Phenols as catalysts

Among the tertiary-butyl phenols, the o- and p-derivatives and 2,6-di-tert-butylphenol are commerically important. They are used in the production of antioxidants. o-tert-Butylphenol and 2,6-di-tert-butylphenol are produced by alkylation of phenol with isobutene at a reaction temperature of 100 °C in the presence of aluminum phenolate as catalyst. 

Figure 4. Br0nsted plot for general acid catalysis of the acid-catalyzed dehydration of acetaldehyde hydrate using carboxylic acids and phenols as catalysts. (Reprinted from Ref. 21 with permission of the Royal Society.)...

R often Me) formed by oxidative polymerization of phenols using oxygen with copper and an amine (pyridine) as catalysts. The products are thermoplastics used in engineering applications and in electrical equipment. 

Phenols, unlike amines, cannot be acetylated satisfactorily in aqueous solution acetylation proceeds readily with acetic anhydride in the presence of a little concentrated sulphuric acid as catalyst. Salicylic acid (o-hydroxy-benzoic acid) upon acetylation yields acetylsalicylic acid or aspirin ... 

With more reactive substances, 2iac or ferric chlorides may be substituted as catalysts (138). More elevated temperatures and high pressure are, however, generally needed, and only very reactive substrates (such as phenols) react readily. 

Other Methods. A variety of other methods have been studied, including phenol hydroxylation by N2O with HZSM-5 as catalyst (69), selective access to resorcinol from 5-methyloxohexanoate in the presence of Pd/C (70), cyclotrimerization of carbon monoxide and ethylene to form hydroquinone in the presence of rhodium catalysts (71), the electrochemical oxidation of benzene to hydroquinone and -benzoquinone (72), the air oxidation of phenol to catechol in the presence of a stoichiometric CuCl and Cu(0) catalyst (73), and the isomerization of dihydroxybenzenes on HZSM-5 catalysts (74). 

The Guerbet reaction can be used to obtain higher alcohols 2-propyl-1-heptanol [10042-59-8] from 1-pentanol condensation and 6-methyl-4-nonanol from 2-pentanol (80—83). Condensations with alkah phenolates as the base, instead of copper catalyst, produce lower amounts of carboxyhc acids and requke lower reaction temperatures (82,83). The crossed Guerbet reaction of 1-pentanol with methanol in the presence of sodium methoxide catalyst afforded 2-heptanol in selectivities of about 75% (84). 

Coumarone—Indene Kesins. These should be called polyindene resins (17) (see Hydrocarbon resins). They are derived from a close-cut fraction of a coke-oven naphtha free of tar acids and bases. This feedstock, distilling between 178 and 190°C and containing a minimum of 30% indene, is warmed to 35°C and polymeri2ed by a dding 0.7—0.8% of the phenol or acetic acid complex of boron trifluoride as catalyst. With the phenol complex, tar acids need not be completely removed and the yield is better. The reaction is exothermic and the temperature is kept below 120°C. When the reaction is complete, the catalyst is decomposed by using a hot concentrated solution of sodium carbonate. Unreacted naphtha is removed, first with Hve steam and then by vacuum distillation to leave an amber-colored resin. It is poured into trays, allowed to cool, and broken up for sale. 

Mild acid converts it to the product and ethanol. With the higher temperatures required of the cyano compound [1003-52-7] (15), the intermediate cycloadduct is converted direcdy to the product by elimination of waste hydrogen cyanide. Often the reactions are mn with neat Hquid reagents having an excess of alkene as solvent. Polar solvents such as sulfolane and /V-m ethyl -pyrrol i don e are claimed to be superior for reactions of the ethoxy compound with butenediol (53). Organic acids, phenols, maleic acid derivatives, and inorganic bases are suggested as catalysts (51,52,54,59,61,62) (Fig. 6). 

ButylatedPhenols and Cresols. Butylated phenols and cresols, used primarily as oxidation inhibitors and chain terrninators, are manufactured by direct alkylation of the phenol using a wide variety of conditions and acid catalysts, including sulfuric acid, -toluenesulfonic acid, and sulfonic acid ion-exchange resins (110,111). By use of a small amount of catalyst and short residence times, the first-formed, ortho-alkylated products can be made to predominate. Eor the preparation of the 2,6-substituted products, aluminum phenoxides generated in situ from the phenol being alkylated are used as catalyst. Reaction conditions are controlled to minimise formation of the thermodynamically favored 4-substituted products (see Alkylphenols). The most commonly used is -/ fZ-butylphenol [98-54-4] for manufacture of phenoHc resins. The tert-huty group leaves only two rather than three active sites for condensation with formaldehyde and thus modifies the characteristics of the resin. 

Alkyl tertiary alkyl ethers can be prepared by the addition of an alcohol or phenol to a tertiary olefin under acid catalysis (Reycler reaction) sulfuric acid, phosphoric acid, hydrochloric acid, and boron trifluoride have all been used as catalysts ... 

Me3SiCH2CH=CH2i TsOH, CH3CN, 70-80°, 1-2 h, 90-95% yield. This silylating reagent is stable to moisture. Allylsilanes can be used to protect alcohols, phenols, and carboxylic acids there is no reaction with thiophenol except when CF3S03H is used as a catalyst. The method is also applicable to the formation of r-butyldimethylsilyl derivatives the silyl ether of cyclohexanol was prepared in 95% yield from allyl-/-butyldi-methylsilane. Iodine, bromine, trimethylsilyl bromide, and trimethylsilyl iodide have also been used as catalysts. Nafion-H has been shown to be an effective catalyst. 

