Electrochemical behavior of amidine hydrochlorides and amidines

Daoust, Benoit; Lessard, Jean

doi:10.1139/v95-048

Cited by 18 publications

(13 citation statements)

References 12 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…In basic solutions at pH > 10, the deprotonated “dehydroFOX − ” (conjugate base) prevails in the solution; and in a strongly alkaline solution, the latter species can be reduced at very negative potentials independently on pH (Equation , Figure A, R3). In contrast to the difficult reducibility of the amidines mentioned by Daoust and Lessard, the attached two electron‐withdrawing nitro groups should shift the reduction potentials of the conjugate base of FOX‐7 to less negative values, enabling their reduction in accessible potential range.

{FOXH}^{+} + e^{-} \to {FOXH}^{•} \to \to product ((), s),

FOX + e^{-} \to {FOX}^{- •} \to \to product ((), s),

{dehydroFOX}^{-} + e^{-} \to {[{dehydroFOX}^{-}]}^{- •} \to \to product ((), s) .

…”

Section: Resultsmentioning

confidence: 89%

See 1 more Smart Citation

Electrochemically triggered degradation of energetic material FOX‐7 (2,2‐dinitroethene‐1,1‐diamine) — Structural, redox, and spectrometric characterization in solution

Šimková

Ludvı́k

2020

J of Physical Organic Chem

View full text Add to dashboard Cite

This work represents systemati11c electrochemical and spectrometric characterization of 2,2‐dinitroethene‐1,1‐diamine, the energetic material (explosive) known as FOX‐7, in aqueous as well as various organic solvents. On the basis of results obtained from combination of electrochemistry with ultraviolet‐visible–near‐infrared (UV‐vis‐NIR), infrared (IR), nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR), mass spectrometry (MS), gas chromatography (GC), and high‐performance liquid chromatography (HPLC) methods, the actual structure of FOX‐7 in various media was revealed, its reducibility was described, and radical intermediates as well as most of the products were intercepted and identified. Instead of expected cathodic reduction of the dinitro derivative, electrochemically initiated spontaneous degradation accompanied by release of gaseous products in all media was found.

show abstract

{FOXH}^{+} + e^{-} \to {FOXH}^{•} \to \to product ((), s),

FOX + e^{-} \to {FOX}^{- •} \to \to product ((), s),

{dehydroFOX}^{-} + e^{-} \to {[{dehydroFOX}^{-}]}^{- •} \to \to product ((), s) .

…”

Section: Resultsmentioning

confidence: 89%

“…Within the whole pH range, three different ways of electrochemical reduction of FOX‐7 are supposed where the amidino group is expected to be reduced formally first instead of the nitro group . (The following discussion deals with steps R1 and R3.…”

Section: Resultsmentioning

confidence: 99%

Electrochemically triggered degradation of energetic material FOX‐7 (2,2‐dinitroethene‐1,1‐diamine) — Structural, redox, and spectrometric characterization in solution

Šimková

Ludvı́k

2020

J of Physical Organic Chem

View full text Add to dashboard Cite

show abstract

“…Bei diesem Film handelt es sich vermutlich um Amidinpolymere a , deren Bildung bereits von anderen Autoren beschrieben wurde [18].…”

Section: Ergebnisse Und Diskussionunclassified

“…Dies folgt u.a. aus einem Vergleich mit Literaturangaben zur elektrochemischen Oxidation von Benzamidinen [18]. Die dort untersuchten, den Verbindungen 6 strukturanalogen, Benzamidine weisen Oxidationspotentiale im gegenu Èber 3 um $ 200 bis 250 mV anodisch verschobenen Potentialbereich von A3 fu Èr 1 und 2 auf.…”

Section: Ergebnisse Und Diskussionunclassified

“…Daoust und Lessard beschrieben neben der Synthese vorrangig das voltammetrische Verhalten einer Vielzahl N-alkyl-und N-arylsubstituierter Amidine sowie deren Hydrochloride [18]. Bei der Untersuchung von Lo È sungen der Narylsubstituierten Amidine in Acetonitril wurde bei Einsatz einer Glaskohlenstoffelektrode ein Oxidationspeak bei 0.7 V vs. Ag/Ag und ein Reduktionspeak bei À3.00 V vs. Ag/Ag beobachtet.…”

Section: Introductionunclassified

See 1 more Smart Citation

Voltammetrische Charakterisierung des elektrochemischen Redoxverhaltens von N-Thiocarbamoyl-benzamidinen und 1,2,4-Thiadiazoliumsalzen

