Ethyl acetate, acid effects

Isopropylidene-a-D-galactopyranose crystallized, on long standing, from a preparation of the diacetal. A more convenient method is described by Unrau, who used nitric acid (1%) in ethyl acetate to effect the partial hydrolysis. A 1,6-aiihydro-3,4-0-isopropylidene-D-galactose has been isolated by fractional distillation of the products from a preparation of the diacetal. ... 

The formation of ethyl isopropylidene cyanoacetate is an example of the Knoevenagel reaction (see Discussion before Section IV,123). With higher ketones a mixture of ammonium acetate and acetic acid is an effective catalyst the water formed is removed by azeotropic distillation with benzene. The essential step in the reaction with aqueous potassium cyanide is the addition of the cyanide ion to the p-end of the ap-double bond ... 

Acid—Base Chemistry. Acetic acid dissociates in water, pK = 4.76 at 25°C. It is a mild acid which can be used for analysis of bases too weak to detect in water (26). It readily neutralizes the ordinary hydroxides of the alkaU metals and the alkaline earths to form the corresponding acetates. When the cmde material pyroligneous acid is neutralized with limestone or magnesia the commercial acetate of lime or acetate of magnesia is obtained (7). Acetic acid accepts protons only from the strongest acids such as nitric acid and sulfuric acid. Other acids exhibit very powerful, superacid properties in acetic acid solutions and are thus useful catalysts for esterifications of olefins and alcohols (27). Nitrations conducted in acetic acid solvent are effected because of the formation of the nitronium ion, NO Hexamethylenetetramine [100-97-0] may be nitrated in acetic acid solvent to yield the explosive cycl o trim ethyl en etrin itram in e [121 -82-4] also known as cyclonit or RDX. 

Although in the dry state carbon tetrachloride may be stored indefinitely in contact with some metal surfaces, its decomposition upon contact with water or on heating in air makes it desirable, if not always necessary, to add a smaH quantity of stabHizer to the commercial product. A number of compounds have been claimed to be effective stabHizers for carbon tetrachloride, eg, alkyl cyanamides such as diethyl cyanamide (39), 0.34—1% diphenylamine (40), ethyl acetate to protect copper (41), up to 1% ethyl cyanide (42), fatty acid derivatives to protect aluminum (43), hexamethylenetetramine (44), resins and amines (45), thiocarbamide (46), and a ureide, ie, guanidine (47). 

Several examples of cost-effective liquid-hquid extraction processes include the recovery of acetic acid from water (Fig. 15-1), using ethyl ether or ethyl acetate as described by Brown [Chem. Eng. Prog., 59(10), 6.5 (1963)], or the recoveiy of phenolics from water as described by Lauer, Littlewood, and Butler [7/Steel Eng., 46(5), 99 (1969)] with butyl acetate, or with isopropyl ether as described by Wurm [Gliickauf, 12, 517 (1968)], or with methyl isobutyl ketone as described by Scheibel [ Liqmd-Liquid Extraction, in Periy Weiss-... 

The gas approximates plug flow except in wide columns, but the liqiiid undergoes considerable oa mixiug. The latter effect can be reduced with packing or perforated plates. The effect on selectivity may become important. In the oxidation of hquid /i-butane, for instance, the ratio of methyl ethyl ketone to acetic acid is much higher in plug flow than in mixed. Similarly, in the air oxidation of isobutane to tei t-huty hydroperoxide, where te/ t-butanol also is obtained, plug flow is more desirable. 

The influence of NH., and CO, on the chromatographic behaviour of benzoic acid and its derivatives (o-, m-, p-hydroxybenzoic, nitrobenzoic, aminobenzoic, chlorobenzoic acids) was studied. The work was carried out by means of upgoing TLC on Sorbfil plates. Isopropanol- and ethyl acetate-containing water-organic eluents were used as mobile phases in the absence or presence of gaseous modifiers in the MP. The novel modification of TLC has been found to separate benzoic acids with different values of their dissociation constants more effectively than water-organic mobile phases. 

The Nenitzescu process is presumed to involve an internal oxidation-reduction sequence. Since electron transfer processes, characterized by deep burgundy colored reaction mixtures, may be an important mechanistic aspect, the outcome should be sensitive to the reaction medium. Many solvents have been employed in the Nenitzescu reaction including acetone, methanol, ethanol, benzene, methylene chloride, chloroform, and ethylene chloride however, acetic acid and nitromethane are the most effective solvents for the process. The utility of acetic acid is likely the result of its ability to isomerize the olefinic intermediate (9) to the isomeric (10) capable of providing 5-hydroxyindole derivatives. The reaction of benzoquinone 4 with ethyl 3-aminocinnamate 35 illustrates this effect. ... 

Strategy A mixed Claisen reaction is effective when only one of the two partners has an acidic cy hydrogen atom. In the present case, ethyl acetate can be converted into its enolate ion, but cliethyl oxalate cannot. Thus, ethyl acetate acts as the donor and diethyl oxalate as the acceptor. 

The reaction is a sensitive one, but is subject to a number of interferences. The solution must be free from large amounts of lead, thallium (I), copper, tin, arsenic, antimony, gold, silver, platinum, and palladium, and from elements in sufficient quantity to colour the solution, e.g. nickel. Metals giving insoluble iodides must be absent, or present in amounts not yielding a precipitate. Substances which liberate iodine from potassium iodide interfere, for example iron(III) the latter should be reduced with sulphurous acid and the excess of gas boiled off, or by a 30 per cent solution of hypophosphorous acid. Chloride ion reduces the intensity of the bismuth colour. Separation of bismuth from copper can be effected by extraction of the bismuth as dithizonate by treatment in ammoniacal potassium cyanide solution with a 0.1 per cent solution of dithizone in chloroform if lead is present, shaking of the chloroform solution of lead and bismuth dithizonates with a buffer solution of pH 3.4 results in the lead alone passing into the aqueous phase. The bismuth complex is soluble in a pentan-l-ol-ethyl acetate mixture, and this fact can be utilised for the determination in the presence of coloured ions, such as nickel, cobalt, chromium, and uranium. 

Ethyl acetate has sometimes been used to destroy lithium tetrahydrogen aluminate (the reaction is similar to the one that results from the effect of a carboxyl acid on this metal hydride described on p.321 the acid formed destroys the metal hydride). Such an attempt had been made for this purpose. It led to a very violent detonation. 

Organoboranes can also be used to construct carbon-carbon bonds by several other types of reactions that involve migration of a boron substituent to carbon. One such reaction involves a-halo carbonyl compounds.20 For example, ethyl bromoac-etate reacts with trialkylboranes in the presence of base to give alkylated acetic acid derivatives in excellent yield. The reaction is most efficiently carried out with a 9-BBN derivative. These reactions can also be effected with (3-alkenyl derivatives of 9-BBN to give (3,y-unsaturated esters.21... 

In summary, the Avada process is an excellent example of process intensification to achieve higher energy efficiency and reduction of waste streams due to the use of a solid acid catalyst. The successful application of supported HP As for the production of ethyl acetate paves the way for future applications of supported HP As in new green processes for the production of other chemicals, fuels and lubricants. Our results also show that application of characterization techniques enables a better understanding of the effects of process parameters on reactivity and the eventual rational design of more active catalysts. 

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