Thermolysis of isatoic anhydride and benzotriazinone

Smalley, R. K.; Suschitzky, H.; Tanner, E. M.

doi:10.1016/s0040-4039(01)82812-4

Cited by 37 publications

(12 citation statements)

References 5 publications

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“…Pyrazolotriazinone 4 could undergo nitrogen extrusion by a retro‐Diels–Alder reaction, as was proposed for the thermolysis of pyrrolotriazines 9 , or following ring‐opening, as was proposed for the photochemical reactions of benzotriazinones . Elimination of nitrogen from 4 could lead to the imidoylketene 6 or even an azetinone intermediate, which can coexist in equilibrium , . These intermediates could react with a nucleophile, in this case a second molecule of 4 or a better suited tautomer of it, to give the final product 5 .…”

Section: Resultsmentioning

confidence: 92%

“…[17] Elimination of nitrogen from 4 could lead to the imidoylketene 6 or even an azetinone intermediate, which can coexist in equilibrium. [15,[18][19][20][21][22] These intermediates could react with a nucleophile, in this case a second molecule of 4 or a better suited tautomer of it, to give the final product 5. Similar nucleophilic reactions have previously been reported for benzoazetinones to give aminobenzamides and anthranilate esters.…”

Section: Resultsmentioning

confidence: 99%

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Thermal Ring‐Opening of Pyrazolo[3,4‐d][1,2,3]triazin‐4‐ones: An Experimental and Theoretical Study

et al. 2018

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Several 3‐pyrazolylcarbonyl‐pyrazolo[3,4‐d][1,2,3]triazin‐4‐ones have been prepared from 5‐amino‐1H‐pyrazole‐4‐carbonitriles through a simple sequence. In the first step, diazotization of the corresponding aminopyrazoles afforded pyrazolo[3,4‐d][1,2,3]triazin‐4‐ones. Next, thermal rearrangement of these compounds through nitrogen elimination gave the final products. The proposed mechanism for the ring‐opening of the pyrazolotriazinones to give the pyrazolylcarbonyl‐pyrazolotriazinones involves the generation of an iminoketene intermediate, which reacts with a second molecule of pyrazolotriazinone. The complete mechanism of product formation involving the iminoketene intermediate, and all other reasonable pathways, have been explored in detail through DFT calculations. Furthermore, additional experiments to corroborate the presence of the iminoketene intermediate were carried out.

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Section: Resultsmentioning

confidence: 92%

Section: Resultsmentioning

confidence: 99%

Thermal Ring‐Opening of Pyrazolo[3,4‐d][1,2,3]triazin‐4‐ones: An Experimental and Theoretical Study

et al. 2018

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“…On the other hand, isatoic anhydrides are extensively utilized as common building blocks in the synthesis of various heterocyclic systems, such as quinazolines, quinazolinones and benzodiazepines . They also undergo decarboxylation under thermal conditions giving highly reactive keteneimines . Alternative decarboxylation of isatoic anhydrides by the catalytic addition of Ni 0 complexes was reported by Matsubara and co‐workers to prepare quinolone and indole derivatives…”

Section: Methodsmentioning

confidence: 99%

“…[20] They also undergo decarboxylation under thermalc onditions giving highly reactive keteneimines. [21] Alternative decarboxylationo fi satoic anhydrides by the catalytic addition of Ni 0 complexes was reported by Matsubara and coworkers to preparequinolonea nd indole derivatives. [22] These reports on isatoic anhydrides and our interest in Rhcatalyzed insertionr eactions [23] prompted us to explore their reactivity in Rh-catalyzed denitrogenative reactiono ft riazoles.…”

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confidence: 99%

Rh‐Catalyzed Denitrogenative Reaction of N‐Sulfonyl‐1,2,3‐triazoles with Isatoic Anhydrides and Oxadiazolones

Pal

Hoque

Volla

2017

Chemistry A European J

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A convenient and simple, Rh -catalyzed denitrogenative method for the synthesis of biologically interesting 2-amino-benzoxazinones and 5-amino-oxadiazoles from readily available isatoic anhydrides and oxadiazolones has been developed. These reactions proceed via an O-H insertion onto α-imino Rh -carbenoid species followed by a rearrangement. The scope of the reaction can also be extended to benzoxazinones to access amino-substituted benzoxazines.

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“…or their derivatives, are so reactive that their ephemeral existence has only been detected by chemical trapping (see, for example, refs. [3][4][5][6] or by the nature of further transformation products dS , -ds 2 Dime.…”

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confidence: 99%

The synthesis, thermochromism, and cycloadditive properties of an O-methylenethioquinone system

Mayo¹,

Ng²

1977

Can. J. Chem.

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). The irradiation of 4,5-benzo-1,2-dithiole-3-thione (1) in the presence of cyclopentene and of tetramethylethylene gives 1 : 1 adducts. In solution these adducts are in equilibrium with eightmembered-ring dimers. The thermodynamic parameters for this equilibrium have been determined. The available evidence suggests a head-to-head configuration. These same monomeric adducts give Diels-Alder addition products with normal dienophiles, but also react similarly with simple thiones (adamantanethione, norbornanethione, cyclohexanethione) to give thioorthoesters. The structures of the latter substances have been demonstrated both spectroscopically and, chemically, by hydrolysis to a thiosalicylic acid derivative. The thioorthoesters have been show11 to undergo stereoisomerization on acid catalysis. Of the two mechanisms considered for this process (reversal to thiones and ion-pair formation) the former has been excluded. P. DE MAYO et H. Y. NG. Can. J. Chem. 55,3763 (1977). L'irradiation du benzo-4,5 dithiol-1,2 thione-3 (1) en presence de cyclopentene et de tetramCthyltthylene conduit a des adduits 1 :l. En solution, ces adduits sont en equilibre avec des dimeres cycliques a huit chainons. On determine les parametres thernlodynamiques pour ces Cquilibres. L'indice connue est en faveur d'une configuration ttte a ttte. Ces mtmes adduits monomeres donnent des produits d'addition Diels-Alder avec des diCnophyles normaux, mais ils rkagissent d'une maniere analogue avec des thlones simples (adamantanethione, norbornanethione, cyclohexanethione) pour conduire a des thioorthoesters. On determine la structure de ces derniers spectroscopiquement et chimiquement en les hydrolysant en derives d'acide thiosalicylique. Les thioorthoesters demontrent une tendance a la stereoisom6risation lors d'une catalyse acide. Deux mtcanismes sont envisages pour ce processus; ]'inversion en thiones et la formation d'une paire d'ions; seul le dernier est retenu.[Traduit par le journal]

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Thermolysis of isatoic anhydride and benzotriazinone

Cited by 37 publications

References 5 publications

Thermal Ring‐Opening of Pyrazolo[3,4‐d][1,2,3]triazin‐4‐ones: An Experimental and Theoretical Study

Thermal Ring‐Opening of Pyrazolo[3,4‐d][1,2,3]triazin‐4‐ones: An Experimental and Theoretical Study

Rh‐Catalyzed Denitrogenative Reaction of N‐Sulfonyl‐1,2,3‐triazoles with Isatoic Anhydrides and Oxadiazolones

The synthesis, thermochromism, and cycloadditive properties of an O-methylenethioquinone system

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