Butyl butyrate, oxidation

Several species of bacteria under suitable conditions cause / -butyraldehyde to undergo the Canni22aro reaction (simultaneous oxidation and reduction to butyric acid and butanol, respectively) this reaction can also be cataly2ed by Raney nickel (7). The direct formation of butyl butyrate [109-21 -7] or isobutyl isobutyrate [97-85-8](Vish.ch.erik.o reaction) from the corresponding aldehyde takes place rapidly with aluminum ethylate or aluminum butyrate as catalyst (8). An essentially quantitative yield of butyl butyrate, CgH2 02, from butyraldehyde has been reported usiag a mthenium catalyst, RuH,[P(C,H,)3], (9). 

Most of the metallic oxidants which have been used for the oxidation of ethers have been based on oxides of the transition metals chromium, manganese and ruthenium, the latter being of greatest synthetic importance. The first reported example of the application of ruthoiium tetroxide in the oxidation of ethers tqipeared over 30 years ago in 1958, although an indication of its reactivity towards ethers had been obt ed some years before. In a systematic study which revealed the powerful oxidizing properties of the reagent, Berkowitz and Rylander demonstrated the quantitative conversion of tetrahydrofuran and R-butyl ether into y-butyrolactone and butyl butyrate, respectively. Significantly, no overoxidation was observed. Apart f m an unsuccessful attempt to oxidize ethylene oxide, no fitter attempts were made by the authors to examine further the scope of this novel transformation. In a series of subsequent publications and a patent, Wolf and his coworkers went on to exploit the reaction in the preparation of aldosterone and relr steroids (equation 1). 

C furnishes a 41-47% yield of butyl butyrate [640]. Butyl butyrate is also obtained in 82% yield by oxidation of butanol by bromine and potassium bromate in 40% hydrobromic acid [742] (equation 237). 

The oxidation of aliphatic alcohols in benzene or petroleum ether with /ert-butyl chromate at 1-2 °C for 6 h leads to mixtures of aldehydes, acids, and their esters. Butanol gives 30% of butanal, 27% of butyric acid, and 36% of butyl butyrate [677], Also, electrolysis of aliphatic alcohols on platinum or carbon electrodes in aqueous potassium iodide at room temperature results in 80-83% yields of the corresponding esters [121]. 

Butyl Butyrate 11098-99-0 Molybdenum Oxide 112-36-7 Diethyl Carbitol... 

Oxidation of alcohols. Grob and Schmid used /-butyl hypochlorite in carbon tetrachloride or ether in the presence of pyridine for oxidation of cyclohexanol to cyclohexanone and of /i-butanol to //-butyl butyrate. Ginsburg et aU oxidized 3-hydroxysteroids by dropwise addition of /-butyl hypochlorite in CCli to a solution of the steroid in CCl, at room temperature. When the ketone was to be chlorinated as formed, the reaction was done in acetic acid at followed by heating on the steam bath. Levin et al. obtained 3-ketosteroids in high yield by oxidation of the 3-atcohols with /-butyl hypochloride in dry /-butanol. 

Oxidation of n-butanol with DCT yields a mixture of butyl butyrate and butanal. Isopropanol and cyclohexanol are oxidized with DCT and TBT to acetone and cyclohexanone, respectively. Under the same conditions a-hydroxypropanoic acid yields acetaldehyde (69ZC325) (Scheme 80). 

BUTYL BUTYRATE or n-BUTYL, n-BUTYRATE (109-21-7) Forms explosive mixture with air (flash point 122°F/50°C). Violent reaction with strong oxidizers. Incompatible with strong acids, nitrates. Attacks some plastics, rubber, and coatings. 

With some primary alcohols, it is possible to establish an equilibrium between the initially formed aldehyde and the precursor alcohol in which unreacted alcohol is converted to an hemiacetal (17), which can be further oxidized to an ester. This often accompanies the oxidation of lower molecular weight primary alcohols. Oxidation of 1-butanol to butyl butyrate with Cr(VI), for example, is an Organic Syntheses preparation. ... 

Methyl esters are produced in the electrolytic oxidation of methanolic solutions of aldehydes in the presence of sodium cyanide at a platinum anode the eight examples that have been studied show yields of 38 to 80%. Carefully purified butyraldehyde reacts with RuHgfPPha) to give butyl butyrate aliphatic and aromatic aldehydes undergo this dimerization process, which may have considerable synthetic potential." The electrolysis of furan-2-carboxylic acid (66) provides an efficient synthesis of 4,4-dimethoxy-esters (67), typically in 77 % yield (Scheme 35). "... 

Johnson and Andino (2001) conducted a detailed smdy of the products obtained from the OH-initiated oxidation of DnBE in the presence of NO Major products identified, with their molar yields in parentheses, were butyl formate (41.0 0.9%), propanal (37.9 2.2%), butanal (11.9 0.3%), and butyl butyrate (1.9 0.1%). 

