Peroxides from dienes

This sequence has been used for preparation of other more elaborate endo-peroxides from dienes. ... 

Vanadium oxide dichloride Cyclic peroxides from dienes Double ring closure... 

Unsaturated transaimular peroxides from cycHc dienes have been selectively reduced to the saturated peroxide analogues (114). For example. 

In contrast to this formation of polymeric peroxides from olefins and oxygen, photosensitized autoxidation of dienes leads to cyclic monomeric... 

By-products formed during their preparation (e.g., ethylbenzene and divin-ylbenzenes in styrene acetaldehyde in vinyl acetate) added stabilizers (inhibitors) autoxidation and decomposition products of the monomers (e.g., peroxides in dienes, benzaldehyde in styrene, hydrogen cyanide in acrylonitrile) impurities that derive from the method of storage of the monomer (e.g., traces of metal or alkali from the vessels, tap grease etc.) dimers, trimers, and polymers that are generally soluble in the monomer, but sometimes precipitate, for example, polyac-rylOTiitrile from acrylonitrile. Likewise, in polycondensation reactions it is important to remove reactive impurities because they can cause considerable interference during the polyreaction. 

Cation radicals are strongly implicated In the series of catalysts discovered by Barton and coworkers (38) which, sone photochemlcally and some thermally, produce peroxides from ergosteryl acetate and other dienes In methylene chloride at -TS. ... 

Ethylene-propylene-diene rubber is polymerized from 60 parts ethylene, 40 parts propylene, and a small amount of nonconjugated diene. The nonconjugated diene permits sulfur vulcanization of the polymer instead of using peroxide. 

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). 

The thermal fragmentation of unsaturated bicyclic 1,4-peroxides, often readily made from 1,4-dienes (Scheme 84), has become an important route to novel bis(oxiranes) (80T833, 81CRV91). 

As in the case of the steroids, introduction of additional nuclear substituents yields morphine analogs of increased potency. The more important of these are derived from one of the minor alkaloids that occur in opium. Thebaine (14), present in crude opium in about one-tenth the amount of morphine, exhibits a reactive internal diene system that is well known to undergo various addition reactions in a 1,4 manner (e.g., bromination). Thus, reaction with hydrogen peroxide in acid may be visualized to afford first the 14-hydroxy-6-hemiketal (15). Hydrolysis yields the isolated unsaturated ketone (16). Catalytic reduction... 

Bengal, Methylene Blue, haematoporphyrin and tetraphenylporphyrin and, generally, in organic solvents. Some examples are illustrated in Scheme 4.15. Peroxide products obtained from fatty acid precursors [61] or from cyclopenta-dienes [62] are of interest as pharmaceuticals or for biomedical studies others are versatile starting materials for further transformation. 

The primary interaction of singlet oxygen, produced by energy transfer from the excited sensitizer, with the diene can give rise to an exciplet that then collapses to peroxide, to a 1,4-biradical or to a 1,4-zwitterion alternatively, the adduct is the result of a concerted action without the involvement of an intermediate. Detailed kinetic Diels-Alder investigations of singlet oxygen and furans indicate that the reactions proceed concertedly but are asynchronous with the involvement of an exciplex as the primary reaction intermediate [63]. 

The peroxide-catalysed addition of dimethyl phosphonate to norborna-diene gives nortricyclenes as well as norbornenes. Usually, radicals react with this diene to give only nortricyclene derivatives. The ease of hydrogen abstraction from the parent phosphonate undoubtedly favours trapping of radical (8). 

This discussion of the structures of diene polymers would be incomplete without reference to the important contributions which have accrued from applications of the ozone degradation method. An important feature of the structure which lies beyond the province of spectral measurements, namely, the orientation of successive units in the chain, is amenable to elucidation by identification of the products of ozone cleavage. The early experiments of Harries on the determination of the structures of natural rubber, gutta-percha, and synthetic diene polymers through the use of this method are classics in polymer structure determination. On hydrolysis of the ozonide of natural rubber, perferably in the presence of hydrogen peroxide, carbon atoms which were doubly bonded prior to formation of the ozonide... 

Second-derivative spectrophotometry has been used to monitor the time-dependent production of cis,tmns-(Xmax 242 nm) and trans, tram- (Xmax 232 nm) diene conjugates of microsomal PUFAs following the exposure of rats to carbon tetrachloride (CCU) (Corongui et al., 1986). These signals have been postulated to be derived from mixtures of peroxidized substrates. Previous studies using chemical model systems have established that autoxidation of linolenic or arachidonic acid results in the production of cis, trans- and tmns, trawr-conjugated diene... 

There is some support for a role for free radicals in the pathogenesis of ischaemic colitis from animal studies. Murthy and Qi (1992) used a spin trap to demonstrate increased production of free radicals up to 60 min after reperfusion, whereas Douglas etal. (1989) demonstrated increases in malondialdehyde and conjugated dienes (presumptive measures of lipid peroxidation) in a rat model of ischaemic colitis. There is no data relating to human ischaemic colitis. 

The reactions were cleaner than those with cis,cis-1,5-cyclooctadiene, and purification of the intermediate bis-mercurated peroxide was unnecessary. Indeed, it was a simple matter to isolate 52 (28 %) and 53 (38 %) from crude products obtained using a sample of 1,4-cyclooctadiene containing 30% of cis,cis-1,5-cyclooctadiene, which is readily accessible via hydrobromination-dehydrobromination of the 1,5-diene. Two of the diastereoisomers of 53 were separately isolated by HPLC and the most... 

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