Phenols alkyl-substituted

The same conclusion was reached in a kinetic study of solvent effects in reactions of benzenediazonium tetrafluoroborate with substituted phenols. As expected due to the difference in solvation, the effects of para substituents are smaller in protic than in dipolar aprotic solvents. Alkyl substitution of phenol in the 2-position was found to increase the coupling rate, again as would be expected for electron-releasing substituents. However, this rate increase was larger in protic than in dipolar aprotic solvents, since in the former case the anion solvation is much stronger to begin with, and therefore steric hindrance to solvation will have a larger effect (Hashida et al., 1975 c). 

Alkyl-substituted phenols have different reactivities than phenol toward reaction with formaldehyde. Relative reactivities determined by monitoring the disappearance of formaldehyde in phenol-paraformaldehyde reactions (Table 7.3) show that, under basic conditions, meta-cresol reacts with formaldehyde approximately three times faster titan phenol while ortho- and para-cresols react at approximately one-third the rate of phenol.18 Similar trends were observed for the reactivities of acid-catalyzed phenolic monomers with formaldehyde. 

Many derivatives of phenol are now made by a synthetic process. Homologous series of substituted derivatives have been prepared and tested for antimicrobial activity. A combination of alkyl substitution and halogenation has produced useful derivatives including clorinated phenols which are constituents of a number of proprietary disinfectants. Two ofthe most widely used derivatives are/ -chloro-m-cresol (4-chloro-3-methylphenol, chlorocresol, Fig. 10.7C) which is mostly employed as a preservative at a concentration of 0.1%, and / -chloro-m-xylenol (4-chloro-3,5-dimethylphenol, chloroxylenol. Fig. 10.7C) which is used for skin disinfection, although less than formerly. Chloroxylenol is sparingly soluble in water and must be solubihzed, for example in a suitable soap solution in conjunction with terpineol or pine oil. Its antimicrobial capacity is weak and is reduced by the presence of organic matter. 

The peroxidase-catalyzed polymerization of m-alkyl substituted phenols in aqueous methanol produced soluble phenolic polymers. The mixed ratio of buffer and methanol greatly affected the yields and the molecular weight of the polymer. The enzyme source greatly affected the polymerization pattern of m-substituted monomers. Using SBP catalyst, the polymer yield increased as a function of the bulkiness of the substituent, whereas the opposite tendency was observed when HRP was the catalyst. 

Certain alkyl-substituted phenol-formaldehyde resins can act as dispersants for asphalts and asphaltenes in crude oils [1681]. The dispersants help keep asphalt and asphaltenes in dispersion and inhibit fouling, precipitation, and buildup in the equipment. 

The most common hydrophobes used as the basis for surfactants are those containing eight to eighteen carbon atoms, such as those listed as carboxylates in Table 9.1. Some hydrophobes are aromatic (benzene or naphthalene) moieties, often containing lower alkyl substituents dodecylbenzene (9.1) is a common example. Alkyl-substituted toluenes, xylenes and phenols, and mono- and di-alkylated naphthalenes (9.2 and 9.3), are also used. 

Alkyl-substituted phenols and alkanes were also oxidized to give the corresponding oxygenated products. In the case of isophorene, 3-formyl-5,5-dimethyl-2-cyclohexen-l-one was obtained selectively [110], The regioselectivity of the oxidation was remarkably different from that observed with the corresponding homogeneous analog, which produced 1,4-diketone as a major product [110] ... 

Two types of complex are formed on reaction of benzene with Cu montmorillonite. In the Type 1 species the benzene retains Its aromaticity and is considered to be edge bonded to the Cu(II), whereas in the Type 2 complex there is an absence of aromaticity (85,86). ESR spectra of the Type 2 complex consist of a narrow peak close to the free spin g-value and this result can be explained in terras of electron donation from the organic molecule to the Cu(II), to produce a complex of Cu(I) and an organic radical cation. Similar types of reaction occur with other aromatic molecules. However with phenol and alkyl-substituted benzenes only Type 1 complexes were observed (87), although both types of complex were seen on the adsorption of arene molecules on to Cu(II) montmorillonites (88) and anisole and some related aromatic ethers on to Cu(II) hectorite... 

Various chloro- and alkyl-substituted anilines, which represent the aromatic base of a large number of organic pollutants, were shown to react with phenolic humic constituents in the presence of a phenoloxidase isolated from R. praticola, while no reaction occurred when only the anilines were incubated with the fungal lactase. 

This system of using the van der Waals volume and ionization potential is much simpler than previous systems. It requires only one homologous series of alkyl compounds and one standard such as phenol for substituted phenols. The precision could be improved for polar compounds if / ara-alkylphenols and / ara-alkylbenzoic acids are used however, only a few such compounds are... 

Reduction of phenyl vinyl sulphones in dimethylformamide containing phenol as proton donor causes loss of phenylsulphinate ion. The reaction probably involves a series of electron and proton addition steps [74]. In absence of a proton source, phenyl vinyl sulphone radical-anion undergoes a dimerization reaction discussed on p. 57. Reactions of alkyl substituted vinyl sulphones are complicated by alkene migration in the presence of electrogenerated bases. Dimers are formed and further reduction leads to loss of phenylsulphinate ion [81] (Scheme 5.3). 

Phenol and alkyl-substituted phenols yield dibenzofuran and alkyldiben-zofurans by catalytic dehydration-dehydrogenation over thorium or cerium oxides. This reaction can also be achieved by thermal cracking of... 

