Quinolines, alkylation amination

These include alkaloids and non-alkaloids that have phenolic functions in addition to a nitrogen atom. Even the alkaloids containing phenolic functions cannot be classified under one group. They may be phenyl alkyl amines, quinolines, isoquinolines, benzylisoquinolines [47-50], carbazole [51, 52] and others. However, they are included in this entry owing to their phenolic nature. Some of these compounds, like opium alkaloids, are of great medicinal importance. 

Primary candidates for the mutagens (and carcinogens ) responsible for activity in the basic fractions include quinoline, substituted quinolines, alkyl pyridines, acridines, aza-arenes, naphthylamines, and aromatic amines in the neutral fractions, potential hazards may be benzanthracenes, dibenzanthracenes, substituted anthracenes, benzopyrenes, benzofluorenes, pyrene, substituted pyrenes, and chrysenes. 

Reductive amination of dihydropyran (which may be regarded as the dehydration product of the cyclic acetal of 5-hydroxy-pentanal) in the presence of isopropylamine and a trace of acid affords the aminoalcohol, 96. Treatment of this compound with thionyl chloride affords the haloamine, 97. Alkylation of the quinoline, 92, with this halide yields pentaquine (98). ... 

Kuroda and Suzuki used reaction of 267a with 2-bromoaniline leading to anilide 312 as the first step of their sequence in the preparation of 1H-imidazo[4,5-c]quinolin-4(5//)-ones (Scheme 77) (91TL6915). Reaction of 267a with amines usually does not require any catalyst and/or base, but in this case use of sodium hydride was reported. The anilide 312 was sequentially alkylated, first with methyl iodide in ethanol with potassium hydroxide at room temperature and then with different alkyl iodides in acetone at reflux to provide intermediate 313. This compound was then cyclized via palladium catalyzed reaction leading to product 314. This reaction provides a new entry to l//-imidazo[4,5-c]quinolin-4(5//)-ones that are of current interest as antiasthmatic agents. 

Praziquantel Praziquantel, 2-(cyclcohexylcarbonyl)-l,2,3,6,7,llb-hexahydro-47f-pyrazino [2,la]isoquinolin-4-one (38.1.15), is a derivative of pyrazinoquinoline that is made in two ways [17-19], According to one of them, l-aminomethyl-l,2,3,4-tetrahydroiso-quinoline is alkylated with chloroacetic acid, and then the resulting amine is acylated with cyclohexanecarbonyl chloride to make l-(iV-carboxymethyl-iV-cyclohexylcarbonyl-aminomethyl)-l,2,3,4-tetra-hydroisoquinoline (38.1.14), which is heated at 150°C to give the desired praziquantel. 

H,6H-Purine, l,7-dimethyl-6-oxo-UV spectra, 5, 517 7H,8H-Purine, 8-oxo-UV spectra, 5, 517 Purinecarboxamides reactions, 5, 550, 551 Purinecarboxylic adds reactions, 5, 550 Purine-6-carboxylic acids synthesis, 5, 593 Purine-8-carboxylic acids synthesis, 5, 593 Purine nucleotides biosynthesis, 1, 87-88 Purine[9,8-a]quinolines, 5, 566 Purines, 5, 499-605 aldehydes reactions, 5, 549 synthesis, 5, 593 alkylation, 5, 505, 528-538 amination, 5, 541-542 anions... 

Particularly lightfast dyes such as 22 are obtained if 1-alkyl derivatives of 2,2,4-trimethyltetrahydro quinoline are used as amine components [50], This dye colors polyacrylonitrile a clear blue shade. 

The study of pyridine-piperidine reactions under high pressure conditions has given much information concerning the kinetics of HDN, but these results are however complicated by alkyl transfer (disproportionation) reactions, and thus the possibility of using such reactions as an easy test for determination of mechanism and as a catalyst probe is partly excluded. The study of polycyclic amines (quinoline, etc.) for the same purpose is limited by the complexity and the number of different possible routes, but is a very interesting test reaction for an overall study of catalytic activity or selectivity toward HDN in industrial conditions. Because no disproportionation occurs and the numbers of products and routes are reasonable, the studies of pyridine-piperidine and alkylpyridine-alkylpiperidine HDN under normal H2 pressure and low amine pressure (< lOTorr) are very powerful test reactions both for mechanism determination and catalyst study, although these conditions are far removed from those of industrial practice. 

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