Ethyl phenyl acetate

Ingold and his co-workers used the competitive method in their experiments, in which nitration was brought about in acetic anhydride. Typically, the reaction solutions in these experiments contained o-8-I 4 mol of nitric acid, and the reaction time, depending on the reactivities of the compounds and the temperature, was 0-5-10 h. Results were obtained for the reactivities of toluene, > ethyl benzoate, the halogenobenzenes, ethyl phenyl acetate and benzyl chloride. Some of these and some later results are summarized in table 5.2. Results for the halogenobenzenes and nitrobiphenyls are discussed later ( 9.1.4, lo.i), and those for a series of benzylic compounds in 5,3.4. 

Ethyl Phenyl-acetate.—This ester has the formula C[Pg.167]

A suspension of sodium amide2 (0.1 mole) in liquid ammonia is prepared in a 500-ml. three-necked, round-bottomed flask fitted with a West condenser, a ball and socket glass mechanical stirrer (Note 1), and a dropping funnel. In the preparation of this reagent a small piece of clean sodium metal is added to 350 ml. of commercial anhydrous liquid ammonia. After the appearance of a blue color, a few crystals of hydrated ferric nitrate are added, whereupon the blue color is discharged. The remainder of the 2.3 g. (0.1 mole) of sodium (Note 2) is then rapidly added as small pieces. After all the sodium has been converted to sodium amide (Note 3), a solution of 16.4 g. (0.1 mole) of ethyl phenyl-acetate (Note 4) in 35 ml. of anhydrous ethyl ether is added dropwise over a 2-minute period, and the mixture is stirred for 20 minutes. To the dark green suspension is added over an 8-minute period a solution of 18.5 g. (0.1 mole) of (2-bromo-... 

Phenylacetamide has been obtained by a wide variety of reactions from benzyl cyanide with water at 250-260° 6 from benzyl cyanide with water and cadmium oxide at 240° 6 from benzyl cyanide with sulfuric acid 7 8 by saturation of an acetone solution of benzyl cyanide with potassium hydrosulfide 9 from benzyl cyanide with sodium peroxide 10 by electrolytic reduction of benzyl cyanide in sodium hydroxide 11 from ethyl phenyl-acetate with alcoholic 12 or aqueous 13 ammonia from phenyl-acetic acid with ammonium acetate 14 or urea 15 from diazoacetophenone with ammoniacal silver solution 16 from phenyl-acetic acid imino ether hydrochloride and water 17 from acetophenone with ammonium poly sulfide at 215° 18 from benzoic acid 19 and by heating the ammonium salt of phenyl-acetic acid.20... 

C8HgCHfNOgJCOOCEH8or C8H6C( N02H) COOC2H6, mw 209.20, oil, dec on distillation. Prepd as die No salt by treating ethyl phenyl acetate with ethyl nitrate in eth in the presence of Na, A Li salt crystallizes from ale as ndls with one molecule of ale of crystallization the ale evaporates at 150°and the remainder melts at 200°... 

Diethyl 2-phenylmalonate is prepared by a mixed Claisen condensation between ethyl phenyl-acetate and diethyl carbonate. 

Ozonolysis of vinylpyrazine in methanol at — 30° furnishes pyrazine aldehyde in 73% yield.196 Vinylpyrazine undergoes a variety of addition reactions and pyrazylethyl derivatives of amines, ketones, ethyl phenyl acetate, phenylacetonitrile, and acetamide have been obtained.197-199 2-(2-Pyrazylethyl)cyclohexanone (42) has been prepared both by the condensation of vinylpyrazine with cyclohexanone in the presence of sodium metal and by interaction of vinylpyrazine with the pyrrolidine enamine of cyclohexanone followed by hydrolysis.200... 

Ethyl 6 methyl aniline acetochlor, metolachlor, propisochlor Ethyl phenyl acetate flurtamone Ethyl phenyl ketone hexythiazox... 

Aromatic esters are hydrogenated without solvent or in alcohol. Ethyl benzoate (eq. 11.49),11 ethyl phenyl acetate,183 methyl salicylate (eq. 11,50),86a and diethyl phthalate (eq. 11.51)183 were hydrogenated almost quantitatively to the corresponding cyclohexane derivatives over Ni-kieselguhr at 150-200°C. The hydrogenation of the ethyl... 

