Butadiene oxides, reaction with

The oxidation reaction between butadiene and oxygen and water in the presence of CO2 or SO2 produces 1,4-butenediol. The catalysts consist of iron acetylacetonate and LiOH (99). The same reaction was also observed at 90°C with Group (VIII) transition metals such as Pd in the presence of I2 or iodides (100). The butenediol can then be hydrogenated to butanediol [110-63-4]. In the presence of copper compounds and at pH 2, hydrogenation leads to furan (101). 

Nylon 12 first beeame available on a semieommercial scale in 1963. The monomer, dodecanelactam, is prepared from butadiene by a multistaged reaction. In one proeess butadiene is treated with a Ziegler-type eatalyst system to yield the cyclic trimer, cyclododeca-1, 5, 9-triene. This may then be hydrogenated to give cyelododeeane, which is then subjeeted to direct air oxidation to give a mixture of cyclododecanol and cyclododecanone. Treatment of the mixture with... 

A wide variety of new approaches to the problem of product separation in homogeneous catalysis has been discussed in the preceding chapters. Few of the new approaches has so far been commercialised, with the exceptions of a the use of aqueous biphasic systems for propene hydroformylation (Chapter 5) and the use of a phosphonium based ionic liquid for the Lewis acid catalysed isomerisation of butadiene monoxide to dihydrofuran (see Equation 9.1). This process has been operated by Eastman for the last 8 years without any loss or replenishment of ionic liquid [1], It has the advantage that the product is sufficiently volatile to be distilled from the reactor at the reaction temperature so the process can be run continuously with built in product catalyst separation. Production of lower volatility products by such a process would be more problematic. A side reaction leads to the conversion of butadiene oxide to high molecular weight oligomers. The ionic liquid has been designed to facilitate their separation from the catalyst (see Section 9.7)... 

Oxidation rate constant k, for gas-phase second order rate constants, kOH for reaction with OH radical, kNQ3 with N03 radical and ko3 with 03 or as indicated, data at other temperatures see reference koll = 6.16 x 10 " cm3 molecule-1 s 1 at 297 2 K (relative rate method, Ohta 1983) koll = 6.35 x 10 " cm3 molecule-1 s-1, 5.85 x 10-11 cm3 molecule-1 s-1 with 1,3-butadiene and propylene as standard substances respectively at 297 2 K (relative rate method, Ohta 1983) koll = 6.2 x 10-11 cm3 molecule-1 s-1 at 298 K (recommended, Atkinson 1997)... 

Pd2+ salts are useful reagents for oxidation reactions of olefins. Formation of acetaldehyde from ethylene is the typical example. Another reaction is the formation of vinyl acetate by the reaction of ethylene with acetic acid (16, 17). The reaction of acetic acid with butadiene in the presence of PdCl2 and disodium hydrogen phosphate to give butadienyl acetate was briefly reported by Stem and Spector (110). However, 1-acetoxy-2-butene (49) and 3-acetoxy-l-butene (50) were obtained by Ishii and co-workers (111) by simple 1,2- and 1,4-additions using PdCl2/CuCl2 in acetic acid-water (9 1). 

Compared with the anodic oxidation of a 1,3-diene, the cathodic reduction of a 1,3-diene may be less interesting since the resulting simple transformation to monoolefin and alkane is more conveniently achieved by a chemical method than by the electrochemical method. So far, only few reactions which are synthetically interesting have been studied15. The typical pattern of the reaction is the formation of an anion radical from 1,3-diene followed by its reaction with two molecules of electrophile as exemplified by the formation of the dicarboxylic acid from butadiene (equation 22)16. 

As mentioned already in CHEC-II(1996) <1996CHEC-II(8)411>, some tetrazolo[l,5- ]pyridines can react with their C(5)-C(6) and C(7)-C(8) double bonds as dienophiles in Diels-Alder reactions. A novel study again supported this recognition Goumont et al. described that 6,8-dinitrotetrazolo[l,5- ]pyridine 11 easily react with some 2,3-disub-stituted butadienes to give bis-cycloadducts 48 <2002T3249>. These products when treated with potassium /-butoxide undergo base catalyzed elimination of nitric acid followed by oxidation reaction to yield the fully aromatic tetracyclic compounds 49 (Scheme 14). 

