Ethanol synthesis

Ethanol, the alcohol present in beer, wine, and other alcoholic beverages, is formed by the fermentation of sugar, quite possibly the oldest example of organic synthesis. Ethanol can also be made in the lab by a totally different process, but the ethanol produced in the lab is identical to the ethanol produced by fermentation. Alcohols including ethanol are discussed in Chapter 9. 

In the first step of the synthesis, ethanol (CH3CH2OH) is taken as the starting material. Ethylene oxide... 

Xie, J.P., Zhang, Q.B., Lee, Y. and Wang, D.I.C. (2007) General method for extended metal nanowire synthesis ethanol induced self-assembly. Journal of Physical Chemistry C, 111, 17158,... 

HCOOCHjCHj. Colourless liquid with the odour of peach-kernels b.p. 54 C, Prepared by boiling ethanol and methanoic acid in the presence of a little sulphuric acid the product is diluted with water and the insoluble ester separated and distilled. Used as a fumigant and larvicide for dried fruits, tobacco and foodstuffs. It is also used in the synthesis of aldehydes. 

Jote 2. We have also carried out this synthesis in ethanol as a solvent but the results were not reproducible. Although a series of experiments with zinc powder from one flask gave reasonable results (50-78% yields), a new flask with the same batch number gave low yields of impure products. The main impurity was probably the non-conjugated diene, H2C=CH-CH2-CH=CH-CH3, possibly resulting from reduction of the 1,2,4-triene by the zinc. The... 

The key step in the total synthesis of rhizobitoxine is the Pd-catalyzed exchange reaction of the methyl alkenyl ether moiety in 4 with the functionalized alcohol, although the yield is low[3]. The enol pyruvate 6 (a-ethoxyacrylic acid) is prepared by the reaction of methyl a-methoxyacrylate or a-methoxy-acrylic acid (5) with ethanol catalyzed by PdCl2(PhCN)2 at room temperature in the presence of CuCli and NaH2P04[4],... 

Methanol ethanol and isopropyl alcohol are included among the readily available starting materials commonly found m laboratories where organic synthesis is carried out So too are many other alcohols All alcohols of four carbons or fewer as well as most... 

When applied to the synthesis of ethers the reaction is effective only with primary alcohols Elimination to form alkenes predominates with secondary and tertiary alcohols Diethyl ether is prepared on an industrial scale by heating ethanol with sulfuric acid at 140°C At higher temperatures elimination predominates and ethylene is the major product A mechanism for the formation of diethyl ether is outlined m Figure 15 3 The individual steps of this mechanism are analogous to those seen earlier Nucleophilic attack on a protonated alcohol was encountered m the reaction of primary alcohols with hydrogen halides (Section 4 12) and the nucleophilic properties of alcohols were dis cussed m the context of solvolysis reactions (Section 8 7) Both the first and the last steps are proton transfer reactions between oxygens... 

This process comprises passing synthesis gas over 5% rhodium on Si02 at 300°C and 2.0 MPa (20 atm). Principal coproducts are acetaldehyde, 24% acetic acid, 20% and ethanol, 16%. Although interest in new routes to acetaldehyde has fallen as a result of the reduced demand for this chemical, one possible new route to both acetaldehyde and ethanol is the reductive carbonylation of methanol (85). 

Currently, almost all acetic acid produced commercially comes from acetaldehyde oxidation, methanol or methyl acetate carbonylation, or light hydrocarbon Hquid-phase oxidation. Comparatively small amounts are generated by butane Hquid-phase oxidation, direct ethanol oxidation, and synthesis gas. Large amounts of acetic acid are recycled industrially in the production of cellulose acetate, poly(vinyl alcohol), and aspirin and in a broad array of other... 

A pepsin hydrolysate of flounder fish protein isolate has been used as the substrate (40% w/v) for plastein synthesis, using either pepsin at pH 5 or alpha chymotrypsin at pH 7, with an enzyme—substrate ratio of 1 100 w/v at 37°C for 24 h (151). The plastein yields for pepsin and alpha chymotrypsin after precipitation with ethanol were 46 and 40.5%, respectively. 

Cyclizine Hydrochloride. l-(Diphenylmethyl)-4-methylpipera2ine monohydrochloride [303-25-3] (Mare2ine) (17) is a white crystalline powder, or small colorless crystals, that is odorless or nearly so and has a bitter taste. It melts indistinctly and with decomposition at ca 285°C. One gram of cycli2ine hydrochloride [303-25-3] is soluble in 115 mL water, 115 mL ethanol, and 5 mL chloroform it is insoluble in diethyl ether. It may be made by the synthesis shown in Reference 15. 

