C with phenols

FIGURES. Voltammograms at a microelectrode of mercury of 2,2-diphenylvinyl phenyl sulphone in DMF, sweep rate 600 mV s , substrate concentration 10 3 m broken line curve (a) without proton donor present, full line curves (b) and (c) with phenol at concentration 0.5 and 4 x 10 3m, respectively, reference electrode Ag/Agl/I" 0.1m in DMF (after Reference 37). 

Method C with phenols The acid chloride (12 mmol) in CH2CI2 (5 ml) is added dropwise to the phenol (10 mmol), TBA-Br (12 mg, 0.04 mmol), and NaOH (1 g, 25 mmol) in... 

The glycosyl fluoride illustrated (from L-rhamnose) in dichloromethane reacted at -78°C with phenol (2 moles), bis-cyclopentadienylhafnium dichloride (3 moles) and silver perchlorate (3 moles) in dichloromethane containing powdered 4A molecular sieve during 45 minutes to give the 0-phenoxy derivative without C-arylglycoside formation (ref.37). 

A unique feature of these substitution reactions is that they iead to o-products. An aiuminium salt has been used to effect this type of reaction. A little aluminium (10-20mesh) was stirred and heated at 130-150°C with phenol under a nitrogen atmosphere untii hydrogen evolutton ceased. After the addition of dimethyidisulphide at 100°C the mixture was refluxed for 18 hours during which methanethiol was formed and after 3 hours at ISS C the product 2-(methylthk))phenol was isolated in 41% yield (ref. 117). 

METHOD 1 [112l-5g phenol in dH20 is stirred 5 hours at 20 C with some ferric sulfate (Fe2(S04)3, an additional 7mLs dH20, 13mLs 6% H2O2 and a pinch of aluminum oxide (AI2O3). Yield of catechol is 2.5g (50%). 

Reaction that can be carried out by the oxidative coupling of radicals may also be initiated by irradiation with UV light. This procedure is especially useful if the educt contains oleflnic double bonds since they are vulnerable to the oxidants used in the usual phenol coupling reactions. Photochemically excited benzene derivatives may even attack ester carbon atoms which is generally not observed with phenol radicals (I. Ninoraiya, 1973 N.C. Yang, 1966). 

Acylatmg agents such as acyl chlorides and carboxylic acid anhydrides can react with phenols either at the aromatic ring (C acylation) or at the hydroxyl oxygen (O acylation)... 

The polyimidazole [XIII] is formed by heating to 350-400°C, with the elimination of phenol and ring closure ... 

Triaryl phosphates are produced by reaction of phosphoms oxychloride with phenoHc compounds at 100—200°C with magnesium or aluminum chloride catalyst. Past use of cresols and xylenols from coal tar or petroleum is replaced for lower toxicity and cost by synthetic phenoHcs, primarily isopropyl phenol, /-butyl phenol, and phenol itself A range of viscosities is achieved by selection and proportioning of the phenols and their isomers used for the starting material. 

Unrefined alkylphenols are generally produced in the simple batch reactors described eadier. An alkene with between 8 and 12 carbon atoms reacts with phenol to produce a mixture of reactants, mono alkylphenols, and dialkylphenols. These mixtures usually do not free2e above 25 °C and so are Hquid at production and storage conditions. The product is generally used in the same factory or complex in which it is produced so shipment typically consists of pumping the material from the reactor to a storage tank. 

The oxidation of cyclohexane to a mixture of cyclohexanol and cyclohexanone, known as KA-od (ketone—alcohol, cyclohexanone—cyclohexanol cmde mixture), is used for most production (1). The earlier technology that used an oxidation catalyst such as cobalt naphthenate at 180—250°C at low conversions (2) has been improved. Cyclohexanol can be obtained through a boric acid-catalyzed cyclohexane oxidation at 140—180°C with up to 10% conversion (3). Unreacted cyclohexane is recycled and the product mixture is separated by vacuum distillation. The hydrogenation of phenol to a mixture of cyclohexanol and cyclohexanone is usually carried out at elevated temperatures and pressure ia either the Hquid (4) or ia the vapor phase (5) catalyzed by nickel. 

Tetrakis (4-hydroxyphenyl)ethane is prepared by reaction of glyoxal with phenol in the presence of HCl. The tetraglycidyl ether [27043-37-4] (4), mp ca 80°C, possesses a theoretical epoxide functionaUty of four with an epoxy equivalent weight of 185—208 (4). 

With Phenols. The 2-hydroxylethyl aryl ethers are prepared from the reaction of ethylene oxide with phenols at elevated temperatures and pressures (78,79). 2-Phenoxyethyl alcohol is a perfume fixative. The water-soluble alkylphenol ethers of the higher poly(ethylene glycol)s are important surface-active agents. They are made by adding ethylene oxide to the alkylphenol at ca 200°C and 200—250 kPa (>2 atm), using sodium acetate or... 

In turn the oxazoline-containing polymer may then react very rapidly (e.g. at 240°C) with such groups as carboxyls, amines, phenols, anhydrides or epoxides, which may be present in other polymers. This reaction will link the two polymers by a rearrangement reaction similar to that involved in a rearrangement polymerisation without the evolution of water or any gaseous condensation products (Figure 7.14). 

Tbe amount of phenolic resin strongly affects the rate of strength development and its ultimate heat resistance. Phenolic has positive effects in both contexts. Strength retained at 80°C with 46-phr phenolic exceeds that with 33 phr by 10-fold... 

Like other alkaloids of this group, quinine forms molecular compounds with a variety of organic substances. With benzene and toluene it produces compounds of the formulae B. CgHg and B. C,Hg respectively, with phenol it gives the crystalline product B. CgHjOH, and similar combinations with polyhydric phenols, ethers, aldehydes and ketones are known. One of the most characteristic of these substances is cupreine-quinine, a combination of the two alkaloids, obtainable from cuprea bark, and at first regarded as a new alkaloid, and named homoquinine. ... 

Examples of palladium-catalyzed reduction are 4-chloro-2,6-di-r-butyl-phenol to 2,6-di-t-butylcyclohexanone (750 psig, 25 C) with loss of halogen 24), 1,8-dihydroxynaphthalene to 8-hydroxy-1-tetralone 30), and 2,4-dimethylphenol to 2,4-dimethylcyclohexanone (27). 

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