L-Butadiene epoxide

Perez, H.L., Lahdetie, J., Landin, H.H., Kilpelainen, I., Koivisto, P, Peltonen, K. Osterman-Golkar, S. (1997) Haemoglobin adducts of epoxybutanediol from exposure to 1,3-butadiene or butadiene epoxides. Chem.-biol. Interact., 105, 181-198... 

Valentine, J.L., Boogaard, P.J., Sweeney, L.M., Turner, M.J., Bond, J.A. Medinsky, M.A. (1997) Disposition of butadiene epoxides in Sprague-Dawley rats. Chem.-biol. Interact., 104, 103-115... 

Tretyakova et al. [67] reported the quantitative analysis of adducts of 1,3-butadiene epoxides with dA and dG in DNA. The butadiene metabolites 3,4-epoxy-1-butene, diepoxybutane, and 3,4-epoxy-l,2butanediol were found to react with dG at the A-7-position and dA at the jV-1-, A-3-, N-6-, and A-7-positions. Quantitative analysis of the modified nucleobases was performed by positive-ion LC-ESI-MS in SRM mode. 

Butadiene epoxidation to epoxybutene (EpB ) was practiced at a semiworks scale of 1.4 x 10 metric tons year by Tennessee Eastman [9] between 1997 and 2004 [10]. Epoxybutene is a versatile intermediate [11] that can be used to produce a large variety of different products such as epoxybutane, 1,4-butane diols and alcohols, 1,2-butane diols and alcohols, 2,3-dihydrofuran, 2,5-dihydrofuran, tetrahydrofuran, N-methylpyrrolidone, cyclopropyl carboxyaldehyde (CPCA) derivatives, vinyl ethylene carbonate (addition of CCT to EpB), and 3,4-dihydroxy-l-butene (addition of H2O to EpB). 

The synthesis of organic chemicals by catalytic reactions of COj has been reviewed. Ben l and allyl halides are carboxylated electrolytically in the presence of Co(saleh) catalysts. Palladium(O) catalysts smoothly carboxylate butadiene epoxide to the carbonate a mechanism x-allyl Pd complexes is proposed (eqn.49). ... 

Such copolymers of oxygen have been prepared from styrene, a-methylstyrene, indene, ketenes, butadiene, isoprene, l,l-diphen5iethylene, methyl methacrjiate, methyl acrylate, acrylonitrile, and vinyl chloride (44,66,109). 1,3-Dienes, such as butadiene, yield randomly distributed 1,2- and 1,4-copolymers. Oxygen pressure and olefin stmcture are important factors in these reactions for example, other products, eg, carbonyl compounds, epoxides, etc, can form at low oxygen pressures. Polymers possessing dialkyl peroxide moieties in the polymer backbone have also been prepared by base-catalyzed condensations of di(hydroxy-/ f2 -alkyl) peroxides with dibasic acid chlorides or bis(chloroformates) (110). 

Isomerization has been observed with many a,j3-unsaturated carboxylic acids such as w-cinnamic 10), angelic, maleic, and itaconic acids (94). The possibility of catalyzing the interconversion of, for example, 2-ethyl-butadiene and 3-methylpenta-l,3-diene has not apparently been explored. The cobalt cyanide hydride will also catalyze the isomerization of epoxides to ketones (even terminal epoxides give ketones, not aldehydes) as well as their reduction to alcohols. Since the yield of ketone increases with pH, it was suggested that reduction involved reaction with the hydride [Co" (CN)jH] and isomerization reaction with [Co (CN)j] 103). A related reaction is the decomposition of 2-bromoethanol to acetaldehyde... 

Both the mono- and diepoxides of butadiene are substrates for epoxide hydrolase [163], In rat liver microsomes, (R)- and (S)-butadiene monoepoxides were hydrolyzed to but-3-ene-l,2-diol (10.104, Fig. 10.24) with complete retention of configuration at C(2), indicating attack at C(l) [164], In mouse liver microsomes, in contrast, 15 - 25% inversion of configuration was observed, suggesting partial attack at C(2). Preliminary results indicate that human liver microsomes are more efficient than mouse or rat liver microsomes in hydrolyzing butadiene monoepoxide [165]. The hydrolysis of diepoxybutane (10.103) yields 3,4-epoxybutan-l,2-diol (10.105), which can be further hydrated to erytritol (10.106) [163]. 

Butadiene is metabolized in experimental animals and human liver microsomes to epoxide metabolites, initially l,2-epoxy-3-butene and subsequently 1,2 3,4-... 

Adler, I.-D., Kliesch, U., Nylund, L. Peltonen, K. (1997) In vitro and in vivo mutagenicity of the butadiene metabolites butadiene diol epoxide, butadiene monoepoxide and diepoxybutane. Mutagenesis, 12, 339-345... 

Krause. R.J.. Sharer, J.E. Elfarra, A.A. (1997) Epoxide hydrolase-dependent metabolism of butadiene monoxide to 3-butene-l,2-diol in mouse, rat, and human liver. DrugMetab. Disp., 25.1013-1015... 

Sweeney, L.M., Himmelstein. M.W., Schlosser. PM. Medinsky. M.A. (1996) Physiologically based pharmacokinetic modeling of blood and tissue epoxide measurements for butadiene. Toxicology, 113, 318-321... 

Another strategy for the synthesis of lycorine commenced with the Diels-Alder reaction of l-methylenedioxyphenyl-2-nitroethylene with butadiene to provide the cyclohexene derivative 85, which on reaction with MCPBA gave 86 together with the diastereomeric epoxide (1 1) (Scheme 6) (112). Hydrogena-... 

Langer also prepared other functionalized 2-alkylidenetetrahydrofurans by cyclization of l,3-fc(trimethylsiloxy)- 1,3-butadienes with epoxides <02CEJ1443>. Mercury(II)-induced cyclization of the hydroxyalkyne below led to the formation of the enol ether <02TL3011>. 

Chlorinated, sulfonated, chlorosulfonated or epoxidized polymers, homopolymers and copolymers of functionalized monomers, e.g. poly(methacryl aldehyde), poly(2,3-epoxypropyl acrylate), poly(4-vinylphenol), poly(propylene-co-10-unde-cene-l-ol), poly(butadiene-co-methacryl aldehyde), poly(butadiene-co-acrylic acid), poly(ethylene-co-alkyl acrylate), poly(alkyl acrylate-co-2,3-epoxypropyl acrylate), poly(alkyl acrylate-co-maleic anhydride), poly(styrene-co-4-vinylbenzyl chloride)... 

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