Methyl acetate and ethyl formate

Esters of high volatility, such as methyl formate, methyl acetate, and ethyl formate, have lower boiling points than those of the corresponding alcohols, and therefore can be readily removed from the reaction mixture by distillation. 

Ofiwald, P. et al.. Isomer-specific fuel destruction pathways in rich flames of methyl acetate and ethyl formate and consequences for the combustion chemistry of esters, /. Phys. Chem. A, 111, 4093,2007. 

Careful measurements by Dittmar showed, however, that methyl acetate and ethyl formate have dijfferent vapour pressures at equal temperatures, and Kopp s later determinations gave different b.ps. The temperatures for equal vapour pressures were ... 

Such careful positivist language avoids any commitment to a corpuscular atom. It precluded speculation about structures of molecules, and indeed his use of the words atom and molecule is not always as clear as we should now wish he wrote, for example, of an atom of chlorhydric acid, HCl, of an atom of chlorine. Cl, and of a molecule of chlorine, CI2. His scheme of things cannot explain the existence of isomers. He noted the existence of these, giving as an example, propionic acid, methyl acetate, and ethyl formate, all of which are C3H6O2, but was content to say only that In many cases we can at present... 

In the forward direction the ester is formed, and in the reverse direction it is hydrolyzed. For esterification, the alcohol can be used as a solvent as described for methyl acetate synthesis [26]. For ester hydrolysis, water can be used as a solvent, as described for hydrolysis of methyl formate, ethyl formate, methyl acetate and ethyl acetate [28]. Usually, the solvent is taken in large excess and it can be assumed in good approximation that its concentration is constant. For constant alcohol... 

Write equations for the hydrolysis of (a) methyl acetate, (b) ethyl formate, (c) butyl acetate, and (d) octyl acetate. Name all products. 

Non-aqueous conductiometric titration has been used181 to determine trialkylsilyl phosphates and bis(trialkylsilyl)sulphates. Methanol, ethanol, butanol, acetone, ethyl methyl ketone, nitromethane, nitrobenzene, methyl cyanide, dimethylformamide, tetra-hydrofuran, butyl acetate and ethyl formate were used as solvents, and methanolic sodium, potassium and lithium methoxides and tetraethylammonium hydroxide as titrants. For the phosphates, characteristic curves were obtained only in nitromethane and methyl cyanide. Titrating in nitromethane with 0.15 N-methanolic potassium methoxide gave the best results. Alcohols, ketones, nitromethane and methyl cyanide were... 

More commonly, sodium hydride is used as a base for carbonyl condensation reactions. For exarrple, Claisen condensations of ethyl acetate and ethyl isovalerate are effected by sodium hydride. Condensations of cyclohexanone with methyl benzoate and ethyl formate (eq 16) are also facile. Sodium hydride can... 

In conclusion, CO hydrogenation catalyzed by Ru-Co bimetallic melt catalysis may lead to the formation of four classes of product (a) alcohols, including methanol, ethanol and propanol, (b) esters, mainly methyl acetate and ethyl acetate plus smaller quantities of propyl acetate and propionate esters, (c) acids, acetic acid, and (d) hydrocarbons, methane. 

As a general guide, however, it may be noted that the following have fairly easily recognisable odours methyl and ethyl formate methyl and ethyl acetate (apples) methyl and ethyl benzoate methyl salicylate (oil of winter-green) and ethyl salicylate methyl and ethyl cinnamate. (It is however usually impracticable to distinguish by odour alone between the methyl and ethyl esters of a particular acid.) Methyl and ethyl o. alate, and methyl and ethyl phthalate are almost odourless. Succinic and tartaric esters have faint odours. 

Intermediate species concentrations in fuel-rich flames (C/O = 0.5) of the two isomeric esters methyl acetate (left) and ethyl formate (right) burnt under identical conditions mole fraction, h height species named on the left side of each graph correspond to left y-axes, species on the right to right y-axes. 

Alderson, N.L., Bhethanabotla, V.R., and Campbell, S.W. Total vapor pressure measurements for 2-ethoxyethanol with methyl acetate, ethyl acetate, propyl acetate, and ethyl propionate at 313.15 K and for 2-ethoxyethanol with methyl formate at 308.15 K, /. Chem. Eng. Data, 48(l) 92-96, 2003. 

