Showing papers on "Phenol published in 1984"

Photocatalytic reactions of hydrocarbons and fossil fuels with water. Hydrogen production and oxidation

Abstract: Photocatalytic H/sub 2/ production from several aliphatic and aromatic compounds with water was investigated with powdered Pt/TiO/sub 2/ catalyst suspended in solution. Various fossil fuels such as coal, tar sand, and pitch also reacted with water, producing both H/sub 2/ and CO/sub 2/ from an early stage of irradiation. The photocatalytic oxidations of their model compounds, especially a linear hydrocarbon and benzene, were studied in the presence of silver ion as an electron acceptor. For aliphatic hydrocarbons, they are oxidized to alcohols, aldehydes, and carboxylic acids, successively. CO/sub 2/ was found to be formed through the photo-Kolbe type of reaction of carboxylic acids produced, which explained well the result of the complete decomposition of n-hexadecane. For benzene, we could detect phenol, catechol, hydroquinone, and muconic acid. On the basis of these results, the possibility of the direct oxidation of benzene by photogenerated holes and its ring-opening process peculiar to the photocatalytic reaction are discussed. The main reaction path for CO/sub 2/ production was suggested in which the benzene ring opens not by way of phenol and catechol, but by way of the intermediates whose reactivities are much larger than that of benzene. 41 references, 5 figures, 4 tables.

Hydroxylation reactions induced by near-ultraviolet photolysis of aqueous titanium dioxide suspensions

Abstract: Aqueous suspensions of titanium dioxide (anatase) containing benzoic acid or sodium benzoate have been illuminated with near-ultraviolet light under a variety of experimental conditions. In the presence of oxygen, o-, m- and p-hydroxybenzoic acids are formed in the same isomeric distribution found for OH-radical attack on benzoic acid. When OH-radical scavengers are present the yield of o-hydroxybenzoic acid is depressed. Ratios of rate constants evaluated on the basis of competition kinetics for the OH radical are in agreement with published rate constants. In the absence of oxygen the yield of the hydroxy compound is quite low, but high yields can be restored by the addition of iron(III). In oxygenated slurries, peroxides are formed in initial yield equivalent to about half the yield of total hydroxybenzoic acids. The addition of hydrogen peroxide to the slurries makes no significant difference to the yield of o-hydroxybenzoate. The results are consistent with the generation of OH radicals via the positive holes of the TiO2 particles, followed by OH-radical attack on the aromatic ring and subsequent oxidation of the hydroxy adduct with oxygen or iron(III) to give the corresponding phenol.

Silica gel as an effective catalyst for the alkylation of phenols and some heterocyclic aromatic compounds

Abstract: t-Butylation du phenol, benzenediols, biphenylediol-4,4', furanne, thiophene et methyl-1 indole par le bromure de t-butyle en presence de gel de silice

Engineering Plastics from Lignin. VIII. Phenolic Resin Prepolymer Synthesis and Analysis

Abstract: A sequential derivatization of lignin with formaldehyde and phenol was investigated as a means of enhancing lignin's reactivity in phenol-formaldehyde resins. Kraft lignin (KL) and two novel biocon version lignins, steam explosion (SEL) and acid (H2SO4) hydrolysis lignin (AHL), were chemically modified by sequential reaction with formaldehyde and phenol. The results with regard to the chemical structure of the phenolic resin prepolymers showed that the ability to hydroxymethylate and phenolate is related to lignin structure. KL from pine proved to be more amenable to chemical modification with formaldehyde and phenol than was either SEL from aspen or AHL from pine. Degrees of substitution were determined by H–NMR spectroscopy and by oxidative analysis with alkaline permanganate. H–NMR spectroscopy revealed degrees of phenolation of 0.42, 0.29 and 0.21 per average C9-unit for KL, AHL, and SEL, respectively; and permanganate oxidation illustrated that approximately 90%, 60%, and 60% of all availabl...