A route to phenol has been developed starting from cyclohexane, which is first oxidised to a mixture of cyclohexanol and cyclohexanone. In one process the oxidation is carried out in the liquid phase using cobalt naphthenate as catalyst. The cyclohexanone present may be converted to cyclohexanol, in this case the desired intermediate, by catalytic hydrogenation. The cyclohexanol is converted to phenol by a catalytic process using selenium or with palladium on charcoal. The hydrogen produced in this process may be used in the conversion of cyclohexanone to cyclohexanol. It also may be used in the conversion of benzene to cyclohexane in processes where benzene is used as the precursor of the cyclohexane. 

In the manufacture of novolaks, 1 mole of phenol is reacted with about 0.8 mole of formaldehyde (added as 37% w/w formalin) in the presence of some acid as catalyst. A typical charge ratio would be ... 

The term novolac refers to the early use of phenolic to replace expensive shellac-based coatings. Novolacs are now those resins made at formaldehyde-to-phenol molar ratios of less than one-to-one. They are generally, though not always, manufactured under acidic conditions. Sulfuric or oxalic acids are most often chosen as catalyst though aromatic sulfonic acids and phosphoric acid are also quite common. Many other acids are used for special purposes. The finished novolac resin is incapable of further polymerization or crosslinking and therefore... 

Usually alkaline NaOH is used as catalyst, in an amount up to one mole per mole phenol (molar ratio NaOH/P), which corresponds to approx. 10 mass% alkali in the liquid resin. The pH of a phenolic resin is in the range of 10-13. The biggest part of the alkali is free NaOH, a smaller part is present as sodium phenate. The alkali is necessary to keep the resin water-soluble via the... 

Me3Si)2NH, Me3SiCl, Pyr, 20°, 5 min, 100% yield. ROH is a carbohydrate. Hexamethyldisilazane (HMDS) is one of the most common silylat-ing agents and readily silylates alcohols, acids, amines, thiols, phenols, hydroxamic acids, amides, thioamides, sulfonamides, phosphoric amides, phosphites, hydrazines, and enolizable ketones. It works best in the presence of a catalyst such as X-NH-Y, where at least one of the groups X or Y is electron withdrawing." Yttrium-based Lewis acids also serve as catalysts. ... 

Phenolic esters (1) of aliphatic and aromatic carboxylic acids, when treated with a Lewis acid as catalyst, do undergo a rearrangement reaction to yield ortho- and para-acylphenols 2 and 4 respectively. This Fries rearrangement reaction is an important method for the synthesis of hydroxyaryl ketones. 

Kinetic data17 with both phenols and carboxylic acids used as catalysts in reaction (10-27) are summarized in Table 10-6. The Brpnsted plot is shown in Fig. 10-6. The slope of the line gives a, which is 0.54. 

Many reactions have been shown to benefit from irradiation with ultrasound (ref. 19). We therefore decided to investigate the effect of ultrasound, different catalysts and the presence of solids on Ullmann diaryl ether synthesis. Indeed, sonication of mixtures of a phenol and a bromoaromatic compound, in the absence of solvent and presence of copper (I) iodide as catalyst and potassium carbonate as base, produces good yields of diaryl ethers at relatively low temperatures (Fig. 10) (ref 20). 

The scope of this reaction is similar to that of 10-21. Though anhydrides are somewhat less reactive than acyl halides, they are often used to prepare carboxylic esters. Acids, Lewis acids, and bases are often used as catalysts—most often, pyridine. Catalysis by pyridine is of the nucleophilic type (see 10-9). 4-(A,A-Dimethylamino)pyridine is a better catalyst than pyridine and can be used in cases where pyridine fails. " Nonbasic catalysts are cobalt(II) chloride " and TaCls—Si02. " Formic anhydride is not a stable compound but esters of formic acid can be prepared by treating alcohols " or phenols " with acetic-formic anhydride. Cyclic anhydrides give monoesterified dicarboxylic acids, for example,... 

Iron impregnated on activated carbon was used as catalyst for the direct synthesis of phenol from benzene. The effect of Sn addition to the catalyst was studied. The prepared catalysts were characterized by BET, SEM and XRD analysis. The catalyst 5.0Fe/AC showed good activity in the conversion of benzene and addition of Sn seemed to improve the selectivity of phenol in the reaction. 

The preparation of iron impregnated activated carbon as catalysts and the catalytic performance of these catalysts were studied in benzene hydroxylation with hydrogen peroxide as oxidant. 5.0Fe/AC catalyst containing 5.0 wt% iron on activated carbon yielded about 16% phenol. The addition of Sn on 5.0Fe/AC catalyst led to the enhancement of selectivity towards phenol. 

Enzymes are generally classified into six groups. Table 1 shows typical polymers produced with catalysis by respective enzymes. The target macromolecules for the enzymatic polymerization have been polysaccharides, poly(amino acid)s, polyesters, polycarbonates, phenolic polymers, poly(aniline)s, vinyl polymers, etc. In the standpoint of potential industrial applications, this chapter deals with recent topics on enzymatic synthesis of polyesters and phenolic polymers by using enzymes as catalyst. 

Phenol, the simplest and industrially more important phenolic compound, is a multifunctional monomer when considered as a substrate for oxidative polymerizations, and hence conventional polymerization catalysts afford insoluble macromolecular products with non-controlled structure. Phenol was subjected to oxidative polymerization using HRP or soybean peroxidase (SBP) as catalyst in an aqueous-dioxane mixture, yielding a polymer consisting of phenylene and oxyphenylene units (Scheme 19). The polymer showed low solubility it was partly soluble in DMF and dimethyl sulfoxide (DMSO) and insoluble in other common organic solvents. 

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