Big Chemical Encyclopedia

Chemical substances, components, reactions, process design ...

Articles Figures Tables About

Ethyl benzoylacetate

ETHYL BENZOYLACETATE (Acetic acid, benzoyl-, ethyl ester) [Pg.35]

three-necked flask is mounted on a steam bath and fitted with a reflux condenser, a separatory funnel, and an efficient sealed stirrer. In the flask is placed 600 cc. of absolute alcohol, and to this is added gradually 46 g. (2 gram atoms) of clean sodium cut into small pieces.1 The sodium ethoxide solution is stirred and cooled to room temperature, after which 267 g. (260 cc., 2.05 moles) of ethyl acetoacetate (Note 1) is added slowly through the separatory funnel. The reflux condenser is then replaced by a short still head, and the alcohol is removed by distillation at approximately room temperature and under the pressure of a water pump. When approximately half the alcohol has been removed, sufficient sodium enolate precipitates so that stirring has to be discontinued. When the residue appears dry (after about two hours) the last traces of alcohol are removed by heating for an hour on the steam bath under a pressure of 2 mm. The flask is allowed to cool to room temperature under reduced pressure. [Pg.35]

To the cooled residue of sodium enolate is added 600 g. (570 cc., 4 moles) of ethyl benzoate. The steam bath is replaced [Pg.35]

For a more convenient method of preparing sodium ethoxide, see Note 1, p. 18. [Pg.35]

The reaction mixture is cooled, 250 cc. of water is added, and the mixture is made acid to litmus by addition of a cooled solution of 100 g. of concentrated sulfuric acid in 200 cc. of water. Clipped ice is added if necessary to keep the mixture cool. The upper ester layer is separated, and the aqueous layer is extracted with 200 cc. of ether. The combined ether and ester layers are sicken with 350 cc. of a saturated sodium bicarbonate solution ur til no more carbon dioxide is evolved, and then the organic layer is hashed with 200 cc. of water. The water layer is combined with the sodium bicarbonate solution and extracted with 400 cc. of ether. The combined ether and ester layers are dried over sodium sulfate. The ether is removed by distillation on the steam bath, aEd the excess ethyl benzoate and acetoacetic ester (Note 3) are then removed by distillation under reduced pressure through a 15 cm. fractionating column. Finally, the ethyl benzoylacetate is distilled (Note 3) at 101-106°/1 mm. (130-135°/3 mm.). The yield of ester boiling over a 5° range is 190-210 g. (50-55 per cent [Pg.36]

To the mixture is added 80 g. of technical ammonium chloride then it is stirred slowly overnight. The specific gravity is brought to 1.13 by the addition of about 90 g. of sodium chloride, after which the mixture is transferred to a separatory funnel. About 10 ml. of benzene is used to rinse the flask and is added to the separatory funnel. The aqueous [Pg.32]

An additional 40 ml. of benzene is added (to accomplish drying on distillation), and the product is distilled under reduced pressure, using a short still head with no fractionating column (Note 6). The yield of ethyl benzoylacetate, b.p. 145-150°/12 mm., is 197-203 g. (68-71%) (Note 4). [Pg.33]

Good stirring is essential. Slow stirring results in low yields. [Pg.33]

Temperatures above 10° did not result in consistently good yields. [Pg.33]

The benzene was dried by distillation, the first portion of the distillate being discarded. [Pg.34]

It is essential that these steps in the isolation be carried through as rapidly as possible. [Pg.34]

Larger amounts gave lower yields. The exact procedure must be followed as to time, temperature, and amounts of reagents, and the procedure completed without interruption. [Pg.34]

Ethyl benzoylacetate has been prepared by the condensation (by means of sodium ethylate) of ethyl acetate with ethyl benzoate,1 acetophenone with ethyl carbonate,2 and acetophenone with ethyl oxalate, with subsequent heating 3 by treatment of ethyl phenylpropiolate4 or a-bromocinnamic acid 5 with concentrated sulfuric acid, and of ethyl diazoacetate with benzalde-hyde 6 by the condensation of benzene with the monoethyl ester of malonyl monoacid chloride and aluminum chloride,7 of benzoyl chloride with the product of the reaction of magnesium and ethyl chloroacetate in ether,8 of alcohol on benzoylacetimino ethyl [Pg.34]

