5-(Arylamino)-1,2,3-triazoles and 5-amino-1-aryl-1,2,3-triazoles from 3-(cyanomethyl)triazenes

Baines, Kim M.; Rourke, Timothy W.; Vaughan, Keith; Hooper, D. L.

doi:10.1021/jo00318a006

Cited by 34 publications

(17 citation statements)

References 3 publications

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“…O mecanismo da reação proposto por Vaughan e colaboradores 70 baseia-se no equilíbrio tautomérico anelar. Ocorre clivagem do anel 5-amino triazólico IV, levando à diazoimina VI que, por ciclização, gera os 5-amino-1-aril-1,2,3-triazóis 88a e 88b (Esquema 24).…”

Section: Ciclização De Triazinasunclassified

Heterociclos 1,2,3-triazólicos: histórico, métodos de preparação, aplicações e atividades farmacológicas

Melo¹,

Donnici²,

Augusti³

et al. 2006

Quím. Nova

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Recebido em 7/4/05; aceito em 21/7/05; publicado na web em 16/2/06 1,2,3-TRIAZOLIC HETEROCYCLES: HISTORY, PREPARATIONS, APPLICATIONS AND PHARMACOLOGICAL ACTIVITIES. The 1,2,3-triazole, known since the end of 19 th century, is a very widely used heterocyclic system present in many synthetic substances and commercial pharmaceutical compounds. In fact, 1,2,3-triazoles show several applications in many areas especially as medicines against many diseases like cancer, AIDS, Parkinson and Alzheimer. Nowadays there is a large variety of known methods to obtain these heterocyclic compounds comprising mainly three synthetic routes. Nevertheless, there is no article that gives an objective overview of the synthetic methods for obtaining these kinds of azoheterocycles. This paper presents a brief history of this class of compounds, and a synthetic discussion concerning the main synthetic methods for its preparation, such as cyclization through hydrazones, concerted cycloadditon [2+3] and pseudopericyclic cyclization -and some others of restricted application, but also important. Finally, this paper also provides a brief overview on pharmacological applications of some 1,2,3-triazoles.

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Section: Ciclização De Triazinasunclassified

Heterociclos 1,2,3-triazólicos: histórico, métodos de preparação, aplicações e atividades farmacológicas

Melo¹,

Donnici²,

Augusti³

et al. 2006

Quím. Nova

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“…The diazonium salt, Ar-N2+ClP, was prepared in the conventional manner by reaction of the appropriate arylamine in hydrochloric acid with sodium nitrite at low temperature, and then coupled with either methyl 3-aminocrotonate (1) or 3-aminocrotonitrile (2). Neutralization of the resulting solution gave a high yield of a single yellow product, which could be readily purified by recrystallization.…”

Section: Resultsmentioning

confidence: 99%

Formation of methyl 2-arylhydrazono-3-oxobutanoates and 2-arylhydrazono-3-oxobutanenitriles during the coupling reaction of arenediazonium ions with methyl 3-aminocrotonate and 3-aminocrotononitrile

Brown¹,

Jollimore²,

Merrin³

et al. 1995

Can. J. Chem.

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Reaction of aryldiazonium salts with methyl 3-arninocrotonate (I) affords high yields of the methyl 2-arylhydrazono-3-oxobutanoates (4); analogous diazonium coupling with 3-aminocrotononitrile (2) gives the 2-arylhydrazono-3-oxobutanenitriles (5). The hydrazones are the product of diazonium coupling at the C2-vinylic carbon, concomitant with hydrolysis of the 3-amino substituent to the 3-0x0 derivative; there is no evidence for the formation of a triazene (6), which would be the product of N-coupling. All hydrazones (4a-e and 5a-6) have been fully characterized by IR and 'H and I3c NMR spectroscopy; the NMR spectra of the methyl 2-arylhydrazono-3-oxobutanoates (4) suggest the presence of two isomeric intramolecularly H-bonded forms in solution. Selected compounds were further characterized by elemental analysis and mass spectrometry. A mechanism is proposed for the conversion of 1 or 2 into 4 or 5, and these observations are compared with previously reported observations of diazonium coupling reactions with unsaturated systems.Key words: hydrazone, diazonium, aminocrotonate, aminocrotononitrile, hydrogen bonding.R6sum6 : La rtaction des sels aryldiazoniums avec le 3-aminocrotonate de mtthyle (1) conduit avec d'excellents rendements aux 2-arylhydrazono-3-oxobutanoates de mtthyle (4); des couplages analogues de diazoiques avec le 3-aminocrotonitrile (2) donne les 2-arylhydrazono-3-oxobutanenitriles (5). Les hydrazones sont les produits du couplage des diazoiques au niveau du carbone vinylique C2, suivi de I'hydrolyse du substituant 3-amino qui conduit au dtrivt 3-0x0; il n'y a pas de preuve de la formation d'un triazkne (6) qui pourrait &tre le produit du couplage avec l'azote. On a caracttrist complktement toutes les hydrazones (4a-e et 50-6) par la spectroscopie IR et de RMN du 'H et du 13c. Les spectres de RMN des 2-arylhydrazono-3-oxobutanoates de mtthyle (4) suggkrent la prksence de deux formes isomkres en solution lites par des liaisons hydrogenes intramoltculaires. On a de plus caracttrist les composts choisis par l'analyse tltmentaire et par la spectromttrie de masse. On propose un mkcanisme pour la transformation du compost 1 ou 2 en compost 4 ou 5 et on a compark ces observations avec les observations rapporttes anttrieurement sur le couplage des diazoiques avec les systkmes insaturts.

