273. Heterocyclic imines and amines. Part X. 1,3-Diaminoisoquinoline, and the fine structures of related nitroso-compounds and pyridine derivatives

Cox, Jason M.; Elvidge, J. A.; Jones, David E. H.

doi:10.1039/jr9640001423

Cited by 13 publications

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“…[6]. O n the other hand, it has been shown that 4- (47,48) solution. Hence, an explanation of the peculiar ionization behaviour of the 4-amino (and 2-amino) pyridinium cation on the basis of a strong dependence of the tautomeric equilibrium of eq.…”

Section: Referencesmentioning

confidence: 99%

Solvent effect on preferred protonation sites in nicotinate and isonicotinate anions

Hallé¹,

Lelièvre²,

Terrier³

1996

Can. J. Chem.

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Potentiometric determinations of the two successive acidities of nicotinic and isonicotinic acids (AH,') have been carried out in aqueous dimethyl sulfoxide mixtures containing up to 95% Me2S0 by volume. In both systems, the results reveal that the addition of Me,SO induces a proton transfer from the pyridinium ring to the carboxylate group, the tautomeric equilibrium between the neutral forms of the two acids being displaced toward the zwitterionic form (AH') in aqueous solution, but toward the molecular form (AH0) in Me,SO. An analysis of the data by means of Hammett relationships previously established for benzoi'c acids over the whole range of H,O/Me,SO mixtures allowed the four microscopic acidity constants as well as the tautomeric equilibrium constant KT pertaining to the complete ionization scheme of the two acids to be determined. At 20°C, there are equal populations of the tautomeric AH0 and AH' species in the mixtures containing 38 and 47% Me,SO for the nicotinic and isonicotinic systems, respectively. Hammett relationships describing the ionization behaviour of a number of substituted pyridinium cations in H,O/Me,SO mixtures are also discussed. Possible reasons accounting for the peculiar effects exerted by the NH,, CONH,, and COOH substituents on the process are suggested.Key words: nicotinic and isonicotinic acids, substituted pyridines, acidities, tautomeric equilibrium, protonation sites, water -dimethyl sulfoxide mixtures.Resume : Les deux aciditts successives des acides nicotinique et isonicotinique (AH,' ) ont Cte determinees par potentiometrie dans des milieux eau-dimCthylsulfoxyde contenant jusqu'a 95% de Me,SO en volume. L'addition de Me,SO provoque le transfert protonique du cycle pyridinium vers le groupement carboxylate, de sorte que la forme zwitterionique AH*, trks majoritaire dans I'eau, ckde progressivement la place B la forme molCculaire AH0 qui devient unique dans le dimethylsulfoxyde. Le traitement des resultats, h I'aide des relations de Hammett d'energie libre prealablement Ctablies pour les acides benzo'iques dans les mtlanges H,O/Me,SO, permet les determinations des quatre constantes microscopiques et de la constante de tautomtrie KT decrivant le schema des ionisations successives de ces deux diacides. A 20°C, on a CgalitC entre les populations des formes zwitterionique (AH') et molCculaire (AH0) dans 1es milieux contenant respectivement 38% (acide nicotinique) et 47% (acide isonicotinique) de MezSO en masse. Les relations de Hammett d'Cnergie libre, dtcrivant l'ionisation d'un grand nombre de pyridines substituCes dans IesmClanges H20/Me,S0, sont discuttes. Les effets particuliers observes pour les substituants NH,, CONH, et COOH sont analysts.

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Section: Referencesmentioning

confidence: 99%

Solvent effect on preferred protonation sites in nicotinate and isonicotinate anions

Hallé¹,

Lelièvre²,

Terrier³

1996

Can. J. Chem.

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“…1,3-Diaminoisoquinoline (32) in the NaNO 2 /HCl/EtOH/H 2 O system gives the oxime 33 with an 86% yield. This oxime was also obtained by nitrosation of isoquinoline-1,3-dione (34) [38] …”

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Quinoline Oximes: Synthesis, Reactions, and Biological Activity. (Review)

Абеле

Lukevics

2005

Chem Heterocycl Compd

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Data on the production and the reactions of quinoline aldoximes and ketoximes and their derivatives are reviewed. The synthesis of new heterocycles based on quinoline oximes is examined separately. The main results from investigation of the biological activity of quinoline oximes are presented.Quinoline oximes are widely used as intermediates in organic synthesis. In the present paper the principal methods for the production of quinoline oximes and their reactions are reviewed. Methods for the synthesis of new heterocyclic systems from derivatives of these oximes are considered under a separated heading. The principal methods for investigation of the structure of quinoline oximes with regard to isomerism are also briefly discussed. In the last section the results from investigation of the biological activity of the derivatives of quinoline oximes are described.