Submitted by R. H. Kimball, George D. Jefferson, and Arthur B. Pike. Checked by C. R. Noller. [Pg.36]


Ethyl benzoate Ethyl acetate Ethyl benzoylacetate. [Pg.265]

Phenyl-4(4H)-ona-5,7-dlhydroxy-1-benzopyran (3) A mixture oi phioroglucino 1 (2 77 g 22 mnx)l) and ethyl benzoylacetate 2 (7 65 g 40 mmol) was heated lo 240 250°C l< I 5 h The cooled mixture was extracted with 5% NaOH and Ihe aqueous solution was extracted with EtaO Acidification afforded a brown product which after sublimation at 250 300°C/0 01 mm and recrystallizalion from EtOH gave 2 2 g of 3 (33 5%) mp 278°C... [Pg.256]

Although phenols have not participated in the Conrad-Limpach reaction under certain conditions thiophenols were not as innocent. Lee and coworkers reported mixtures of thiochromenones and quinolones from reactions of amino-thiophenols with ethyl benzoyl acetate. Amino-thiophenol 67 reacted with ethyl benzoylacetate 68 in PPA to give a mixture of thiochromenone 70 and quinolone 69 in which the quinolone predominated. [Pg.405]

Chlorobenzamidine (26) (15 g, 78 mmol), ethyl benzoylacetate (25) (20 g, 129 mmol), sodium carbonate (15 g, 141 mmol) and water (30 mL) were mixed and this mixture was brought to homogeneity by adding ethanol. The solution which resulted was stirred at rt for 16 h. The thick mixture was diluted with water (50 mL) and the solid was collected and washed with ethanol. The crude product was crystallized from acetic acid which furnished 9g of the title compound 27 (30%). m.p. 305-307°C. ... [Pg.539]

Boron trifluoride etherate, is also a good catalyst for this hydride transfer to chalcone. Unlike triphenylmethyl perchlorate, however, chalcone is able to enter Michael additions with the 1,5-diketone followed by eliminations leading to unexpected products, e.g., 3-benzyl-2,4,6-triphenylpyrylium from 2-carbethoxy-l,3,5-tri-phenylpentane-l,5-dione and chalcone the benzyl group originates from chalcone, the elimination product being ethyl benzoylacetate. ... [Pg.281]

This procedure appears to be general and has been successfully applied to the following examples ethyl acetoacetate from acetone (68 %) ethyl benzoylacetate from acetophenone (74%) ethyl a-propionylpropionate from diethyl ketone (81%) ethyl 2-methylcyclohexanone-6-carboxylate from 2-methylcyclohexanone (67%). [Pg.90]

The reaction of pyridine-2,3-diamine with ethyl benzoylacetate gives a single product whose structure 8 follows from the fact that fusion gives the rearranged product 9296 (see Section 4.1.3.3.2.2.2.). [Pg.436]

A solution of pyridine-2,3-diamine (1.09 g. 10 mmol) and ethyl benzoylacetate (2.88 g, 15 mmol) in xylene (80 mL) was refluxed for 4 h with azeotropic removal of H20. The solution was cooled, the precipitate was collected and was twice recrystallized (xylene) to give the pale-yellow product yield 1.5 g (65%) mp 258 C. [Pg.436]

B) Hydrolysis of Ethyl Benzoylacefoacetate.—Thirty-two grams (0.6 mole) of ammonium chloride is dissolved in 150 cc. (8.3 moles) of water, in a 500-cc. Erlenmeyer flask, and 10 cc. (0.15 mole) of ammonia (sp. gr. 0.9) added. After the solution is warmed to 420, 58.5 g. (0.25 mole) of ethyl benzoylacetoacetate at 200 is added quickly, and the mixture shaken (Note 3). The flask is placed in a water bath at 420 for exactly ten minutes and then cooled rapidly by placing it in an ice bath. The solution is extracted twice with 100-cc. portions of ether, and the ether solution dried with anhydrous magnesium sulfate. The ether is distilled, and the residue distilled in vacuo the yield is 37.0-37.5 g. (77-78 per cent of the theoretical amount) of ethyl benzoylacetate boiling at 132-1370 at 4 mm., or 165-169° at 20 mm. [Pg.34]

