Quinone imides, reactions

Corey s retrosynthetic concept (Scheme 9) is based on two key transformations a cationic cyclization and an intramolecular Diels-Alder (IMDA) reaction. Thus, cationic cychzation of diene 50 would give a precursor 49 for epf-pseudo-pteroxazole (48), which could be converted into 49 via nitration and oxazole formation. Compound 50 would be obtained by deamination of compound 51 and subsequent Wittig chain elongation. A stereocontroUed IMDA reaction of quinone imide 52 would dehver the decaline core of 51. IMDA precursor 52 should be accessible by amide couphng of diene acid 54 and aminophenol 53 followed by oxidative generation of the quinone imide 52 [28]. 

The final B ring formation by intramolecular N-alkylation requires a C2 side chain attached to the A ring of the C5-spiroisoquinoIine educt, e.g. 133. This has been similarly obtained as the related educt 119 (Scheme 16) by reaction of the lithiated phenethyl derivative 131 with the N-protected quinone imide ketal 132. After deprotection the crude amine undergoes cyclization to form the 15-0-methylerysodienone (134) in 80% yield (77) (Scheme 18). 

Adams R, Winnick CN (1951) Quinone imides. VIII. Synthesis and reactions of o-quinone diimides. J Am Chem Soc 73(12) 5687-5691. doi 10.1021/ja01156a058... 

The photoreduction of carboxylic acids and their derivatives has not been widely reported, although cyclic imides do behave like ketones in such reactions (4.39). Quinones are readily photore-duced, and this is of particular importance for anthraquinone dyes or pigments used on cellulose materials such as cotton. Some quinone dyes cause what is known as phototendering—the fabric progressively weakens and can be torn easily after exposure of the dyed... 

The most important applications of peroxyacetic acid are the epoxi-dation [250, 251, 252, 254, 257, 258] and anti hydroxylation of double bonds [241, 252, the Dakin reaction of aldehydes [259, the Baeyer-Villiger reaction of ketones [148, 254, 258, 260, 261, 262] the oxidation of primary amines to nitroso [iJi] or nitrocompounds [253], of tertiary amines to amine oxides [i58, 263], of sulfides to sulfoxides and sulfones [264, 265], and of iodo compounds to iodoso or iodoxy compounds [266, 267] the degradation of alkynes [268] and diketones [269, 270, 271] to carboxylic acids and the oxidative opening of aromatic rings to aromatic dicarboxylic acids [256, 272, 271, 272,273, 274]. Occasionally, peroxyacetic acid is used for the dehydrogenation [275] and oxidation of aromatic compounds to quinones [249], of alcohols to ketones [276], of aldehyde acetals to carboxylic acids [277], and of lactams to imides [225,255]. The last two reactions are carried out in the presence of manganese salts. The oxidation of alcohols to ketones is catalyzed by chromium trioxide, and the role of peroxyacetic acid is to reoxidize the trivalent chromium [276]. 

Quinoneimides add hydrazoic acid in a similar manner to quinones . The equilibrium in the amide-imide prototropic shift is more one-sided than that of the keto-enol system and thus, even in the naphthalene series, reaction with hydrazoic acid affords an azide (equation 83). 

Substrates for this type of cycloadditions are not limited to o-quinones and o-benzoquinone imides but can be extended to o-benzoquinone diimides also. In a preliminary study, it was found that some unidentified byproducts as well as the desired quinoxalinone were formed, which made the reaction sluggish and resulted... 

Aryl isocyanates react at elevated temperatures with benzoquinone to give p-quinone-bis-imides with elimination of carbon dioxide. When the reaction of 2,5-dihydroxy-1,4-benzoquinone with aryl isocyanates is conducted in DMSO, in the presence of triethylamine, addition across the C=C bond occurs with formation of the rearrangement products, 2,5-dihydroxy-3,6-bis(anilinocarbonyl)-l,4-benzoquinones in 19-68 % yields ". ... 

---