Amyl alcohol oxidation

Koch Ro- ction. C-6-neoacids are readily available from amyl alcohols by the Koch reaction. Greater than 95% 2,2-dimethylbutyric acid [595-37-9] was obtained from 2-methyl-1-butene at 304 kPa (3 atm) CO and 35°C for 1 h with cupric oxide and sulfuric acid catalyst (31). Likewise,... 

Oxidation. Oxidation of the -amyl alcohols produces aldehydes, which after continued oxidation can yield acids. This route to aldehydes has httle merit. However, oxidative esterifications with alkah metal hypohaUtes (eg, calcium chlorite, Ca(OCl)2) (49), bromates (eg, sodium bromate, NaBrO )... 

Other examples of oxidation of amyl alcohols using hydrogen peroxide (54), Ru02/NaCl0 (55), BaMnO (56), and chromic acid (57,58) have been described for laboratory synthesis, but have not been utili2ed commercially. 

Etherification. Ethers of amyl alcohols have been prepared by reaction with ben2hydrol (63), activated aromatic haUdes (64), dehydration-addition reactions (65), addition to olefins (66—71), alkoxylation with olefin oxides (72,73) and displacement reactions involving thek alkah metal salts (74—76). 

Aqueous sodium thiosulfate solutions ate neutral. Under neutral or slightly acidic conditions, decomposition produces sulfite and sulfur. In the presence of air, alkaline solutions decompose to sulfate and sulfide. Dilute solutions can be stabilized by small amounts of sodium sulfite, sodium carbonate, or caustic, and by storage at low temperatures away from air and light. Oxidation is inhibited by Hgl2 (10 Ppm) amyl alcohol (1%), chloroform (0.1%), borax (0.05%), or sodium benzoate (0.1%). 

On oxidation with permanganate of potassium it yields sabinol-glycerine, CjoH,5(011)3, melting at 152° to 153°, and by further oxidation, tanacetogene-dicarboxylic acid, CpHj Og, melting at 140°. On reduction with sodium and amyl alcohol, sabinol yields thujyl alcohol, CjoHj OH. 

Raffinate-II typically consists of40 % 1-butene, 40 % 2-butene and 20 % butane isomers. [RhH(CO)(TPPTS)3] does not catalyze the hydroformylation of internal olefins, neither their isomerization to terminal alkenes. It follows, that in addition to the 20 % butane in the feed, the 2-butene content will not react either. Following separation of the aqueous catalyts phase and the organic phase of aldehydes, the latter is freed from dissolved 2-butene and butane with a counter flow of synthesis gas. The crude aldehyde mixture is fractionated to yield n-valeraldehyde (95 %) and isovaleraldehyde (5 %) which are then oxidized to valeric add. Esters of n-valeric acid are used as lubricants. Unreacted butenes (mostly 2-butene) are hydroformylated and hydrogenated in a high pressure cobalt-catalyzed process to a mixture of isomeric amyl alcohols, while the remaining unreactive components (mostly butane) are used for power generation. Production of valeraldehydes was 12.000 t in 1995 [8] and was expected to increase later. 

Methyl Methacrylate Propylene Oxide Methyl Parathion Isohexane Hexylene Glycol Methyl Amyl Alcohol Methyl Isobutyl Carbinol Methyl Akyl Acetate... 

Indeed, it was found that amyl alcohol is converted into amyl nitrite and nitrate by the action of nitric oxides resulting from the decomposition of nitrocellulose. These substances are then oxidized to form valeric acid and amyl valerate products distinguishable by their characteristic smell. 

Marqueyrol [74] reported experiments carried out in France over a period of 15 years to compare the efficiency of various stabilizers. The results are shown in Table 175. In addition to amyl alcohol and diphenylamine, the action of N-nitrosodiphenyl-amine (diphenylnitrosamine), carbazole, diphenylbenzamide, nitronaphthalene and naphthalene was also tested. The powder was stored at temperatures of 40, 60 or 75°C. The experiments were stopped when the powder showed signs of intense decomposition, giving off nitric oxides. This was also manifested by a sudden fall pf the nitrogen content in nitrocellulose isolated from the samples. 

Later, it was realized that while amyl alcohol reacts with nitrogen oxides liberated from deteriorating propellant to form amyl nitrate or nitrite, these in turn were not very stable in the presence of acidic decomposition products and would decomp with the liberation of oxides of nitrogen which would further accelerate the decomposition of the propellant. Since any aliphatic alcohol could be expected to behave similarly, subsequent stabilizers were made from aromatic compds or derivatives which formed stable NOa compounds with oxides of nitrogen... 

The amyl alcohols undergo the typical reactions of alcohols which are characterized by cleavage at either the oxygen—hydrogen or carbon—oxygen bonds. Important reactions include dehydration, eslenficalion, oxidation, animation, etherification, and condensation. 

