Butene, hydration

This paper describes our efforts to synthesize a series of thermally stable sulfonated resins and to evaluate their activity in a model reaction of 1-butene hydration to sec-butanol. 

The kinetics of 1-butene, cis-2-butene and trans-2-butene hydration to butanol was examined on the strong-acid ion-exchange resin, XE-307, with 0.6—0.7 mm particle sizes over a 75-150 °C temperature range (33]. Besides hydration, isomerization of the butenes was also observed. The analysis of kinetic data showed the hydration and isomerization of butenes to proceed in equilibrium through formation of secondary butylcarbonium ions. 

During the butene hydration on catalysts with 0.65 mm particle size, the reactions were retarded by internal diffusion occurring at temperatures above or equal to 115 C. Equilibrium constant values of butene hydration reactions beyond a 120-150 °C temperature range proved to be much lower than for propene hydration. 

Other processes include the alkylation of phenol using alkenes, and the manufacture of acrylate and methacrylate esters from alcohols and the corresponding acids. Olefin hydration reactions require more extreme conditions but Deutsche Texaco have developed a resin-catalysed propene hydration process to form isopropyl alcohol [125]. The reaction is run at 130 C near the upper limit for sulphonic acid resins, but a species with sufficient lifetime is available. There is even some evidence that butene hydration is now carried out similarly. Finally, B.P. Chemicals have recently disclosed [126] a new olefin isomerisation process yielding 2,3-dimethylbut-l-ene. Here the conditions required to favour the isomerisation versus rapid oligomerisation had to be identified to establish a viable process. 

Like butadiene, allene undergoes dimerization and addition of nucleophiles to give 1-substituted 3-methyl-2-methylene-3-butenyl compounds. Dimerization-hydration of allene is catalyzed by Pd(0) in the presence of CO2 to give 3-methyl-2-methylene-3-buten-l-ol (1). An addition reaction with. MleOH proceeds without CO2 to give 2-methyl-4-methoxy-3-inethylene-1-butene (2)[1]. Similarly, piperidine reacts with allene to give the dimeric amine 3, and the reaction of malonate affords 4 in good yields. Pd(0) coordinated by maleic anhydride (MA) IS used as a catalyst[2]. 

Methyl Isopropyl Ketone. Methyl isopropyl ketone [563-80-4] (3-methyl-2-butanone) is a colorless Hquid with a characteristic odor of lower ketones. It can be produced by hydrating isoprene over an acidic catalyst at 200—300°C (150,151) or by acid-catalyzed condensation of methyl ethyl ketone and formaldehyde to 2-methyl-l-buten-3-one, foUowed by hydrogenation to the product (152). Other patented preparations are known (155,156). Methyl isopropyl ketone is used as an intermediate in the production of pharmaceuticals and fragrances (see Perfumes), and as a solvent (157). It is domestically available from Eastman (Longview, Texas) (47). 

Furalazine, Acetylfuratrizine, Panfuran-S. Heating nitrovin in butanol or dimethylformamide at 100—130°C affords furalazine, 6-[2-(5-nitro-2-furanyl)ethenyl]-l,2,4-triazine-3-amine (34). An improved synthesis originates with 5-nitro-2-furancarboxaldehyde and acetone, proceeds through 4-(5-nitro-2-furanyl)-3-buten-2-one followed by a selenium dioxide oxidation to the pymvaldehyde hydrate, and subsequent reaction with aininoguariidine (35). Furalazine, acetylfuratrizine (36), and the A[-A/-bis(hydroxymethyl) derivative, Panfuran-S, formed from the parent compound and formaldehyde (37), are systemic antibacterial agents. 

Butanol is produced commercially by the indirect hydration of / -butenes. However, current trends are towards the employment of inexpensive Raffinate 11 type feedstocks, ie, C-4 refinery streams containing predominandy / -butenes and saturated C-4s after removal of butadiene and isobutylene. In the traditional indirect hydration process, / -butenes are esterified with Hquid sulfuric acid and the intermediate butyl sulfate esters hydroly2ed. DEA Mineraloel (formerly Deutsche Texaco) currentiy operates a 2-butanol plant employing a direct hydration of / -butenes route (18) with their own proprietary catalyst. 

The other significant industrial route to /-butyl alcohol is the acid cataly2ed hydration of isobutylene (24), a process no longer practiced in the United States. Raffinate 1, C-4 refinery streams containing isobutylene [115-11-7], / -butenes and saturated C-4s or C-4 fluid catalytic cracker (ECC) feedstocks (23)... 

