1-Butene, oxidation

BUTYLENE OXIDE 1-Butene Oxide, alpha-Butylene Oxide, 1,2-Epoxybutane Flammable Liquid 2 3 2... 

Another interesting monomer for copolymerisation with carbon dioxide is isomeric 2-butene oxide. In copolymerisation in a ternary comonomer system consisting of 2-butene oxide, 1-butene oxide and carbon dioxide with the diethylzinc-water catalyst, m-2-butene oxide was incorporated in the copolymer, while trans-2-butene oxide hardly underwent an enchainment [230]. Thus, the smaller steric hindrance for the r/.v-isomer than for the irans-isomer throughout the coordination copolymerisation with carbon dioxide is to be taken into account. 

Butylene Oxide 1-Butene Oxide 1,2-Butylene Oxide Alpha- Butylene Oxide 1,2-Epoxybutane ... 

Among new initiators for the polymerization of propylene oxide, ethylene oxide, 1-butene oxide, and isobutylene oxide are zinc hexacyanocobaltate [54] and aluminum porphyrin [55]. 

From this study and the previous two, it can be concluded that the efficiency of hydroxyl functionalizations with homologous epoxides is in the order EO (100%) > 1-butene oxide (99%) > propylene oxide (93%). The reactivity order for these oxiranes is EO > propylene oxide - 1-butene oxide. The properties of these epoxides are also of importance with respect to their utility for functionalization reactions. EO is an explosive gas (b.p. 10.7 °C) while propylene oxide and 1-butene oxide are liquids with boiling points of 34.2 and 63.3 °C, respectively. ... 

Ni(acac>2 supported on inorganic oxide- 1-butene, 2-butene, 1-hexene 410... 

Petro-Tex A process for oxidizing butenes to maleic anhydride. Developed by the Petro-Tex Chemical Corporation and used at its plant in Houston, TX. 

Finally, it may be noted that vanadium-based catalysts can oxidize butenes to acetic acid. Kaneko et al. [168,169] report a selectivity of 50% at a relatively high conversion of 67%. V2Os is not active but combinations with Sn, W, Ti are, especially at temperatures in the range 200— 300° C. In accordance with the hypothesis of Ai about the effect of the catalyst acidity, a deep oxidation is favoured by the highest acidity. Hence Sn—V—O catalysts with 50% V, which display the maximum acidity per unit of weight, are the most suitable. 

On alkaline earth metal oxides butene is adsorbed as methylallyl anions (CH3—CH—CH—CH2). This carbanion is an intermediate in the double bond isomerization of butene. Adsorption was shown to be stronger on CaO (higher basicity) than on MgO. Activation of CaO at 700-900 °C results in maximum Lewis basicity and optimum activity for the isomerization to 2-butene. 

Test reactioTL The results of non-oxidative butene dehydrogenation experiments are represented in Figs. 3-5. 

Oxidative rearrangement takes place in the oxidation of the 1-vinyl-l-cyclo-butanol 31, yielding the cyclopentenone derivative 32[84], Ring contraction to cyclopropyl methyl ketone (34) is observed by the oxidation of 1-methylcyclo-butene (33)[85], and ring expansion to cyclopentanone takes place by the reaction of the methylenecyclobutane 35. [86,87]... 

Difunctionalization with similar or different nucleophiles has wide synthetic applications. The oxidative diacetoxylation of butadiene with Pd(OAc)i affords 1,4-diacetoxy-2-butene (344) and l,2-diacetoxy-3-butene (345). The latter can be isomerized to the former. An industrial process has been developed based on this reaction. The commercial process for l,4-diacetoxy-2-butene (344) has been developed using the supported Pd catalyst containing Te in AcOH. 1,4-Butanedioi and THF are produced commercially from 1,4-diacetoxy-2-butene (344)[302]. 

