88424-90-2

Upstream product

• 3048-64-4 5-vinyl-2-norbornene 
• 3048-64-4 5-vinyl-bicyclo[2.2.1]hept-2-ene 
• 2886-88-6 6-epoxyethyl-3-oxatricyclo<3.2.1.0^2,4>octane 

Relevant academic research and scientific papers

Oxidative dihydroxylation of alicyclic unsaturated hydrocarbons with vinyl- and norbornene fragments in pseudohomogenic system

Oxidation of alicyclic unsaturated hydrocarbons (4-vinylcyclohexene, 5-vinylnorbornene, 5-cyclohexenylnorbornene, and 5-vinylbicyclooctene) with 30% hydrogen peroxide solutions and percarbamide is studied. Reaction was carried out at 40-70 C in the presence of heterogenized peroxocomplex compounds of molybdenum and tungsten formed "in situ" in the reaction of metal oxohalides with H3PO4, nano-dimensional particles of carbon material, and hydrogen peroxide. Main oxidation products of alicyclic diene hydro-carbons are the corresponding unsaturated epoxides and diols. Depending on the reaction condition their ratio varies in a wide range.

Manganese(III) porphyrin catalysts for the oxidation of terpene derivatives: A comparative study

A comparative study involving four manganese(III) porphyrin catalysts combined with two different oxidants (sodium hypochlorite and potassium monopersulfate) has been performed in the epoxidation of three terpene derivatives. The catalytic oxidation of α-pinene produces selectively 100% of the epoxide or 65% of allylic oxidation products, only by modification of the substituents on the meso-positions of the metalloporphyrin catalyst. The catalytic oxidation of the 5-vinyl-2-norbornene is regio- and stereoselective, producing only the exo-2,3-epoxy-5-vinylnorbornane. With α-terpinene, a conjugated di-olefin, an oxidative dehydrogenation reaction was surprisingly observed, producing p-cymene as a major compound.

Hydrogen Peroxide Oxidation Catalyzed by Heteropoly Acids Combined with Cetylpyridinium Chloride: Epoxidation of Olefins and Allylic Alcohols, Ketonization of Alcohols and Diols, and Oxidative Cleavage of 1,2-Diols and Olefins

A general and versatile oxidation catalyst has been developed by using hydrogen peroxide as the oxidant.Olefins and allylic alcohols were epoxidized with commercially available hydrogen peroxide (30-35percent H2O2) using a combination of Mo- or W-based heteropoly acids, H3PMo12O40 (MPA) or H3PW12O40 (WPA), with an appropriate ammonium salt such as cetylpyridinium chloride (CPC), under two-phase conditions using chloroform as the solvent (Tables I and II).The tris(cetylpyridinium) 12-tungtophosphate (CWP), +(CH2)15CH3>3(PW12O40)3-, prepared independently from WPA and 3 equiv of CPC, catalyzes the efficient ketonization of the secondary hydroxy group of alcohols and diols with H2O2 under homogeneous conditions using tert-butyl alcohol as the solvent (Table III).Under the same conditions, oxidative cleavage of vic-diols was successfully conducted by the CWP-H2O2 system to give carboxylic acids in good yields (Table IV).This catalyst-oxidant system was also efficient for the oxidative cleavage of carbon-carbon double bonds of olefins which provides a new valuable conversion of olefins to carboxylic acids (Table V).

REACTION OF CYCLIC EPOXIDE COMPOUNDS WITH TRIPHENYLPHOSPHINE

Significant differences were found in the reactivity of a series of epoxides of cycloalkenes and methylenecycloalkanes and diepoxides in reaction with triphenylphosphine, depending both on the steric effects of the cyclic fragments and on their strain.The level of the strain can be judged indirectly from the chemical shifts of the 1H and 13C nuclei and the spin-spin coupling constants of the C-H bonds in the epoxide ring.

Oxygen-Transfer Reactions Catalyzed by Nitropalladium(II) Complexes. Reactivity of Bis(μ-chloro)bishept-2-yl-C,N>dipalladium: Cleavage of the C-Pd Bond

The oxidation of various norbornene derivatives and several mono- and nonconjugated diolefines with the catalyst (CH3CN)2PdCl(NO2) (1) is described.In contrast with the results previously observed with Wacker-type catalysts (PdCl2-CuCl2), the epoxidation process is selective for the strained norbornene double bond with dienes 5 or 7.Methyl ketones such as 14, 16, 18, and 20 are obtained with unhindered terminal olefins (e.g., 20 from 19).The solution structure of bis(μ-chloro)bishept-2-yl-C,N>dipalladium (32) as analyzed by 1H and 13C NMR spectroscopy shows that there is a slight distortion of the palladacycle.The reactivity of isolated complex 32 has been studied.In aprotic solvents (benzene, toluene) and in the absence of any nucleophilic reagents, a pure oxygen-transfer reaction yielding epoxide 4 is the sole process.In the presence of nucleophiles or oxidants like CuCl2 or Pb(OAc)4 in protic or aprotic solvents (HOAc, CH2Cl2), the cleavage mode of the C-Pd bond is quite different.The formation of disubstituted norbornane derivatives 34 and 35 and nonrearranged products 36 and 37 are observed.The formation of various products from isolated complex 32 is discussed in terms of reaction mechanisms, particularly relative to the C-Pd bond reactivity.

EPOXIDATION WITH MOLECULAR OXYGEN IN THE PRESENCE OF PdCl(NO2)(CH3CN)2

Several mono or non conjugated diolefins are submitted to the action of oxygen in presence of catalytic amounts of PdCl(NO2)(CH3CN)2.Depending on the olefin structures methylketones or epoxides are obtained.