Benzyl acetate alcohol

Mix 31 g. (29-5 ml.) of benzyl alcohol (Section IV, 123 and Section IV,200) and 45 g. (43 ml.) of glacial acetic acid in a 500 ml. round-bottomed flask introduce 1 ml. of concentrated sulphuric acid and a few fragments of porous pot. Attach a reflux condenser to the flask and boil the mixture gently for 9 hours. Pour the reaction mixture into about 200 ml. of water contained in a separatory funnel, add 10 ml. of carbon tetrachloride (to eliminate emulsion formation owing to the slight difference in density of the ester and water, compare Methyl Benzoate, Section IV,176) and shake. Separate the lower layer (solution of benzyl acetate in carbon tetrachloride) and discard the upper aqueous layer. Return the lower layer to the funnel, and wash it successively with water, concentrated sodium bicarbonate solution (until effervescence ceases) and water. Dry over 5 g. of anhydrous magnesium sulphate, and distil under normal pressure (Fig. II, 13, 2) with the aid of an air bath (Fig. II, 5, 3). Collect the benzyl acetate a (colourless liquid) at 213-215°. The yield is 16 g. 

In detergent perfumes, the stabiUty of vanillin is not always certain. It depends on the association made with other raw materials, eg, with patchouli, frankincense, cloves, most of the animal notes, and such chemicals as amyl saUcylate, methyl ionones, heflotropin, gamma undecalactone, linalool, methyl anthrarulate, benzyl acetate, phenyl ethyl alcohol, cedar wood derivatives, oak mosses, coumarin, benzoin. Pern balsam, and cistus derivatives. In some cases, these mixtures can cause discoloration effects. 

Nearly all uses and appHcations of benzyl chloride are related to reactions of the active haUde substituent. More than two-thirds of benzyl chloride produced is used in the manufacture of benzyl butyl-phthalate, a plasticizer used extensively in vinyl flooring and other flexible poly(vinyl chloride) uses such as food packaging. Other significant uses are the manufacture of benzyl alcohol [100-51-6] and of benzyl chloride-derived quaternary ammonium compounds, each of which consumes more than 10% of the benzyl chloride produced. Smaller volume uses include the manufacture of benzyl cyanide [140-29-4], benzyl esters such as benzyl acetate [140-11-4], butyrate, cinnamate, and saUcylate, benzylamine [100-46-9], and benzyl dimethyl amine [103-83-8], and -benzylphenol [101-53-1]. In the dye industry benzyl chloride is used as an intermediate in the manufacture of triphenylmethane dyes (qv). First generation derivatives of benzyl chloride are processed further to pharmaceutical, perfume, and flavor products. 

Methyl benzoata, tnelbvl salicylate, benzyl acetate, benzyl benzoate, and Iren benzyl alcohol are present in small amounts, as well as methyl anthraniJale and oreosol in Iraoea. Tliicod has also recently identified lormic acid, and aatrol or iso-saliol. 

Phenyl-propyl alcohol, CgH. CHj. CH.2. CHj. OH, is the next highest homologue of phenyl-ethyl alcohol, and is also known as hydro-cinnamyl alcohol. Like the last described bodies it has been known for many years, its first preparation being described in the Aivnalen (188, 202). It occurs as a cinnamic acid ester in storax, and as an acetic ester in cassia oil. It is prepared synthetically by the reduction of cinnamyl alcohol with sodium amalgam and water, or by the reduction of cinnamic or benzyl acetic esters with sodium and absolute alcohol. It has the following characters —... 

The above section already introduced the influence of leaving groups at the benzylic position that eliminate to form and regenerate QM3, and the trend extends beyond adducts formed by the deoxynucleosides as expected. The standard benzylic acetate of QMP4 eliminates completely from the deprotected phenol under neutral aqueous conditions and ambient temperature within approximately 20 h, while an equivalent benzyl bromide eliminates completely within 5 min.48 Benzylic phosphates are also extremely labile, and, if the phosphate backbone of DNA is able to trap QM, the resulting products are likely to be too labile for standard detection.53,54 In contrast, amines and thiols are much less susceptible to elimination from the benzylic position and require forcing conditions to regenerate the parent QM.26,30 The benzylic alcohol derivative also appears stable under almost all thermal conditions and only eliminates routinely to form a QM after photochemical excitation.55... 

