Ethanol from methyl formate

Acid Amides can be produced by acylating ammonia with esters, acid anhydrides, or the acids themselves (above 100 °C) an important product is formamide from methyl formate. Alternatively acid amides can be synthesized by reacting acid halides with ammonia. Catalytic hydrogenation converts the acid amides to primary amines. Ammonia and aldehydes or ketones are the basis for different stable products. With formaldehyde hexamethylenetetramine (urotropine) is obtained with acetaldehyde, ammono acetaldehyde with benzaldehyde, hydrobenzamide with ethylene and propylene oxides, aqueous ammonia reacts to form ethanol- or propanolamine. 

Synergistic effects are observed in the Ru/Rh [30] and Ru/Co [29, 31] catalytic systems. Ethanol is efficiently formed from methyl formate with a Ru/HCl catalyst. CO and hydrogen are produced in situ at pressures sufficiently high to induce homologation of the methyl group [32]. 

Diphenyl carbonate from dimethyl carbonate and phenol Dibutyl phthalate from butanol and phthalic acid Ethyl acetate from ethanol and butyl acetate Recovery of acetic acid and methanol from methyl acetate by-product of vinyl acetate production Nylon 6,6 prepolymer from adipic acid and hexamethylenediamine MTBE from isobutene and methanol TAME from pentenes and methanol Separation of close boiling 3- and 4-picoline by complexation with organic acids Separation of close-boiling meta and para xylenes by formation of tert-butyl meta-xyxlene Cumene from propylene and benzene General process for the alkylation of aromatics with olefins Production of specific higher and lower alkenes from butenes... 

Table 2 shows the composition of the liquid products obtained from the operation under the conditions of pressure = 5 MPa, SV = 10,000 h , purge rate = 1% of the Inlet gas and different temperatures 503 K, 523 K and 543 K. The main compositions of the liquid products were methanol and water, but a very low concentration of methyl formate, ethanol, higher alcohol and so on were observed as the byproducts. The purity of the methanol produced at any reaction temperature tested was higher than 99.9 wt%. The purity of the methanol produced at 523 K was the highest, mainly because there was more production of methyl formate at 503 K and more higher alcohols were formed at 543 K. 

Hydrogen-bond formation with phenol has been used in an i.r. study of v-(P=0) in the dioxaphospholans (98) to show that basicity depends on the nature of R and increases in the order OMeeight-membered 1,3,6,2-dioxazaphosphocines (99), which are currently of interest for comparison with the better known six-membered analogues, can be obtained from methyl-phosphonic dichloride and the appropriate 2,2 -iminobis(ethanol)." ... 

In a proposed preparation of tricyclic trisaminomethanes (45) (Table 6) tbe reaction of uncatalyzed exchange between etbyl ortboformate HC(OEt)3 and tbe macrocyclic triamine 1,4,7-triazacyclo-nonane (205) was initially unsuccessful. However tbe exchange reaction proceeded smoothly when the more reactive dimethylformamide dimethylacetal HC(OMe)2NMe2 was substituted for HC(OEt)3 to afford (45) in 88% yield <80JA6364> a stoichiometric amount of reactants either neat or in the presence of inert solvent at 120°C were used for performing the reaction. When (45) was treated with either Mel or methyl fluorosulfate, the dication (69) was formed. Compound (45) was reported to be prepared in 84% yield by the reaction of (205) with HC(OEt)3 in THE in the presence ofp-TsOH at 135°C for 60 h <80JA6365>. Most plausibly, such drastic conditions are needed because of the involvement of two unfavorable steps the formation of a strained formamidinium ion (95) as intermediate or the direct displacement of ethanol from the ester aminal intermediate (206) (Scheme 20). 

The usage of metal sulfates as catalysts is not new. In 1901, aluminum sulfate was used as the dehydration catalyst for the formation of 2-methylpropene from 2-methyl-2-propanol (29) and, in 1923, as the hydration catalyst for the formation of ethanol from ethylene 30). 

Fattee et al. ( ) isolated and identified the volatiles of "normal-flavored" raw peanuts. They found pentane, acetaldehyde, methanol, acetone, ethanol, and hexanal as major components and methyl formate, octane, 2-butanone, and pentanal as minor components. The characteristic aroma and flavor of raw peanuts were suggested to arise from a physical interaction of the components Isolated, with hexanal the most significant contributor to this aroma. Brown et al. (J ) isolated the aldehydes and ketones from raw peanuts as their 2,4-dinitro-phenylhydrazones. Concentrations of hexanal and octanal exceeded their flavor thresholds. The concentration data suggested that in addition to hexanal, octanal and possibly nonanal and 2-nonenal contribute to the "green or beany" flavor of raw peanuts. 

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