Quinoline Reissert compounds

In the early days, greatest interest was focused on the acid-catalyzed hydrolysis (by hydrochloric acid in the presence of 2,4-dinitrophenylhydrazine) of Reissert compounds to aldehydes and the corresponding heterocyclic carboxylic acid derivatives. This reaction is fairly general for compounds of quinoline (178) and isoquinoline (179) (Table 18), but it is not applicable to pyridines as they rarely form Reissert compounds. The 3-hydroxyquino-line Reissert compound does not yield benzaldehyde, probably because acylation of the 3-hydroxy group prevents formation of the required cyclic intermediate (180). Some nitroquinolines and isoquinolines give low yields of benzaldehyde. Rather curiously, disub-stituted quinoline Reissert compounds yield less of the aldehyde than of the corresponding... 

Reactions of quinoline Reissert compounds were less satisfactory than those of the corresponding isoquinolines. The hydrochloride of 64 with DMAD gave 65 in only 7% yield in methylene chloride ethanol, and 10% in DMF. From a study of the mechanism of the 1,3-dipolar addition of Reissert salts to arylpropiolate esters, McEwen et a/.499 concluded that a concerted cyclization was more probable than a two-step process. 

Photolysis of the quinoline Reissert compound (7) showed a marked dependence on the wavelength of the ultraviolet source. With 2537 A light in acetonitrile an 8 % yield of 2-cyanoquinoline and a trace of... 

Polymeric aldehydes such as47 ° and poly(vinylbenzaldehyde-co-vinylbenzaldehyde hydrate) react with 26 to give polymers such as 48. The anion of the quinoline Reissert compound (1) reacts with 47 to give a similar polymer. ... 

Treatment of the Reissert compound derived from 4-chloroisoquinoline with phosphorus pentachloride yielded 4-chloro-l-cyanoisoquinoline. Similar treatment of the benzo[/]quinoline Reissert compound gave a mixture of nitrile and amide." The Reissert compound from 2-bromo-benzo[/]quinoline with thionyl chloride gives 2-bromo-3-cyanobenzo-[/]quinoline." Oxidation of a Reissert compound in the presence of 50% sodium hydroxide and a phase transfer catalyst also gives the isoquinaldonitrile. ... 

The anion of the isoquinoline Reissert compound (26) has also been alkylated with a wide variety of other alkyl halides.519-35 38 48-62-66,90 93 The alkylation product from 26 and allyl chloride undergoes isomerization to 38 on base-catalyzed hydrolysis.90 The phthalazine Reissert compound (3) has also been alkylated, in the presence of sodium hydride, with methyl iodide39 and with benzyl halides40 to give, after hydrolysis, 1-substituted phthalazines. A phthalazine analog of 34 (n = 3) has been prepared.1511 An additional example of the alkylation of the quinoline Reissert compound in the 4-position has appeared.943... 

Treatment of the isoquinoline Reissert compound (2) with sodium hydride in dimethylformamide,96 with 50% aqueous sodium hydroxide-TEBA chloride,61 or with 50% aqueous sodium hydroxide-TBA chloride963 and an activated aryl halide, such as 2,4-dinitrofluorobenzene,96 2-bromo-3-nitropyridine,96 4-nitrochlorobenzene,61 t-butyl 2-chloro-5-nitrobenzoate,61 2-chloro-3-nitropyridine,963 4-chloro-3-nitropyridine,96a or 9-chloroacri-dine96b leads to the arylation product 43. Arylation of the quinoline Reissert compound (1) with 4-nitrofluorobenzene in the presence of sodium hydride in dimethylformamide leads to 44.96 It should be noted that alkylation of... 

Hydrogenation of several 6- and 7-substituted quinoline Reissert compounds (1) in the presence of Raney nickel leads to the 2-aminomethyl-1,2,3,4-tetrahydroquinoline derivatives 68.114 A similar reduction of the Reissert compound derived from benzo[/]quinoline, followed by reaction of the crude product with carbon disulfide, gave the diazacyclopentaphenan-threne derivative 69.115... 

Monographs on Contemporary Heterocyclic Chemistry and quinoline chemistry have appeared. The latter work contains reviews on alkyl- and aryl-quinolines, Reissert compounds and related dihydroquinolines, and quinoline N-oxides. The chemistry of quinolizines, 0 1, 7-naphtliyridines, azaphenalenes, 2... 

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