A Methylamino)phenol. This derivative (15) is easily soluble ia ethyl acetate, ethanol, diethyl ether, and benzene. It is also soluble ia hot water, but only spatingly soluble ia cold water. Industrial synthesis is by heating 3-(A/-methylamino)benzenesulfonic acid with sodium hydroxide at 200—220°C (179) or by the reaction of resorciaol with methylamiae ia the presence of aqueous phosphoric acid at 200°C (180). 

A A Diethylamino)phenol. This derivative (16) forms rhombic bipyramidal crystals. Industrial synthesis is analogous to the previously described synthesis of 3-(/V,/V-dimethy1amino)pheno1 from resorciaol and diethylamiae, by reaction of 3-(Ai,A/-diethylamiQo)benzenesulfonic acid with sodium hydroxide, or by alkylation of 3-amiaophenol hydrochloride with ethanol. 

A Methylamino)phenol. This derivative, also named 4-hydroxy-/V-methy1ani1ine (19), forms needles from benzene which are slightly soluble in ethanol andinsoluble in diethyl ether. Industrial synthesis involves decarboxylation of A/-(4-hydroxyphenyl)glycine [122-87-2] at elevated temperature in such solvents as chlorobenzene—cyclohexanone (184,185). It also can be prepared by the methylation of 4-aminophenol, or from methylamiae [74-89-5] by heating with 4-chlorophenol [106-48-9] and copper sulfate at 135°C in aqueous solution, or with hydroquinone [123-31 -9] 2l. 200—250°C in alcohoHc solution (186). 

Sasol Fischer-Tropsch Process. 1-Propanol is one of the products from Sasol s Fischer-Tropsch process (7). Coal (qv) is gasified ia Lurgi reactors to produce synthesis gas (H2/CO). After separation from gas Hquids and purification, the synthesis gas is fed iato the Sasol Synthol plant where it is entrained with a powdered iron-based catalyst within the fluid-bed reactors. The exothermic Fischer-Tropsch reaction produces a mixture of hydrocarbons (qv) and oxygenates. The condensation products from the process consist of hydrocarbon Hquids and an aqueous stream that contains a mixture of ketones (qv) and alcohols. The ketones and alcohols are recovered and most of the alcohols are used for the blending of high octane gasoline. Some of the alcohol streams are further purified by distillation to yield pure 1-propanol and ethanol ia a multiunit plant, which has a total capacity of 25,000-30,000 t/yr (see Coal conversion processes, gasification). 

Another appHcation of 4-chlorophenol is in the synthesis of a dmg, ethyl a, a-dimethyl-4-chlorophenoxy acetate [637-07-0] (60), used as a cholesterol-reducing agent. This synthesis involves reaction with acetone and chloroform, followed by ethanol esterification. 

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). 

Industrial ethyl alcohol can be produced synthetically from ethylene [74-85-17, as a by-product of certain industrial operations, or by the fermentation of sugar, starch, or cellulose. The synthetic route suppHes most of the industrial market in the United States. The first synthesis of ethanol from ethylene occurred in 1828 in Michael Faraday s lab in Cambridge (40). 

There are two main processes for the synthesis of ethyl alcohol from ethylene. The eadiest to be developed (in 1930 by Union Carbide Corp.) was the indirect hydration process, variously called the strong sulfuric acid—ethylene process, the ethyl sulfate process, the esterification—hydrolysis process, or the sulfation—hydrolysis process. This process is stiU in use in Russia. The other synthesis process, designed to eliminate the use of sulfuric acid and which, since the early 1970s, has completely supplanted the old sulfuric acid process in the United States, is the direct hydration process. This process, the catalytic vapor-phase hydration of ethylene, is now practiced by only three U.S. companies Union Carbide Corp. (UCC), Quantum Chemical Corp., and Eastman Chemical Co. (a Division of Eastman Kodak Co.). UCC imports cmde industrial ethanol, CIE, from SADAF (the joint venture of SABIC and Pecten [Shell]) in Saudi Arabia, and refines it to industrial grade. 

Other Methods of Preparation. In addition to the direct hydration process, the sulfuric acid process, and fermentation routes to manufacture ethanol, several other processes have been suggested. These include the hydration of ethylene by dilute acids, the hydrolysis of ethyl esters other than sulfates, the hydrogenation of acetaldehyde, and the use of synthesis gas. None of these methods has been successfilUy implemented on a commercial scale, but the route from synthesis gas has received a great deal of attention since the 1974 oil embargo. 

Synthesis Ga.s, Since petroleum prices rose abmpdy in 1974, the production of ethanol from synthesis gas, a mixture of carbon monoxide and hydrogen, has received considerable attention. The use of synthesis gas as a base raw material has the same drawback as fermentation technology low yields limited by stoichiometry. 

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