Ethene derivatives, quinones

Figure 7.31 Ethane and ethene linkages derived from quinone methide structures.

DFT theory at the B3LYP/6-31G(d,p) level was used to investigate the Diels-Alder reactions of o-quinone methides with various ethenes. Calculations show that solvent decreases the activation energy and increase the asynchronicity.116 The Diels-Alder reaction of ortho-quinone methides derived from 3//-1,2-benzoxathiole 2,3-dioxides with maleimides produces chroman 2,3-dicarboxylic acid derivatives.117... 

Similar to ketones, quinones have also been known for a long time to undergo PET processes with several donors such as aromatic hydrocarbons, olefins and amines etc. [10b, 11]. It is pertinent here to illustrate one of the synthetically important quinone-olefin [186] reactions which has been utilized for the preparation of Benz (a) anthracene 7,12-dione derivatives (237). In the present example, the excited state of naphthaquinone (234) reacts with ethene (235) to give 236, provided the electron transfer is thermodynamically allowed (ca. AGet < 0). In the follow up processes, (236) is transformed to (237) in 30-50% yield. Another report from the same group has described [187] a novel method of photoallylation of naphthaquinone by allyl stannane. 

The photochemical addition of ethene at 0°C in methylene chloride to the enedione (77) affords a high yield of the adduct (78). This was converted to the monochloro derivative (79) which also undergoes photoaddition of ethene to yield the Z> adduct (80). This on elimination of HCl yielded the quinol (81) which can be oxidised to the quinone (82). Cycloaddition of alkenes (cyclopentene, cyclohexene, and cycloheptene) has been carried out to the same enedione (77) to yield the adducts (83). lyoda et al. have also described a convenient synthesis of the bicyclo-octanediones(84) by a photochemical addition of alkenes to the enedione (77). The adducts (84) can be reduced by zinc in acetic acid to the desired products. Cycloaddition of ethyne to the same enedione followed by reduction affords the bicyclooctanes (85). The photoaddition of alkenes to the dibromo-enedione (86) is also effective and yields, after reduction, the adducts (87). 

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