Ethanol from methanol

The carbonylation of methanol, dimethyl ether and methyl acetate using as catalyst precursors [RuI2(CO)4] and [Ru(acac)3] (88) with Nal, HI or Mel as promoter has been reported.381 The major products were ethanol from methanol, methyl acetate from dimethyl ether, and acetic anhydride plus acetic acid from methyl acetate (equations 67-69). 

Discuss the energetics and feasibility of reactions (5.14) and (5.15) to produce ethanol from methanol. 

Chomet, E., et al., 2013. Production of Ethanol from Methanol. Google Patents. 

Add 0 1 g. of the aldehyde in 5 ml. of 50 per cent, ethanol to 2 ml. of a 10 per cent, or saturated alcoholic solution of dimedone. If a precipitate does not form immediately, warm for 5 mintues if the solution is still clear at the end of this period, add hot water until the mixture is just cloudy and cool to about 6°. Collect the crystalline derivative and recrystallise it from methanol - water or ethanol - water. 

Dimethylbutadiene and 1 4-naphthoquinone. 2 3-Di-methylanthraquinone. In a small round-bottomed flask, fitted with a reflux condenser, place a solution of 8 g. of freshly-distUled 2 3-dimethyl-butadiene (Section 111,147) and 8 g. of 1 4-naphthoquinone (Section IV,149) in 30 ml. of ethanol, and reflux for 5 hours. Keep the resulting solution in a refrigerator for 12 hours break up the crystaUine mass, filter, and wash with 5 ml. of alcohol. The yield of crude adduct, m.p. 147-149°, is 11-5 g. recrystaUisation from methanol raises the m.p. to 150°. 

Prepare a saturated solutiotr of sodium bisulfite at the laboratory temperature from 40g of finely powdered sodium bisulphite about 70ml. of water are required. Measure the volume of the resulting solution and treat it with 70 per cent, of its volume of rectified spirit (or methylated spirit) [ethanol or methanol or both, dude] add sufficient water (about 45mL.) to just dissolve the precipitate which separates. ... 

Bromo-2-nitrophenylacetic acid (26 g, 0.10 mol) was dissolved in a mixture of 50% HjSO (400 ml) and ethanol (600 ml) and heated to 90°C. Over a period of 1 h, zinc dust (26.2 g, 0.40 mol) was added. slowly and then heating was continued for 2 h. The excess ethanol was removed by distillation. The solution was cooled and filtered. The filtrate was extracted with EtOAc. The filtered product and extract were combined, washed with 5% NaCOj and brine and then dried (MgSO ). The solvent was removed in vacuo and the residue recrystallized from methanol to give 20.5 g (97% yield) of the oxindole. 

Additional research for both ethanol and methanol showed that the amount of ignition improver could be reduced by systems increa sing engine compression (63). Going from 17 1 to 21 1 reduced the amount of TEGDN requited for methanol from 5% by volume to 3%. Ignition-improved methanol exhibited very low exhaust emissions compared to diesels particulate emissions were eliminated except for small amounts associated with engine oil, NO was even lower with increased compression, and CO and hydrocarbons were also below diesel levels. 

Ethanol from grains, and ethanol, methanol, and gasoline from energy crops. 

Ethers, such as MTBE and methyl / fZ-amyl ether (TAME) are made by a catalytic process from methanol (qv) and the corresponding isomeric olefin. These ethers have excellent octane values and compete on an economic basis with alkylation for inclusion in gasoline. Another ether, ethyl tert-huty ether (ETBE) is made from ethanol (qv) and isobutylene (see Butylenes). The cost and economic driving forces to use ETBE vs MTBE or TAME ate a function of the raw material costs and any tax incentives that may be provided because of the ethanol that is used to produce it. 

LynestrenoL Lynestrenol (73) has been used in oral contraceptives and to treat menstrual disorders. It is converted in vivo to its active metabohte norethindrone (102,103). It can be recrystallized from methanol, and is soluble in ethanol, ether, chloroform, and acetone, and insoluble in water (102). The crystal stmcture (104) and other spectral and analytical data have been reported for lynestrenol (62). 

The separation and analysis of 1-propanol are straightforward. Gas chromatography is the principal method employed. Other iastmmental techniques, eg, nmr, ir, and classical organic quaHtative analysis, are useful. Molecular sieves (qv) have been used to separate 1-propanol from ethanol and methanol. Commercial purification is accompHshed by distillation (qv). 

Biofuels. Biofuels are Hquid fuels, primarily used ia transportation (qv), produced from biomass feedstocks. Identified Hquid fuels and blending components iaclude ethanol (qv), methanol (qv), and the ethers ethyl /-butyl ether (ETBE) and methyl /-butyl ether (MTBE), as well as synthetic gasoline, diesel, and jet fuels. 

Cyclopentadiene itself has been used as a feedstock for carbon fiber manufacture (76). Cyclopentadiene is also a component of supported metallocene—alumoxane polymerization catalysts in the preparation of syndiotactic polyolefins (77), as a nickel or iron complex in the production of methanol and ethanol from synthesis gas (78), and as Group VIII metal complexes for the production of acetaldehyde from methanol and synthesis gas (79). 