In order to make these oxidative reactions of 1,3-dienes catalytic, several reoxidants are used. In general, a stoichiometric amount of benzoquinone is used. Furthermore, Fe-phthalocyanine complex or Co-salen complex is used to reoxidize hydroquinone to benzoquinone. Also, it was found that the reaction is faster and stereoselectivity is higher when (phenylsulflnyl)benzoquinone (383) is used owing to coordination of the sulfinyl group to Pd, Thus the reaction can be carried out using catalytic amounts of PdfOAcji and (arylsulfinyl)benzoquinone in the presence of the Fe or Co complex under an oxygen atmosphere[320]. Oxidative dicyanation of butadiene takes place to give l,4-dicyano-2-butene(384) (40%) and l,2-dicyano-3-butene (385)[32l]. 

The reaction of a halide with 2-butene-1,4-diol (104) affords the aldehyde 105, which is converted into the 4-substituted 2-hydroxytetrahydrofuran 106, and oxidized to the 3-aryl-7-butyrolactone 107[94], Asymmetric arylation of the cyclic acetal 108 with phenyl triflate[95] using Pd-BINAP afforded 109, which was converted into the 3-phenyllactone 110 in 72% ee[96]. Addition of a molecular sieve (MS3A) shows a favorable effect on this arylation. The reaction of the 3-siloxycyclopentene 111 with an alkenyl iodide affords the. silyl... 

Convincing evidence for oxidative addition by inversion has been presented by the reaction of chiral (5)-( )-3-acetoxy-l-phenyl-1-butene (4) with Pd(0)(dppe), followed by the treatment with NaBF4 to give optically active the TT-allylpalladium complex (l/ ,25,35) 5 with 81% stereoselectivity[19]. 

Furthermore, the catalytic allylation of malonate with optically active (S)-( )-3-acetoxy-l-phenyl-1-butene (4) yields the (S)-( )-malonates 7 and 8 in a ratio of 92 8. Thus overall retention is observed in the catalytic reaction[23]. The intermediate complex 6 is formed by inversion. Then in the catalytic reaction of (5 )-(Z)-3-acetoxy-l-phenyl-l-butene (9) with malonate, the oxidative addition generates the complex 10, which has the sterically disfavored anti form. Then the n-a ir rearrangement (rotation) of the complex 10 moves the Pd from front to the rear side to give the favored syn complex 6, which has the same configuration as that from the (5 )-( )-acetate 4. Finally the (S)-( )-mal-onates 7 and 8 are obtained in a ratio of 90 10. Thus the reaction of (Z)-acetate 9 proceeds by inversion, n-a-ir rearrangement and inversion of configuration accompanied by Z to isomerization[24]. 

Diacetates of 1,4-butenediol derivatives are useful for double allylation to give cyclic compounds. l,4-Diacetoxy-2-butene (126) reacts with the cyclohexanone enamine 125 to give bicyclo[4.3.1]decenone (127) and vinylbicy-clo[3.2.1]octanone (128)[85,86]. The reaction of the 3-ketoglutarate 130 with cij-cyclopentene-3,5-diacetate (129) affords the furan derivative 131 [87]. The C- and 0-allylations of ambident lithium [(phenylsulfonyl)methylene]nitronate (132) with 129 give isoxazoline-2-oxide 133, which is converted into c -3-hydroxy-4-cyanocyclopentene (134)[S8]. Similarly, chiral m-3-amino-4-hyd-roxycyclopentene was prepared by the cyclization of yV-tosylcarbamate[89]. 

Hydroboration-oxidation of (E) 2 (p anisyl) 2 butene yielded an alcohol A mp 60°C in 72% yield When the same reaction was performed on the Z alkene an isomenc liquid alcohol B was obtained in 77% yield Suggest reasonable structures for A and B and describe the relation ship between them... 

This oxidation process for olefins has been exploited commercially principally for the production of acetaldehyde, but the reaction can also be apphed to the production of acetone from propylene and methyl ethyl ketone [78-93-3] from butenes (87,88). Careflil control of the potential of the catalyst with the oxygen stream in the regenerator minimises the formation of chloroketones (94). Vinyl acetate can also be produced commercially by a variation of this reaction (96,97). 

Prospective Processes. There has been much effort invested in examining routes to acetic acid by olefin oxidation or from ethylene, butenes, or j -butyl acetate. No product from these sources is known to have reached the world market the cost of the raw materials is generally prohibitive. 