Constituents of Agaricus xanthodermus Genevier: The First Naturally Endogenous Azo Compound and Toxic Phenolic Metabolites

Abstract: Extraction of fresh sporophores of the fungus Agaricus xanthodermus yields 4,4'-dihydroxy-azobenzene, phenol, p-quinol, and 4,4'-dihydroxybiphenyl. This is the first report of an azo compound arising endogenously in nature, while phenol, p-quinol and 4,4'-dihydroxybiphenyl have not previously been isolated from higher fungi. Phenol is present in fruitbodies in sufficiently high concentration to account for the toxicity of A. xanthodermus.

Positive type photoresist composition

Abstract: OF THE DISCLOSURE A positive type photoresist composition com-prising a novolak resin and a quinonediazide compound, the novolak resin being one which is obtained by the addition condensation reaction of a phenol and formal-dehyde which is performed in one stage by using as a catalyst an organic acid salt of a divalent metal which is more electropositive than hydrogen, or in two stages by using an acid catalyst in the subsequent stage, the phenol being at least one compound represented by the formula wherein R is hydrogen or an alkyl group of carbon number 1 to 4, the compound being such that the average carbon number in the substituent per one phenol nucleus is 0.5 to 1.5 and the ones with the substituent at the ortho-or para-position with respect to the hydroxyl group account for less than 50 mol%, is disclosed. The positive type photoresist composition of the invention has an improved resolving power, i.e., .gamma.-value.

Production of phenol

Abstract: Phenol and acetone are produced by the cleavage of cumene hydroperoxide in the presence of a solid heterogeneous catalyst with acidic activity comprising zeolite beta.

A Convenient Procedure for Iodination of Electron-rich Aromatic Compounds using Iodine–Copper(II) Acetate

Abstract: The iodination of some electron-rich aromatic compounds, namely, three polymethylbenzenes, aniline, phenol, anisole, and phenetole, using iodine–copper(II) acetate in acetic acid, afforded the corr...

Conversion of phenol formaldehyde resin to glass-like carbon

Abstract: Glass-like carbons have been produced for many years by the careful carbonization of a variety of starting materials such as cellulose, phenol formaldehyde, polyfurfuryl alcohol, acetone furfuryldehyde and other suitable thermosetting resins. A number of publications have appeared in the literature concerning their characteristics and applications. However, little is known about the preparation procedure and its influence on the development of this form of carbon. The present paper incorporates the studies on the carbonization behaviour of a suitable phenol formaldehyde resin and on the optimization of the phenol to formaldehyde molar ratio in the resin, carried out with respect to the various physical characteristics of the resins and the resulting carbons. The implications of these studies have been disucussed in detail.

Inhibitory interactions of aromatic organics during microbial degradation

Abstract: Phenol, benzene and naphthalene were exposed, both singly and in combination, to oil refinery settling pond inocula. Although all three aromatic organics degraded rapidly when dosed singly, benzene and naphthalene were not metabolized in the presence of phenol. These results illustrate the difficulty of predicting environmental fates of complex chemical mixtures.

Polymerization of 2,6-Dimethylphenol on Smectite Surfaces

Abstract: Air-dried samples of homoionic Na-, Ca-, AI-, and Fe-smectite were equilibrated with 2,6- dimethylphenol vapor for 24 hr. Infrared spectra of the complexes formed indicated that a portion of the sorbed phenol was transformed into quinone-type compounds. Both sorption and transformation were greatly influenced by the nature of the exchangeable cation and followed the order Fe >> AI > Ca > Na. Changes in the electron spin resonance spectra of the clays following interaction with the phenol fol- lowed the same order, indicating that these reactions are enhanced by a transition metal cation, such as Fe 3+, on the exchange complex. The reaction products from the clay complexes were extracted with methanol and identified using ultraviolet/visible spectrophotometry, high-pressure liquid chromatography (HPLC), and mass spectrometry. The extracts contained mixtures of products including the parent phenol, di-, tri-, and tetramers of the phenol, as well as quinone and quinone dimers. The identities of these compounds were further confirmed by the coincidence of the retention times of HPLC peaks obtained from extracts of the clays with those from compounds produced by oxidation of 2,6-dimethylphenol with Ag20.