The angularly fused pyridazino[l,6- ]quinazolines were prepared by tandem [6+0 (a), 6+0 (7)] cyclization of functionalized, diazotized anthranilic acid derivatives. Depending on the order of reacting ethyl benzoylacetate, malonitrile, and the diazotized anthranilonitrile, the pyridazino[l,6- ]quinazolines 103 or 105 were obtained by alkaline or thermal cyclizations, respectively (Scheme 11) <2001T1813>. [Pg.272]

Since there appeared to be strong evidence for a nonthermal effect in this type of reaction, we repeated the reaction of o-phenylenediamine 34 (Scheme 4.13, Rj = R2 = H) with ethyl acetoacetate 35 (R = CH3) [19], which was one of the reactions reported by Soufiaoui [53] to give the diazepine only on MW heating. However, when the same reaction mixtures were heated forlO min with the same temperature profile, almost identical yields of the diazepines were obtained by MW and classical heating. Later, this was also found to be the case in the reaction of 34 with ethyl benzoylacetate 35 (R = Ph). [Pg.130]

A mixture of ethyl acetoacetate and ethyl benzoate (100-15 g.) was collected at 75-90°/12 mm., after which 250-300 g. °f pure ethyl benzoate, b.p. 90-93°/12 mm., was recovered. TlieSe products were removed through a 15-cm. fractionating C0Wn. The remaining ethyl benzoylacetate was distilled though a short still head without a fractionating column. [Pg.18]

The reactions of D-glucose with 2,4-pentanedione (acetylacetone), diethyl 3-oxoglutarate, ethyl benzoylacetate, ethyl propionylacetate, ethyl butyrylacetate, ethyl isovalerylacetate, and methyl acetoacetate have been effected, with formation of crystalline products. [Pg.128]

Diethyl benzoylmalonate has been prepared by treatment of the copper derivative of ethyl benzoylacetate with ethyl chlorocarbonate.9 It... [Pg.12]

Ethylamine, 2-chloro-N,N-dimethyl-, HYDROCHLORIDE, 31, 37 N-methyl-1,2-diphenyl-, 34, 64 N-Ethylaniline, 36, 22 Ethyl benzalmalonate, 37, 5 Ethyl benzoylacetate, 32, 85 37, 3 Ethyl benzoylacetate, 37, 32 Ethyl N-benzylcarbamate, 35, 91 Ethyl 3-benzyl-2-cyano-3-methylpenta-noate, 35, 7... [Pg.49]

A mixture of 105.7 g. (0.55 mole) of ethyl benzoylacetate and 46.6 g. (0.5 mole) of aniline (Note 1) is placed in the dropping funnel D (Fig. 1) at the top of the continuous reactor (Notes 2 and 3) after the column has been heated to 135° (transformer set at 80 volts) (Notes 4 and 5). The reactants are then admitted to the column during about 15 minutes (this corresponds to a rate of amide formation of 396-400 g. per hour). Alcohol distils (Note 5) noticeably from the column during the addition and collects in flask G. At the completion of the reaction,... [Pg.60]

Commercial grades of ethyl benzoylacetate and aniline were freshly redistilled before use. [Pg.60]

The naphtha layer may be used without further treatment for the next run. Yields of 76% have been obtained on such a second run without making allowance for recovered ethyl acetoacetate. Distillation of the naphtha layer together with the fore-run from the final distillation of ethyl benzoylacetate yields 11-14 g. of recovered ethyl acetoacetate and about 235 ml. of naphtha. [Pg.75]

Lin et al. [106] studied the hydrogenation of yS-aryl ketoester using a ruthenium BINAP system with different substituents at the 4,4 -position of the BINAP ligand. The best enantioselectivities were achieved with steric demanding and electron-donating 4,4 -substituents. For example, ee-values of 97.2% and 99.5% were obtained for the hydrogenation of ethyl benzoylacetate with R=trimethylsilane (5,... [Pg.1407]

