Butyl acetate, oxidation

Interestingly, the major fate of the analogous alkoxy radical formed in the oxidation of tert-butyl formate is isomerization rather than decomposition via C—C bond scission. Isomerization is presumable favored by the six-membered transition state and lower C—H bond strength in the tert-butyl formate system. Further work is needed to identify the tert-butyl acetate oxidation products required for a 100% carbon balance. 

Prospective Processes. There has been much effort invested in examining routes to acetic acid by olefin oxidation or from ethylene, butenes, or j -butyl acetate. No product from these sources is known to have reached the world market the cost of the raw materials is generally prohibitive. 

In typical processes, the gaseous effluent from the second-stage oxidation is cooled and fed to an absorber to isolate the MAA as a 20—40% aqueous solution. The MAA may then be concentrated by extraction into a suitable organic solvent such as butyl acetate, toluene, or dibutyl ketone. Azeotropic dehydration and solvent recovery, followed by fractional distillation, is used to obtain the pure product. Water, solvent, and low boiling by-products are removed in a first-stage column. The column bottoms are then fed to a second column where MAA is taken overhead. Esterification to MMA or other esters is readily achieved using acid catalysis. 

A process to convert butenes to acetic acid has been developed by Farbenfabriken Bayer AG (137) and could be of particular interest to Europe and Japan where butylenes have only fuel value. In this process a butane—butylene stream from which butadiene and isobutylene have been removed reacts with acetic acid in the presence of acid ion-exchange resin at 100—120°C and 1500—2000 kPa (about 15—20 atm) (see Acetic acid and its derivatives, acetic acid). Both butenes react to yield j -butyl acetate which is then oxidized at about 200°C and 6 MPa (about 60 atm) without catalyst to yield acetic acid. 

Acetic acid may also be produced by reacting a mixture of n-butenes with acetic acid over an ion exchange resin. The formed sec-butyl acetate is then oxidized to yield three moles of acetic acid ... 

The reaction scheme is rather complex also in the case of the oxidation of o-xylene (41a, 87a), of the oxidative dehydrogenation of n-butenes over bismuth-molybdenum catalyst (87b), or of ethylbenzene on aluminum oxide catalysts (87c), in the hydrogenolysis of glucose (87d) over Ni-kieselguhr or of n-butane on a nickel on silica catalyst (87e), and in the hydrogenation of succinimide in isopropyl alcohol on Ni-Al2Oa catalyst (87f) or of acetophenone on Rh-Al203 catalyst (87g). Decomposition of n-and sec-butyl acetates on synthetic zeolites accompanied by the isomerization of the formed butenes has also been the subject of a kinetic study (87h). 

In this study butyl acetate (AcOBu) was hydrogenolysed to butanol over alumina supported Pt, Re, RePt and Re modified SnPt naphtha reforming catalysts both in a conventional autoclave and a high throughput (HT) slurry phase reactor system (AMTEC SPR 16). The oxide precursors of catalysts were characterized by Temperature-Programmed Reduction (TPR). The aim of this work was to study the role and efficiency of Sn and Re in the activation of the carbonyl group of esters. 

The /V -hydroxylamino compounds (404) and (405), obtained from the reaction of tert-butyl acetate with 3,4-dihydroisoquinoline-A-oxide or 5,5-dimethyl-pyrroline-/V-oxide, when boiled in methylene chloride in the presence of triphenylphosphine, carbon tetrachloride and triethylamine, are transformed to (1,2,3,4- tetrahydroisoquinolin-l-ilidene) acetate (406) or (pyrrolidin-2-ilidene) acetate (407) (Scheme 2.181) (645). 

In the hydroxycyclopropanation of alkenes, esters may be more reactive than N,N-dialkylcarboxamides, as is illustrated by the exclusive formation of the disubstituted cyclopropanol 75 from the succinic acid monoester monoamide 73 (Scheme 11.21) [91]. However, the reactivities of both ester- as well as amide-carbonyl groups can be significantly influenced by the steric bulk around them [81,91]. Thus, in intermolecular competitions for reaction with the titanacydopropane intermediate derived from an alkylmagnesium halide and titanium tetraisopropoxide or methyltitanium triisoprop-oxide, between N,N-dibenzylformamide (48) and tert-butyl acetate (76) as well as between N,N-dibenzylacetamide (78) and tert-butyl acetate (76), the amide won in both cases and only the corresponding cyclopropylamines 77 and 79, respectively, were obtained (Scheme 11.21) [62,119]. 

