Epoxy norbornene

By treating norbornene with benzenesulfonyl azide in benzene at room temperature, a crystalline product is obtained in quantitative yield.264-265 On the basis of chemical and nmr evidence, an aziridine structure (85) similar to exo-2,3-epoxy-norbornene (86) is attributed to the adduct. The addition thus occurs at the least hindered exo side of the bicyclic nucleus. 

Steele, W.V., Chirico, R.D., Cowell, A.B., Knipmeyer, S.E., and Nguyen, A. Thermodynamic properties and ideal-gas enthalpies of formation for 2-aminoisobutyric acid (2-methylalanine), acetic acid, ( -5-ethylidene-2-norbornene, mesityl oxide (4-methyl-3-penten-2-one), 4-methylpent-l-ene, 2,2 -bis(phenylthio)propane, and glycidyl phenyl ether (1,2-epoxy-3-phenox3q>ropane), / Chem. Eng. Data, 42(6) 1053-1066, 1997. 

Irradiation of the epoxy dinitrile 90 in a solution of acetonitrile formed the stabilized ylide 91 that was trapped with ethyl vinyl ether, producing both exo and endo adducts 92 and 93 in 25 and 8% yields. Studies with other dipolarophiles (27) such as norbornene and methyloxazoline generated cycloadducts 94 and 95, respectively, in low overall yield. 

However the epoxidation of olefins lacking allylic and other reactive C-H bonds with molecular oxygen has recently been achieved on silver catalysts (Table 1). In 1997 the Eastman Chemical Company started the manufacture of 3,4-epoxy-1-butene, the product of mono-epoxidation of butadiene, on a semiworks production scale (entry 1). Remarkably enough the presence of benzylic hydrogen, as in / -methyl styrene (entry 5), drives the oxidation towards combustion, while sterically hindered allylic C-H s, as in norbornene (entry 6), are inert to oxidation. 

Key Words Ethylene oxide, Propylene oxide. Epoxybutene, Market, Isoamylene oxide. Cyclohexene oxide. Styrene oxide, Norbornene oxide. Epichlorohydrin, Epoxy resins, Carbamazepine, Terpenes, Limonene, a-Pinene, Fatty acid epoxides, Allyl epoxides, Sharpless epoxidation. Turnover frequency, Space time yield. Hydrogen peroxide, Polyoxometallates, Phase-transfer reagents, Methyltrioxorhenium (MTO), Fluorinated acetone, Alkylmetaborate esters. Alumina, Iminium salts, Porphyrins, Jacobsen-Katsuki oxidation, Salen, Peroxoacetic acid, P450 BM-3, Escherichia coli, lodosylbenzene, Oxometallacycle, DFT, Lewis acid mechanism, Metalladioxolane, Mimoun complex, Sheldon complex, Michaelis-Menten, Schiff bases. Redox mechanism. Oxygen-rebound mechanism, Spiro structure. 2008 Elsevier B.V. 

In this study we show that it is possible to selectively epoxidize higher olefins to their corresponding epoxides if the olefins do not contain reactive allylic hydrogen atoms. Many olefins, including styrene, substituted butadienes, and norbornene have been selectively epoxidized. Because of the usefulness of 3,4-epoxy-1-butene as a new chemical intermediate, most of the data and discussion will involve the selective epoxidation of butadiene. The catalyst composition and overall kinetics of the reaction will be discussed in some detail. 

Ethylene dioxythiophene monomer, emulsion polymerization PEG-5 methacrylate Sodium allyloxy hydroxypropyl sulfonate monomer, EPDM elastomers Ethylidene-2-norbornene monomer, epoxy coatings Bis [f[4-(ethenyloxy) methyl] cyclohexyl] methyl] terephthalate Bis (4-vinyl oxy butyl) hexanediyibiscarbamate monomer, EVA copolymers Vinyl acetate... 

A soln. of 85%-m-chloroperoxybenzoic acid in methylene diloride added to a stirred ice-cooled soln. of 5-norbornen-2-ol in the same solvent, after 2 hrs. treated with a soln. of 2,2,6,6-tetramethylpiperidine hydrochloride in methylene chloride followed by additional m-chloroperoxybenzoic acid soln., and the product isolated after 1.5 hrs. exo-5,6-epoxy-2-norbornanone. Y 86%. J. A. Celia, J. A. Celia, J. A. Kelley, and E. F. Kenehan, J. Org. Chem. 40, 1860 (1975) oxidation of alcohols with N-oxide radicals cf. B. Ganem, ibid. 40, 1998 ketones from sec. alcohols with m-chloroperoxybenzoic acid/HCl cf. J. A. Celia, J. P. McGrath, and S. L. Regen, Tetrah. Let. 1975, 4115 review of N-oxide radicals s. H. G. Aurich and W. Weiss, Topics Curr. Chem. 59, 65 (1975). 

Chlorendic anhydride (1,4,5,6,7,7-hexa-chloro-5-norbornene-2,3-dicar-boxylic anhydride, HET anhydride, a difunctional acid anhydride) n. HET anhydride is a white, crystalline powder used as a hardening agent and flame retardant in epoxy, alkyd, and polyester resins (See image). 

The homogeneous (3) and hybrid salicylaldimine catalyst system were tested on norbornene, cyclooctene, 5,6-epoxy-1-cyclooctene and 3,4-epoxy-1-cyclooctene. 

DMTA together with other techniques such as DSC have been used in morphological studies on a variety of polymers including epoxy-polyaniline resin [53], ethylene-propylene 5-ethylidene-2-norbornene terpolymer-polyaniline blends [54], Nylon 6-ethylene vinyl alcohol blends [55], polyoxymethylene [56], ethylene-propylene-... 

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