Malonates ethyl methyl

Substitution Derivatives of Ethyl Malonate, Ethyl malonate resembles ethyl acetoacetate in that it gives rise to mono- and di-substituted derivatives in precisely similar circumstances. Thus when ethanolic solutions of ethyl malonate and of sodium ethoxide are mixed, the sodium derivative (A) of the enol form is produced in solution. On boiling this solution with an alkyl halide, e.g, methyl iodide, the methyl derivative (B) of the keto form is obtained. When this is treated again in ethanolic solution with sodium ethoxide, the... 

Ethyl 2 carboethoxy 5 oxohexanoate (from diethyl malonate and methyl vinyl ketone)... 

Halogenopyrimidines react with active methylene groups, such as those in diethyl malonate, ethyl cyanoacetate, ketene diethylacetal, etc. For example, 4-chloro-6-methyl-5-nitropyrimidin-2-amine (454) and dimethyl sodiomalonate give dimethyl 2-amino-6-methyl-5-nitropyrimidin-4-ylmalonate (455) (63ZOB3132) 2-chloro-4,6-... 

Ethyl bromide Acetaldehyde Diethyl malonate Ethanol Methyl urea... 

C17H17NO3S 13623-32-0) see Protizinic acid 7-methoxy-10-methylphenothiazine-2-malonic acid ethyl methyl ester... 

The first successful attempt in asymmetric synthesis was made by Marckwald in 1904 who prepared an active (-) -valeric acid by heating the half brucine salt of ethyl methyl malonic acid at 170°C. 

The monoethyl A -(6-methyl-2-pyridyl)aminomethylenemalonate was prepared in 34% yield in the reaction of monoethyl malonate, ethyl orthoformate, and 2-amino-6-methylpyridine in the presence of catalytic amounts of A1C13 at 110-115°C for 45 min (72AF815). 

This work was repeated by several groups7 11 in the reaction of sodium dimethyl-malonate with methyl sorbate, Farmer and Metha9 observed small amounts of the 1,4-adduct besides the 1,6-addition product. Difficulties in conducting the transformations and analyzing the products are evident from reports on malonate additions to ethyl muconate12-14 depending on the reaction conditions, the expected 1,4-adduct (equation 4) or isomerization products formed by double bond displacement were isolated. Nucleophilic 1,4- and 1,6-addition reactions to 2,4-pentadienenitrile were also reported15-17. 

Rearrangement of Alkylcobalt Carbonyls Takegami et al. [25) reported that when ethyl ot-bromopropionate is treated with KCo(CO)4 in toluene at 0° in the presence of 1 atm of CO and the product cleaved with iodine, both the expected ester, ethyl methyl-malonate, and the rearranged ester, diethyl succinate, are formed, the latter in smaller quantity. At 25°, however, the succinate predominates. 

One route to o-nitrobenzyl ketones is by acylation of carbon nucleophiles by o-nitrophenylacetyl chloride. This reaction has been applied to such nucleophiles as diethyl malonate[l], methyl acetoacetate[2], Meldrum s acid[3] and enamines[4]. The procedure given below for ethyl indole-2-acetate is a good example of this methodology. Acylation of u-nitrobenzyl anions, as illustrated by the reaction with diethyl oxalate in the classic Reissert procedure for preparing indolc-2-carboxylate esters[5], is another route to o-nitrobenzyl ketones. The o-nitrophenyl enamines generated in the first step of the Leimgruber-Batcho synthesis (see Section 2.1) are also potential substrates for C-acylation[6,7]. Deformylation and reduction leads to 2-sub-stituted indoles. 

Methyl 3-ethoxy-3,3-difluoro-2-(trifluoromethyl)propanoate is hydrolyzed by sulfuric acid to give ethyl methyl (trifluoromethyl)malonate (29).151... 

Different cyclic products are formed in the double Michael addition of malonic acid ethyl methyl ester to ( vE)-l,5-diphenylpenta-l,4-dien-3-one under basic conditions. Label the stereogenic units in the reaction products with the appropriate stereodescriptors. 

Lithium477 and potassium478 enolates of P-dicarbonyl compounds are aminated by azodicarboxylic esters in good to excellent yields. Diethyl malonate, ethyl acetoacetate, /V,/V-diethyI acetoacetamide, and acetylacetone have also been aminated with diethyl azodicarboxylate under nickel acetylacetonate catalysis,479 and nickel salicylideneimine complexes catalyze the analogous amination of acetylacetone and its 2-methyl derivative.480... 

Several structurally different diketones (acetylacetone, methyl 2-oxocyclohex-ane carboxylate) and active methylene compounds (diethyl malonate, ethyl aceto-acetate) and thiols (methyl thioglycolate) underwent clean, fast, and efficient Michael addition with methyl vinyl ketone, acrolein, and methyl acrylate over NaY and Na beta zeolites [88] in high yield (70-80%). The reactions were performed in the absence of solvent, at room temperature, with 1 g catalyst per mmol donor. When HY zeolite was used instead of NaY formation of the desired Michael adduct was low and polymerization of Michael acceptor was the main reaction. 

Ethyl-2-fluorobenzothiazolium tetra-fluoroborate, 223-225 Ethyl indolepropionates, 313-314 Ethyl ketals, 262 Ethyl lactate, 298 Ethyl lithioacetate, 225 Ethyl malonate, 311 Ethyl mandelate, 298 Ethyl mesityl ketone, 295 Ethyl methyl ketone, 340 N-Elhyl-5-phenylisoxazoiium 3 -sulfonate, 226... 

Ammonium ceric nitrate dissolved in 8 4 1 methanol/ethyl methyl ketone/isopropenyl acetate, after 20-25 min at room temp. aq. NaHC03 added, and the mixture heated at 40° for ca. 45 min with vigorous stirring -> product. Y 78%. The method is highly regiospecific. F.e., also synthesis of y-ketoacetals with addition of 2 C-atoms using vinyl acetate, and with dimethyl malonate in place of ketones, s. E. Baciocchi et al.. Tetrahedron Letters 28, 5357-60 (1987). 

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