The lanthanide oxide cations [LnO]+ and the bare lanthanide ions Ln+ react differently with butadiene (162). Some bare Ln+ ions (La, Ce, Pr, Gd) activate butadiene but their oxide cations are inert toward butadiene. The lanthanides with weak M-O bonds, EuO and YbO, react by oxygen transfer to the butadiene. The oxide cations of Dy, Ho, Er, and Tm activate butadiene, whereas the bare metals of these lanthanides are unreactive with butadiene. The [HoO]+ ion has been studied in detail and is able to polymerize butadiene the mechanism of this reaction has been discussed. 

The hydrogenation of 1,3-butadiene over metal oxide catalysts with D2 or H2 gives rise to predominantly 2-butene, whereas conventional metal catalysts give rise to 1-butene as the main product. Explain the differences in the product distribution in light of the reaction mechanisms. 

Reactions of the sulfonylsulfines 56 (e.g. R1 = R2 = Bn R1 — Me, R2 — Ph R1 — CPh3, R2 = ph etc.) derived from (S)-proline with 2,3-dimethyl-l,3-butadiene afford dihy-drothiopyran S-oxides 57 with asymmetric induction of up to 40% (equation 38)34. Methyl cyanodithioformate 58 is a very reactive dienophile with cyclopentadiene it forms a mixture of 40 parts of the endo-adduct 59 and 60 parts of the exo-isomer 60 (equation 39)35. 

Selenosulfonylation of olefins in the presence of boron trifluoride etherate produces chiefly or exclusively M products arising from a stereospecific anti addition, from which vinyl sulfones can be obtained by stereospecific oxidation-elimination with m-chloroper-benzoic acid134. When the reaction is carried out on conjugated dienes, with the exception of isoprene, M 1,2-addition products are generally formed selectively from which, through the above-reported oxidation-elimination procedure, 2-(phenylsulfonyl)-l,3-dienes may be prepared (equation 123)135. Interestingly, the selenosulfonylation of butadiene gives quantitatively the 1,4-adduct at room temperature, but selectively 1,2-adducts at 0°C. Furthermore, while the addition to cyclic 1,3-dienes, such as cyclohexadiene and cycloheptadiene, is completely anti stereospecific, the addition to 2,4-hexadienes is nonstereospecific and affords mixtures of erythro and threo isomers. For both (E,E)- and ( ,Z)-2,4-hexadienes, the threo isomer prevails if the reaction is carried out at room temperature. 

Anodic oxidation of catechols enables the unstable quinones to be prepared and reacted in situ. Reaction of the 1,2-quinone with a 1,3-dicarbonyi compound gives a high yield of a benzofuran [123, 124]. Both 1,2- and 1,4-quinones, prepared electrochemically in nitromethane, are efficiently topped in Diels-Alder reactions with butadienes [125]. 

Anodic oxidation of Grignard reagents (5) in the presence of styrene (30), butadiene (36) or vinyl ethyl ether (37) was investigated by Schafer and Kuntzel as an interesting (for preparative use) extension of other anodic reactions with olefins. The electrolysis was carried out at constant current density at Pt, Cu or graphite electrodes. It was found that the products obtained depend on the electrode material, as is seen from the data presented in Table 9. 

Carbinolamines, 87 Carbodiimides, 205-222 reaction with alcohols, 170 Carbon monoxide, as reducing agent, 336 a-Carbonyl azo compounds, 324, 326 Caro s add (permonosulfuric add), 408 oxidation with, 409 preparation of, 409 Chloramine T, 377 Chloroacetylenes 120-122 4-Chloro-l, 2-butadiene, 33 Chlorocyclohexenyl acetylene, 121 1 -Chloro-2-JV,N-diphenylaminoacetylene, 128-129... 

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