Thermolysis of 1,2,3-benzotriazin-4(3H)-one

Murray, Alistair; Vaughan, Keith

doi:10.1039/j39700002070

Cited by 11 publications

(20 citation statements)

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“…When 10a is treated with neat benzylamine, a vigorous exothermic reaction occurs, after a short induction period, and copious effervescence is observed. The solid product obtained from this reaction was not N-benzylanthranilamide but, surprisingly, was found to be the benzylammonium salt of anthranilic acid (12). The same salt was obtained when 10a and benzylamine reacted in acetonitrile solution.…”

Section: Fitzroy D Eddy Keith Vaughan Et Malcolm F G Stevens Canmentioning

confidence: 75%

Anthraniloylanthranilamide (o-amino-N-(o-carbamoylphenyl)benzamide): Preparation and use as a synthetic precursor for quinazolino[1,2,3]benzotriazinones

Eddy¹,

Vaughan²,

Stevens³

1978

Can. J. Chem.

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Several synthetic routes to anthraniloylanthranilamide (6) are described; the problems involved in o-aminobenzoylation reactions are explored. Reduction of N-(o-nitrobenzoyl)anthranilamide by stannous chloride gave a low yield of 6, which was also obtained in low yield by reaction of isatoic anhydride with o-aminobenzamide. The possible use of O-(o-aminobenzoyl)hydroxylamines for o-aminobenzoylation was investigated but proved impractical. Diazotisation of 6 affords 3-(o-carbamoylphenyl)-1,2,3-benzotriazin-4(3H)-one (2), which undergoes base-catalysed cyclisation to the quinazolino[3,2-c]benzotriazine (4). The conversion 2 → 4 probably involves the isomeric quinazolino[1,2-c]benzotriazine (3), which could not be isolated.

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Section: Fitzroy D Eddy Keith Vaughan Et Malcolm F G Stevens Canmentioning

confidence: 75%

Anthraniloylanthranilamide (o-amino-N-(o-carbamoylphenyl)benzamide): Preparation and use as a synthetic precursor for quinazolino[1,2,3]benzotriazinones

Eddy¹,

Vaughan²,

Stevens³

1978

Can. J. Chem.

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“…Only a small recovery of 13 was obtained when 1 and 13 were refluxed together in p-xylene and the only product in addition to 13 was the N-(oaminobenzoy1oxy)triazinone 6, the yield of which was greater than could be accounted for on the basis of the amount of 1 used. Evidently, at least some of 6 arises by direct interaction of 1 and 13. where the nucleo~hile 1 attacks the 4-0x0 group in 13, as observed previously in the reaction of benzotriazinone 13 with alcohols and other nucleophiles (13) [5].…”

mentioning

confidence: 49%

“…Filtration of the benzene solution and evaporation of the filtrate afforded n-amyl o-aminobenzoate (0.6 g, 9473, identical with an authentic sample (13).…”

Section: -Benzoyloxy-i23-benzotriazin-4-one 5cmentioning

confidence: 99%

“…Tlzernzolysis of 2 in Aniline 1 (0.5 g) was refluxed in freshly distilled aniline (20 ml) for 0.5 h. The excess aniline was removed under vacuum and the brown, gummy residue was triturated with benzene -petroleum ether to give a pale yellow solid, which was recrystallized from benzene -petroleum ether to afford N-phenylanthranilamide (0.252 g, 3573, mp 120°C, identical (ir spectrum) with an authentic sample (13). Anal.…”

Section: -Benzoyloxy-i23-benzotriazin-4-one 5cmentioning

confidence: 99%

“…Thermolyses of the latter in diglyme (13), and in reactive methylene compounds (16), have been shown to be bimolecular, whereas Herlinger (8) and Crabtree et al (9) have suggested that the ketenimine 11 is an intermediate in the thermolysis of benzotriazinone. Herlinger's hypothesis was based on the observation that thermolysis of 13 with phenyl isocyanate afforded the oxazinone 16, which was explained as a Diels-Alder adduct of the ketenimine and the isocyanate.…”

mentioning

confidence: 99%

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A study of 3-hydroxy-1,2,3-benzotriazin-4-one and its O-methyl and O-acyl derivatives

Ahern¹,

Navratil²,

Vaughan³

1977

Can. J. Chem.

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3-Hydroxy-1,2,3-benzotriazin-4-one, 1, was prepared by diazotization of o-aminob-enz-hydroxamic acid, 2. 3-Methoxy-1,2,3-benzotriazin-4-one, 5a, was obtained by reaction of 1 with dimethyl sulphate and was found to be stable to thermolysis. Acetylation and benzoylation of 1 yielded the N-acetoxy-5b and benzoyloxy-5c derivatives respectively. The N-benzoyloxy derivative 5c is converted into the acetate 5b by a novel 'acyl-exchange' reaction in acetic anhydride. Acid hydrolysis of 1 gives anthranilic acid, and thermolyses of 1 in amyl alcohol and aniline afford amyl anthranilate and N-phenylanthranilamide, respectively. The ketenimine 11 is postulated as an intermediate in the thermal breakdown of 1, and this is confirmed by the isolation of the Diels–Alder adduct 12 from reaction of 1 with phenyl isocyanate. Thermolysis of 1 in inert solvents affords a novel compound, 3-(o-aminobenzoyloxy)-1,2,3-benzotriazin-4-one, 6, which polymerizes when 1 is subjected to prolonged thermolysis in diglyme. 6 resisted methylation and acid hydrolysis, but underwent acyl-oxygen cleavage when diazotization of 6 was attempted and suffered 'acyl-exchange' when acylation was attempted. The formation of 6 from 1 also involves the ketenimine 11. The importance of these observations to an understanding of previously reported reactions of benzotriazinones is discussed. The o-aminobenzoyloxy derivative 6 shows potential as an o-aminobenzoylating agent.

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1996

Chemistry of Heterocyclic Compounds: A Series of Monographs

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Thermolysis of 1,2,3-benzotriazin-4(3H)-one

Cited by 11 publications

References 0 publications

Anthraniloylanthranilamide (o-amino-N-(o-carbamoylphenyl)benzamide): Preparation and use as a synthetic precursor for quinazolino[1,2,3]benzotriazinones

Anthraniloylanthranilamide (o-amino-N-(o-carbamoylphenyl)benzamide): Preparation and use as a synthetic precursor for quinazolino[1,2,3]benzotriazinones

A study of 3-hydroxy-1,2,3-benzotriazin-4-one and its O-methyl and O-acyl derivatives

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