Diethyl propyl malonate

Dimethylamino-(1.2-Dihydro-1,2,4-ben20trla2ine) Diethyl Propyl Malonate 3-Dimethylamlno-1,2,4-ben2otria2ine Oxide Propyl Malonyl Chloride... 

Piperacillin sodium Diethyl-d -phenyl propyl) malonate Phenprocoumon Diethylpropyl malonate Apazone... 

Meprobamate has been synthesized by several procedures (See Figure U). The first step is to synthesize 2-methyl-2-propyl-1,3-propanediol. This has been done1 1 by reacting 2-methyl pentanal and formaldehyde in presence of KOH. The diol has also been prepared by reducing 2-methyl-2-n-propyl malonic acid, diethyl ester with lithium aluminum... 

Synthesis CH, 1 H5C2OOC—C—CH2CH2CH3 COOC2H5 Diethyl methylpropyl-malonate Ether LiAlH4 CH3 1 HOCH2—C>-CH2CH2CH3 CH20H 2-Methyl-2-propyl-l, 3-propanediol ... 

Methyl-2-propyl-l, 3-propanediol is prepared by reacting diethyl methylpropyl malonate in ether in the presence of lithium aluminium hydride and then treated with dilute sulphuric acid. This on treatment with phosgene in toluene by means of dimethylaniline yields 2-methyl-2-propyl-3 -hydroxypropyl chlorocarbonate, which on reaction with n-butylamine forms 2-methyl-2-propyl-3-hydroxypropyl butylcarbamate. The resulting product on treatment with ethyl urethane in the presence of aluminium isopropoxide in boiling xylene yields ethanol during transesterification which is removed from the reaction mixture simultaneously and tybamate is obtained. 

C10H18O4 2-propyl-malonic acid diethyl ester 2163-48-6 ... 

C12H22O4 2-(l-ethyl-propyl)-malonic acid diethyl ester 71691-56-0... 

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. 

Synthesis of Compound I. As shown in Scheme II, 3-(thiophene-3-yl)propyl bromide can be prepared by a two-carbon homologation(2 ) of 3-thenyl bromide via reaction with diethyl malonate to form diethyl 3-thenylmalonate. This is followed by saponification, decarboxylation, reduction of acid to alcohol, (2 ) and replacement of the hydroxyl group with bromide by reacting with PBr3.(22) Compound 2 is synthesized by mono-quaternization of an excess of 4,4 -bipyridine with 3-(thiophene-3-yl)propyl bromide followed by N-methylation with CH3I. All the intermediates in Scheme II have been identified by NMR spectroscopy. 2 has been characterized by NMR and high resolution mass spectroscopy and by electrochemistry. 

From the hint given in the problem, it can be seen that synthesis of 2-methyl-2-propyl-l,3-propane-diol is required. This diol is obtained by a sequence involving dialkylation of diethyl malonate. 

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. ... 

Reifenrath WG, Mershon MM, Brinkley FB, Miura GA, Broomfield CA, Cranford HB. Evaluation of diethyl malonate as a simulant for 1,2,2-trimethyl-propyl methylphosphonofluoridate (somem) in shower decontamination of the skin. J Pharm Sci. 1984 73 1388-92. 

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