Nucleophilic Reactions on 1-Trifluoromethanesulfonylpyridinium Trifluoromethanesulfonate (Triflylpyridinium Triflate, TPT). Ring-Opening and "Unexpected" 1,4-Dihydropyridine Reaction Products.

Toscano, Rubén A.; Hernández-Galindo, María del Carmen; Rosas, Raul; García-Mellado, Olivia; Rı́o-Portilla, Federico del; Amábile-Cuevas, Carlos F.; Álvarez-Toledano, Cecilio

doi:10.1248/cpb.45.957

Cited by 36 publications

(30 citation statements)

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“…16 Under these circumstances, the reaction mechanism for the formation of the new material from DS1, involved an electrocyclic aperture preceded by an aniline nucleophilic attack on the pyridinium salt. 17 The molecule existed in the betainic form 17 where a negative charge was distributed on the trifluoromethansulfonylamide group and a positive charge was distributed on the amine group. The synthesis of compound 2 was formed from the attack of the aniline to the trifluoromethansulfonate N-trifluoromethansulfonyl-3-cloropyridone salt.…”

Section: Resultsmentioning

confidence: 99%

Electrochemical and atomic force microscopy investigations of new materials from N-trifluoromethanesulfonyl-1-azahexa-1,3,5-trienes derivatives

Rivera¹,

Álvarez-Toledano²,

Moreno³

et al. 2005

J. Braz. Chem. Soc.

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Filmes finos foram crescidos sobre a superfície de elétrodos de grafito pirolizado altamente orientado a partir de precursores p-doadores utilizando a técnica cíclica de voltametria cíclica e eletroquímica-microscopia de força atômica. Os resultados indicam que é possível a formação de novos compostos chamados materiais moleculares, estes são formados pelo acoplamento de espécies N-trifluormetanosulfonil-1-aza-hexa-1,3,5-trieno eletro-oxidadas e o anion [Cr(C 2 O 4 ) 3 ] 3-. Diferentes técnicas foram empregadas para caracterizar a morfologia e composição dos filmes formados. Os resultados indicam que os materiais novos exibiram uma resposta eletroquímica particular e uma textura diferente dependendo da composição química dos materiais de partida.Thin films have been created on the surface of highly oriented pyrolytic graphite electrodes from chemically synthesized -donor species by using the cyclic voltammetry technique and in situ electrochemistry-atomic force microscopy. Results indicate that it is possible to form new compounds called molecular materials from the coupling of electro-oxidized N-trifluoromethanesulfonyl-1-azahexa-1,3,5-triene species and a [Cr(C 2 O 4 ) 3 ] 3-anion. Different techniques such as AFM, SEM and EDS were employed to characterize the films morphology and composition. Results indicate that the new materials exhibited a particular electrochemical response and a different film texture depending on the chemical composition of the starting compounds. Keywords: thin films, electrodeposition, in situ AFM IntroductionOver the last few years, there have been an increasing number of reports regarding the formation of molecular materials (MMs) with electronic or opto electronic properties based on organic and organometallic derivatives.1,2 For example, it has been reported the formation of supramolecular building blocks with tailored pore structures by Plaud et al. to generate predictable and robust structures for specific applications.3 Moreover, recent research work has been oriented to the formation and characterization of molecular-material thin films. 4 For instance, the use of the chemical vapor deposition to grow thin films of molecular conductors such as (TTF)(TCNQ) (TTF= tetrathiafulvalene, TCNQ = tetracyanoquinodimethane) has been reported. [5][6][7][8] It has been observed, that a regular stacking of molecules such as those found in MMs allows the formation of semiconducting, conducting or superconducting thin films. These thin films exhibit in general preferential directions for electrical conductivity. The electrical conductivity of MMs is associated with an extensive delocalization of electrons that depends on their 317 Electrochemical and Atomic Force Microscopy Investigations of New Materials Vol. 16, No. 3A, 2005 planarity and the orbital overlap extension between their molecular units. N-Trifluoromethanesulfonyl-1-azahexa-1,3,5-trienes (TFSAT) compounds, which are highly functionalized pentametines, have been previously studied due to its interesting physical and chemical p...