Guttmann

Schröder

Beyer

1999

Monatshefte fuer Chemie

View full text Add to dashboard Cite

Zusammenfassung. Das elektrochemische Redoxverhalten der N-(Diethylamino-thiocarbamoyl)-benzamidine Et 2 N-C(S)-N=C-(NHR)-Ph (1: R H; 2: R n-C 3 H 7 ; 3: R Ph) und von 2,3-Diphenyl-5-diethylamino-1,2,4-thiadiazoliumiodid (4) bzw. -perchlorat (5) wurde mittels cyclischer Voltammetrie in ethanolischer Lo Èsung an einer Glaskohlenstoffelektrode im Potentialbereich zwischen À1.2 V und 1.5 V vs. Ag/AgCl untersucht. Der Mechanismus der irreversiblen anodischen Oxidation der Benzamidine 1±3 und die dabei gebildeten Produkte (1,2,4-Thiadiazoliumkationen bzw. 1,2,4-Thiadiazol) werden unmittelbar durch die am terminalen Benzamidinstickstoffatom gebundenen Substituenten R (n-C 3 H 7 , Ph, H) bestimmt. Im kathodischen Potentialbereich unterliegen die Benzamidine 1±3 einer irreversiblen reduktiven Spaltung, die ebenfalls direkt durch die N-gebundenen Substituenten R beein¯uût wird. Die Reduktionsprodukte, die indirekt elektrochemisch durch Vergleichsvoltammogramme identi®ziert wurden, ko Ènnen an der Elektrodenober¯a Èche adsorbiert und anschlieûend wieder oxidiert werden. Das 1,2,4-Thiadiazoliumkation von 4 und 5 ist im untersuchten anodischen Potentialbereich redoxinert. Die bei 4 beobachteten Peaks resultieren aus den Redoxreaktionen der Iodidgegenionen. Jedoch wird das 1,2,4-Thiadiazoliumkation bei kathodischen Potentialen ebenfalls einer irreversiblen reduktiven Spaltung unterworfen, deren Mechanismus dem der substituierten Benzamidine 1±3 entspricht. Der fu Èr die charakterisierten Verbindungen 1±5 beschriebene elektrochemische Redoxmechanismus steht im Einklang mit bekannten Syntheseergebnissen. Voltammetric Characterization of the Electrochemical Redox Behaviour of N-Thiocarbamoyl-benzamidines and 1,2,4-Thiadiazolium SaltsSummary. The electrochemical redox behaviour of N-(diethylamino-thiocarbamoyl)-benzamidines Et 2 N-C(S)-N=C-(NHR)-Ph (1: R H; 2: R n-C 3 H 7 ; 3: R Ph) and 2,3-diphenyl-5-diethylamino-1,2,4-thiadiazolium iodide (4) as well as of its perchlorate (5) was studied by cyclic voltammetry in ethanolic solution at a glassy carbon electrode between À1.2 V and 1.5 V vs. Ag/AgCl. The mechanisms for the irreversible anodic oxidation of the benzamidines 1±3 and the formed products (1,2,4-thiadiazolium cations or 1,2,4-thiadiazole) are in¯uenced directly by the substituents bound to Ã Corresponding author; present address: the terminal benzamidine nitrogen atom. In the cathodic potential range, an irreversible reductive cleavage of the benzamidines 1±3 occurs which also depends on the N-bound substituents. The products of this reduction, which are identi®ed indirectly electrochemically by comparing voltammogramms, can be adsorbed on the electrode surface and reoxidized in the following anodic scan. The 1,2,4-thiadiazolium cation of 4 and 5 is redox inert in the investigated anodic potential range. The obtained anodic peaks in the case of 4 result from redox reactions of the iodide counter ions only. However, the 1,2,4-thiadiazolium cation is also subject of a reductive cleavage in a similar way to the mechanism wh...

show abstract

ChemInform Abstract: Electrochemical Behavior of Amidine Hydrochlorides and Amidines

Daoust

Lessard

1995

ChemInform

View full text Add to dashboard Cite

show abstract

Electrochemical behavior of amidine hydrochlorides and amidines

Cited by 18 publications

References 12 publications

Electrochemically triggered degradation of energetic material FOX‐7 (2,2‐dinitroethene‐1,1‐diamine) — Structural, redox, and spectrometric characterization in solution

Electrochemically triggered degradation of energetic material FOX‐7 (2,2‐dinitroethene‐1,1‐diamine) — Structural, redox, and spectrometric characterization in solution

Voltammetrische Charakterisierung des elektrochemischen Redoxverhaltens von N-Thiocarbamoyl-benzamidinen und 1,2,4-Thiadiazoliumsalzen

ChemInform Abstract: Electrochemical Behavior of Amidine Hydrochlorides and Amidines

Contact Info

Product

Resources

About