Interactions between phenol and carbon monoxide under cryogenic conditions: evidence for a phenol-CO complex

Abstract: Phenol has been matrix-isolated in argon, nitrogen, and carbon monoxide. The magnitude of the shifts of key OH bands from gas-phase values indicates that phenol-matrix interactions increase in the series Ar < N/sub 2/ < CO. Phenol forms a 1:1 complex with CO in argon-doped matrices. On the basis of the downward shift of nu/OH/ (the OH stretch) and the shift of nu/sub c identical with o/ to higher frequency, it is concluded that phenol is hydrogen bonded to the carbon terminal of carbon monoxide. Phenol in solid carbon monoxide behaves as if there is an equilibrium between free and complexed forms. The observation of a 1:1 complex between phenol and CO in argon offers the novel prospect of assessing substituent effects under cryogenic conditions. 35 references, 4 figures, 2 tables.

Orientation in the chlorination of phenol and of anisole with sodium and t-butyl hypochlorites in various solvents

Abstract: The effects of several factors on orientation in the chlorination of phenol and of anisole have been studied. The ortho/para ratio in the chlorination of phenol with aqueous NaOCl increases with increasing pH (0.64 at pH 4.0 and 4.3 at pH 10.0), whereas the ratio in the chlorination of anisole is almost constant (0.63–0.66) at pH 4.0–10.0. In chlorination with t-butyl hypochlorite, phenol gives an ortho/para ratio of 0.61 in methanol and 0.20 in acetonitrile, whereas anhydrous sodium phenoxide gives 1.23 in methanol and 2.54 in acetonitrile. The chlorination temperature and the concentration of phenol in hydroxylic solvents have virtually no effect on the ortho/para ratio. On the basis of these observations and literature information, the mechanism of reaction is discussed.

High temperature catalytic hydrogenolysis and alkylation of anisole and phenol

Abstract: Hydrogenation of phenol at 2.8 MPa pressure with MoO3–NiO–Al2O3 catalyst at 450 °C gave 60% benzene, 16% cyclohexane, and 7% methylcyclopentane, while anisole under the same conditions gave 60–70% ...

Coating resin composition

Abstract: PURPOSE:To obtain the titled composition having excellent adhesivity and especially high corrosion protection to steel plate, etc., by reacting an epoxy resin having a specific structural formula with a compound having adjacent hydroxyl groups, and using the resultant reactive chelate resin having high molecular weight as an active component of the resin composition. CONSTITUTION:(A) An epoxy resin of formula I (R1 is H or CH3; R2 is CH2 or group of formula II; n is 5-30) (e.g. bisphenol A diglycidyl ether) is mixed with (B) a polyhydric phenol carboxlic acid polyhydric alcohol ester having adjacent hydroxyl groups (e.g. glycerol protocatechuic acid triester) and/or a polynucleus polyhydric phenol having adjacent hydroxyl groups (preferably condensate of pyrogallol and formaldehyde, etc.), and the mixture is heated in a solvent preferably at 50-150 deg.C to obtain a reaction product having high molecular weight (preferably >=10,000). The ratio of the component A to the component B is selected preferably to leave the residual phenol group in the reaction mixture. The reaction product is used as an active component of the objective resin composition.

