactions - Arene Hydrogenation

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Chapter 7 - Arene Reactions - Arene Hydrogenation

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CHAPTER 7 ARENE REACTIONS

Professor Bassam El Ali

Professor Bassam El Ali

ELECTROPHILIC AROMATIC SUBSTITUTION

Professor Bassam El Ali

ELECTROPHILIC AROMATIC SUBSTITUTION

ELECTROPHILIC AROMATIC SUBSTITUTION

Professor Bassam El Ali

ELECTROPHILIC AROMATIC SUBSTITUTION

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Figure 7.3. Alternative pathways for arene-arene coupling.

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Figure 7.5. Oxidation of phenols by copper(I) chloride/amine/oxygen.

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Professor Bassam El Ali

Figure 7.6. A chain-growth step in the copper-catalyzed oxidative polymerization of 2,6-xylenol.

Professor Bassam El Ali

Professor Bassam El Ali

COUPLING REACTIONS OF ARYL HALIDES

Professor Bassam El Ali

COUPLING REACTIONS OF ARYL HALIDES

Professor Bassam El Ali

COUPLING REACTIONS OF ARYL HALIDES

COUPLING REACTIONS OF ARYL HALIDES

Professor Bassam El Ali

COUPLING REACTIONS OF ARYL HALIDES

Professor Bassam El Ali

COUPLING REACTIONS OF ARYL HALIDES

Professor Bassam El Ali

COUPLING REACTIONS OF ARYL HALIDES

Professor Bassam El Ali