4096-42-8

Basic information

• Product Name: Hydroperoxide, 2-cycloocten-1-yl
• CAS NO: 4096-42-8
• Molecular Formula: C8H14O2
• Molecular Weight: 142.198
• Mol File: 4096-42-8.mol
• Article Data: 5

Chemical Properties

• CAS DataBase Reference: Hydroperoxide, 2-cycloocten-1-yl(CAS DataBase Reference)
• NIST Chemistry Reference: Hydroperoxide, 2-cycloocten-1-yl(4096-42-8)
• EPA Substance Registry System: Hydroperoxide, 2-cycloocten-1-yl(4096-42-8)

Safety Data

• Hazardous Substances Data: 4096-42-8(Hazardous Substances Data)

Upstream product

• 931-88-4 cis-Cyclooctene 
• 931-89-5 (E)-cyclooctene 
• 64-17-5 ethanol 

Downstream Products

• 3212-75-7 2-cycloocten-1-ol 
• 85866-03-1 cyclooctane-1,2,3-triol 
• 85866-03-1 (1R,3R)-cyclooctane-1,2,3-triol 
• 85866-03-1 cyclooctane-1,2,3-triol 
• 71245-79-9 cis-10-bromo-8,9-dioxabicyclo<5.2.1>decane 
• 17123-56-7 oxacyclonon-2,8-diene 

Relevant articles and documents

Photoinitiated catalysis in nafion membranes containing palladium(II) meso-tetrakis(N-methyl-4-pyridyl)porphyrin and iron(III) meso-tetrakis-(2,6-dichlorophenyl)porphyrin for O2-mediated oxidations of alkenes

Immobilisation of both palladium(II) meso-tetrakis(N-methyl-4-pyridyl)porphyrin (PdTMPyP4+) and iron(III) meso-tetrakis(2,6-dichlorophenyl)-porphyrin (FeTDCPP+) in the same membrane of Nation creates a new composite system, in which the photo-excited palladium complex induces the O2-mediated oxidation of cyclohexene to the corresponding allylic hydroperoxide and the iron porphyrin works as a catalyst for specific oxygenations of cyclohexene and cyclooctene. The role of PdTMPyP4+ is to induce the photo-activation of O2 with visible light (λ > 500 nm) to generate singlet oxygen (1O2) by means of energy transfer from the excited triplet state. Consequently, the 1O2-mediated oxidation of cyclohexene to cyclohexenyl hydroperoxide can be realised with a selectivity greater than 90%. Spectroscopic and photophysical investigations show that the tetracationic palladium porphyrin is mainly fixed to the external part of the Nafion membrane, it is characterised by a triplet-state lifetime significantly higher than that in the solution phase. The monocationic FeTDCPP+ is able to diffuse into the anionic cavities of Nafion, where it works as a catalyst for O2-mediated autooxidation processes that are initiated by the photogenerated hydroperoxides. These processes continue in the dark for many hours giving cyclohex-2-en-1-ol and trans-cyclohexane-1,2-diol monoethyl ether as main oxidation products. The presence of this ether, indirectly, reveals the formation of cyclohexene epoxide which undergoes a nucleophilic attack by ethanol and epoxide opening because of the strong acidic environment inside Nafion. The good photocatalytic efficiency of the oxidation process is demonstrated by an overall quantum yield of 1.1, as well as by a turnover value of 4.7 × 103 with respect to the iron porphyrin. When cyclooctene is present as co-substrate, it also undergoes oxygenation. In contrast to what was observed for cyclohexene, cyclooctene epoxide can be accumulated in a significant amount. As far as the stability of the system is concerned, FeTDCPP+ undergoes about 1% degradation during the process, while the Nafion matrix can be utilised several times without observable modification.

Reaction of cyclooctenes with singlet oxygen. Trapping of a perepoxide intermediate

The products and rate constants for total physical and chemical quenching (kq + kr) of singlet oxygen (1O2) by cis- and trans-cyclooctene were determined in two solvents of different polarity. Small amounts of cis-cyclooctene are produced during the reaction of the trans-isomer. In CDCl3 and acetone-d6, kq + kr for cis-cyclooctene was 1.3 × 104 M-1 s-1 while the rate constants (kr) for the reaction of trans-cyclooctene were 2.3 × 104 and 3.4 × 104 M-1 s-1, respectively. Competition experiments with 2-methyl-2-pentene (2M2P) suggest a substantial contribution of physical quenching for the trans-alkene while the cis-alkene removes 1O2 mostly by chemical reaction. The physical quenching of 1O2 by trans-cyclooctene is explained by a perepoxide intermediate which can open to a zwitterion that can abstract an allylic hydrogen to give the 3-hydroperoxycyclooctene ene product or isomerize and lose O2 to form cis-cyclooctene. A perepoxide intermediate can be trapped using triphenyl phosphite with trans-but not cis-cyclooctene. trans-Cyclooctene quenches 3C70 with a rate constant of 3.4 × 105 M-1 s-1.

Studies on the Autoxidation of Some Monocyclic Olefins

The autoxidations of cyclopentene, cyclohexene, cycloheptene, cyclooctene, cycloocta-1,5-diene, 1-methylcyclopentene, 1-methylcyclohexene, 1-methylcycloheptene, 1-methylcyclooctene, methylene cyclopentene, and methylene cyclohexene with pure oxygen under normal pressure were studied.The epoxides formed were determined gaschromatographically.In most cases also the products of allylic oxidation were analyzed and their structures elucidated after reduction to the corresponding allyl alcohols.The portions of high boiling or polymeric products which could not be detected gaschromatographically and also the real yields of epoxides were determined by balance experiments in the presence of inert internal standards.