Diethyl-n-butyl malonate

Hydrazobenzene Diethyl-n-butyl malonate Sodium Ethanol... 

Successful results have been obtained (Renfrew and Chaney, 1946) with ethyl formate methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl and iso-amyl acetat ethyleneglycol diacetate ethyl monochloro- and trichloro-acetates methyl, n-propyl, n-octyl and n-dodecyl propionates ethyl butyrate n-butyl and n-amyl valerates ethyl laurate ethyl lactate ethyl acetoacetate diethyl carbonate dimethyl and diethyl oxalates diethyl malonate diethyl adipate di-n-butyl tartrate ethyl phenylacetate methyl and ethyl benzoates methyl and ethyl salicylates diethyl and di-n-butyl phthalates. The method fails for vinyl acetate, ieri.-butyl acetate, n-octadecyl propionate, ethyl and >i-butyl stearate, phenyl, benzyl- and guaicol-acetate, methyl and ethyl cinnamate, diethyl sulphate and ethyl p-aminobenzoate. 

Dialkylation of malonic ester proceeds in most cases almost as readily as monoalkylation. Diethyl ethylmalonate is alkylated equally well by s-octyl and n-butyl halides. Di-n-propylmalonic ester is prepared in one step from malonic ester and n-propyl bromide. Methylmalonic ester is alkylated by /3-phenylethyl bromide, and even a-naphthyl-malonic ester may be further alkylated by n-alkyl iodides. Difficulty is encountered, however, in introducing two s alkyl groups into malonic ester. A 23% yield of diisopropylmalonic ester is obtained from iso-ptopylmalonic ester, sodium triphenylmethide, and isopropyl iodide. ... 

Phenylbutazone may be prepared by condensation either from diethyl- -butyl malonate or n-butyl malonyl chloride with hydrazobenzene in either solution at 0°C with the aid of pyridine. Subsequently, the pyridine is extracted with aqueous hydrochloric acid, the phenylbutazone is extracted with aqueous sodium bicarbonate and finally precipitated by addition of hydrochloric acid. 

The synthesis of this carboxylic acid begins with the deprotonation of diethyl malonate with NaOEt, and alkylation with methyl iodide. A second deprotonation and alkylation with n-butyl bronaide installs the necessary carbon chain. Hydrolysis followed by heat causes the decarboxylation that removes the extra carboxyl group and afford the desired TM. 

A sodium ethoxide solution freshly prepared from 2.5 liters of anhydrous ethanol and 115 gm (5 gm atom) of sodium is warmed to 50°C and stirred while 825 gm of diethyl malonate is added. To the clear solution is added slowly 685 gm of n-butyl bromide. The reaction commences almost immediately and considerable heat is generated. The addition rate is adjusted so that the reaction does not become violent. Cooling may be necessary. After the addition, the reaction mixture is refluxed until neutral to moist litmus (about 2 hr). Then a distillation column is attached to the flask and approximately 2 liters of alcohol are distilled off in 6 hr, using a water bath. The... 

Palladium-Catalyzed Arylation of Enolates. Very substantial progress has been made in the use of Pd-catalyzed cross coupling for arylation of enolates and enolate equivalents. This reaction provides an important method for arylation of enolates, which is normally a difficult transformation to accomplish.171 A number of phosphine ligands have been found to promote these reactions. Bulky trialkyl phosphines such as /n. v-(/-butyl)phosphinc with a catalytic amount of Pd(OAc)2 results in phenylation of the enolates of aromatic ketones and diethyl malonate.172... 

Nucleophiles A, dibenzylamine, B, sodium diethyl malonate, C, lithium salt of tert-butyl N-(diphenylmethylene)glycinate. 

The rearrangement of a-sulfonimidoyl-/3,y-unsaturated esters paved the way for a promising synthesis of y-amino acids in fair yields (Scheme 24). In the presence of a chiral ligand, such as BINAP, moderate asymmetric induction has been reported (20-60% ee). The demonstrated leaving capability of the sufoximino group has been utilized in allylic substitution with typical nucleophiles, such as sodium diethyl malonate, dibenzy-lamine, and t-butyl N-(diphenyhnethylene)glycinate. ... 

Method One, Goldsmith, and Tishler (347). Diethyl aoetamido-(2-methylmercaptoethyl) malonate (A) is prepared as a crude solid from sodium, diethylacetamidomalonate and 2>methylmercaptoethyl eblo-ride in tert. butyl alcohol by refluxing the mixture for 6 hours. (A) is refluxed for 9 hours with 12 N HCl, the mixture is evaporated to dryness, the residue is dissolved in ethanol, pyridine is added, and the resulting DL-methionine is recrjrstaUized from 50 ethanol. The yield of nearly pure product is about 60%. 

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