18428-16-5

Upstream product

• 591-49-1 1-methylcyclohex-1-ene 
• 3426-71-9 Benzyl N-hydroxycarbamate 

Downstream Products

• 23758-27-2 1-methylcyclohex-2-en-1-ol 
• 4065-80-9 2-methylenecyclohexanol 

Relevant academic research and scientific papers

Confined space-controlled hydroperoxidation of trisubstituted alkenes adsorbed on pentasil zeolites

Photosensitized oxidation of trialkylalkenes 2-methyl-2-pentene (1), 1-methylcyclohexene (2), trans-3-methyl-2-pentene (3), cis-3-methyl-2-pentene (4), and 2-methyl-2-butene (5) included in the internal framework of Na-ZSM-5 zeolites was investigated. The zeolite samples having adsorbed the alkenes were suspended in isooctane, and the sensitizer, tetraphenylporphyrin (TPP), was dissolved in the solution. Singlet oxygen produced in the solution diffused into the internal framework of the zeolites and reacted with alkenes. For all the substrates studied, the ene-type allylic hydroperoxides were obtained in a highly regioselective manner. The regiochemistry for 1-4 in favor of the allylic hydrogen abstraction from the largest substituents is in contrast to their photooxidation within the dye-supported zeolite Na-Y, where the secondary hydroperoxides are preferentially produced. The tight confinement of the alkenes within the narrow channels of the ZSM-5 zeolites is likely to be responsible for this selectivity.

Porphyrin-functionalized dendrimers: Synthesis and application as recyclable photocatalysts in a nanofiltration membrane reactor

The convergent synthesis of a series of porphyrin-functionalized pyrimidine dendrimers has been accomplished by a procedure involving the nucleophilic aromatic substitution (NAS) as a key reaction step. The resulting dendritic porphyrin catalysts show hig

Initiated, tert-Butyl Hydroperoxide-loaded, Low-temperature Autoxidation of Alkenes: A Chemoselective Synthesis of Allylic Hydroperoxides, allowing Analysis of the Regioselectivity of Hydrogen Atom Abstraction from some Unsymmetrically Substituted Substrates

A method for the preparation of allylic hydroperoxides is introduced: the method involves the rapid, low-temperature, initiated autoxidation of an alkene (in these instances 1-methylcyclohexene and the isomeric 4-methyloct-4-enes) in the presence of tert-butyl hydroperoxide.The success of the method relies upon the selectivity of hydrogen atom abstraction from the substrate by the chain-carrying tert-butylperoxyl radicals, according to the preference for formation of the most stable intermediate allylic radicals, and the reduced rates of chain termination via thesesame radicals.The method gives a regioselectivity for attack broadly in agreement with predictions from Bolland's rules, and a sufficiently high chemoselectivity for allylic hydroperoxide formation that ready isolation of these products in good yields is achieved.

Sunlight induced oxidative photoactivation of N-hydroxyphthalimide mediated by naphthalene imides

We report the aerobic photoactivation of N-hydroxyphthlimide (NHPI) to the phthalimido-N-oxyl (PINO) radical mediated by naphthalene monoimides (NI) for promoting the selective oxidation of alkylaromatics and allylic compounds to the corresponding hydroperoxides. In the absence of either NI or NHPI no oxidation was observed, meaning that the two molecules operate in a synergistic way. Sunlight as well as artificial UV-light irradiation was necessary in order to perform the process at low temperature (30-35 °C). EPR spectroscopy confirmed the role of NI and oxygen in promoting the formation of the superoxide radicals O2.- which, in turn, increased the concentration of PINO radicals during the UV light irradiation of NI/NHPI mixtures in MeCN. The investigation was extended to NI bearing different substituents on the naphthalene moiety. Finally, the synthesis and application of a unique photocatalyst including the NI and NHPI moieties linked by a suitable spacer was also considered. In this case the photocatalyst showed a substrate-dependent behaviour with some peculiarities in comparison to the system where NI and NHPI are independent units in the same reacting system. This photocatalytic system paves the way to a non-thermal, metal-free approach for C-H bond activation towards aerobic oxidation under very mild conditions. Copyright

Controlling photoreactions with restricted spaces and weak intermolecular forces: Exquisite selectivity during oxidation of olefins by singlet oxygen

Highly regioselective photooxidation of methyl cycloalkenes has been performed in an aqueous medium by selectively blocking two of the three allylic hydrogens through supramolecular steric effect. Hydrophobic, steric, and weak intermolecular C-H-π interac

9-Mesityl-10-methylacridinium: An efficient type II and electron-transfer photooxygenation catalyst

The visible-light irradiation of 9-mesityl-10-methylacridinium perchlorate 1 in the presence of monoalkenes and molecular oxygen leads to typical products of singlet oxygen addition (type II photooxygenation). The molecular probes 1-methylcyclohexene and limonene, respectively, result in hydroperoxide mixtures with a characteristic product pattern. A switch in the oxidative mechanism (electron-transfer photooxygenation) is observed for naphthalene derivatives as electron-rich acceptor molecules, revealing that the 9-mesityl-10- methylacridinium cation serves as a dual sensitizer with the capacity of efficient singlet oxygen formation and electron-transfer reaction.

An entirely solvent-free photooxygenation of olefins under continuous flow conditions

Photooxygenations of alkenes with singlet oxygen are a versatile, atom-economical transformation. The choice of solvents is key to the success of this oxyfunctionalization with direct impact on the solubility of substrates, the lifetime of the reactive oxygen species, and the up-scaling of the process. We report an entirely solvent-free continuous-flow photooxygenation that operates at very high substrate/sensitizer ratios and enables high space-time yields.

Organic Dye-Photocatalyzed Acylnitroso Ene Reaction

Rose bengal, an inexpensive and readily available organic dye, is demonstrated to be a photoredox catalyst for the formation of transient acylnitroso intermediates under visible light irradiation. This method is operationally simple and uses air as the te

Strategies for cleaner oxidations using photochemically generated singlet oxygen in supercritical carbon dioxide

Photochemically generated singlet oxygen, 1O2, has been reacted with four different substrates in supercritical carbon dioxide. By using fluorous surfactants and a co-solvent to solubilise more polar photosensitisers and reactants respectively, the applicability of the system is greatly enhanced. The Royal Society of Chemistry 2009.

Glycol-modified molybdate catalysts for efficient singlet oxygen generation from hydrogen peroxide

Pretreatment of molybdate-exchanged layered double hydroxides in polyalcohols such as ethylene glycol affords heterogeneous catalysts showing largely improved oxidant efficiency compared to the unmodified materials. The Royal Society of Chemistry.