Alkenes myrcene

Conjugated dienes take part readily in triplet-sensitized photodimerization. and the products obtained from buta-1.3-diene (2.691 include a (4 + 2) adduct as well as slereoisomeric (2 + 2) adducts. The reaction is non-concerted. and a rationalization for the products is provided on the basisof the formation of a biradical intermediate as shown (which is the most stable of the three possible biradicals that might be formed in the first step), by the attack of triplet diene on ground-state diene. Cross-addition takes place in some systems, such as myrcene (2.70) where a triplet diene group attacks the alkene within the same molecule direct irradiation of myrcene gives mainly... 

Alkyl tethered alcohols such as D-mannitol and L-erythritol [20], have been used to bring cinnamyl units together for photocycloadditions. However, this probably involves cycloaddition between an excited enone moiety and the tethered alkene. Other examples of carbon linked alkenes include perhaps the earliest example of alkene+alkene photocycloaddition. Liu and Hammond [21] reported the formation of cyclobutane from the triplet irradiation of myrcene (see Sch. 11). 

The photo-NOCAS process has also been reported with P-myrcene (57) as the reactant. The resultant radical cation, generated using dicyanobenzene as the sensitiser, affords the five products (58-62) shown and cyclization within the myrcene radical cation is an essential feature of this reaction sequence. SET photochemistry of aliphatic electron donors can provide a source of radicals. Thus irradiation of donors such as (63), (64), (65) and (66) results in bond fission and the formation of alkyl radicals which undergo addition to alkenes e.g. 67) or alkynes e.g. 68) to give the adducts (69) and (70), respectively. ... 

The iron tricarbonyl unit has been described as a protecting group for a 1,3-diene, as in the acetylation of the complex of myrcene at low temperature (Scheme 20). The usual combinations of a,p- and p,"y-un-saturated ketones were formed. At higher temperatures, some acylation at the terminus of the diene complex was also observed. In an interesting extension, reaction of the complex with oxalyl chloride resulted in cyclization of the acid chloride initially formed by reaction at the alkene. ... 

Alkenes (e.g. camphene) are readily prepared by the BF3,Et20-catalysed elimination of secondary borate esters.Terminal conjugated dienes may be prepared by Pd(OAc)2-PPh3-catalysed elimination from allyl phenyl ethers or allylic acetates [e.g. geranyl, neryl, and linalyl acetates to form similar mixtures of myrcene (60—74%), trans-ocimene (8—20%), and c -ocimene (14—20%)], and the complex [(i7-CsH5)Cr(NO)2]2 dehalogenates n/c-dihalides (e.g. limonene tetrabromide) without affecting other halides (except for benzyl halides). 

Olefins react extremely rapidly with HO, with most rate constants within an order of magnitude of the diffusion-controlled limit (Atkinson, 1986). Probably the most reactive hydrocarbon yet tested is the monoterpene myrcene (18), with two vinyl groups and a trisubstituted double bond. It reacts with OH about three times as fast as isoprene and about thirty times as fast as ethylene (Altshuller, 1983). Aromatic compounds usually react somewhat faster than alkanes and somewhat slower than alkenes. 

Since nonaromatic compounds do not usually exhibit strong peaks corresponding to cleavage of an allylic bond, the locations of double bonds in alkenes is difficult. However, in specific cases such as myrcene, which has a doubly allylic bond, cleavage may be highly favored. An intense C5H9+ ion (miz 69) is formed from myrcene (Equation 2.39), but it is not formed from the isomeric compound allo-ocimene (Equation 2.40). 

Several forms of aging of SOA vapors have been observed. One clear form is oxidation of multiply unsaturated alkenes. Many terpenes have multiple unsaturations, and in some cases different double bonds have very different rate constants for reaction with ozone. Examples include terpinolene, myrcene, hmo-nene, a-humulene, and p-caryophyllene [149, 150]. In these systems, ozone will react with one double bond in the terpene and produce some SOA. However, after the precursor is completely removed, SOA levels can continue to rise as the first-generation semi-volatile products continue to react with ozone to produce less volatile second-generation products [149]. 

Increasing the concentration of triphenylphosphane was found to accelerate the rhodium-catalyzed hydroformylation of conjugated dienes, such as isoprene and myrcene. The hydroformylation of the nonconjugated diene, limonene, followed a contrary tendency common to the most of alkenes [57,58]... 

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