Phenyl benzoate, preparation

Uses Antiseptic and disinfectant pharmaceuticals dyes indicators slimicide phenolic resins epoxy resins (bisphenol-A) nylon-6 (caprolactum) 2,4-D solvent for refining lubricating oils preparation of adipic acid, salicylic acid, phenolphthalein, pentachlorophenol, acetophenetidin, picric acid, anisole, phenoxyacetic acid, phenyl benzoate, 2-phenolsulfonic acid, 4-phenolsulfonic acid, 2-nitrophenol, 4-nitrophenol, 2,4,6-tribromophenol, 4-bromophenol, 4-/ert-butylphenol, salicylaldehyde, and many other organic compounds germicidal paints laboratory reagent. 

The method described is adapted from the procedures of Kym 3 and Engelhardt, Latschinoff, and Malyscheff.4 Thio-benzoic acid has been prepared by the reaction of benzoyl chloride with potassium sulfide,4 hydrogen sulfide in pyridine,6 6 and magnesium bromide hydrosulfide.7 It is formed from dibenzoyl disulfide with potassium hydrosulfide,4 potassium hydroxide,4 8 and ammonia.9 It is also formed from dibenzoyl sulfide, from phenyl benzoate, and from benzoic anhydride with alcoholic potassium hydrosulfide.4 It has been obtained from dibenzoyl sulfide and hydrogen sulfide,10 carbon oxysulfide and phenyl-magnesium bromide,11 12 dibenzyl disulfide and sodium ethoxide,13 benzyl chloride and sulfur in the presence of potassium hydroxide,14 and benzylthiosulfuric acid and alkali.18 16... 

Preparation 213.—Phenyl Benzoate (Phenyl ester of benzenemono-carboxylic add). 

Reaction with the ester is relatively exothermic. Sensitivity of the substrate-product to heating varies and should be considered for each particular compound. Phenyl benzoate can be methylenated at room temperature with no significant decrease in product yield. By contrast, dihydrocoumarin (Preparation B) gives no product under these conditions and must be methylenated at -78°C to obtain a good yield. For most substrates it is satisfactory to carry out reactions at 0°C. 

Flavanols are similarly accessed from 2-(2-(benzoyloxy)acetyl)phenyl benzoates 752 via a Baker-Venkataraman rearrangement to form 3-benzoyloxy flavones followed by deprotection of the hydroxyl group (Scheme 194) <2000JOC583>. 3-Aroyl flavones are prepared form or/ o-hydroxyacetophenones and aroyl chlorides in modest yield, using a Kostanecki-Robinson approach (Equation 305) <2005SC315>. 

Ringsdorf and his co-workers [127] have prepared SCLC copolymers with acrylate, 62, or methacrylate, 63, main chains, phenyl benzoate mesogenic side-... 

Ester iealUm of phenols. The direct esterification of phenols is catalyzed by a combination of boric acid and sulfuric acid. Thus phenyl benzoate (I) can be prepared... 

In the application of this methodology to the preparation of C-glycosides, Beau and Sinay [183] utilized dimethyl carbonate as an electrophile. As shown in Scheme 7.65, the resulting product mixture favored the (3 oriented ester group in a ratio of 20 1. Subsequent reductive cleavage of the phenylsulfone was accomplished on treatment with lithium naphthalide giving the a-C-glycoside in 72% overall yield. Similar results were observed when phenyl benzoate was used as an electrophile. 

F) Preparation of Phenyl Benzoate (Sm.). The use of acyl chlorides in the formation of esters is illustrated in the following preparation. Place in an eight-inch tube 1 g of phenol, 15 ml of 10 per cent sodium hydroxide solution, and 1.5 ml of benzoyl chloride. Place a solid rubber stopper firmly in the mouth of the tube and shake vigorously at intervals for 10 minutes. Remove the stopper, warm the mixture slightly, and shake again for one minute. The ester which separates is filtered, washed with cold water, and dried. The yield is about 2 g. 