The carbonyl functionality of MIBK can be hydrogenated over nickel catalysts to yield methyl isobutyl carbinol (4-methyl-2-pentanol or methyl amyl alcohol) [108-11-2]. Industrial processes coproduce methyl isobutyl carbinol during the hydrogenation of mesityl oxide to MIBK. The product ratio of methyl isobutyl carbinol—MIBK during this reaction can be shifted toward methyl isobutyl carbinol by adopting a higher than normal pressure and H2 organic ratio (59). Methyl isobutyl carbinol is used as an ore flotation frother and to produce zinc dialkyl dithiophosphate lube oil additives. It is produced in the United States by Shell and Union Carbide ( 1.12/kg, October 1994). 

Tetrahydro- (133) and trcm.s-decahydronaphthyridines (134) can be selectively prepared from the parent ring systems by reduction in the presence of either platinum oxide or palladium or by reduction with sodium in ethanol or amyl alcohol.79"8- Hydrogenation in acetic acid with platinum catalyst affords a cis- and traas-decahydro mixture (135 and 134).81... 

This is the solid residue left when turpentine is distilled for the preparation of oil of turpentine. It consists essentially of resin acids and their oxidation products and forms brittle, translucent masses with a peculiar resinous odour and a colour varying from pale yellow to dark brown D = 1 05-1 085. It is readily soluble in alcohol (1 part in 10 parts of 70% alcohol) and dissolves also in methyl or amyl alcohol, ether, acetone, benzene, chloroform, carbon disulphide or oil of turpentine in petroleum ether it is not completely soluble. It is easily and completely saponified by caustic soda solution. Addition of a drop of concentrated sulphuric add to a solution of a small quantity of colophony in acetic anhydride produces an intense violet-red or purple coloration, soon changing to yellowish-brown. Different types or grades of colophony are sold, distinguished mainly by the colour and origin. 

Fusion with Alkali and Cupric Oxide in Nonaqueous Solvents. Alkali lignin was fused with potassium hydroxide and cupric oxide in methanol under conditions suggested by Tiemann (20) and in n-amyl alcohol as suggested by Klages (4). These procedures were very effective in earlier model compound studies in our laboratories (12). Ether extracts obtained were less than those from corresponding experiments in aqueous solution, and qualitative compositions were essentially the same. In the case of the amyl alcohol experiments, artifacts with the cupric oxide were obtained. Again, experiments were conducted under more dilute conditions in a bomb under superatmospheric conditions, but results were no better. 

The remaining 30 percent of 1-butene is divided among several uses. About 10-15 percent of the 1-butene is polymerized in the presence of a Ziegler-type catalyst to produce polybutene-1 resin. The markets for this resin are pipe, specialty films, and polymer alloys. Approximately the same volume of 1-butene is reacted with synthesis gas in an oxo reaction to produce valeraldehydes. These C5 aldehydes are then hydrogenated to amyl alcohols or oxidized to valeric acid. Amyl alcohols are consumed in the production of lube oil additives and amyl acetate and in solvent uses. Valeric acid goes into lubricant base stocks and specialty chemicals. 

A third alkaloid contained sulfur (a rare feature in higher plant nitrogen heterocycles) and was shown to be 4-methylthiocanthin-6-one (XIV) (9). Hydrolysis with amyl alcoholic alkali gave methyl mercaptan and the phenol XV which, upon permanganate oxidation, furnished /3-carboline-l-carboxylic acid. The phenol did not form a quinoxaline with o-phenylenediamine, and its acetate in moist ethereal diazomethane... 

A closer relationship between foam stability and HLB has been reported for two- or three-phase systems surfactant solution-oil or oil-surfactant phase-water [60,109-111]. The effect of various parameters changing HLB on the stability of foams and emulsions has been studied in [111]. These were the concentration of amyl alcohol and sodium chloride, the number of the ethylene oxide groups in the molecule of the oxyethylated octylphenol. As a general parameter of HLB the authors used the surfactant affinity difference concept (SAD) which is an empirical generalised formulation. It measures the deviation from the optimum formulation for three phase behaviour. For anionic surfactants... 

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. 

Removal of the mercapto (or thione) function is most commonly achieved using Raney nickel, although concentrated HCl at high temperatures or nickel boride have been employed. Thiohydantoins are transformed into imidazolidin-4-ones by sodium in amyl alcohol (70JHC439). Oxidative desulfurization procedures too are often used the reactions probably proceed through the unstable sulfinic acid species which very readily eliminates sulfur dioxide. The high resistance of sulfonic acids to acid hydrolysis renders unlikely the possibility that they are reaction intermediates. 

Form Supplied in red solid prepared from optically pure d-camphor oxime in a five-step sequence (eq 1) reduction with sodium in n-amyl alcohol followed by fractional recrystallization of the resulting hydrochloride salts of bornylamines gives the endo-isomer in enantiomerically pure form treatment with phosgene and direct condensation of the isocyanate with (ethoxycarbonyl)hydrazine gives a compound which cyclizes upon treatment with base subsequent nitrogen dioxide oxidation furnishes (-)-en[Pg.145]

FUlvones. 2 -Hydroxychalcones are oxidized in good yield to flavones in boiling amyl alcohol or xylene. This was the first example of use of the reagent for oxidative cyclization and is still one of the two best methods for the synthesis of flavones. ... 

---