N-Butanol, oxidation

Ceria, titania, and zirconia supported ruthenium and eopper catalysts were tested in the production of n-butanal by n-butanol oxidation. These eatalysts were characterized by means of X-ray diffraction (XRD), N2 adsorption-desorption isotherms, temperature-programmed reduction (TPR), and X-ray photoelectron spectroscopy (XPS) techniques. The activity tests were performed in a fixed bed reaetor at 0.1 MPa and 623 K and pure mixture of reactants, air and n-butanol, in stequiometric proportion was introduced to the reactor. The rathenium catalysts showed a higher activity and stability than the copper catalysts, nevertheless the copper system showed a higher selectivity toward butyraldehyde production by n-butanol oxidation. 

Influence of oxygen containing species on methanol, ethanol, n-propanol and n-butanol oxidation reaction/cyclic voltammetry quasisteady-state analysis Pt(lll), Pt (755) and Pt (332) NaOH solution Pt was treated electrochemically to get the desired surface structure... 

General mechanism for methanol, ethanol, n-propanol and n-butanol oxidation is suggested. 

Normal butyl alcohol, propyl carbinol, n-butanol, 1-buianol, CH3CH2CH2CH2OH. B.p. 117 C. Manufactured by reduction of crotonaldehyde (2-buienal) with H2 and a metallic catalyst. Forms esters with acids and is oxidized first to butanal and then to butanoic acid. U.S. production 1978 300 000 tonnes. 

Izumi and Urabe [105] found first that POM compounds could be entrapped strongly on active carbons. The supported POMs catalyzed etherization of ferf-butanol and n-butanol, esterification of acetic acid with ethanol, alkylation of benzene, and dehydration of 2-propanol [105], In 1991, Neumann and Levin [108] reported the oxidation of benzylic alcohols and amines catalyzed by the neutral salt of Na5[PV2Mo10O40] impregnated on active carbon. Benzyl alcohols were oxidized efficiently to the corresponding benzaldehydes without overoxidation ... 

Oxidation of a thiomethyl group in indolo azepines to a sulfoxide and a sulfone has been reported (2004AP486). Thione 415 with a variety of hydrazides 416 under thermal conditions (n-butanol, reflux) gives fused triazoles 417 in moderate to good yields as the products of a substitution/cyclization sequence (Scheme 87, Section 5.2.1.3 (1993LA1141)). 

However, copper alkoxides with longer chains appear to be more soluble in their parent alcohol. S. Shibata et al. (20) have used the n-butoxides of Y, Ba and Cu dissolved in n-butanol and hydrolyzed with water. They obtain a precipitate of oxides that is composed of a very fine submicron powder that readily sinters starting above 250°C. However, the different reaction rates for the hydrolysis and the precipitation of the three different cations lead to cationic segregation. 

N 6.70% wh crysts (from n-butanol+ n-dibutyl ether), mp 156-57° shows mutarotation was pre-pd by condensation of 1, 2-acetone-D-xylo-trihy-droxyglutaric dialdehyde (made from monoacetone -D-glucose by oxidation with Pb tetracetate) with nitromethane. The two diastereoisomers resulting were separated by a process,called desaceto-nation,with dil H2S0 (Ref 2)... 

Primary alcohols are oxidized to aldehydes, n-butanol being the substrate oxidized at the highest rate. Although secondary alcohols are oxidized to ketones, the rate is less than for primary alcohols, and tertiary alcohols are not readily oxidized. Alcohol dehydrogenase is inhibited by a number of heterocyclic compounds such as pyrazole, imidazole, and their derivatives. 

In hydrocarbons a variety of by-products was formed. Propylene oxide gave some j8-hydroxyisobutyraldehyde as well as the normal product, also acetone, isobutyraldehyde, methacrolein, n-butyraldehyde, isobutanol, crotonaldehyde, and n-butanol. Presumably these by-products were formed by dehydration and hydrogenation of the hydroxyaldehydes, except for acetone which was formed by isomerization. The side reactions can be kept to a minimum by operating below 95° C (160). Fewer by-products appear to be formed using alcohols as solvents. Using methanol, Eisenmann (24) noted that carbon monoxide had an inhibitory effect at high pressures. 

