Phenolics copper carbonate

The second processing step, in which benzoic acid is oxidized and hydrolyzed to phenol, is carried out in two reactors in series. In the first reactor, the benzoic acid is oxidized to phenyl benzoate in the presence of air and a catalyst mixture of copper and magnesium salts. The reactor is operated at 234°C and 147 kPa gauge (1.5 kg/cm g uge). The phenyl benzoate is then hydrolyzed with steam in the second reactor to yield phenol and carbon dioxide. This occurs at 200°C and atmospheric pressure. The overall yield of phenol from benzoic acid is around 88 mol %. Figure 2 shows a simplified diagram for the toluene—benzoic acid process. 

The oxidative carbonylation of alcohols and phenols to carbonates can be catalyzed by palladium or copper species [154-213]. This reaction is of particular practical importance, since it can be developed into an industrial process for the phosgene-free synthesis of dimethyl carbonate (DMC) and diphenyl carbonate (DPC), which are important industrial intermediates for the production of polycarbonates. Moreover, DMC can be used as an eco-friendly methylation and carbonylation agent [214,215]. The industrial production of DMC by oxidative carbonylation of methanol has been achieved by Enichem [216] and Ube [217]. 

When benzoic acid is heated above its melting point in a sealed container, some formation of benzoic anhydride and water takes place [8]. When the acid is heated to 370°C, it is irreversibly decomposed to benzene and carbon dioxide, and a small portion (2-8%) decomposes into phenol and carbon monoxide. Copper and cadmium powder increase the reaction rate by factors of approximately 9-fold and 200-fold, respectively. 

The p-cyclodextrin-catalyzed reaction of phenols and carbon tetrachloride in an alkaline medium in the presence of copper powder also results in almost exclusive attack at the para-position to give 4-hydroxybenzoic acids. 2-Methylphenol also undergoes almost exclusive para-carboxylation. P-Cyclodextrin has only a negligible effect on the carbox-ylation of 3-methylphenol.-... 

In a detailed paper, Rogic and Demmin [40] reported on several "copper" reagents that can effect the oxidation of catechol, o-benzoquinone, 4-t-butylcatechol and phenol, with carbon-carbon bond cleavage, both in the absence and presence of dioxygen. 

ABSTRACT. Selective formylation of phenol at the 4-position is achieved by using 3-cyclodextrin as catalyst in the reaction of phenol with chloroform in aqueous alkali. The reactions of 1,3-dihydroxybenzene and indol, respectively, in the place of phenol give 2,4-dihydroxybenz-aldehyde and indole-3-aldehyde in virtually 100% selectivies and high yields. The reactions of para-substituted phenols, 4-methylphenol and 5,6,7,8-tetrahydro-2-naphthol, instead of phenol, effect the selective dichloromethylation at the para-positions. Selective carboxylation of phenol at the 4-position is achieved in the reaction of phenol with carbon tetrachloride in aqueous alkali by using 3-cyclodextrin and copper powder as catalyst. 

Almost all the trichloromethyl cations should form inclusion complexes with 3-CyD prior to the attack at phenols, since the selective carboxylation is achieved at quite a small molar ratio of 3 CyD to phenol or carbon tetrachloride. Trichloromethyl cations can be trapped in the cavity of 3-CyD immediately after being formed on the surface of copper powder. Alternatively, the trichloromethyl cation can be formed predominantly from the carbon tetrachloride included in the cavity, also with catalysis by copper powder, and thus be trapped in the cavity. There, the electrostatic attraction between the positive charge of the cation and the negative charges of 3-CyD is cooperatively functioning with the apolar interaction between the cation and the 3-CyD. Then, the trichloromethyl cation should attack overwhelmingly at the para-carbon atom of phenols, which is located in close proximity. 4-Hydroxybenzoic acid is formed by the hydrolyses of the C-Cl bonds in the resulting intermediates. 

Calcium Carbonate (cold) Calcium Chlorate (dilute) Calcium Chloride Calcium Hydroxide Cane Sugar Liquors Carbolic Acid (Phenol) Carbonic Acid I Carbon Dioxide Carbon Disulfide Carbon Tetrachloride Caustic Potash Caustic Soda Chlorine (anhydrous) Chromic Acid Citric Acid (to 15%) Copper Acetate Copper Carbonate Core Oils Cotton Seed Oil... 

Amongst heat stabilisers are copper salts, phosphoric acid esters,phenyl-3-naphthylamine, mercaptobenzothiazole and mercaptobenzimidazole. Of these, copper salts in conjunction with halides have been found particularly effective, and some automotive specifications require the use of copper for heat stabilisation. Light stabilisers include carbon black and various phenolic materials. 