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“…By analogy with the easy cyclization of 3-cyanornethyltriazenes (2). the 3-ethoxycarbonylmethyltriazenes might be expected to be readily converted to the hydroxytriazoles (4) on refluxing in ethanol.…”

Section: Discussionmentioning

confidence: 99%

“…Y = CN and C02R) was described. In a further study (2), the a-cyanomethyl triazenes were found to undergo cyclization to afford 5-amino-I-aryl-1,2,3-triazoles (1) which in turn undergo rearrangement in H protic media to give the isomeric 5-(aryla1nino)-l.2,3-triazoles (2). The results reported in this paper originate from the logical extension of the amino-triazole synthesis to the synthesis of the 5-hydroxy-l,2,3-triazole system (4) via the analogous I-aryl-3-(ethoxycarbony 1methyl)triazenes (3).…”

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confidence: 95%

Open-chain nitrogen compounds. Part IV. Synthesis of 5-hydroxy-1,2,3-triazoles from 1-aryl-3-(ethoxycarbonylmethyl)triazenes: a new route to α-diazo-N-arylacetamides

Baines¹,

Vaughan²,

Hooper³

et al. 1983

Can. J. Chem.

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. LEVECK. Can. J . Chcm. 61, 1549 (1983).A scries of triazcncs of typc ArN=N-NH-CH2C02Et.N-arylazoglycinc cthyl cstcrs. have becn prcpalrd by coupling the arcne diazonium salt, ArNZi.X , with cthyl glycinatc, NHZCH2C02Et; an clcctron-withdrawing substitucnt, c.g. NOZ, CN. C 0 2 R , and CI. in thc ortho or partr position of thc aryl group is csscntial for efficient coupling. Thc p-substituted arylazoglycinc cthyl cstcrs cyclizc when trcated with alcoholic potassium hyclroxidc to afford thc potassium salts of thc I-aryl-5-hydroxy-1.2.3-triazoles, which can bc obtained frcc by acidification of thc potassium salt solution with acctic acid. Rcaction of thc potassium salts with acctic anhydride yiclcls thc I-aryl-5-acetoxy-1.2.3-triazolcs. The 5-hydroxytriazolcs, whcn heatcd in ethanol, rcarrangc to a-diazoacctanilitlcs. ArNH .COCHN2. Thc diazoamidcs can be obtaincd in low yicld dircctly from thc triazcnes by prolonged rctluxing in cthanol. o-Substituted aryltriazcncs do not cyclizc undcr the samc conditions but fragmcnt to the arylaminc.

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5-(Arylamino)-1,2,3-triazoles and 5-amino-1-aryl-1,2,3-triazoles from 3-(cyanomethyl)triazenes

Cited by 34 publications

References 3 publications

Heterociclos 1,2,3-triazólicos: histórico, métodos de preparação, aplicações e atividades farmacológicas

Heterociclos 1,2,3-triazólicos: histórico, métodos de preparação, aplicações e atividades farmacológicas

Formation of methyl 2-arylhydrazono-3-oxobutanoates and 2-arylhydrazono-3-oxobutanenitriles during the coupling reaction of arenediazonium ions with methyl 3-aminocrotonate and 3-aminocrotononitrile

Open-chain nitrogen compounds. Part IV. Synthesis of 5-hydroxy-1,2,3-triazoles from 1-aryl-3-(ethoxycarbonylmethyl)triazenes: a new route to α-diazo-N-arylacetamides

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