Direct photolysis of aqueous solutions of the 2-chloro-.v-iriaz.ine herbicides (atrazine, simazine, propazine) proceeds via excitation of the triazine molecule, followed mainly by dechlorination and hydroxylation to form the corresponding hydroxytriazine (Pape and Zabik, 1970 Khan and Schnitzer, 1978 Chan et al, 1992 Lai et al, 1995 Schmitt et al, 1995 Sanlaville et al, 1997 Torrents et al, 1997 Texier et al, 1999b Hequet et al, 2001). This observation - plus the fact that when 2-chloro-v-triazine herbicides are photolyzed in methanol, ethanol, and n-butanol, the respective 2-alkoxy derivatives are formed - indicates a mechanism involving photochemical solvolysis rather than the involvement of hydroxyl radicals. This conclusion is supported by the fact that the rate of oxidation of atrazine was unaffected by the presence of either bicarbonate ion (Beltran et al, 1993) or ferf-butanol (Torrents et al, 1997), both strong hydroxyl radical scavengers. 

Ferroverdin can be crystallized following chromatography on alumina. C3oH2o08N2Fe-H20. No decomp. <300°. Moderately soluble in alcoholic solvents, sparingly soluble in ether and practically insoluble in water. Rf in n-butanol-pyridine-water 60 40 30, 0.91. Rt values known in three other solvents. Absorption peaks in the visible at approximately 4300 and 6750 A with amM = 8.2 and 8.8, respectively. Iron is diamagnetic (36) and resistant to EDTA, dipyridyl, ortho-phenanthroline and l-nitroso-2-napthol-3,6-disulfonic acid. The color is discharged with Na2S204 and other reductants but is unaffected by various oxidative treatments. 

The direct condensation of ethanol to form n-butanol was investigated by Dolgov and Vol nov in 1933, using titanium oxide promoted with iron-aluminum oxides on charcoal as the catalyst (71). They suggest, with insufficient proof, that ethanol is dehydrated to form ethylene which then reacts with more ethanol to form the butanol. 

The phase diagram of the quaternary system, n-tetradecane, water, A-B-A block copol3nner (where A Is poly— (12-hydroxystearlc acid) and B Is poly(ethylene oxide)) and n-butanol was Investigated at 7, 23 and 47 C. Two A-B-A polymer concentrations of 10 and 20Z were used. 

The gas phase oxidation of n-butanol proceeds quite rapidly at temperatures around 290 °C. Between 305 and 340 °C Cullis and Warwicker [26] observed single and multiple cool flames, while at still higher temperatures a region of very high maximum rates without ignition was observed. Above and below the cool flame region the overall activation energy was about 39 kcal. mole". ... 

This alcohol oxidizes somewhat less readily than n-butanol [26]. Between 300 and 350 °C the maximum rate of reaction varies only sightly with temperature, while above and below this region the apparent activation energy is about 40 kcal. mole". The corresponding variation of induction period with temperature shows no such behaviour, the induction period decreasing smoothly with temperature with an activation energy of 21 kcal. mole". ... 

The 2-D TLC was successfully applied to the separation of amino acids as early as the beginning of thin-layer chromatography. Separation efficiency is, by far, best with chloroform-methanol-17% ammonium hydroxide (40 40 20, v/v), n-butanol-glacial acetic acid-water (80 20 20, v/v) in combination with phenol-water (75 25, g/g). A novel 2-D TLC method has been elaborated and found suitable for the chromatographic identification of 52 amino acids. This method is based on three 2-D TLC developments on cellulose (CMN 300 50 p) using the same solvent system 1 for the first dimension and three different systems (11-IV) of suitable properties for the second dimension. System 1 n-butanol-acetone -diethylamine-water (10 10 2 5, v/v) system 11 2-propanol-formic acid-water (40 2 10, v/v) system 111 iec-butanol-methyl ethyl ketone-dicyclohexylamine-water (10 10 2 5, v/v) and system IV phenol-water (75 25, g/g) (h- 7.5 mg Na-cyanide) with 3% ammonia. With this technique, all amino acids can be differentiated and characterized by their fixed positions and also by some color reactions. Moreover, the relative merits of cellulose and silica gel are discussed in relation to separation efficiency, reproducibility, and detection sensitivity. Two-dimensional TLC separation of a performic acid oxidized mixture of 20 protein amino acids plus p-alanine and y-amino-n-butyric acid was performed in the first direction with chloroform-methanol-ammonia (17%) (40 40 20, v/v) and in the second direction with phenol-water (75 25, g/g). Detection was performed via ninhydrin reagent spray. 

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