Diphenyl benzoate

B. Polymers with phenyl, diphenyl benzoate and diphenyl groups... 

Phenyl benzoate (PB) was chosen as a model for the double Fries rearrangement of diphenyl benzoate into diphenol para monomers (Eq. 4) [4] and its transformation over several solid catalysts was investigated [4,8]. 

The reaction rate was shown to be related to the accessibility of the acid sites-H-MFI zeolite was practically inactive and Nafion was the most active catalyst. With all the catalysts, not only the desired p-hydroxybenzophenone (/ -HBP) product but also j3-benzoxybenzophenone (p-BXBP) and o-hydroxybenzophenone (o-HBP) were formed. The para products result from benzoylation of phenol (formed by hydrolysis of PB) or of PB and o-HBP from the intramolecular rearrangement of PB. The selectivity to p-HBP can, therefore, be significantly improved by adding phenol to the reactant mixture [4]. Unfortunately, thermodynamic limitations arising from the low polarity of the medium employed (even with very polar solvents such as sulfolane) seems to preclude the use of a solid acid for the production of diphenol monomers from diphenyl benzoate [4]. 

The following liquids may be used (boiling points are given in parentheses) — chlorobenzene (132-3°) bromobenzene (155°) p cymene (176°) o-dichloro-benzene (180°) aniline (184°) methyl benzoate (200°) teti-alin (207°) ethyl benzoate (212°) 1 2 4-trichlorobenzene (213°) iaopropyl benzoate (218°) methyl salicylate (223°) n-propyl benzoate (231°) diethyleneglycol (244°) n-butyl benzoate (250°) diphenyl (255°) diphenyl ether (259°) dimethyl phth ate (282°) diethyl phthalate (296°) diphenylamine (302°) benzophenone (305)° benzyl benzoate (316°). 

It was found that the 1,3-diphenyl-1,3-propanedionate anion behaved as a bidentate ligand whereas the benzoate acted as a monodentate ligand. The Ag-C bonds in 21a and 21b were more or less similar to that found in 18 (21a 2.064(6) A, 21b 2.085(10) A). It is interesting to note that 21b crystallizes as dimers with the presence of short intermolecular Ag-Ag distance of 3.000(10) A, in contrast to the monomeric nature of 21a with a longer Ag-Ag distance of 3.2177(13) A. 

In addition to studying the behavior of benzoyl chloride. Cheek and Horine [72] have examined the reduction of benzoyl fluoride electrolysis of the latter compound affords benzyl benzoate, diphenyl-acetylene, stilbenol benzoate, and some polymers. Another feature of the reduction of benzoyl chloride is the possibility that both acyl radicals and acyl anions are involved as intermediates [71]. 

The oxidation of benzaldoxime with perchloryl fluoride (FClOj) has been reported [29 a) to give a complex mixture in which benzaldoxime benzoate and diphenyl oxadiazole are the main products. Sodium nitrohydroxamate [Na2(02NN0)] has been reported [99b) to oxidize benzyl chloride to a mixture of compounds from which benzyl alcohol, benzaldehyde, benzoic acid, 3,4,5-triphenylisoxazole, benzyl-ethyl-ether, phenylnitromethane and diphenyloxadiazole have been isolated. 

In 1961, the catal5dic reduction of 3.5-diphenyl-, 3-phenyl-5-methyl and 3-methyl-S-phenyl oxadiazole has been reported by Palazzo [61b) who studied the influence of various reaction conditions such as the temperature, the solvent and the nature of the catalyst Pd on C, Adams-Pt and Raney-Ni. The opening of the N—O linkage occurs in each experiment. In the reduction of diphenyloxadiazole with Pd on C under 3 atm. one equivalent of hydrogen is absorbed and benzamidine benzoate is isolated in high yield. A small amount of benzoyl benzamidine is also formed ... 