Reaction of ethyl iodoacetate with an excess (5 equiv) of pyrrole in the presence of 2-methyloxirane and BusSnSnBus led to the desired substitution product 1011 in 43% yield, in addition to an undetermined quantity of ethyl phenyl-acetate 1012 (Equation 239), indicating reactivity with the benzene solvent under the reaction conditions <1999TL2677>. The less toxic solvent, methyD-butyl ether (MTBE), provided product 1011 in improved (64%) yield. 

The boiling point of ethyl phenyl acetate is near that of benzyl cyanide. However, a Kjeldahl analysis of the product shows that only a trace of nitrogen compounds is present. 

Phenylethyl alcohol is prepared by reduction of ethyl phenyl-acetate with sodium in absolute alcohol by hydrogenation of phenylacetaldehyde in the presence of a nickel catalyst or by addition of ethylene oxide or ethylene chlorohydrin to phenylmagnesium bromide, followed by hydrolysis. Phenylethyl alcohol also occurs naturally in a number of essential oils, especially rose oil. 

Esters, such as ethyl acetate, linalyl acetate, ethyl phenyl acetate, and methyl dihydrojasmonate... 

Ethyl acetate Ethyl butyrate Ethyl caproate Ethyl cinnamate Ethyl heptoate Ethyl laurate Ethyl oxyhydrate Ethyl phenyl acetate Ethyl propionate Ethyl undecylinate Ethyl valerinate Eucalyptol Eugenol Benzyl isobutyrate Benzyl isovalerinate Benzyl methyl... 

PROBLEM 21.3 Give the structure of the product obtained when ethyl phenyl-acetate (C6H5CH2CO2CH2CH3) is treated with each of the following esters under conditions of the mixed Claisen condensation ... 

Table 8-10. Catalytic Effect of Water on Aminoltsis of Ethyl Phenyl Acetate ...

Phenobarbital is prepared by treating benzyl ehloride with sodium eyanide when benzyl eyanide (or a-phenyl acetonitrile) is formed with the elimination of a moleeule of sodium chloride. Benzyl cyanide, first on hydrolysis yields phenyl aeetic acid which on subsequent esterification with ethanol forms the eorresponding ester as ethyl phenyl acetate. This on reaction with diethyl oxalate in the persence of absolute ethanol and sodium metal gives diethyl phenyl oxalo acetate which on distillation at 180°C results into phenyl malonic ester. When it is treated with ethyl bromide and sodium ethoxide, the lonely active hydrogen atom gets replaced with an ethyl group thus forming ethyl phenyl malonic ester. Lastly, this on condensation with urea loses two molecules of ethanol and finally forms the desired compound phenobarbital. 

The atropic ester typically is produced by condensation of ethyl phenyl-acetate and formaldehyde. The condensation reaction can be performed in the presence of ethyl oxalate to obtain the product in higher yield. A more modern approach is the Pd-catalysed alkoxylcarbonylation of phenylacetylene. 

In 2001, Buchwald reported the a-arylation of esters using not only biphenyl-type ligands but also t-Bu-MAP [217]. The t-butyl acetates could be successfully arylated using DavePhos as ligand and LHMDS as base, and the same system was employed for the formation of a-aryl propionic esters and for the a-arylation of ethyl phenyl acetates. Aryl chlorides could also be used as coupling partners for... 

In 1949 Arnold and Searles [13] reported that allyl, crotyl and 1-methylallyl diphenylacetates, when treated with mesitylmagnesium bromide or sodium hydride, rearrange to the respective a-substituted diphenylacetic acids. Rearrangement of allyl a-ethyl phenyl acetate could also be effected with stronger base like MgBrNEtj, albeit in very low yields (Scheme 5.1.2). The method was further extended to the synthesis of 9-fluorenecarboxylic acid [14] (Scheme 5.1.3). 

You have synthesized phenylalanine by the following sequence. Ethyl phenyl acetate is brominated at the a-position and then treated with ammonia. Treatment with aqueous NaOH and then acidification to pH 4 are followed by extraction with dichloromethane. You do not obtain any phenylalanine in the dichloromethane. Why not ... 

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