Oxy-aldehyd, n, hydroxy aldehyde, -ammo-niak, n, oxyammonia (hydroxylamine), -azoverbindung, /. hydroxyazo compound, -benzol, n, hydroxybenzene (phenol), -bem-steinsaure. /, hydroxysuccinic acid (malic acid). -biazol, n. oxadiazole, oxdiazole. -bitumen, n, oxidized bitumen, -carbon-s ure, /, hydroxycarboxylic acid, -chlnoltn, n. hydroxyquinoline, -clunon, n. hydroxy-quinone. -chlorid, n. oxychloride, -chlor-kupfer, n. copper oxychloride, -cyan, n. oxycyanogen. 

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). 

Typically, the stereospecific formation of quaternary centers is as problematic as selective nucleophilic attack at the more substituted carbon of aziridines. Interestingly, a copper mediated methodology has been reported that does both <060L5105>. Although N-tosyl aziridines show favorable results, A-nosyl aziridines gave the best results. The reaction of 89 with a variety of phenols yielded 90 in moderate yields. 

When two electrons are transferred from a phenoxide anion to the copper dimer, we form the phenoxonium cation and two copper(I) ions are formed. Most likely, the phenoxonium cations are not free in solution, but they are still coordinated to copper. The valence state cannot be rapidly deducted from the picture and thus we have indicated that below the respective complexes. A nucleophilic attack by another phenol (or phenoxide anion) takes place at carbon-4 of the phenoxonium ion (Figure 15.17). 

In addition to the conventional pollutant constituents, USEPA made a survey of the presence of the 126 toxic pollutants listed as priority pollutants in refinery operations in 1977 [5]. The survey responses indicated that 71 toxic pollutants were purchased as raw or intermediate materials 19 of these were purchased by single refineries. At least 10% of aU refineries purchase the following toxic pollutants benzene, carbon tetrachloride, 1,1,1-trichloroethane, phenol, toluene, zinc and its compounds, chromium and its compounds, copper and its compounds, and lead and its compounds. Zinc and chromium are purchased by 28% of all refineries, and lead is purchased by nearly 48% of all plants. 

The surveyed data also indicate that there were net increases in all of the following compounds total dissolved solids, total suspended solids, total organic carbon, total residual chlorine, free available chlorine 2,4-dichlorophenol, 1,2-dichlorobenzene, phenolics, chromium, lead, copper, mercury, silver, iron, arsenic, zinc, barium, calcium, manganese, sodium, methyl chloride, aluminum, boron, and titanium. 

Other reported syntheses include the Reimer-Tiemann reaction, in which carbon tetrachloride is condensed with phenol in the presence of potassium hydroxide. A mixture of the ortho- and para-isomers is obtained the para-isomer predominates. -Hydroxybenzoic acid can be synthesized from phenol, carbon monoxide, and an alkali carbonate (52). It can also be obtained by heating alkali salts of -cresol at high temperatures (260—270°C) over metallic oxides, eg, lead dioxide, manganese dioxide, iron oxide, or copper oxide, or with mixed alkali and a copper catalyst (53). Heating potassium salicylate at 240°C for 1—1.5 h results in a 70—80% yield of -hydroxybenzoic acid (54). When the dipotassium salt of salicylic acid is heated in an atmosphere of carbon dioxide, an almost complete conversion to -hydroxybenzoic acid results. They>-aminobenzoic acid can be converted to the diazo acid with nitrous acid followed by hydrolysis. Finally, the sulfo- and halogenobenzoic acids can be fused with alkali. 

Diffusion-type models have been used for the adsorption of lead, copper, p-nitrophenol, phenol, p-bromophenol, p-toluene sulfonate and dodecyl benzene sulfonate on activated carbon (Hashimoto etal., 1977 Xiu and Li, 2000 Chen and Wang, 2004 Crittenden and Weber, 1978), and ion exchange of ammonia, lead, and other heavy metals on clinoptilolite (Inglezakis and Grigoropoulou, 2003 Cincotti et al, 2001 Semmens et al, 1978 Cooney et al, 1999). 

The cyclodehydration of o-phenoxybenzoic acids has been widely used to synthesize xanthones carrying variety of substituents. An Ullmann reaction provides a useful route to the required acids a 2-chlorobenzoic acid and a phenol react in an inert solvent such as nitrobenzene in the presence of copper bronze and potassium carbonate (53JCS1348). In a modified procedure sodium methoxide is used without solvent at 200 °C (79JA665). Cyclization is accomplished in concentrated sulfuric acid or in acetyl chloride containing a little sulfuric acid (61JCS2312). 

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