Sulfuric acid is about one thousand times more reactive with isobutylene than with the 1- and 2-butenes, and is thereby very useful in separating isobutylene as tert-huty alcohol from the other butenes. The reaction is simply carried out by bubbling or stirring the butylenes into 45—60% H2SO4. This results in the formation of tert-huty hydrogen sulfate. Dilution with water followed by heat hydrolyzes the sulfate to form tert-huty alcohol and sulfuric acid. The Markovnikov addition implies that isobutyl alcohol is not formed. The hydration of butylenes is most important for isobutylene, either directiy or via the butyl hydrogen sulfate. 

Fig. 5.5.15 Spatially resolved 13C DEPT spectra recorded for the competitive etherification and hydration reactions of 2-methyl-2-butene (2M2B) to 2-methoxy-2-methylbutane (tert-amyl methyl ether, TAME) and 2-methyl-butan-2-ol (tert-amyl alcohol, TAOH), respectively. The molar composition of the feed was in the ratio 2 10 1 for 2M2B methanol water. The...

Dimethyl-2-butanol is the major product in the acid-catalyzed hydration of 3,3 -dimethyl-1 -butene. 

With secondary alcohols the picture is different. By measuring rates of hydration, isomerization, dehydration, and exchange, in the system of butenes and 2-butanol, Manassen and Klein (7S) proved that the hydration-dehydration intermediate in dilute acid solution is equally bonded to two water molecules ... 

The first natural product synthesis that utilized the Stetter reaction was reported by Stetter and Kuhhnann in 1975 as an approach to aT-jasmone and dihydrojas-mone (Scheme 21) [93]. Thiazolium pre-catalyst 74 was effective in catalyti-cally generating the acyl anion equivalent with aldehydes 144 and 145, then adding to 3-buten-2-one 146 in good yield. Cyclization followed by dehydration gives cii-jasmone and dihydrojasmone in 62 and 69% yield, respectively, over two steps. Similarly, Galopin coupled 3-buten-2-one and isovaleraldehyde in the synthesis of ( )-rran5-sabinene hydrate [94]. 

Water has also been shown to be essential for the liquid phase polymerization of isobutylene with stannic chloride as catalyst (Norrish and Russell, 87). The rates of reaction were measured by a dilatometric method using ethyl chloride as common solvent at —78.5°. With a mixture consisting of 1.15% stannic chloride, 20 % isobutylene, and 78.8% ethyl chloride, the rate of polymerization was directly proportional to the amount of added water (up to 0.43% of which was added). A rapid increase in the rate of polymerization occurred as the stannic chloride concentration was increased from 0.1 to 1.25% with higher concentrations the rate increased only gradually. It was concluded that a soluble hydrate is formed and functions as the active catalyst. The minimum concentration of stannic chloride below which no polymerization occurred was somewhat less than half the percentage of added water. When the concentration of the metal chloride was less than about one-fifth that of the added water, a light solid precipitated formation of this insoluble hydrate which had no catalytic activity probably explains the minimum catalyst concentration. The addition of 0.3% each of ethyl alcohol, butyl alcohol, diethyl ether, or acetone in the presence of 0.18% water reduced the rate to less than one-fifth of its normal value. On the other hand, no polymerization occurred on the addition of 0.3 % of these substances in the absence of added water. The water-promoted reaction was halved when 1- and 2-butene were present in concentrations of 2 and 6%, respectively. 

Liaw, B.J. Cheng, D.S. Yang, B.L. (1989) Oxidative dehydrogenation of 1-butene on iron oxyhydroxides and hydrated iron oxides. J. Catalysis 118 312-326... 

Bei der Behandlung von N-Phenyl-3.6-dihydro-1.2-oxazin mit Phos-phorsaure erfolgt Hydratation unter Ringspaltung und Orton-Umlage-rung bei Zimmertemperatur und mit 20%iger Saure entsteht N-p-Hydroxyphenyl-4-amino-buten-(2)-ol-(l), bei 60° mit 33%iger Saure cyclisiert dieses wahrend der Reaktion zu N-p-Hydroxyphenyl-A -pyr-rolin 28). 

Di-/i-chloro-bis(7)4-1,5-cyclooctadiene)dirhodium(l), [RhCl(l,5-C8Hi2)]2, has been prepared in 60% yield by reducing rhodium trichloride hydrate in the presence of excess olefin in aqueous ethanol.1 In the present preparation the yield has been greatly increased (to 94%). Two related complexes, [RhCl(l,5-C6Hio)]22 and [RhCl(C6H12)2]2, are similarly prepared in high yield from 1,5-hexadiene and 2,3-dimethyl-2-butene, respectively. 

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