For example, the reaction of methyl acetate and synthesis gas at 170 C and 5000 psig with a Co-Lil-NPh catalyst results in the formation of acetaldehyde and acetic acid. The rate of acetaldehyde formation is 4.5 M/hr, and the yield based on Equation 15 is nearly 100%. Methane (1-2%) and ethyl acetate (1-2%) are the only by-products. The product mixture does not contain water, methanol or 1,1-dimethoxyethane. The acetic acid can easily be recycled by esterification with methanol in a separate step. 

Methyl acetate homologation - Our recent work on the effect of formation of ion-pairs in the homologation of methyl acetate to ethyl acetate (eq. 6) has clarified the role played by HRu(00)3X3 and M [Ru(CO)3l3] salts (M = alkali metal) (5,10). 

FIGURE 10. Relative quantum yields for exciplex fluorescence (filled symbols) and addition product formation (open symbols) versus solvent dielectric constant for trans-stilbene with di isopropyl methyl amine (0)> ethyldiisopropylamine (A), and triethylamine ( ) in hexane-ethyl acetate and ethyl acetate-acetonitrile mixed solvents. From ref. (114) with permission of the American Chemical Society. 

This section deals only with solvents whose reduction products are insoluble in the presence of lithium ions. The list includes open chain ethers such as diethyl ether, dimethoxy ethane, and other polyethers of the glyme family cyclic ethers such as THF, 2Me-THF, and 1,4-dioxane cyclic ketals such as 1,3-dioxolane and 1,3-dioxane, esters such as y-butyrolactone and methyl formate and alkyl carbonates such as PC, EC, DMC, and ethylmethyl carbonate. This list excludes the esters, ethyl and methyl acetates, and diethyl carbonate, whose reduction products are soluble in them (in spite of the presence of Li ions). Solutions of solvents such as acetonitrile and dimethyl formamide are also not included in this section for the same reasons. Figure 6 presents typical steady state voltammo-grams obtained with gold, platinum, and silver electrodes in Li salt solutions in which solvent reduction products are formed and precipitate at potentials above that of lithium metal deposition. These voltammograms are typical of the above-mentioned solvent groups and are characterized by the following features ... 

A procedure for the synthesis of 3-cyano-6-methyl-2(l)-pyridone (3) requires isolation of the sodio derivative of formylacetone, (1), and this was accomplished by stirring a suspension of sodium methoxide in ether with ice cooling, dropping in a mixture of acetone and ethyl formate, and removing the ether at a temperature below 70°. The solid residue was treated with an aqueous solution of cyanoacetamide (Eastman) and piperidine acetate and the solution was refluxed, for 2 hrs. After... 

There are many examples of the application of CD or RD for esterification.f" Esterification of methanol or ethanol with acetic acid forms methyl acetate or ethyl acetate, respectively. Methyl acetate is important in the manufacture of polyesters and is an important solvent for cellulose while ethyl acetate is used in inks, fragrances, and pharmaceuticals. The manufacture of high-purity methyl acetate is difficult because of the equilibrium limitation and also the formation of azeotropes. The production of methyl acetate by Eastman Chemical Co. was the first commercial application of RD using a homogeneous liquid acid catalyst. Only one RD column and two smaller columns for processing sidestreams are required while in the conventional methyl acetate synthesis, two reactors and eight distillation columns are required. 

In the second series of experiments, the products from the photo-oxidation of diethyl ether, carried out in a Teflon bag reactor at ppm and ppb levels, have been determined by withdrawing vapour samples and monitoring by gas chromatography, HPLC and by chemiluminescence analysis. The major reaction products which have been measured are ethyl formate, ethyl acetate, acetaldehyde, formaldehyde, PAN, methyl nitrate and ethyl nitrate. The products observed arise from the decomposition reactions of the 1-ethoxyethoxy radical and from its reaction with oxygen. The data enable the establishment of a quantitative mechanism for the photo-oxidative reaction. In addition the rate of conversion of NO to NO2, determined by chemiluminescence analysis, shows that for each molecule of ether reacted only one molecule of NO is converted to NO2. In further end-product analyses experiments, the OH radical initiated photo-oxidation of n-hexane or the photolyses of 2- or 3-hexyl nitrites were studied to examine the... 

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