Adsorption of methanol and ethanol from gas phase on the surfaee of VO, was smdied by isotherms of resistanee (R, Om - t, s). 

Aminoboranes can be prepared from diborane to protect a tertiary amine during oxidation they are cleaved by refluxing in ethanol or methanolic sodium carbonate. ... 

Solid esters are easily crystallisable materials. It is important to note that esters of alcohols must be recrystallised either from non-hydroxylic solvents (e.g. toluene) or from the alcohol from which the ester is derived. Thus methyl esters should be crystallised from methanol or methanol/toluene, but not from ethanol, n-butanol or other alcohols, in order to avoid alcohol exchange and contamination of the ester with a second ester. Useful solvents for crystallisation are the corresponding alcohols or aqueous alcohols, toluene, toluene/petroleum ether, and chloroform (ethanol-free)/toluene. Esters of carboxylic acid derived from phenols... 

It was recrystd twice as the free base from ethanol or methanol/water by dropwise addition of NaOH (less than O.IM). The ppte was washed with water and dried under vacuum. It was dissolved in CHCI3 and chromatographed on alumina the main sharp band was collected, concentrated and cooled to -20 . The ppte was filtered, dried in air, then dried for 2h under vacuum at 70°- [Stone and Bradley J Am Chem Soc 83 3627 1961 , Blauer and Linschitz J Phys Chem 66 453 1962.]... 

The crude ketal from the Birch reduction is dissolved in a mixture of 700 ml ethyl acetate, 1260 ml absolute ethanol and 31.5 ml water. To this solution is added 198 ml of 0.01 Mp-toluenesulfonic acid in absolute ethanol. (Methanol cannot be substituted for the ethanol nor can denatured ethanol containing methanol be used. In the presence of methanol, the diethyl ketal forms the mixed methyl ethyl ketal at C-17 and this mixed ketal hydrolyzes at a much slower rate than does the diethyl ketal.) The mixture is stirred at room temperature under nitrogen for 10 min and 56 ml of 10% potassium bicarbonate solution is added to neutralize the toluenesulfonic acid. The organic solvents are removed in a rotary vacuum evaporator and water is added as the organic solvents distill. When all of the organic solvents have been distilled, the granular precipitate of 1,4-dihydroestrone 3- methyl ether is collected on a filter and washed well with cold water. The solid is sucked dry and is dissolved in 800 ml of methyl ethyl ketone. To this solution is added 1600 ml of 1 1 methanol-water mixture and the resulting mixture is cooled in an ice bath for 1 hr. The solid is collected, rinsed with cold methanol-water (1 1), air-dried, and finally dried in a vacuum oven at 60° yield, 71.5 g (81 % based on estrone methyl ether actually carried into the Birch reduction as the ketal) mp 139-141°, reported mp 141-141.5°. The material has an enol ether assay of 99%, a residual aromatics content of 0.6% and a 19-norandrost-5(10)-ene-3,17-dione content of 0.5% (from hydrolysis of the 3-enol ether). It contains less than 0.1 % of 17-ol and only a trace of ketal formed by addition of ethanol to the 3-enol ether. 

A 250-mI round-bottom flask fitted with a condenser (drying tube) is charged with a mixture of 2-bromocholestanone (4.7 g, 0.01 mole), lithium carbonate (7.4 g, 0.10 mole), and 100 ml of dimethylformamide. The system is flushed with nitrogen and then refluxed (mantle) for 18-24 hours. After the reflux period, the solution is cooled and poured into 500 ml of water. The aqueous mixture is extracted with 50 ml of ether, the ether extract is dried (sodium sulfate), and the ether is removed (rotary evaporator). The residue may be recrystallized from ethanol or methanol. J -Cholestenone is a white solid, mp 98-100°. 

Chloro-1 -methyl-5-phenyl-s-trizolo[4,3-a]quinoline A stirred mixture of 6triethyl-orthoacetate (0.925 g,0.0057 mol) and xylene (100 ml) was refluxed, under nitrogen, for 2 hours 40 minutes. During this period the ethanol formed in the reaction was removed by distillation through a short,glass helix-packed column. The mixture was concentrated to dryness In vacuo and the residue was crystallized from methanol-ethyl acetate to give 1.28 g of 7-chloro-1-methyl-5-phenyl-s-triazolo[4,3-a]-quinoline (83.9% yield). The analytical sample was crystallized from methylene chloride methanol and had a melting point 252.5°-253.5°C. 

A mixture consisting of 13.5 g of 4-(4 -hydroxyanilino)-7-chloroquinoline hydrochloride dissolved In absolute ethanol is treated with a solution of 4.3B g of diethylamine and 1. B g of paraformaldehyde in 20 cc of absolute ethanol. The reaction mixture is heated under reflux for 16 hours, evaporated to one-half volume and the warm solution treated with an excess of hydrogen chloride dissolved in absolute ethanol. Acetone is added to the warm solution until it becomes turbid and then the solution is cooled. The crude dihydrochloride which separates is collected and purified by recrystallization from methanol MP 240°-242°C. 

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