The preparation of phenyl benzoate is an example of this l,r-Carbonyldiimidazole (3.24 g) is added to benzoic acid (2.44 g) in dry tetrahydrofuran (30 ml) at room temperature. When evolution of carbon dioxide ceases, the mixture is treated with phenol (1.88 g) and heated under reflux for a further hour. Evaporation of the tetrahydrofuran and washing with water leaves pure phenyl benzoate, m.p. 70°, in 85 % yield. 

Phenylalanylglycine, synthesis of, 1077-1081 Phenyl benzoate, Fries rearrangement of, 952 2-Phenyl-2-butanol p-nitrobenzoate, 595 preparation of, 559 Phenylbutazone, 856 2-Phenylethanol... 

Block copolymers of butadiene and styrene are therefore readily synthesized an-ionically, with either of the two monomers polymerized first. Precursor copolymers of poly(styrene-h/oc -butadiene) have been used to prepare well-defined liquid crystalline block copolymers by the same polymer analogous reaction described in Sec. 2.5 of this chapter (Scheme 21) [201-203]. Following anionic polymerization by sequential monomer addition, the polymer analogous reactions of the cholesterol (PS-PBCh) [201] and azobenzene (PS-PBAz) [203] derivatives were essentially quantitative, while that of the phenyl benzoate (PS -PBBz) block went to up to 94% conversion [202]. The polydispersities of the liquid crystalline copolymers (pdi= 1.13-1.23) were nearly as narrow as those of their precursor copolymers (pdi = 1.08 -1.21, M =8.09-9.2xl0 ) [201, 203]. 

Particular emphasis should be placed on the preparation and smdies of oligomeric cholesteric cyclic siloxanes containing cholesterol (Choi) and various mesogeitic fragments (R), such as binaphol phenyl benzoate, azobenzene derivatives. ... 

The similar procedure was adopted for the synthesis of LCER 2, LCER 3 and LCER 4 as described for the synthesis of LCER 1 with small variations. LCER 2 [4,4 -Di(2,3-epoxypropenyloxy)phe-nyl benzoate] was prepared by oxidizing the diallyl monomer 4,4 -Di(2-propenyloxy)phenyl benzoate (31 g, 0.1 mol) with 3-chlo-roperoxybenzoic acid and recrystallizing the product in acetonitrile/ isopropanol (1 1). Yield 75% (25 g) T 116°C. LCER 3 [p-Phenylene-di[4-(2,3-epoxypropenyloxy)benzoate] was synthesized by oxidizing diallyl monomer p-phenylene-di[4-(2-propenyloxy)benzoate] (13 g, 0.030 mol), obtained pure product after recrystallization from ethylacetate/isopropanol. Yield 68% (8.9 g). The pure product of LCER 4 [4,4 -di[4"-(2,3-epoxypropenyloxy)benzoyloxy]phenyl benzoate] was obtained by oxidizing the diallyl monomer 4,4 -di[4"-(23-epoxypropenyloxy)benzoyloxylphenyl benzoate. "Vleld 66% (7.7 g). 

The starting keto ester was obtained by reaction of benzoyl chloride with phenyl benzoate in the presence of zinc chloride at 175-180° [ 128,157,159] or by reaction of benzotrichloride with the same ester in the presence of zinc oxide [157], This same keto ester (m.p. 112°5) can be also prepared by heating a benzoyl chloride/phenol mixture in the presence of zinc powder [158] ... 

Preparation by reaction of phenyl benzoate with hydroquinone in the presence of boron trifluoride-etherate in refluxing benzene for 3 h (60%) [34],... 

Preparation by Fries rearrangement of 2,4-difluoro- — / — / phenyl benzoate with aluminium chloride at 150-180°... 

Preparation by Fries rearrangement of 3-chloro-phenyl benzoate without solvent,... 

Preparation by Fries rearrangement of o-chloro-phenyl benzoate with aluminium chloride without solvent for 2 h at 152-155° (88%) [506] or at 160° [490,491]. 

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