Nitrobenzyl acetate has been prepared by the action of alcoholic potassium acetate on />-nitrobenzy] chloride 1 or bromide 2 and by the nitration of benzyl acetate.3... 

The procedure given here is essentially that described previously by the submitters2 and is based on the early work of Knoevenagel.8 2-Phenylindazole has been prepared by reduction of N-(o-nitrobenzyl)aniline with tin and hydrochloric acid,4 by reduction of N-(o-nitrobenzyl) -N-nitrosoaniline with tin and hydrochloric acid,5 by dehydration of 2-(phenylazo)benzyl alcohol,6 by elimination of acetic acid from 2-(phenylazo)benzyl acetate,7 by dehydrogenation of 3,3a,4,5,6,7-hexahydro-2-phenyl-indazole with sulfur,8 and by thermal decomposition of o-azido-benzalaniline.9... 

The chemical structures of the majority of FMs that have been studied in wastewater treatment are given in Figs. 1-3. Figure 1 shows a variety of FM structures that include alcohols, aldehydes, and ketones, including benzyl acetate (phenylmethyl ester acetic acid), methyl salicylate (2-hydroxy-methyl ester benzoic acid), methyl dihydrojasmonate (3-oxo-2-pentyl-methyl ester cyclopentaneacetic acid), terpineol (4-trimethyl-3-cyclohexene-1-methanol), benzyl salicylate (2-hydroxy-phenylmethyl ester benzoic acid), isobornyl acetate... 

Uses Manufacture of perfumes, benzyl compounds (e.g., benzyl alcohol, benzyl acetate). 

Oeavage of esters to acids and hydrocarbons mentioned above was achieved not only with hydrides but also by catalytic hydrogenation and reduction with metals. For example the acetate of mandelic acid was converted to mandelic acid and acetic acid by hydrogenation at 20° and 1 atm over palladium on barium sulfate in ethanol in the presence of triethylamine in 10 minutes [1035], and a,a-diphenylphthalide was reduced by refluxing for 5 hours with zinc in formic acid to a,a-diphenyl-o-toluic acid in 92% yield [1036]. Such reductions are of immense importance in esters of benzyl-type alcohols where the yields of the acids are almost quantitative. 

Scheme 8 Bi(OTf)3-catalyzed arylation of 1-phenylethanol, benzyl alcohol and benzyl acetate...

Esters of araliphatic alcohols and aliphatic acids are interesting as flavors and fragrances because of their characteristic odor properties. Acetates are the most popular esters. Benzyl acetate is particularly important commercially and occupies a prominent position in the fragrance and flavor industry. 

The metabolism of benzyl acetate involves very rapid hydrolysis to acetate and benzyl alcohol. The latter is subsequently mainly oxidized to benzaldehyde and benzoic acid. A small part of the benzyl alcohol may be conjugated with sulfate, leading, ultimately, to fonnation of a glutathione conjugate that is excreted as mercapturate in urine. The benzoic acid is excreted mainly as hippurate and, to a lesser extent, as acyl glucuronide (see Figure 1). 