Electrophiles other than protons were indeed shown to react with lignin model compounds at the 2- and 6-positions in acidic media Kratzl and Wagner investigated the reaction of paraphenolic benzyl alcohols in alkaline and acidic solutions (10). When 4-hydroxy-3-methoxybenzyl alcohol 4 was reacted with the 4-alkyl substituted phenol 5 under alkaline conditions, the expected ortho linked product (6) was isolated. However, under acidic conditions the methylene linkage formed meta to the phenolic hydroxy group (Fig. 2). 

When two polymeric systems are mixed together in a solvent and are spin-coated onto a substrate, phase separation sometimes occurs, as described for the application of poly (2-methyl-1-pentene sulfone) as a dissolution inhibitor for a Novolak resin (4). There are two ways to improve the compatibility of polymer mixtures in addition to using a proper solvent modification of one or both components. The miscibility of poly(olefin sulfones) with Novolak resins is reported to be marginal. To improve miscibility, Fahrenholtz and Kwei prepared several alkyl-substituted phenol-formaldehyde Novolak resins (including 2-n-propylphenol, 2-r-butylphenol, 2-sec-butylphenol, and 2-phenylphenol). They discussed the compatibility in terms of increased specific interactions such as formation of hydrogen bonds between unlike polymers and decreased specific interactions by a bulky substituent, and also in terms of "polarity matches" (18). In these studies, 2-ethoxyethyl acetate was used as a solvent (4,18). Formation of charge transfer complexes between the Novolak resins and the poly (olefin sulfones) is also reported (6). 

It has been found that oxygen-containing substitutents (particularly phenols) and alkyl substitutents on an aromatic nucleus increase dramatically the susceptibility to oxidation of the original aromatic compound (18, 24, 25). Oxidation of the aromatic nuclei in coal undoubtedly takes place at periphery sites hence, an increase in size of aromatic nuclei would be expected to lower the oxidation rate owing to a decrease in the number of oxidation sites per unit area of coal surface. 

Hydroxyl-substituted naphthimidazoles, benzothiazoles, benzimidazoles, benzotriazoles, benzoselenazoles and benzoxathiolones may be regarded as substituted phenolic couplers. Compound (121) is a specific example of the latter type which yields intense brown images (51USP2547843). In the absence of hydroxyl groups, alkyl-substituted derivatives of imidazoles or thiazoles may be couplers in their own right by virtue of their active alkyl substituent. 

NAPHTHENIC ACIDS. The term naphthenic acid, as commonly used in the petroleum industry, refers collectively to all of the carboxylic adds present m crude oil. Naphthenic adds are classified as monobasic carboxylic acids of the general formula RCOOH, where R represents the naphthene moiety consisting of cyclopentine and cyclohexane derivatives. Naphthenic adds are composed predominantly of alkyl-substituted cycloaliphatic carboxylic adds, with smaller amounts of acyclic aliphatic (paraffinic or fatty) acids. Aromatic, okfinic. hydroxy, and dibasic acids are considered to be minor components. Commercial naphthenic aads also contain varying amounts of unsaponifiable hydrocarbons, phenolic compounds, sulfur compounds, and water. The complex mixture of adds is derived from straight-run distillates of petroleum, mostly from kerosene and diesel fractions. See also Petroleum. 

Hydrodesulfurization of certain hydroxy-437 and methoxy-sub-stituted615 alkybenzo[6]thiophenes is a useful means of preparing some otherwise inaccessible alkyl-substituted phenols [e.g., Eq. (15)].015 Various p-methoxyphenylbenzo[6]thiophenes have been employed similarly to prepare the corresponding hydroxydiphenyl-alkanes.464 Catalytic hydrodesulfurization of a-alkyl-/ -(3-benzo[6]-thienyl)propionic acids affords a convenient method of preparing a,y-disubstituted y-phenylbutyric acids.636 Treatment of / -(3-benzo[6]thienyl)acrylic acid with Raney nickel alloy, sodium meth-oxide, and deuterium oxide affords the deuterated acid (366).667... 

Distillation from a brush-type molecular still separated the isolated lignins into three fractions containing alkyl-substituted monomeric phenols in the most volatile fraction, a mixture of monomeric phenolic alcohols and alkyl-substituted dimeric phenols in the intermediate fraction, and nonvolatiles which presumably contained dimeric phenolic alcohols and higher molecular weight material. Unfortunately, separation of monomeric alcohols and alkyl-sbustituted dimers was not complete, and this greatly hampered separation of the alkyl-substituted dimers in later chromatographic separations. 

Oil-containing adhesives might emit fatty acid oxidation products like saturated and unsaturated aldehydes which can contribute to odor (Wilke, Jann and Brodner, 2004). Adhesives on a phenol resin base have been found responsible for odor annoyance in several office buildings in former East Berlin. Alkyl-substituted phenols, methyl, dimethyl and ethyl phenols, some of which have very low odor thresholds, have been detected in indoor air as well as in different floor samples and were most likely responsible for the off-odor (Kirchner and Pernak, 2004). 

Friedel-Crafts type reactions of strongly deactivated arenes have been the subject of several recent studies indicating involvement of superelectrophilic intermediates. Numerous electrophilic aromatic substitution reactions only work with activated or electron-rich arenes, such as phenols, alkylated arenes, or aryl ethers.5 Since these reactions involve weak electrophiles, aromatic compounds such as benzene, chlorobenzene, or nitrobenzene, either do not react, or give only low yields of products. For example, electrophilic alkylthioalkylation generally works well only with phenolic substrates.6 This can be understood by considering the resonance stabilization of the involved thioalkylcarbenium ion and the delocalization of the electrophilic center (eq 4). With the use of excess Fewis acid, however, the electrophilic reactivity of the alkylthiocarbenium ion can be... 

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