Thus, -butyl [71-36-3] [71-36-3] and isobutyl alcohol [78-83-1] [78-83-1] are obtained by hydrogenation of their respective aldehydes and butyric and isobutyric acid are produced by oxidation. 

Complementary to the work with aqueous acidic media is the study of the homolytic decompositions of Co(III) carboxylates in carboxylic acid media by Lande and Kochi . For example, Co(III) is reduced in pivalic acid media with first-order kinetics with E = 30.6 kcal.mole , AS = 8 eu and k ko = 1.28+0.10 (69 °C). The main oxidation products were found to be isobutylene and tert-butyl pivalate, which suggests that (CH3)3C- is an intermediate. Oxidative decarboxylation is the probable course in the analogous oxidations of n-butyric and isobutyric acids, in view of the production of propane and CO2 under normal... 

Skinner, Molnar Suarez (1964) studied the cement-forming potential of 28 liquid aromatic carboxylic acids with zinc oxide. Twelve yielded cohesive products of some merit. Of particular interest were cements formed with hydrocinnamic, cyclohexane carboxylic, p-tertiary butyl-benzoic, thiobenzoic and cyclohexane butyric acids. One of these cements is on the market as a non-eugenol cement. It is very weak with a compressive strength of 4 0 MPa, a tensile strength of 11 MPa and a modulus of 177 MPa, and is only suitable as a temporary material (Powers, Farah Craig, 1976). 

Condensation of butanol has been carried out on alkaline earth metal oxides at 273 K (13,121). This condensation reaction yields 2-ethyl-3-hydroxy-hexanal as a main product other products, such as 2-ethyl-2-hexenal (arising from the dehydration of 2-ethyl-3-hydroxy-hexanal), n-butyl-K-butyrate (arising from the Tishchenko reaction of butyraldehyde), and 2-ethyl-3-hydroxy- -hexyl butyrate (arising from the Tishchenko reaction of 2-ethyl-3-hydroxy-hexanal), are also formed (Scheme 12). 

Ethyl alcohol has been made by the hydration of ethylene (9) since 1930. Like isopropyl alcohol, part of the output is used as a solvent, but most is converted to other oxygenated chemicals. Its most important raw material use is conversion to acetaldehyde by catalytic air oxidation. Acetaldehyde, in turn, is the raw material source of acetic acid, acetic anhydride, pentaerythritol, synthetic n-butyl alcohol (via aldol condensation), butyraldehyde, and other products. Butyraldehyde is the source of butyric acid, polyvinyl butyral resin, and 2-ethylhexanol (octyl alcohol). The last-named eight-carbon alcohol is based on the aldol condensation of butyraldehyde and is used to make the important plasticizer di-2-ethylhexyl phthalate. A few examples of the important reactions of acetaldehyde are as follows ... 

K-Butyl M-butyrate (5, 23). If after the addition of the -butyl alcohol, the oxidation mixture is heated on the steam bath to 90-100° until the supernatant liquid is practically colorless and then the reaction mixture is worked up as described, the yield of ester is increased to 147 149 g. (64-65 per cent of the theoretical amount). 

When M-butyl alcohol is oxidized to butyric acid in the presence of a high concentration of sulfuric acid, esterification takes place at once, even in the cold, as long as an excess of the alcohol is present. 

Tetra-n-butyltin is oxidised by chromium trioxide (1 1 molar ratio) to yield tri-n-butyltin acetate and compounds derived from the n-butyl group cleaved from the tin atom (mainly n-butyraldehyde and butyric acid)29. In the initial stages of the oxidation, the reaction follows the simple rate expressions v = k2 [Bu Sn] [Cr03]. Values of the second-order rate coefficient for the oxidation of a number of tetraalkyitins by Cr03 in solvent acetic acid at 20 °C were reported29 to be as follows... 

Mixed ethers result when alcohols and phenols are used with thoria at 390°—420° and esterification takes place when alcohol and acid interact at 350°-400°. Esterification10 is more complete in the presence of titanic oxide at 280°—300°. One molecule of acid is used with twelve molecules of alcohol, and in this way methyl, ethyl, propyl, butyl, and benzyl esters have been prepared from acetic, propionic and butyric acids. 

The one-step synthesis of isoamyl butyrate from isoamyl alcohol and n-butyral-dehyde, possibly through the formation and subsequent oxidation of an acetal intermediate, could represent a special case in TS-1 catalysis, since the oxidant was molecular oxygen [114]. The authors did not advance any mechanistic hypothesis. -Butyl hydroperoxide, however, produced in situ by the autoxidation of n-butyraldehyde, could have been the true oxidant, by virtue of its dimensional compatibility with the narrow pores of TS-1. 

Oxidation of primary alcohols in acid media is often accompanied by esterification. By the use of the proper proportions of reactants, fair yields of esters may be obtained directly from the alcohols e.g., -butyl n>butyrate (47%) by chromic acid oxidation of n-butyl alcohol. Aqueous acid chlorate solutions in the presence of vanadium pentoxide have been used for this purpose. ... 

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