Addition of halogens proceeds stepwise, sometimes accompanied by oxidation. Iodine forms 2,3-diiodo-2-butene-l,4-diol (53). Depending on conditions, bromine gives 2,3-dibromo-2-butene-l,4-diol, 2,2,3,3-tetrabromobutane-l,4-diol, mucobromic acid, or... 

Asymmetric Hydroboration. Hydroboration—oxidation of (Z)-2-butene with diisopinocampheylborane was the first highly enantioselective asymmetric synthesis (496) the product was R(—)2-butanol in 87% ee. Since then several asymmetric hydroborating agents have been developed. Enantioselectivity in the hydroboration of significant classes of prochiral alkenes with representative asymmetric hydroborating agents is shown in Table 3. 

The dehydrogenation of 2-butanol is conducted in a multitube vapor-phase reactor over a zinc oxide (20—23), copper (24—27), or brass (28) catalyst, at temperatures of 250—400°C, and pressures slightly above atmospheric. The reaction is endothermic and heat is suppHed from a heat-transfer fluid on the shell side of the reactor. A typical process flow sheet is shown in Figure 1 (29). Catalyst life is three to five years operating in three to six month cycles between oxidative reactivations (30). Catalyst life is impaired by exposure to water, butene oligomers, and di-j -butyl ether (27). 

Another attractive commercial route to MEK is via direct oxidation of / -butenes (34—39) in a reaction analogous to the Wacker-Hoechst process for acetaldehyde production via ethylene oxidation. In the Wacker-Hoechst process the oxidation of olefins is conducted in an aqueous solution containing palladium and copper chlorides. However, unlike acetaldehyde production, / -butene oxidation has not proved commercially successflil because chlorinated butanones and butyraldehyde by-products form which both reduce yields and compHcate product purification, and also because titanium-lined equipment is required to withstand chloride corrosion. 

R. H. Schwaar and S. Morimoto, Methyl Ethyl Ketone by Direct Oxidation of n-Butenes, Process Economics Program, Review No. 87-2-3, SRI International, Menlo Park, Calif., Oct. 1988. 

Process Technology Evolution. Maleic anhydride was first commercially produced in the early 1930s by the vapor-phase oxidation of benzene [71-43-2]. The use of benzene as a feedstock for the production of maleic anhydride was dominant in the world market well into the 1980s. Several processes have been used for the production of maleic anhydride from benzene with the most common one from Scientific Design. Small amounts of maleic acid are produced as a by-product in production of phthaHc anhydride [85-44-9]. This can be converted to either maleic anhydride or fumaric acid. Benzene, although easily oxidized to maleic anhydride with high selectivity, is an inherently inefficient feedstock since two excess carbon atoms are present in the raw material. Various compounds have been evaluated as raw material substitutes for benzene in production of maleic anhydride. Fixed- and fluid-bed processes for production of maleic anhydride from the butenes present in mixed streams have been practiced commercially. None of these... 

Methyl-1-pentene [691-37-2] is alight, colorless, flammable fiquid its physical constants are also given in Table 1. It is an irritant and, in high concentrations, a narcotic. Like 1-butene, this chemical compound has a low flash point and represents a significant fire hazard when exposed to heat, flame, or oxidizing agents. 

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,... 

Manufacture of oBenzoylbenzoic Acid from l-Methyl-3-phenylindane. In 1909 it was reported that treatment of styrene with concentrated sulfuric acid resulted in its dimerization (51). However, the wrong stmcture was assigned to this dimer (52). Years later it was suggested, without proof, that the dimer consisted primarily of l-methyl-3-phenylindane (13) [6416-39-3] and some 1,3-diphenyl-l-butene (53). In 1950, oxidative studies on the dimer proved that this supposition was correct (54) ... 

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. 

Trimethyl aluminum and propylene oxide form a mixture of 2-methyl-1-propanol and 2-butanol (105). Triethyl aluminum yields products of 2-methyl-1-butanol and 2-pentanol (106). The ratio of products is determined by the ratio of reactants. Hydrolysis of the products of methyl aluminum dichloride and propylene oxide results ia 2-methylpropeae and 2-butene, with elimination of methane (105). Numerous other nucleophilic (107) and electrophilic (108) reactions of propylene oxide have been described ia the Hterature. 

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