The sapphyrin-modified silica gels also proved effective for HPLC separation of various anions other than phosphates, but not neutral or cationic species. For instance, various monoanionic species such as diphenyl phosphate, benzene sulfonic acid, phenyl arsenate, phenyl phosphate, and benzoate could all be separated from each other. Nucleotide mono-, di-, and triphosphates such as AMP, ADP, and ATP were also retained on these columns and were found to be readily separable from one another under isochratic HPLC conditions. Likewise, in what is still unpublished work, it has been found that these columns can be used to separate... 

The reduction of cupric salts of various other organic acids (e.g., benzoate cinnamate o-toluate o- and m-chlorobenzoate) has been examined using either the corresponding acid or diphenyl as solvent (Chalk and Halpern, 88). In most cases the behavior was found to be qualitatively similar to that described for cupric heptanoate. For several salts, compared in diphenyl, there was an indication that the activity of the cuprous salt increased and that of the cupric salt decreased with increasing basicity of the anion. 

Bisglycidylacrylate, ethoxylated bisphenol A dimethacrylate, diurethane dimethacrylate, triethyleneglycol dimethacrylate, tricycle[5.2.1.02,6]decanedimethanol diacrylate, camphorquinone, ethyl 4-(/V,/V-dimcthylamino)benzoate, diphenyl iodonium hexafluorophosphate, 2,6-di-t-butyl-4-methylphenol, benzotriazole... 

Methyl benzoate, anisole, and diphenyl ether each give sandwich compounds with chromium vapor, although in rather low yield (32, 55, 110). Chromium appears to attack alkyl ethers and this deoxygenation probably competes with complexation with the aromatic oxygen compounds. No simple product has been isolated from chromium atoms and aniline, but bis(7V,7V-dimethylaniline)chromium has been prepared (32). The behavior of molybdenum and tungsten vapors closely resembles that of chromium in reactions with oxygen- and nitrogen-substituted arenes (113). 

This procedure appears to be fairly general for the aroylation of /3-diketones to give 1,3,5-triketones. Using this method, the submitters2 have aroylated benzoylacetone with methyl benzoate (87%), methyl />-chlorobenzoate (78%), and ethyl nicotinate (69%). Also, acetylacetone has been monobenzoylated with methyl benzoate to form l-phenyl-l,3,5-hexanetrione in 75% yield or dibenzoylated with the same ester to form 1,7-diphenyl-... 

Orthoesters. As model experiments (1) phenyl Cellosolve and tetraphenyl orthocarbonate, and (2) hydroxyethyl benzoate and tetra-phenyl orthocarbonate reacted at 275°C. Diphenyl carbonate was obtained from the latter reaction but not from the former. The facts that the distillate from the latter reaction contained ethylene oxide and that diphenyl carbonate was formed quantitatively from the reaction of carboxylic acid and tetraphenyl orthocarbonate suggest the following reaction mechanism ... 

Diphenyl succinate Phenyl benzoate Phenyl cinnamate Diphenyl carbonate... 

As an ideal catalyst-directing group for that particular problem the ortho-diphenyl-phosphino benzoate system (o-DPPB) was introduced [10]. 

N. P, S COMPOUNDS Acetophenone Methyl acetophenone Phthalic Anhydride Methyl benzoate Indanone Dibenzofuran Diethyl phthal ate Di butylphthalate Di i sobutylphthalate Di (2-ethyl hexyl) phthal ate Diphenyl amine... 

In general, the excited radicals shown have been found to possess enhanced donor/acceptor properties, especially in interactions with such quenchers as oxygen, dienes, amines, and halides. To date, the most well-characterized intermolecular processes are charge (electron) transfer reactions between excited diphenyl-methyl radicals and electron donors and acceptors. Thus, excited 132 reacts with methyl benzoates and benzyl bromides (Schemes 23 and 24) with rates that increase with the increasing electron withdrawing ability of substituents on the... 