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“…spectrum showed two cyano groups with characteristically low wave numbers, l and the presence of a primary amino function. absorption for imine, cyano, and y-lactam carbonyl groups, and the yellow colour characteristic also of the related 12-phenylisoindolo [2,I-b]isoquinol-7(5H)-one and -5,7-dioneY A methoxy analogue of the isoquinoline (19) was obtained by addition of o-cyanobenzyl cyanide to the dicyanostilbene (7) in the presence of methoxide, indicating that the foregoing preparation of the isoquinoline (19) could be extended. spectrum (in MeCN) at 8 6.46 which was eliminated on shaking the deuteriochloroform solution with deuterium oxide.…”

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“…That the cyc1isation-dehydrogenation reactions with alkoxides (and sodamide) were not unique to the dicyanostilbene (I) was shown by the analogous behaviour of the pmethoxy analogue (7) with methoxide in methanol to yield 4-cyano-l-methoxy-3-(4-methoxyphenyl)isoquinoline (11; R = Me, Ar = p-C6H40Me). This last, with hot aqueous acid, yielded the corresponding isoquinolin-l(2H}-one (12; Ar = p-C6H 40Me).…”

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confidence: 99%

“…When heated to 210°C, the amino acid (18) lost water, giving the expected y-lactam C I7H 9N 30, with structure (20), as indicated by the sharp i.r. absorption for imine, cyano, and y-lactam carbonyl groups, and the yellow colour characteristic also of the related 12-phenylisoindolo[2,I-b]isoquinol-7(5H)-one and -5,7-dioneY A methoxy analogue of the isoquinoline (19) was obtained by addition of o-cyanobenzyl cyanide to the dicyanostilbene (7) in the presence of methoxide, indicating that the foregoing preparation of the isoquinoline (19) could be extended.…”

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Heterocyclic imines and amines. Part 19. Isoquinoline and other products from α,o-dicyanostilbene and basic reagents

Barnard¹,

Elvidge²

1983

J. Chem. Soc., Perkin Trans. 1

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a,o-Dicyanostilbene (1) was cleaved by hydrazine or hydroxylamine under mildly acid conditions to 0cyanobenzyl cyanide (2) and benzaldehyde, isolated as derivatives. Sodamide with compound (1) gave 1-amino-4-cyano-3-phenylisoquinoline: alkoxides similarly gave the 1 -alkoxy compounds, the presumed intermediate 3,4-dihydroisoquinoline from the methoxide reaction being isolated and separately dehydrogenated. Acid hydrolysis of the 1-ethoxy compound gave the known 4-cyano-3-phenylisoquinolin-1 (2H)-one. With the anion of o-cyanobenzyl cyanide, compound (1) gave a 1-amino-4-cyano-3-(2substituted phenyl)isoquinoline, which was oxidised to 1-amino-4-cyano-3-(2-carboxyphenyl)isoquinoline. The latter lost water at 210 ·C to give yellow 12-cyano-5-iminoisoindolo[2, 1-b]isoquinolin-7 (5H) -one, closely related to known compounds.Many 1,2-and 1,3-dicyano compounds add basic reagents to form heterocyclic products. 2 In continuing studies in this field, we have examined the behaviour of a,o-dicyanostilbene (1) towards hydrazine, hydroxylamine, sodamide, sodium ethoxide, and the anion of o-cyanobenzyl cyanide: isoquinoline products arise. The starting 1,3-dicyanide (1) is readily accessible 3 through Knoevenagel condensation of benzaldehyde with o-cyanobenzyl cyanide (2).

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273. Heterocyclic imines and amines. Part X. 1,3-Diaminoisoquinoline, and the fine structures of related nitroso-compounds and pyridine derivatives

Cited by 13 publications

References 0 publications

Solvent effect on preferred protonation sites in nicotinate and isonicotinate anions

Solvent effect on preferred protonation sites in nicotinate and isonicotinate anions

Quinoline Oximes: Synthesis, Reactions, and Biological Activity. (Review)

Heterocyclic imines and amines. Part 19. Isoquinoline and other products from α,o-dicyanostilbene and basic reagents

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