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Section: Resultsmentioning

confidence: 99%

Electrochemical and atomic force microscopy investigations of new materials from N-trifluoromethanesulfonyl-1-azahexa-1,3,5-trienes derivatives

Rivera¹,

Álvarez-Toledano²,

Moreno³

et al. 2005

J. Braz. Chem. Soc.

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“…Further evidence is provided by 19 F NMR where signals corresponding to the triflate anion (-79.8 ppm) and N-(trifluoromethylsulfonyl)pyridinium 11 (-75.9 ppm) are exclusively observed, the latter compound arising from the reaction of the excess triflic anhydride with pyridine (23,24). Pyridinium 6 proved to be very stable under the reaction conditions, showing no signs of decomposition after 6 days at -3°C under dry atmosphere.…”

Section: Reaction Of Secondary Amides With Triflic Anhydride In the Pmentioning

confidence: 94%

Spectroscopic studies of the electrophilic activation of amides with triflic anhydride and pyridine

Charette¹,

Grenon²

2001

Can. J. Chem.

148

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The reaction of amides with trifluoromethanesulfonic (triflic) anhydride in the presence of pyridine was thoroughly investigated by NMR spectroscopic techniques. Different pyridinium intermediates were generated from secondary amides, tertiary amides with enolizable protons, and tertiary amides lacking enolizable protons. It was found that the actual triflating reagent is N-(trifluoromethylsulfonyl)pyridinium triflate 11 which is formed by the initial reaction of triflic anhydride with pyridine. The alcoholysis of these intermediates yields O-alkyliminium ethers which can then be easily hydrolyzed under mild acidic conditions to the corresponding esters.Résumé : La réaction entre un amide et l'anhydride trifluorométhanesulfonique (triflique) en présence de pyridine a été examinée minutieusement à l'aide de nombreuses techniques de spectroscopie RMN. Des intermédiaires pyridiniums différents ont été générés à partir d'amides secondaires, d'amides tertiaires avec des protons énolisables et d'amides tertiaires ne possédant pas de protons énolisables. Nous avons aussi démontré que le triflate de N-(trifluorométhylsulfonyl)pyridinium 11, formé lors de la réaction initiale entre l'anhydride triflique et la pyridine, est le véritable agent de triflation. L'alcoolyse de ces intermédiaires donne des éthers O-alkyliminiums qui peuvent être facilement hydrolysés dans des conditions légèrement acides aux esters correspondants. Charette and Grenon 1695Scheme 1. Functional group interconversion involving amides as starting materials.Scheme 2. Postulated intermediates formed in the reaction of amides with triflic anhydride.

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“…As an important antecedent, early studies of trifluoromethanesulfonyl derivatives with pyridine ( 29 ) in the presence of trifluoromethanesulfonic anhydride were undertaken and 1‐trifluoromethanesulfonylpyridinium trifluoromethanesulfonate ( 30 ) was obtained. Subsequent treatment with Me 2 NH and Et 2 NH gave the corresponding N ‐trifluoromethanesulfonyl‐ N′ , N′ ‐dialkyl‐1,6‐diazahexa‐1,3,5‐trienes 33 and 1,4‐dihydropyridines 34 (Scheme ), which displayed significant antibacterial activity …”

Section: Reactions Involving Other Activating Agentsmentioning

confidence: 99%

Reactions of Bis(trimethylsilyl)ketene Acetals with Several Activated Organic Substrates

Toledano

Penieres‐Carrillo

2018

Eur J Org Chem

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Nucleophilic Reactions on 1-Trifluoromethanesulfonylpyridinium Trifluoromethanesulfonate (Triflylpyridinium Triflate, TPT). Ring-Opening and "Unexpected" 1,4-Dihydropyridine Reaction Products.

Cited by 36 publications

References 1 publication

Electrochemical and atomic force microscopy investigations of new materials from N-trifluoromethanesulfonyl-1-azahexa-1,3,5-trienes derivatives

Electrochemical and atomic force microscopy investigations of new materials from N-trifluoromethanesulfonyl-1-azahexa-1,3,5-trienes derivatives

Spectroscopic studies of the electrophilic activation of amides with triflic anhydride and pyridine

Reactions of Bis(trimethylsilyl)ketene Acetals with Several Activated Organic Substrates

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