Amyl alcohol synthesis

An example of a specialty olefin from an amyl alcohol is Phillips Petroleum s new process for 3-methyl-1-butene (used in the synthesis of pyrethroids) from the catalytic dehydration of 3-methyl-1-butanol (21,22). The process affords 94% product selectivity and 94% alcohol conversion at 310°C and 276 kPa (40 psig). 

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. 

Uses Denaturant for ethyl alcohol solvent for paints, varnishes, cellulose acetate, nitrocellulose lacquers, resins, fats, oils, and waxes preparation of methyl amyl alcohol in hydraulic fluids and antifreeze extraction of uranium from fission products organic synthesis. 

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. 

The 0x0 process is used to convert the C4 fraction to C5 derivatives. Synthesis gas is catalytically reacted with 1-butene to give pentanal which can be hydrogenated to 1-pentanol ( -amyl alcohol), giving a route to C5 compounds in larger amounts than what would be available from C5 alkanes in petroleum. 

In general, alcohols, such as methanol, ethanol, propanol, butanol, amyl alcohol, etc., can be used with acid-catalyzed transesterifications to obtain high biodiesel yields. " Methanol is preferred due to its low cost and wide availability, but bioderived ethanol would be ideal for the synthesis of a fully biogenerated fuel. On the other hand, the use of heavier alcohols like butanol... 

Tertio-amylic alcohol was retained for glycerides synthesis, as a solvent able to dissolve either fatty acids or triglycerides and glycerol,... 

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. 

The optimum conditions are molar ratio of n-amyl alcohol to cinnamic acid is 4 1, the mass ratio of catalyst to reactants is equal to 2.0 %, the reaction temperature 122-126 °C, and reaction time 1.5 h. Under this condition, the yield of n-amyl cinnamate can reach over 93.3 %. From the above results and discussion, we can see that the synthesis of n-amyl cinnamate catalyzed by TiSiWi204o/Ti02 instead of H2SO4 has a great prospect of application. 

Particle aggregation during and after the synthesis of the sol can have a significant effect on the properties of the resulting ceramic membrane. Figure 1 illustrates the effect of aging on particle size for titania sols prepared with different H20/Ti mole ratios, using 2-methyl-2-butanol (t-amyl alcohol) as the solvent. 

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. ... 

The condensation of a, dicarbonyl compounds (49) with aj3-diamino compounds (50), which proceeds through the dihydropyrazine (51), has been much used for the synthesis of alkyl- and arylpyrazines (52). These reactions are usually carried out in methanol, ethanol, or ether in the presence of sodium or potassium hydroxide. The dihydropyrazines may be isolated, or oxidized directly to the pyrazine. Dehydrogenating agents that have been employed include oxygen in aqueous alkali (329), air in the presence of potassium hydroxide (330), sodium amylate in amyl alcohol (330a), alcoholic ferric chloride (24), and copper chromite catalyst at 300° (331) (see also Section 1). Pyrazines prepared by this method and modifications described below are listed in Table II.8 (2, 6, 24, 60, 80,195, 329-382) and some additional data are provided in Sections VI. 1 A, VlII.lA(l), and IX.4A(1). 

Preparation. Johnson and co-workers give a procedure for the preparation of a solution of potassium r-butoxide in r-butanol under nitrogen. Skattebpl and Solomon describe preparation of the solution by the same method and for evaporating it to solvent-free solid (for a summary, see Methyllithium, allene synthesis). The reagent can be prepared also from potassium purified with /-amyl alcohol see Potassium, Pearson s procedure). 

