Sodium 1 - butyl - 2 - methyl - 5 - -, ethyl ester

A solution of 69g of sodium in 1,380 ccof absolute alcohol is mixed with 257.4 g of /3-methyl-thioethyl-d -methyl)-n-butvl-cyano-acetic acid ethyl ester and 114 g of thiourea and the whole mass boiled under reflux with stirring for six hours. After concentration under vacuum the residue is taken up in 1.5 liters of water and shaken up thrice, each time with 300 cc of ether. The aqueous alcoholic layer is stripped, under vacuum, of the dissolved ether and mixed with 300 cc of 30% acetic acid under stirring and ice cooling. The precipitated material is sucked off, washed with water, dried and recrystallized from isopropyl alcohol. The thus obtained j3-methvl-thioethyl-(1 -methyD-n-butyl-cyano-ecetyl thiourea forms yellowish green crystals having a melting point of 229°C to 230°C. [Pg.978]

When sodium ethoxide is used in place of sodium hydroxide in the carbonylation reaction of benzyl halides with dicobalt octacarbonyl, ethyl esters are produced instead of the acids [15], Esters are also produced directly from iodoalkanes through their reaction with molybdenum hexacarbonyl in the presence of tetra-/i-butylammo-nium fluoride [16]. Di-iodoalkanes produce lactones [16]. The reaction can be made catalytic in the hexacarbonyl by the addition of methyl formate [16]. t-Butyl arylacetic esters are produced in moderate yield (40-60%) under phase-transfer catalytic conditions in the palladium promoted carbonylation reaction with benzyl chlorides [17]. [Pg.372]

The distilled alcohol product mixture was also esterified by refluxing with glacial acetic acid in the presence of a catalytic amount of sulfuric acid. The product was extracted with water followed by extraction with saturated sodium bicarbonate solution. It was further washed with water and dried over anhydrous sodium sulfate. The crude ester was distilled, and the distillate was stored for further use. The percent yield of esters was 86%. The mixed ester was determined by GC to be composed of (1.3%) methyl acetate, (1.3%) ethyl acetate, (11.5%) n-propyl acetate, (81.7%) isobutyl acetate, (1.2%) 2-methy 1-1-butyl acetate, and (1.9%) other components. The composition corresponded closely to that of the parent alcohol mixture. The fuel characteristics of the alcohol mixture and the ester mixture prepared from it were reported earlier (24). [Pg.930]

Glyoxal-sodium bisulfite, 30, 86 GlYOXYLIC acid, n-BUTYL ESTER, 35, 18 ETHYL ESTER, DIETHYL ACETAL, 35, 59 Grignard reaction, addition to ethyl sec-butylidenecyanoacetate, 35, 7 allylmagnesium bromide with o , 8-di-bromoethyl ethyl ether, 36, 61 allylmagnesium chloride with a,/3-di-bromoethyl ethyl ether, 36, 63 ethylmagnesium bromide with tin tetrachloride, 36, 86 N-methyl-l,2-diphenylethylamine,... [Pg.56]

This reaction is similar to the Williamson synthesis of ethers (method 115). Otthofotmates in which the alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and isoamyl have been prepared from chloroform. The yield of ethyl orthoformate is 45%. Mixed esters are obtained from a mixture of sodium alkoxides and chloroform. Benzotrichloride, C,HjCClj, is converted to methyl orthobenzoate in 86% yield by sodium methoxide in methanol, ... [Pg.723]

Halogenated aiyloxyphenoxypropionic acids are a new class of herbicides used for the selective removal of grass species. In commercial preparations, they are present as alkyl esters. In negative-ion ESI, haloxifop, fluazifop, and diclofop all show similar behaviour. The deprotonated molecule is the base peak in the spectrum. Weak formate and acetate adducts occur, and a fragment due to the loss of the propionate part [45]. The analysis of fluazifop and its butyl ester, fenoxaprop, quizalofop and haloxyfop and their ethyl esters, and diclofop and its methyl ester was reported. The free acids were analysed in negative-ion mode, and the esters in positive-ion mode. The esters showed sodium and potassium adducts next to the protonated molecules. The adduct formation was suppressed by the addition of 25 mmol/1 formic acid to the mobile phase. The influence of the orifice potential on the appearance of their mass spectra was studied [46-47]... [Pg.187]