Coal liquefaction model studies: radical-initiated and phenol-inhibited decomposition of 1,3-diphenylpropane, dibenzyl ether and phenethyl phenyl ether

Abstract: The thermal decompositions of 1,3-diphenylpropane (1), dibenzyl ether (2), and phenethyl phenyl ether (3) have been studied in the temperature range of 138-250 /sup 0/C in the presence of various free-radical initiators. Thermodynamic calculations of the conversion of 1 to toluene and styrene indicate the reaction is unfavorable below 330/sup 0/C, and 1 was found to be unreactive with di-tert-butyl peroxide (TPO) at 138 /sup 0/C, di-tert-butyldiazene (TBD) at 200 /sup 0/C, and 1,1,2,2-tetraphenylethane (TPE) at 250 /sup 0/C. Reaction of 2 to toluene and benzaldehyde and of 3 to phenol and styrene were calculated to be energetically favorable at these temperatures. 2 reacted in the presence of TPO, TBD, and TPE to give toluene, benzaldehyde, and 1,2-diphenylethane in a free-radical chain process. 3 reacted in the presence of TBD and TPE to give phenol and styrene but did not react with TPO. Reaction of 2 can be inhibited with 2,6-di-tert-butyl-4-methylphenol. With TPO as the initiator the reaction was -0.61 order in phenol, while with TBD as the initiator the reaction was -1.1 order in phenol. The change in reaction order is due to changes in the rates of the various hydrogen-transfer reaction. The hindered phenol did not inhibit reactionmore » of 2 at temperatures above 200 /sup 0/C. The mechanisms of these reactions and the implications for coal liquification processes are discussed.« less

Methanesulfonic Acid Catalyzed Addition of Aromatic Compounds to Oleic Acid

Abstract: The addition of aromatic compounds to the double bond of oleic acid has been studied using methanesulfonic acid as the acid catalyst. When alkylbenzenes were reacted with oleic acid, the yield of addition product was dependent on the electron density of the benzene ring. For example, a 76% yield of addition product was obtained with toluene, whereas for benzene and monochlorobenzene, the yields of addition products were 60% and 2%. The addition of phenol to oleic acid gave 2 types of addition products, an ethertype (phenylether) product and a ring-substituted product (hydroxy-phenylstearic acid). The ratio of the 2 products varied with the reaction temperature and the amount of methanesulfonic acid. The ring-substituted product predominated at a high molar ratio of methanesulfonic acid to oleic acid (6:1) and elevated reaction temperature (50 C). Thiophenol was found to add to oleic acid to form a thioether derivative exclusively.

The extraction of total RNA by the detergent and phenol method.

Abstract: Successful extraction of RNA depends on the quantitative recovery of pure nucleic acids in an undegraded form. In practice, this means that a selective extraction process is required to remove all the unwanted cellular material in a manner that minimizes degradation of the RNA by hydrolysis or ribonuclease activity. The method described here relies on cell homogenization in an aqueous medium containing a strong detergent (sodium tri-isopropylnaphthalene sulfonate) and a chelating agent (sodium 4-aminosalicylate) to solubilize the cell components. An immiscible solution of phenol is then added to selectively extract hydophobic components and to denature protein. Following phase separation, the RNA is recovered by precipitation from the aqueous phase by the addition of absolute alcohol, thereby separating the RNA from small molecular weight contaminants such as carbohydrates, amino acids, and nucleotides.

Acclimation of activated sludge to mono-substituted derivatives of phenol and benzoic acid

Abstract: Successful adaptation of sludge to 24 out of 35 phenolic and benzoic acid derivatives was achieved by incubating domestic activated sludge samples with increasing amounts of the various compounds tested. In addition, with manometric techniques it was found that sludges which had adapted to one compound were able to oxidize other compounds to which they had not been previously exposed. However, no strict relationship between the nature and position of substituents in the aromatic ring and the effectivness of the processes of acclimation was found.

