The Synthesis of Certain 5-Aminotetrazole Derivatives. IV. The Rearrangement of Certain Monosubstituted 5-Aminotetrazole Derivatives

Garbrecht, William L.; Herbst, Robert

doi:10.1021/jo50016a006

Cited by 23 publications

(14 citation statements)

References 10 publications

(16 reference statements)

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“…However, the ease of rearrangement to 1 -benzyl-5-acetylaminotetrazole would be difficult to explain on this basis. The easy conversion of 1-aryl-5-aminotetrazoles to 5-arylaminotetrazoles and of the 5-alkylaminotetrazoles to 1 -alkyl-5-aminotetrazoles (6) support the assumption of acetylation in the 1-position. It is interesting to note that palladium-charcoal can effect selective hydrogenolysis of the benzylaminotetrazoles.…”

mentioning

confidence: 64%

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The Acylation of some 5-Aminotetrazole Derivatives

Herbst¹,

Garbrecht²

1953

J. Org. Chem.

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confidence: 64%

“…It was known that 5-benzylaminotetrazole would rearrange at elevated temperature with the formation of l-benzyl-5-aminotetrazole (6). The question arises whether rearrangement precedes acetylation or whether a labile acetyl derivative is first formed.…”

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confidence: 99%

The Acylation of some 5-Aminotetrazole Derivatives

Herbst¹,

Garbrecht²

1953

J. Org. Chem.

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“…Since Dimroth rearrangement is successfully employed as a method of attaining various heterocyclic structures, applied to industrial processes and even observed in biological systems, as a continuation of this research, we wanted to further study the said transformation on this heterocyclic system . Dimroth rearrangement of 1 H -tetrazole-5-amine derivatives was first observed in 1953, , during heating of various monosubstituted 5-aminotetrazoles and some 5-alkyl-1-aryl-1 H -tetrazole-5-amines. A similar transformation was noticed by Dimroth in 1 H -1,2,3-triazole-5-amine derivatives and later recognized as a valuable method for acquiring some previously unavailable aminotetrazoles .…”

Section: Resultsmentioning

confidence: 99%

Controlling Pd-Catalyzed N-Arylation and Dimroth Rearrangement in the Synthesis of N,1-Diaryl-1H-tetrazol-5-amines

et al. 2021

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The Pd-catalyzed N-arylation method for the synthesis of eighteen N,1-diaryl-1H-tetrazol-5-amine derivatives is reported. By running the reactions at 35 ºC, compounds were isolated as single isomers since the undesired Dimroth rearrangement was completely suppressed. Furthermore, the Dimroth rearrangement of N,1-diaryl-1H-tetrazol-5-amines was rationalized by conducting comprehensive experiments and NMR analysis as well as DFT calculations of thermodynamic stability of the compounds. It was established that the Dimroth rearrangement is thermodynamically controlled and the equilibrium of the reaction is determined by the stability of the corresponding isomers. The mechanism was investigated by additional DFT calculations and the opening of the tetrazole ring was shown to be the rate-determining step. By maneuvering Pd-catalyzed N-arylation and the subsequent Dimroth rearrangement two more N,1-diaryl-1H-tetrazol-5-amine derivatives were acquired, that otherwise cannot be synthesized by employing the C-N cross-coupling reaction.

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“…Tab. 1) und korrespondieren hinsichtlich der Abstufung der Säurestärke in ver- (2) __________________________________________________________________________________ PROCEDURES/DATA schiedenen Lösungsmittelsystemen mit den für Methanol/Wasser (50:50, v/v) bestimmten pK a -Werten [5].…”

Section: Ergebnisse Und Diskussionunclassified

“…Die in [5] für R = H, 3-NO 2 und 4-NO 2 angegebenen pK a -Werte im Lösungsmittelsystem Methanol/Wasser korrelieren vergleichbar mit elektronischen Substituentenparametern und bestätigen damit die hier gefundenen Struktur-Aciditäts-Beziehungen. Dagegen wird ein "normaler" Substituenteneinfluß der 4-NO 2 -Gruppe auf die in Ethanol/Wasser und Dimethylsulfoxid/Wasser bestimmte Acidität von 5-Phenyl-1H-tetrazolen beobachtet [13].…”

Section: Ergebnisse Und Diskussionunclassified

Zur physikalisch-chemischen Charakterisierung von 5-Amino-1-aryl-1H-tetrazolen: Elektronische Molekülparameter aus der thermischen Isomerisierung zu 5-Arylamino-1H-tetrazolen

Schelenz

Schäfer

2000

J. prakt. Chem.

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197 Die Untersuchung quantitativer Zusammenhänge zwischen chemischer Struktur und biologischer Aktivität von Wirkstoffen setzt die Kenntnis direkter Moleküldeskriptoren, geeigneter Substituentenkonstanten oder physikalisch-chemischer Meßgrößen zur Molekülbeschreibung voraus. Für eine Serie algistatisch wirksamer 5-Amino-1-aryl-1H-tetrazole [1] wurde bisher über ihre Octan-1-ol/ Wasser-Verteilungskoeffizienten [2], -Transportgeschwindigkeiten [3] und Wasserlöslichkeiten [4] als Indikatoren der hydrophil-hydrophoben Eigenschaften dieser Verbindungen berichtet.Elektronische Molekülparameter lassen sich in effizienter Weise aus der bekannten [5, 6] thermischen Isomerisierung von 5-Amino-1-aryl-1H-tetrazolen (A) zu entsprechenden 5-Arylamino-1H-tetrazolen (HB) ableiten.

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The Synthesis of Certain 5-Aminotetrazole Derivatives. IV. The Rearrangement of Certain Monosubstituted 5-Aminotetrazole Derivatives

Cited by 23 publications

References 10 publications

The Acylation of some 5-Aminotetrazole Derivatives

The Acylation of some 5-Aminotetrazole Derivatives

Controlling Pd-Catalyzed N-Arylation and Dimroth Rearrangement in the Synthesis of N,1-Diaryl-1H-tetrazol-5-amines

Zur physikalisch-chemischen Charakterisierung von 5-Amino-1-aryl-1H-tetrazolen: Elektronische Molekülparameter aus der thermischen Isomerisierung zu 5-Arylamino-1H-tetrazolen

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