Benzyl acetate is quite soluble in lipids and therefore readily absorbed from the gastrointestinal tract and lung, as well as through the skin, in the species investigated. The absorption after oral administration in the rat was delayed if it was administered in com oil or propylene glycol as compared to neat [wet/zy/ene- Cjbenzyl acetate (Chidgey Caldwell, 1986) the peak plasma concentration of benzyl acetate-derived radioactivity occurred later after 1 h versus 4-6 h) and was lower at a 500 mg/kg benzyl acetate dose at 5 mg/kg benzyl acetate, there was no difference. The urinary excretion of the metabolites was also delayed by com oil, but the extent of absorption seemed not to be affected more than 80% was absorbed and excreted within 24 h, mainly in urine and, ultimately, less than 5% in faeces. In plasma and urine, no intact benzyl acetate was detected at any time only its metabolites were present (Chidgey Caldwell, 1986). Benzyl acetate is rapidly hydrolysed by esterases to benzyl alcohol and acetate (Yuan et al., 1995). These esterases are present in plasma and probably also in the tissues it is... 

Since no data are available on humans except for skin penetration data in vitro, no direct comparison can be made. Because in humans most of the dose seems to be excreted as hippurate (lARC, 1986) and because the metabolism of the primary hydrolysis product of benzyl acetate, benzyl alcohol, is very similar in rodents and humans (see, e.g., the monograph on toluene (this volume)), it is to be expected that the fate of benzyl acetate in humans is very similar to that in rodents. 

Beckmann rearrangement of, 729,741 p-Benzoquinone, 745 Benzoylacetone, 865 o-Benzoylbenzoic acid, 728, 739 Benzoyl chloride, 791, 792 Benzoyl glycine, 584 Benzoyl peroxide, 807 determination of, 809 Benzoyl piperidine, 489, 492 P-Benzoylpropionic acid, 728, 737 P-Benzoylpropionitrfle, 911, 912 Benzoyl-p-toluidide, 582, 583 Benzyl acetate, 780, 783 Benzylacetophenone, 726, 734 Benzyl alcohol, 706,711, 811,812,884 N-Benzylamid es 394 table of, 395 ... 

Purification. Small amounts of reaction by-products are produced during the liquid-phase oxidation of toluene. These by-products include acetic and formic acids, benzene, benzaldehyde, benzyl alcohol, aliphatic benzyl esters such as benzyl formate and benzyl acetate, biphenyl, 2-, 3-, and 4-methylbiphenyls, and phthalic acid. Of these only benzaldehyde and benzene [71 -43-2] are currendy separated commercially. 

Further evidence of nuclear attack was furnished by the oxidation of toluene- -d3 under conditions identical to those in Table IV. After 90 minutes the product contained an estimated 6% benzaldehyde-di and 11% benzyl alcohol-d2 plus benzyl acetate-d2. In addition, samples taken at three intervals gave these isotopic analyses for the recovered toluene ... 

Flowery Anisyl alcohol Benzyl acetate, phenylaceiate Cinnamic acid Cinnamyl acetate Citronellyl formate Crcsyl acetate Decanal Dimethyl benzyl carbinol Dimethyl benzyl carbinyl acetate Ethyl anthranilate Geranyl acetate Hydroxycitronellal dimethyl acetate Linalool Linalyl acetate Methyl benzoate Pcnethyl acetate 2-Phcnylpropionaldehyde 3-Phenylpropionaldehvde. 

Essential oils are obtained from fruits and dowers (61,62). Volatile esters of short- and medium-chain carboxylic acids or aromatic carboxylic acids with short- and medium-chain alcohols are primary constituents of essential oils, eg, ethyl acetate in wines, brandy, and in fruits such as pineapple benzyl acetate in jasmine and gardenia methyl salicylate in oils of wintergreen and sweet birch. Most of these naturally occurring esters in essential oils have pleasant odors, and either they or their synthetic counterparts are used in the confectionery, beverage, perfume, cosmetic, and soap industries (see Oils,... 

Benzyl acetates react with trimethylsilane and CO in the presence of Co2(CO)8 as catalyst to give P-phenethyl alcohols by a one-carbon homologation. The active catalyst is assumed to be (CH3)3SiCo(CO)4. The reaction proceeds under CO at atmospheric pressure at 25°. It fails with benzyl alcohol itself, but is successful with benzyl formate and benzyl methyl ether.5... 

---