Butyl acetate malonic acid

The separate extracts are made acid to Congo paper with concentrated HOI, extracted with ethyl acetate, the extracts are washed neutral with a little water, dried and concentrated under vacuum. The colorless oil which remains is recrystallized twice from ether/petroleum ether, whereupon n-butyl malonic acid-N,N -diphenylhydrazide is obtained in the form of short needles which melt at 116°-118°C. 

The application of 3-aminopropyl phosphine (3) [41,46] as a building block for incorporation into -COOH functionalized frameworks provides an excellent example of the utility of preformed primary phosphine frameworks (Scheme 8) [46]. The reactions involved Michael addition of ferf-butyl acrylate to malonic acid dimethyl ester to produce the intermediate adduct, 2-methoxycarbonyl-pentanedioc acid 5-ferf-butyl ester 1-methyl ester, which upon treatment with trifluro-acetic acid (TFA) produced the corresponding diester acid,2-methoxy-carbonyl-pentanedioic acid 1-methyl ester, in near quantitative yield. It is remarkable to note that the reaction of NH2(CH2)3PH2 (3) with the diester acid is highly selective as the -COOH group remained unattacked whereas the reaction occurred smoothly and selectively at the -COOMe groups to pro-... 

A variety of other carbon nucleophiles have been alkylated with alcohols including malonate esters, nitroaUcanes, ketonitriles [119, 120], barbituric acid [121], cyanoesters [122], arylacetonitriles [123], 4-hydroxycoumarins [124], oxi-ndoles [125], methylpyrimidines [126], indoles [127], and esters [128]. Selected examples are given in Scheme 35. Thus, benzyl alcohol 15 could be alkylated with nitroethane 147, 1,3-dimethylbarbituric acid 148, phenylacetonitrile 149, methyl-pyrimidine 150, and even f-butyl acetate 151 to give the corresponding alkylated products 152-156. 

Bomyl butyrate Bornyl formate Bomyl isovalerate Bornyl valerate p-Bourbonene 2-Butanol Butan-3-one-2-yl butyrate Butter acids Butter esters n-Butyl acetate Butyl acetoacetate Butyl alcohol n-Butylamine Butyl anthranilate Butyl butyrate Butyl butyryl lactate a-Butylcinnamaldehyde Butyl cinnamate Butyl 2-decenoate Butyl ethyl malonate... 

Transesterification of an ester is catalyzed by acid or base and has been used in the preparation of simple alkyl, benzyl, and t-butyl esters. Thus the mono (13) and benzyl ester (14) of malonic acid are prepared from diethyl malonate by alkoxide catalysed transesterification [49]. Benzyl cyanoacetic ester may be similarly prepared. t-Butyl acetate in the presence of either an A -acyl or a free amino acid and perchloric acid catalyst forms the t-butyl esters of the amino acid by analogous transesterification [50]. 

Carboxylic acids add to olefinic linkages under acid catalysis to form esters and the method has been employed to prepare tetrahydropyranyl (reagent dihydropyran) [52] and t-butyl (reagent wo-butene) [53, 54, 55] esters. The little used isopropylidene malonate (15) is similarly produced from iso-propenyl acetate and malonic acid in the presence of sulphuric acid [56, 57]. 

The original method of synthesis of [fl5-di(4-ieh-butylbenzo)diquinox-alinoporphyrinato]zinc(II) 188 involves the interaction of excess quinoxaline-2,3-dicarboximide 186, and malonic acid in the presence of zinc(II) acetate with the 5-iert-butyl-3-(5-tert-butyl-3-oxo-2,3-didihydro-lH-isoindol-l-ylidenemethyl)-lf/-isoindol-l-one 187 (2007RJOC1080). In this case imide 186 has been prepared by passing dry NH3 through molten quinoxaline-2,3-dicarboxylic acid at 250 °C over 10 min. 

Nitro compounds, or. Nitrobenzene Oxonium fluoroborate Trialkyloxonium salt Trialkyloxonium fluoroborate Carboxylic acid esters Isopropenyl acetate Chloroformic acid esters Ethyl chloroformate Methyl trichloroacetate Ethyl malonate Orthoformic acid esters. Ethyl orthoformate (CH C0)20,(C2H C0)20, (CF2C0)20 n-Octanoic anhydride Butyl hydroperoxide Cumene hydroperoxide Peroxides... 

A 250-mL, one-necked, round-bottomed flask is equipped with a magnetic stirrer and a reflux condenser protected by a calcium chloride drying tube. Into the flask are placed 30.0 g (0.14 mol) of di-tert-butyl malonate (Note 1) 8.4 g (0.28 mol) of paraformaldehdye (Note 2), 1.4 g (0.014 mol) of potassium acetate, 1.4 g (0.007 mol) of cupric acetate monohydrate, and 70 mL of glacial acetic acid. The resulting green-white suspension is placed in an oil bath preheated to 90-100°C and stirred for 2 hr (Note 3). The reaction mixture is allowed to cool to room temperature, and the reflux condenser is replaced with a short-path distillation apparatus, the vacuum outlet of which 1s connected in sequence to a trap cooled in acetone-dry ice, a potassium hydroxide trap, another trap cooled in acetone-dry ice, and a vacuum pump. The receiving flask 1s cooled in acetone-dry 1ce, and the system is evacuated over approximately 1 hr to remove acetic acid and other volatile material... 

Olefin elimination and decarboxylation of ethyl t-butyl acylmalonates proceeds easily on treatment with toluenesulfonic acid to form /3-keto esters of the type RCOCH,CO,C,Hj. By this procedure, acyl acetates where R is ethyl (63%), cyclohexyl (65%), 2-furyl (70%), benzyl (46%), or propenyl (35%) have been prepared. The limiting factor in this excellent method is the availability of ethyl t-butyl malonate its synthesis has been described. ... 

The present procedure affords 4-hydroxy[1-13C]benzoic acid from ethyl [2-13C]acetate in three steps with 72% overall yield. It is based on an observation of Woodward17 that ethyl 4-hydroxy benzoate is formed by base-catalyzed condensation of 4H-pyran-4-one with diethyl malonate. The submitters studied several solvent-base combinations for this reaction and found that tert-butyl alcohol/potassium tert-butoxide gave the highest yields. When a stoichiometric amount of the base is used, an excess of 4H-pyran-4-one has to be used.4b This can be avoided by the use of substoichio-metric amounts as given in the procedure. 

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