R)-2-hydroxy-2-phenylacetate (mandelate) in 59% yield, ethyl 2-keto-2-(a-thienyl)acetate to ethyl (—)-(R)-2-hydroxy-2-(a-thienyl)acetate in 49% yield, and ethyl benzoylacetate to ethyl (—)(S)-3-hydroxy-3-phenylpropa-noate in 70% yield. Ethyl acetoacetate gave also optically pure ethyl (+)-(S)-3-hydroxybutanoate (yield 80%) whereas the optical yield of ethyl (+)-lactate from ethyl pyruvate was only 92% [1089],... [Pg.162]

The reduction of other carbonyHc compounds such as 1,3-diketones or 3-oxo esters has also been extensively successfully described in the literature. In this manner, (R)-fluoxetine can be also synthesized through the bioreduction of ethyl benzoylacetate using Geotrichum sp. G38 that shows a complementary selectivity to the one shown by baker s yeast (Scheme 10.19) [47]. [Pg.226]


See other pages where Ethyl benzoylacetate is mentioned: [Pg.688]    [Pg.288]    [Pg.254]    [Pg.245]    [Pg.79]    [Pg.128]    [Pg.71]    [Pg.33]    [Pg.35]    [Pg.95]    [Pg.688]    [Pg.81]    [Pg.103]    [Pg.75]    [Pg.214]    [Pg.352]   
See also in sourсe #XX -- [ Pg.7 , Pg.23 , Pg.25 , Pg.35 ]

See also in sourсe #XX -- [ Pg.32 , Pg.85 ]

See also in sourсe #XX -- [ Pg.539 ]

See also in sourсe #XX -- [ Pg.23 , Pg.35 ]

See also in sourсe #XX -- [ Pg.23 , Pg.35 ]

See also in sourсe #XX -- [ Pg.32 , Pg.85 ]

See also in sourсe #XX -- [ Pg.32 , Pg.85 ]

See also in sourсe #XX -- [ Pg.32 , Pg.85 ]

See also in sourсe #XX -- [ Pg.18 , Pg.33 ]

See also in sourсe #XX -- [ Pg.7 , Pg.23 , Pg.26 , Pg.35 ]

See also in sourсe #XX -- [ Pg.23 , Pg.35 ]

See also in sourсe #XX -- [ Pg.3 , Pg.32 , Pg.37 , Pg.85 ]

See also in sourсe #XX -- [ Pg.32 , Pg.85 ]

See also in sourсe #XX -- [ Pg.332 ]

See also in sourсe #XX -- [ Pg.332 ]

See also in sourсe #XX -- [ Pg.705 , Pg.719 ]

See also in sourсe #XX -- [ Pg.7 , Pg.23 , Pg.25 , Pg.35 ]

See also in sourсe #XX -- [ Pg.7 , Pg.23 , Pg.25 , Pg.35 ]

See also in sourсe #XX -- [ Pg.242 ]

See also in sourсe #XX -- [ Pg.3 , Pg.32 , Pg.32 , Pg.37 , Pg.85 ]

See also in sourсe #XX -- [ Pg.7 , Pg.23 , Pg.25 , Pg.35 ]

See also in sourсe #XX -- [ Pg.3 , Pg.32 , Pg.37 , Pg.85 ]

See also in sourсe #XX -- [ Pg.18 , Pg.33 ]

See also in sourсe #XX -- [ Pg.23 , Pg.35 ]

See also in sourсe #XX -- [ Pg.705 , Pg.719 ]

See also in sourсe #XX -- [ Pg.3 , Pg.32 , Pg.37 , Pg.85 ]

See also in sourсe #XX -- [ Pg.7 , Pg.23 , Pg.25 , Pg.35 ]

See also in sourсe #XX -- [ Pg.1071 ]

See also in sourсe #XX -- [ Pg.168 , Pg.212 ]




SEARCH



© 2024 chempedia.info