Bis[4-methylphenyl] ditellurium, bis[4-methoxyphenyl] ditellurium, and bis[4-ethoxy-phenyl] ditellurium, but not diphenyl or bis[2-naphthyl] ditcllurium, reacted with 2-(phenyliodonio)-benzoates producing compounds with two vicinal aryltelluro substituents in the aromatic ring. The reactions are postulated to proceed via the thermally generated singlet benzyne and concerted addition of the diaryl ditellurium compounds. 

Bis[4-methoxyphenyl] tellurium, obtained from 4-methoxybenzene and tellurium tetrachloride and reduction of the resultant bis[4-methoxyphenyl] tellurium dichloride, was converted to methyl 4-methoxybenzoate in 99% yield1. Methyl benzoate was similarly obtained from diphenyl tellurium in yields higher than 90%. These reactions can be carried out with catalytic amounts of palladium(II) chloride when copper(II) chloride is used as an oxidant1. 

Diphenyl Tellurium Dibenzoate4 3.5 g (10 mmol) of diphenyl tellurium dichloride are dissolved in 50 ml of dioxane and 5 g (22 mmol) of silver benzoate are added to the stirred dioxane solution at 20°. The mixture is then heated under reflux for 4h, filtered, and the filtrate evaporated. The residue is recrystallized from benzene/hexane (1/9, v/v) yield 4.8 g (92%) m.p. 161°. 

Diphenyl Methyl Telluronium Benzoate8 1.0 g (2 mmol) of diphenyl methyl telluronium iodide and 0.46 g (2 mmol) of silver benzoate in 50 ml of distilled water are stirred at 20° for 0.5 h and then heated under reflux for 4 h. Silver iodide is filtered off, the filtrate is concentrated under vacuum at 20°, and the precipitate is filtered off and dried over phosphorus pentoxide m.p. 105". 

Methyl diphenyl telluronium benzoates slowly eliminated methyl benzoates9. 

According to the investigations of Schali,1 diphenyl docs, however, occur if a solution of sodium benzoate in molten benzoic acid is electrolyzed at 100 volts between silver electrodes. 

PB PBI PBMA PBO PBT(H) PBTP PC PCHMA PCTFE PDAP PDMS PE PEHD PELD PEMD PEC PEEK PEG PEI PEK PEN PEO PES PET PF PI PIB PMA PMMA PMI PMP POB POM PP PPE PPP PPPE PPQ PPS PPSU PS PSU PTFE PTMT PU PUR Poly(n.butylene) Poly(benzimidazole) Poly(n.butyl methacrylate) Poly(benzoxazole) Poly(benzthiazole) Poly(butylene glycol terephthalate) Polycarbonate Poly(cyclohexyl methacrylate) Poly(chloro-trifluoro ethylene) Poly(diallyl phthalate) Poly(dimethyl siloxane) Polyethylene High density polyethylene Low density polyethylene Medium density polyethylene Chlorinated polyethylene Poly-ether-ether ketone poly(ethylene glycol) Poly-ether-imide Poly-ether ketone Poly(ethylene-2,6-naphthalene dicarboxylate) Poly(ethylene oxide) Poly-ether sulfone Poly(ethylene terephthalate) Phenol formaldehyde resin Polyimide Polyisobutylene Poly(methyl acrylate) Poly(methyl methacrylate) Poly(methacryl imide) Poly(methylpentene) Poly(hydroxy-benzoate) Polyoxymethylene = polyacetal = polyformaldehyde Polypropylene Poly (2,6-dimethyl-l,4-phenylene ether) = Poly(phenylene oxide) Polyp araphenylene Poly(2,6-diphenyl-l,4-phenylene ether) Poly(phenyl quinoxaline) Polyphenylene sulfide, polysulfide Polyphenylene sulfone Polystyrene Polysulfone Poly(tetrafluoroethylene) Poly(tetramethylene terephthalate) Polyurethane Polyurethane rubber... 

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