Ethyl phenylacetate, reaction with

Ethyl phenylacetate, reaction with (2-bromoethyl)benzene, 47, 72 Ethyl 2-phenylhexanoate, 47, 74 Ethyl 2-phenylpropionate, 47, 74 Exchange of oxygen by sulfur in preparation of chloromethylphospho-nothioic dichlonde, 46, 21 Extractor, stirred in isolation of 3-hydroxyglutaromtnle, 46, 49... 

Butylation of ethyl phenylacetate, /-butyl phenylacetate, and ethyl 2-phenylhexanoate has also been accomplished with M-butyl bromide and sodium hydride in refluxing monoglyme in 64%, 66%, and 56% yields, respectively.6 In contrast to the sodium amide reactions above, however, careful fractionation of the crude products was required to obtain pure products. 

Bromoethyl)benzene, reaction with ethyl phenylacetate, 47, 72 ic-Bromofluorides from olefins, 46,12 Bromofluorination of olefins, 46, 39... 

Silver fluoborate, reaction with ethyl bromide in ether, 46, 114 Silver nitrate, complexing with phenyl-acetylene, 46, 40 Silver oxide, 46, 83 Silver thiocyanate, 45, 71 Sodium amide, in alkylation of ethyl phenylacetate w ith (2-bromo-ethyl)benzene, 47, 72 in condensation of 2,4-pentanedione and 1 bromobutane to give 2,4-nonanedione, 47, 92 Sodium 2 ammobenzenesulfinate, from reduction of 2 mtrobenzenesul-finic acid, 47, 5... 

The hydrochloride of 3-amino-4-hydrazinopyridine 65 was prepared by reaction of the 4-chloro-3-nitropyridine derivative with ethoxycarbonyl-hydrazine in phenol to give the hydrochloride of ethyl 3-(3-nitro-4-pyridyl)carbazate 64 (R2 = OEt), which on successive heating in concentrated hydrochloric acid and hydrogenation over Pd/C gave 65. Its reaction with phenylacetic acid or with phenoxyacetic acid gave the hydrochloride... 

Recently, Smulik and Vedejs have reported that amination of ester enolates and enim-inates with 0-(p-nitrobenzoyl)hydroxylamine 21 takes place with good yields . However, reaction of enolates derived from ethyl phenylacetate and phenylacetonitrile gave lower yields compared with stabilized enolates derived from diethyl malonate, diethyl 2-phenylmalonate and 2-phenyl-2-cyanopropionate (Scheme 23). 

Michael addition of ethyl phenylacetate to a number of ethyl 2-acetylcinnamates leads to dihydropyran-2-ones (Scheme 199) (76IJC(B)739), as does a Reformatski reaction of ethyl 4-bromo-3-methoxybut-2-enoate with unsaturated aldehydes (81JHC363). 

Therefore, it seems that tridireotional zeolites HY and HB are the most promi sing ones for liquid phase reactions. In the case of HB zeolites, two items deserve special comments. Firstly, the yield (82%) of ethyl phenylacetate for the equimolar esterification of phenylacetic acid and ethanol in the presence of the fl-10 sample is substantially higher than that of the equilibrium (69%) at the same temperature and solvent (Table 3). Analogous results have been already observed with dealuminated acidic Y faujasites and can be due to zeolite water adsorption and/or to the hydrophobicity of the in surfaces (ref. 2). The hydrophobic character of high silica... 

The pyridine derivatives (183) underwent addition reactions with ethyl phenylacetate to give adducts 184, which could be reductively cyclized in the presence of a platinum catalyst, to give the indolizidines 185.2 3... 

Benzyl halides have been reported to react with nickel carbonyl to give both coupling and carbonylation (59). Carbonylation is the principal reaction in polar nonaromatic solvents, giving ethyl phenylacetate in ethanol, and bibenzyl ketone in DMF. The reaction course is probably similar to that of allylic halides. Pentafluorophenyl iodide gives a mixture of coupled product and decafluorobenzophenone. A radical mechanism has been proposed (60). Aromatic iodides are readily carbonylated by nickel carbonyl to give esters in alcoholic solvents or diketones in ethereal solvent (57). Mixtures of carbon monoxide and acetylene react less readily with iodobenzene, and it is only at 320° C and 30 atm pressure that a high yield of benzoyl propionate can be obtained (61). Under the reaction conditions used, the... 

Another instance is the benzylation of AW-dimethylanilines and derivatives upon irradiation of benzyl cyanides, which cleave via the radical anion formed by electron transfer [212]. Yet another path for the benzylation of (hetero)aromatics is the SRN1 reaction, as shown by the smooth photoassisted reaction of the enolate from ethyl phenylacetate with 2-bromopyridine (77% yield) [213]. 

Ethyl phenylacetate and even the tertiary carbanion methyl diphenylacetate gave 84 and 42%, respectively, of the disubstitution product in their reaction with 2,6-dibromopy-ridine179. However, only monosubstitution product at position 4,134 was obtained in 70% yield in the reaction of 4,7-dichloroquinoline (133) with pinacolone enolate ion (equation 90)179. 

The pyrolysis of f-butyl peroxy esters in suitable hydrogen donor solvents has been reviewed by RQchardt. Die method involves the reaction of an acyl chloride with t-butyl hydroperoxide followed by thermolysis of the resulting peroxy ester in cumene or p-cymene. Yields are moderate, but the pyrolysis step tolerates a certain degree of functionality as illustrated in equation (8). ° More recently, the use of ethyl phenylacetate as the pyrolysis solvent and hydrogen donor has been advocated. ... 

In a 2-1. three-necked flask fitted with a mercury-sealed stirrer, reflux condenser, and dropping funnel is placed 500 cc. of absolute ethyl alcohol (Note i), and 23 g. (i gram atom) of cleanly cut sodium is added in portions. When the sodium has dissolved the solution is cooled to 60°, and 146 g. (i mole) of ethyl oxalate (Org. Syn. Coll. Vol. i, 256) (Note 2) is added in a rapid stream through the funnel with vigorous stirring. This is washed down with a small quantity of absolute alcohol, and is followed immediately by the addition of 175 g. (1.06 moles) of ethyl phenylace-tate (Org. Syn. Coll. Vol. i, 265) (Note 2). Stirring is discontinued at once, the reaction flask is lowered from the stirrer, and a 2-1. beaker is made ready. Within four to six minutes after the ethyl phenylacetate has been added crystallization sets in. The contents of the flask are transferred immediately to the beaker at the first sign of crystallization, which is nearly Instantaneous. 

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