Diethyl benzyl malonate

Note. (1) 2-Benzyl-1,3-dibromopropane may be prepared from diethyl benzyl-malonate (Expt 5.132), by lithium aluminium hydride reduction to give 2-benzyl-propane-1,3-diol (for conditions compare Expt 5.38), and subsequent conversion into the dibromo derivative using the conditions described in Expt 5.54 as a guide. 

In the presence of carbon dioxide or diethyl malonate, some of the benzyl anion is converted, respectively, into benzyl phenylacetate or the diethyl ester of benzyl malonate. 

Heating a SchifFs base with diethyl malonate for 0.5 h in the presence of catalytic amounts of piperidine (or acetic acid, hydrochloric acid, or ammonium chloride) in closed ampoules affords the diethyl [(arylamino)benzyl]malonate in 50% yield.242... 

Finally, sodium <%-(phenylamino)-with elimination of the sulfonate group 864... 

Method Five, Albertson and Archer (46). Ethyl 2-acetamido-2-car-bethoxy-3-phenylpropionate (A) is prepared in 90% yield from benzyl chloride and ethyl acetamidomalonate. DL-Phenylalanine is prepared in 65% yield by HBr or NaOH-HCl hydrolysis of (A). The over-all yield is 58%. (Comparable syntheses of phenylalanine from benzyl chloride and diethyl aminomalonate (144, 526) or diethyl benzamido-malonate (660) have been reported). 

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. 

Reaction of 2-aminopyridine with dimethyl 2-methylmalonate in the presence of some drops of cone. HCl at 150°C for 1 h (96EUP733633), and with diethyl 2-(l-decyl)malonate at 120°C for 5 min (94JCR(S)206) gave 2-hydroxy-3-methyl- and 2-hydroxy-3-(l-decyl)-4//-pyrido[l, 2-n]pyrimidin-4-ones in 2.2% and 7.5% yields, respectively. Reaction of 3-benzyl-2-aminopyridine and diethylmalonate at 190-200 °C for 4 h yielded 9-benzyl-2-hydroxy-4//-pyrido[l, 2-n]pyrimidin-4-one (01MIP9). Cyclocondensation... 

Reaction of ethyl (V-(cyanoacetyl)urethane with trifluoroacetonitrile gave 5-cyano-6-trifluoromethyluracil (85JOC4642). Trifluoroacetonitrile reacted with benzyl cyanide (86JOU1408) and diethyl malonate (89JHC7) to yield 2,6-bis(trifluoromethyl)pyrimidines. Cycloaddition of trifluoroacetonitrile with enamines having a /3-H offered a general route to 2,4-bis(trifluoromethyl)pyrimidines (84LA991). 

C7HA Benzyl bromide C7H12O4 Diethyl malonate... 

Diethyl phenyl ethyl malonate. 1 mole of benzyl cyanide is added dropwise to a solution of 1 mole of ethyl carbonate in 2 liters of anhydrous ethanol containing 5 g of clean sodium metal. This mixture is refluxed (preferably on a steam bath) for 5 hours. It is then cooled and to it is added a cooled mixture of 40 g of sulfuric acid in 100 ml of anhydrous ethanol. This alcoholic solution is refluxed for 5 hours, cooled, neutralized with sodium ethylate (use external indicator). The mixture is evaporated to half bulk, filtered from the sodium sulphate and to it is added 1 mole of clean metallic sodium. Reflux while adding 1 mole of ethyl bromide dropwise. Heat for another 2 hours after the addition is completed. Remove the alcohol by distillation and dissolve the remaining residue in water. Extract the substance from the water with benzene and after drying, the benzene is recovered and the ester should be purified by distilling in vacuo. 

Condensation, of paraldehyde with diethyl malonate, 32, 54 of a-phene thyl chloride with diphenylacetonitrile, 39, 74 of phenylacetylene with ethyl orthoformate, 39, 59 of 1-phenylbiguanide with ethyl chloroacetate, 38,1 of potassium diphenylacetonitrile with benzyl chloride, 39, 73 of potassium trithiocarbonate with potassium chloroacetate, 39, 77 of sodium acetylacetonate to tetraacetylethane, 39, 61 of sodium formylacetone with cyano-acetamide, 32, 32 of tetracyanoethylene with N,N-dimethylaniline, 39, 68 of thiophene, paraldehyde, and hydrogen chloride, 38, 86 of thiourea with furfuryl alcohol, 36,66... 

Benzo[6]thiophene aldehydes have been condensed with a variety of active methylene compounds, including cyclic511, 644 and open-chain645-647 ketones, aliphatic aldehydes,90 benzyl cyanides,93-436 malononitrile,487 rhodanine,144,648 hippuric acid,477 barbituric acid,487 diethyl malonate,487 and malonic acid (Section VI,M). Aliphatic nitro compounds condense smoothly with most benzo[6]-thiophene aldehydes03,141,337,343, 556,640,650 (except 5-hydroxy- and... 

The data on kp and kt as reported in the literature differ considerably. Therefore, we conducted new studies on methyl methacrylate (MMA), benzyl methacrylate (BMA), and styrene (St) as monomers. The constants were obtained by applying the method of intermittent illumination (rotating sector) combined with stationary state methods. The viscosity of the solvents varied between 0.5 and 100 cP. No mixed solvents composed of low- and high-molecular components were used but pure solvents only, the molecules of which did not deviate very much from a spherical form (methyl formate, diethyl phthalate, diethyl malonate, dimethyl glycol phthalate, etc.). 

Substitution by the soft anion derived from diethyl malonate occurs with ring opening at the 6-position of 172. Subsequent cyclization gives the corresponding thiocarbonyl compound 173 after elimination of the labile benzyl mercaptan (Scheme 68) (83TL3713). It has been shown that 173 is different from its isomer (174) which is obtained elsewhere (81UP1). 

Alkylation of diethyl malonate with benzyl bromide is the first step in the preparation of 3-phenylpropanoic acid. 

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