Ethyl acetone dicarboxylate

Ethylacetoacetic ester (ethyl), 7, 62 Ethyl Acetone Dicarboxylate, 5,... 

The reaction of l-(2-pyridyl)-3,5-dinitro-2-pyridone 14 with ethyl sodio acetoacetate or diethyl sodio acetone-dicarboxylate gave a mixture of N-(2-pyridyl)nitroacetamide 15, phenol derivatives 16, and a low yield of 2-oxo-2,5-dihydropyrido[1,2-b [ 1,2,4]triazine 4-oxide 17 (79TL1393). The mechanism of the reaction is shown in Scheme 5. 

The crude acetone dicarboxylic acid ontained from 700 g. of citric acid, as described on page 5, is treated with 700 g. of absolute ethyl alcohol (Note 1) to which has been added at least 130-150 g. of dry hydrogen chloride. The mixture is placed in a flask fitted with a stopper holding a calcium chloride tube and then is heated to 450. It is kept in a water bath at 450 (bath temperature) with frequent shaking until all of the acid is dissolved (fifteen to twenty minutes). The solution is allowed to cool down to room temperature in the bath and finally to stand about twelve hours (Note 2). 

This ester has been prepared by the esterification of acetone dicarboxylic acid1 and of ethyl 7-cyanoacetoacetate.2... 

The Hantzsch pyrrole synthesis was employed to prepare pyrrole-2-acetic acids as anti-inflammatory agents. A transient precipitate of a white crystalline solid was formed when diethyl acetone-dicarboxylate was mixed with aqueous methylamine. After chloroacetone was added rapidly with cooling before the disappearance of the precipitate, a good yield of ethyl 1,4-dimethyl-3-ethoxycarbonylpyrrole-2-acetate was produced. Further functional group transformations then produced pyrrole-2-acetic acids as anti-inflammatory agents. 

Treibs and Ohorodnik [4] prepared this ring system by the reaction of ethyl 2-methyl-4-hydroxypyrrole-3-carboxylate (IV) with ethyl acetoacetate (EAA) in the presence of sodium ethoxide and in this way ethyl 2,6-dimethyl-7-oxopyrano[3,2-b]pyrrole-3-carboxylate (V) was prepared. A similar reaction of (IV) with acetone dicarboxylic ester (ADE) gave (VI), but, no yields were given for either reaction. 

The Knorr pyrrole synthesis was also employed for the synthesis of 3-trifluoropyrroles [91]. Treatment of ethyl trifluoroacetoacetate 267 with sodium nitrite in acetic acid led to the oxime 268. Refluxing with zinc dust and addition of 1,3-dicarbonyl compounds 269 afforded the 3-trifluoromethylpyrroles 270 in moderate yields. Using more acidic trifluoroacetic acid allowed to lower the reaction temperature to 70 °C [92]. Using a similar approach, the tricarboxylic acid ester 273 was prepared starting from the acetone dicarboxylic acid ester 271 and the fluorinated keto ester 272 [93]. 

A mixture of 4.98 g of acetoacetic acid N-benzyl-N-methylaminoethyl ester, 2.3 g of aminocrotonic acid methyl ester, and 3 g of m-nitrobenzaldehyde was stirred for 6 hours at 100°C in an oil bath. The reaction mixture was subjected to a silica gel column chromatography (diameter 4 cm and height 25 cm) and then eluted with a 20 1 mixture of chloroform and acetone. The effluent containing the subject product was concentrated and checked by thin layer chromatography. The powdery product thus obtained was dissolved in acetone and after adjusting the solution with an ethanol solution saturated with hydrogen chloride to pH 1 -2, the solution was concentrated to provide 2 g of 2,6-dimethyl-4-(3 -nitrophenyl)-1,4-dihydropyridlne-3,5-dicarboxylic acid 3-methylester-5- -(N-benzyl-N-methylamino)ethyl ester hydrochloride. The product thus obtained was then crystallized from an acetone mixture, melting point 136°Cto 140°C (decomposed). 

The condensation of 5-acetyl derivative 404 instead of the corresponding 5-formyl compound, with ethyl acetoace-tate, ethyl benzoylacetate, and diethyl acetone-1,3-dicarboxylate, by heating in the absence of base gave the respective 6-acylpyrido[2,3-4]pyrimidin-7(8//)-ones 406. The reaction of 404 with diethyl malonate afforded the 6-carboxylate 407 <2005RCB784>. Reaction of 405 with triethyl phosphonoacetate yielded 408 <2001W02001070741>. 

Oxopyran-2,6-dicarboxylic acid (chelidonic acid) is obtained from the base-catalyzed condensation of acetone with ethyl oxalate. The initial product is cyclized in acid... 

Ethyl 2-(4,5-dihydro-5-oxo-lH-p)U azol-3-yl)acetate (5), prepared from diethyl acetone-l,3-dicarboxylate (1) and hydrazine hydrate in ethanol at room temperature, was transformed with DMFDMA in toluene at room temperature into ethyl (Z)-2- 4-[(dimethylamino)methylidene]-4,5-dihy-dro-5-oxo-lH-p5u-azol-3-yl acetate (6) in 76% yield (07H657) (Scheme 2). 

We have reported syntheses of 1-substituted 1,4-dihydropyridines and their fused analogues by treatment of primary amines with bis-enaminones, derived from alkyl acetone-1,3-dicarboxylates (00H2033), and ethyl 2-(5-oxo-4,5-dihydro-lH-pyrazol-3-yl)acetates (07H657,06T8126, 05TA2187, 04H609, 02H791). 

The 11-deoxyprostaglandins, a group not found in nature, have been synthesised by workers at the Ayerst Laboratories [115, 148-151]. 11-Deoxy-PGFy (LXXI) has been prepared starting from the enone (LXXII), obtained by the action of sulphuric acid on the monobromo derivative of the condensation product of ethyl 2-cyclopentanone carboxylate and (o-bromoethylheptanoate [115, 148, 149]. Reaction of (LXXII) with acetone cyanohydrin, hydrolysis of the ester-nitrile to the dicarboxylic acid and reaction with methanol and />-toluenesulphonic acid gave the mono ester (LXXIII) of which the acid chloride was converted with heptyne and aluminium chloride into the chlorovinylketone (LXXIV). The sequence was then completed by replacement of chloro with methoxyl, ester hydrolysis and borohydride reduction to the unsaturated ketone (LXXV) followed by borohydride reduction of the side chain carbonyl group. 

If methyl ethyl ketone is used instead of acetone, 2,3-dimethylpyridine is obtained this lutidine compound is used for the manufacture of 2,3-pyridine dicarboxylic acid (see Chapter 14.5.5))... 

Pig pancreatic lipase added to a mixture of ethyl butyrate, ethyl isobutyrate, and ethyl pivalate in phosphate buffer (pH 8), and quenched with 10 M NaOH when reaction complete (pH-stat method) - butyric acid. Y 65% (> 95% purity). The enzyme only hydrolyzed straight-chain esters. F.e., preferential cleavage of functionalized esters, and comparison with horse liver acetonic powder, s. B. De Jeso et al., Synth. Commun. 18, 1699-705 (1988) preferential hydrolysis of dicarboxylic acid esters s. ibid. 1691-7. 

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