The following plastic compns contg EGDN, patented by WASAG-Chemie AG, Essen (DAS 1148924) are described in Ref 22b 1) EGDN 38.0, CC (collodion cotton) 0.75, Lackwolle 33 (in 33% soln of butyl acetate) 0.75, liquid DNT/TNT (probably like Tropfol= Dripoil) 2.0, TNT 2.0, AN 52.3, woodmeal 4.0 and iron oxide 0.2% 2) EGDN 34.7,... 

Other important raw material uses of ethyl alcohol are conversion to esters and ethers, vinegar, ethyl chloride, butadiene, styrene, and chloral (for DDT). Nearly all the new developments in chemicals from ethyl alcohol, particularly the four-, six-, and eight-carbon derivatives are based on alcohol derived from petroleum. The butyl alcohol and butyl acetate so made supplement the production by fermentation and from oxidation of hydrocarbons and synthesis gas operations. The consumption of ethyl alcohol for all industrial uses (denatured alcohol) exceeded 1.2 billion pounds (100% basis) in 1950. More than 700,000,000 pounds of this were made from petroleum. 

Keller, V., P. Bernhardt and F. Garin (2003). Photocatalytic oxidation of butyl acetate in vapor phase on Ti02, Pt/Ti02 and W03/Ti02 catalysts. Journal of Catalysis, 215(1), 129-138. 

Another class of ruthenium catalysts, which has attracted considerable interest due to their inherent stability under oxidative conditions, are the polyoxome-talates [161]. Recently, Mizuno et al. [162] reported that a mono-ruthenium-sub-stituted silicotungstate, synthesized by the reaction of the lacunary polyoxometa-late [SiWu039]8- with Ru3+ in an organic solvent, acts as an efficient heterogeneous catalyst with high turnover frequencies for the aerobic oxidation of alcohols (see Fig. 4.63). Among the solvents used 2-butyl acetate was the most... 

Use and exposure Sec-butyl acetate is a colorless liquid with a pleasant odor. The vapor mixes well with air and it becomes an explosive mixture. It reacts with strong oxidants, strong bases, and strong acids and nitrates, causing fire and explosion hazards. - ... 

Cleavage of acetals. In the presence of a Pd(II) catalyst, /-butyl hydroperoxide oxidatively cleaves a five- or six-membered acetal to an ester of a diol. Pd(OAc), and PdCl2 can catalyze this reaction, but CFjCOjPdtJOCfCHj), (10, 299) is most effective. The cleavage of acetals derived from unsymmeti ical diols is not regioselective. Example ... 

Olefins add anhydrous acetic acid to give esters, usually of secondary or tertiary alcohols propylene [115-07-1] yields isopropyl acetate [108-21-4], isobutylene [115-11-7] gives / /7-butyl acetate [540-88-5]. Minute amounts of water inliibit the reaction. Unsaturated esters can be prepared by a combined oxidative esterification over a platinum group metal catalyst. For example, ethylene-air-acetic acid passed over a palladium—lithium acetate catalyst yields vinyl acetate. 

Examples are given of common operations such as absorption of ammonia to make fertilizers and of carbon dioxide to make soda ash. Also of recovery of phosphine from offgases of phosphorous plants recovery of HF oxidation, halogenation, and hydrogenation of various organics hydration of olefins to alcohols oxo reaction for higher aldehydes and alcohols ozonolysis of oleic acid absorption of carbon monoxide to make sodium formate alkylation of acetic acid with isobutylene to make fert-butyl acetate, absorption of olefins to make various products HCl and HBr plus higher alcohols to make alkyl halides and so on. 

SAFETY PROFILE Moderately toxic by intraperitoneal route. Human systemic effects by inhalation conjunctiva irritation, headache, and somnolence. A human eye irritant. Apparently more toxic than butyl acetate. Chronic toxicity is of a low order. Dangerous fire hazard when exposed to heat or flame can react with oxidizing materials. Moderately explosive in the form of vapor when exposed to flame. To fight fire, use alcohol foam, dry chemical. When heated to decomposition it emits acrid smoke and irritating fumes. See also ESTERS, AMYL ALCOHOL, and ACETIC ACID. 

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