When cross-linked crystals of thermolysin were applied in peptide synthesis in ethyl acetate, they were stable for several hundred hours at amazingly low enzyme consiunption, whereas a soluble enzyme preparation became inactive within a short period of time. Again it is worthwhile to consider the quality of the soluble enzyme preparation. When soluble thermolysin was stored in mixed aqueous-organic solutions, it lost about 50% of its activity within the first day of incubation only to be then quite stable for the next 15 days. It is possible that the initial inactivation was caused by an unstable fraction of thermolysin and that crystals of thermolysin no longer contained this unstable fraction [118]. Productivity comparable to that of crystals was achieved with thermolysin adsorbed on Amberlite XAD-7 resin which was employed in continuous plug flow reactors with tert-amyl alcohol as solvent [119]. 

The use of organic halogen compounds as the starting products for the synthesis of other organic chemicals is too immense a field to do more than indicate some of the commercial applications. In his book I4S) on the chemistry of petroleum derivatives, Ellis includes a chapter on the production of alcohols and esters from alkyl halides, and also one on miscellaneous reactions of halo-paraffins and cycloparaffins. The manufacture of amyl alcohols and related products from the chlorides has been well covered 14 ) 1 )-A two-step process for the synthesis of cyclopropane by chlorinating propane from natural gas and dechlorinating with zinc dust was devised in 1936 152). A critical review of syntheses from l,3-dichloro-2-butene was published in Russia in 1950 (1-54). The products obtainable from the allylic chlorides are covered in a number of articles 14If 14 157). 

Monomer Synthesis - l,3-Bis(etheny1oxy)benzene [1 1. A flask, equipped with nitrogen inlet, mechanical stirrer and condenser, was flame dried under N . After cooling, 1.5 1 of t-amyl alcohol was placed in the flask, and 92 g (2.35 mol) potassium was added slowly under N2. The N2 inlet was replaced with a pressure-equilizing addition funnel, and the condenser protected with a drying tube. A solution of 240 g (1.02 mole) 1,2-bis-(2-chloroethoxy)benzene in 250 ml hot t-amyl alcohol was dropped into the flask and refluxed for 36 hours. 

Remark. Pentanols or amyl alcohols, and more specifically 1-pentanok 2-methyl 1-butanol, and 3-methyl 1-butanol, do not enjoy the industrial importance of the above alcohols. They are prepared by Oxo synthesis and hydrogenation from n-butenes and isobutene. They are used as solvents and their esters as perfumes. 

The synthesis of rubber on a commercial scale has been the subject of much investigation. The chief difficulty has been to prepare isoprene from a substance that can be obtained in large quantities at a low cost. Turpentine yields but a small percentage of isoprene when heated and cannot serve, therefore, as the source of the hydrocarbon. The amyl alcohol which is obtained from fusel oil (76) can be converted into a dichloro-pentane of the structure (CH3)2CC1CH2CH2C1, which, when passed over lime at a high temperature, yields isoprene as the result of the loss of two molecules of hydrochloric acid —... 

An important contribution to the synthetic problem was made in 1921 by E. Koenigs and Ottmann (204), who extended previous work by Babe and Kindler (205), on the preparation of /8-(4-piperidyl)-propionic acid (CLXVIII), to the synthesis of dl-homocincholoipon (CLXXII). /8-Collidine (CLXIX) was condensed with chloral, and an intermediate (CLXX) was obtained which yielded /8-(3-ethylpyridyl)-4-acrylic acid (CLXXI) on alkaline hydrolysis. Reduction of this product with sodium and amyl alcohol furnished a mixture from which dLhomocin-choloipon (CLXXII) could be isolated. 

Cis and trans crotonamides can also polymerize by hydrogen transfer polymerization. Sodium r-butoxide in pyridine yields identical polymers from both isomers. Also, hydrogen transfer polymerization of acrylamide with optically active, basic catalysts yields optically active polymers. The reactions can be carried out in toluene, using optically active alcotxolates of amyl alcohol. The initiating ability of the metal ions is in the following order, Na > Ba > Ca > Mg > Al. Optically active polymethacrylamide forms with optically active barium and calcium alcoholates, but not with the other cations.In this reaction, however, the asymmetric synthesis takes place... 

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