Addition of aromatic compounds to oleic acid catalyzed by heterogeneous acid catalysts

Abstract: The addition of aromatic compounds to the double bond of oleic acid was studied using solid acid catalysts. For example, in the presence of an acid clay catalyst (bentonite), phenol reacted with oleic acid to yield 96% of an alkylphenol addition product. When toluene was used as the aromatic reactant, however, the yield of alkylbenzene addition product was less than 2%. In this instance, the major reactions observed were elaidinization and migration of the double bond of oleic acid. The addition of phenol to oleic acid in greater than 95% yield also was accomplished with the use of a sulfonic acid ion-exchange resin catalyst. This same catalyst also catalyzed the addition of toluene and benzene to oleic acid to yield 82% and 22%, respectively, of alkylbenzene-type addition products. In the latter instances, the major side product formed was γ-stearolactone. Capillary gas chromatographic (GC) analyses of the alkylbenzene addition products obtained showed them to be mixtures of positional isomers. The isomer distributions were subsequently determined by GC-mass spectrometry (MS).

Photoresist composition containing a novolak resin

Abstract: A positive type photoresist composition comprises (a) a novolak resin and (b) a quinonediazide compound in wt. ratio of 1:1 to 6:1. The novolak resin is obtained by the addition condensation of a phenol and formaldehyde, in one stage by using as a catalyst an organic acid salt of a divalent metal more electropositive than hydrogen, or in two stages by using the acid catalyst in the subsequent stage, the phenol being at least one compound of formula: wherein R is hydrogen or C1-4 alkyl group and being such that the average C number in the substituent per phenol nucleus is 0.5 to 1.5 and less than 50 mol% of the molecules have substituents at the ortho- or para-position with respect to the -OH group. Preferred salts are acetates of Mg, Mn, Zn, Cd, Co, and Pb. NMR spectra are shown of the resins. The composition in solvent is coated on a support, and has a good resolving power.

Adsorption equilibria of phenol on anion exchange resins in aqueous solution.

Abstract: therms can be expressed by Freundlich equations as indicated by solid lines in Fig. 1. In the case of the hydroxide form, in particular, two lines are obtained on log-log paper to express the isotherm. For any concentration, the amount of phenol adsorbed is lower than the total capacity of the ion exchange resin as shown by the broken line in Fig. 1. Phenol may be adsorbed by physical interaction in

Radiation sensitive composition and pattern forming method using its composition

Abstract: PURPOSE: To enable a formation of a fine pattern by preparing the titled composition from a resist comprising a mixture of cis-(1,3,5,7-tetrahydroxyl)-1,3,5,7- tetraphenylcyclotetrasi-loxane and a specific polysilsesquioxane and a phenolic resin soluble to an alkaline aqueous solution. CONSTITUTION: The resist is composed of 5W100wt% prescribed mixture and the phenol resin soluble to the alkaline aqueous solution. Said mixture consists of (A) cis-(1,3,5,7-tetrahydroxy)-1,3,5,7-tetraphenylcyclotetrasil-oxane and (B) polysilsesquioxane shown by the formula wherein R 1 is a phenyl group and/or 1W4C alkyl group, a ratio of the phenyl group/the alkyl group is ≥1, R 2 is at least one of an element or a substituent selected from the groups of a hydrogen atom, the phenyl and 1W4C alkyl groups, the hydrogen atom is ≥1/2 the whole R 2 group. COPYRIGHT: (C)1986,JPO&Japio

Thermal cracking of aromatic urethane

Abstract: PURPOSE:To carry out the thermal cracking of an aromatic urethane, by cracking an aromatic urethane in the presence of an inert solvent heated above the heat-decomposition temperature of the urethane, adding an alcohol or phenol to the used inert solvent, and reusing the mixture as the solvent. CONSTITUTION:An aromatic urethane (e.g. dimethyltoluene dicarbamate) is made to contact with an inert solvent such as triaryldimethane, alkylbenzene, diphenyl, etc. heated above the heat-docomposition temperature of the urethane. In the recovery of the corresponding aromatic isocyanate and an alcohol or a phenol in vapor phase, the inert solvent used in the thermal cracking reaction is mixed with an alcohol or a phenol, maintained at 40-140 deg.C for 5min-20hr, and reused. The amount of the alcohol or phenol to be added is 1-100 equivalent based on the isocyanate group remaining in the inert solvent.