Malonic 2- -, diethyl

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. 

The major advantage of the capillary hydrodynamic chromatography is that the mobile phase does not need to have similar solubility parameter as the sample and packing material. (In SEC, nonsize exclusion effects may be observed if the solubility parameter of the sample, packing material, or mobile phase is considerably different.) Therefore, the hydrodynamic size of polymers can be studied in a 0 solvent and even in a solvent that is not compatible with any currently available SEC packing material (9). Figure 22.4 is an example of polystyrene separation in both THF and diethyl malonate. Diethyl malonate is the 0 solvent of polystyrene at 31-36 C. 

In a Vilsmeier-Haack-Amold reaction, A/,Ar-disubstituted amino-methylenemalonates (329) were prepared in good yields from the sodium derivative of diethyl malonate or from diethyl malonate in the presence of triethylamine in benzene or toluene at a temperature below 20°C with imidoyl chlorides, which were prepared in situ from N./V-disubstituted formamides and phosphoryl chloride (63BRP917436). Instead of diethyl malonate, diethyl ethoxymagnesiummalonate could also be used (63 BRP917436). 

Preparation of the intermediate for Allobarbitone (diethyl diallyl malonate). Diethyl malonate is dissolved in anhydrous alcohol and treated with one mole of clean sodium meted per every one mole of the ester. To this solution add one mole of allyl chloride and reflux for about 4 hours. Another equimolar ratio (1 mole of sodium per mole of ester) of sodium is added, followed by the same ratio of allyl chloride (1 mole per 1 mole), and this mixture is boiled for 2 hours. The alcohol is removed by distillation and the ester is extracted with benzene and distilled or evaporated in vacuo, recrystallized with a suitable "dry" solvent, and filtered. Evaporate again to remove traces of solvent. Keep this product, and any other substances that require dry reagents or solvents, stored away from contact with the atmosphere. When evaporating, filter the air coming into the evaporating vessel with a suitable drying agent. Use a little common sense. 

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). 

Diethyl malonatc13 gives four products upon reaction with perchloryl fluoride diethyl difluoro-malonate, diethyl ethylmalonate, diethyl ethylfluoromalonate and diethyl fluoromalonate the product distribution depends on the reaction conditions. A number of esters are fluo-rinated,14 15 while (pentafluorophenyl)acetonitrile is converted into mono- and disubstituted products in the presence of cesium fluoride.16... 

H2C=CHCH2CH2CH2Br + CH2(COOCH2CH3)2 Na H,> H2C=CHCH2CH2CH2CH(COOCH2CH3)2 5-Bromo-l-pentene Diethyl malonate Diethyl 2-(4-pentenyl)malonate (85%)... 

Preparation 202.—Diethyl Malonate [Diethyl ester of yrroy>an-diadd ... 

Other 1,3-dicarbonyl compounds also exist largely in the enol form. In some examples there is an additional stabilizing factor, intramolecular hydrogen bonding. Diethyl malonate (diethyl propane-dioate) has a symmetrical enol stabilized by conjugation. The enol form is also stabilized by a very diethyl maionate favourable intramolecular hydrogen bond in a six-membered ring. 

Epilepsy is a disease that is characterized hy recurring convulsive seizures. Phenoharhital, 58, possess specific usefulness in epilepsy. In general, harhituric acid derivatives are synthesized from phenylethyl-malonic diethyl ester [8]. 

Tetrahedral intermediates have been shown to be kinetically important in the S->N transfer reaction of S-acetylmercaptoamine (Martin and Hedrick, 1962) the O N transfer reaction of 0-acetylethanolamine (Hansen, 1963), intramolecular-aminolysis of ethyl y-aminobutyrate, ethyl 8-aminovalerate, and related reactions (Martin et al., 1964), hydrolysis of thiazolines (Martin et al., 1959 Martin and Parcell, 1961a Schmir, 1965), hydrolysis of oxazolines (Martin et al., 1964 Greenhalgh et al., 1963 Martin and Parcell, 1961b), hydrolysis of 2-imidazolines (Harnsberger and Riebsomer, 1964), and in the hydrolysis of acetyl-malonate diethyl ester (Lienhard and Jencks, 1965). 

Monomers. The following monomers were obtained from Eastman Organic Chemicals and used as received diethylene glycol, ethylene glycol, hexamethylene glycol, diethyl succinate, diethyl malonate, diethyl adipate, and 1,4-cyclohexane dimethanol. The following monomers were... 

Diethylene glycol monoethyl ether acetate Diethylene glycol monomethyl ether Diethyl ether Diethyl malonate Diethyl oxalate Diethyl sulfide trans-trans) Diethyl sulfide trans-gauche)... 

Dicyclonexylnonane Diethanolacetylene Diethyl acetaldehyde Diethylal lylacetophenone Diethyl allylmalonate Diethvlamine Diethylcyclohexylamine Diethjl ethylmalonate Diethyl ketone Diethyl ketoxime Diethyl malonate Diethyl-3-(l-methyl butane) ethyl... 

Diethyl malonate Diethyl 2-ethyl-2-(l-methylbutyl)malonate ... 

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