Theil et al. developed a method for chemoenzymatic synthesis of both enantiomers of cispentacin [89]. frans-2-Hydroxymethylcyclopentanol, obtained by the sodium borohydride reduction of ethyl 2-oxocyclopentanecarboxylate, was monosilylated with tert-butyldimethylsilyl (TBDMS) chloride to afford 55. Lipase PS-catalysed transesterification with vinyl acetate in /erf-butyl methyl ether furnished the ester 56 and the alcohol 57. The deacetylated 58 was obtained by the Mitsunobu reaction with phthalimide, triphenylphosphine and diethyl azodicarboxylate (DEAD) to furnish the cis oriented 59 with inversion of configuration (not retention as mentioned in the original article) (Scheme 9). Desilylation, Jones oxidation and subsequent deprotection with aqueous methylamine gave the ( R,2S) enantiomer 5 [89]. The (15, 2/f) enantiomer was prepared by the same route from the silyl alcohol 57. [Pg.283]

Applications. In many countries the methyl, ethyl and n-propyl esters of p-hydroxybenzoic acid, as well as their sodium salts, are permitted for preservation of some foods. The maximum permissible quantity is around 0.1%. In the USA methyl- and propyl-paraben are considered GRAS. The maximum permissible quantity is 0.1%. Their main field of use is not food preservation but the preservation of pharmaceutical and cosmetic fat emulsions. The usage of the butyl ester is not allowed in food applications. [Pg.295]

Cool the mixture and decant the solution from the sodium bromide wash the salt with two 20 ml. portions of absolute alcohol and add the washings to the main solution. Distil off the alcohol, which contains the slight excess of n-propyl bromide used in the condensation, through a short fractionating column from a water bath. The residue A) of crude ethyl n-propylacetoacetate may be used directly in the preparation of methyl n-butyl ketone. If the fairly pure ester is required, distil the crude product under diminished pressure and collect the fraction boihng at 109-113727 mm. (183 g.) (R). [Pg.481]

To prepare methyl n-butyl ketone, add the crude ester (A) or the redistilled ethyl n-propylacetoacetate B) to 1500 ml. of a 5 per cent solution of sodium hydroxide contained in a 4-litre flask equipped with a mechanical stirrer. Continue the stirring at room temperature for... [Pg.481]

Palladium catalyst foe partial ee DUCTION OF ACETYLENES, 46, 89 Palladium on charcoal, catalyst for reductive methylation of ethyl p-mtrophenylacetate, 47, 69 in reduction of l butyl azidoacetate to glycine J-butyl ester 4B, 47 Palladium oxide as catalyst for reduction of sodium 2 nitrobenzene sulfinate, 47, S... [Pg.135]

The diazo transfer reaction between p-toluenesulfonyl azide and active methylene compounds is a useful synthetic method for the preparation of a-diazo carbonyl compounds. However, the reaction of di-tert-butyl malonate and p-toluenesulfonyl azide to form di-tert-butyl diazomalonate proceeded to the extent of only 47% after 4 weeks with the usual procedure." The present procedure, which utilizes a two-phase medium and methyltri-n-octylammonium chloride (Aliquat 336) as phase-transfer catalyst, effects this same diazo transfer in 2 hours and has the additional advantage of avoiding the use of anhydrous solvents. This procedure has been employed for the preparation of diazoacetoacetates, diazoacetates, and diazomalonates (Table I). Ethyl and ten-butyl acetoacetate are converted to the corresponding a-diazoacetoacetates with saturated sodium carbonate as the aqueous phase. When aqueous sodium hydroxide is used with the acetoace-tates, the initially formed a-diazoacetoacetates undergo deacylation to the diazoacetates. Methyl esters are not suitable substrates, since they are too easily saponified under these conditions. [Pg.35]

Thiopentone. (Pentothal, Intraval.) 34 g of clean metallic sodium are dissolved in 1 liter of dry ethanol. To this solution add 130 g of ethyl-1-methyl butyl malonic ester. This mixture is stirred, 60 g of powdered thiourea is added and the whole is refluxed for 10 hours. Remove the alcohol by distilling under reduced pressure, dissolve the residue with water and acidify with hydrochloric... [Pg.102]

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