Mechanism of the formation of phenylpyridium chloride from 1,7-diphenyl-1,7-diazahepta-1,3,5-triene

Marvell, Elliot N.; Caple, G.; Shahidi, Iraj

doi:10.1016/s0040-4039(00)90530-6

Cited by 11 publications

(5 citation statements)

References 4 publications

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“…The ir spectrum (KBr pellet) of the product shows a weak, broad absorption in the region 3 120-2480 cm-', characteristic of intramolecular hydrogen binding (Nakanishi, 1962), a strong carbonyl absorption at 1745 cm-l. a peak at 950 cm-' characteristic of trans-cis conjugation (Lunde and Zechmeister, 1954) not present in glutaconaldehyde dianilide HCI [which is known to have an all-trans conformation (Marvel et al. 1967)], and two peaks a t 790 and 732 cm-', characteristic of cis double bonds and also not present in glutaconaldehyde anilide hydrochloride.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, structure determination, spectral properties, and energy-linked spectral responses of the extrinsic probe oxonol V in membranes

Smith¹,

Russ²,

Cooperman³

et al. 1976

Biochemistry

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The direct synthesis of bis[3-phenyl-5-oxoisoxazol-4-yl]pentamethineoxonol, which is shown to be the fluorescent probe OX-V (formerly MC-V), is described. The emission lifetime (0.9 f 0.1 ns) and the spectral properties of this dye in a number of systems are presented as well as the relative polarizations associated with the transition moments of the observable electronic transitions. The structure of OX-V was determined using elemental analysis and infrared and H nuclear magnetic resonance ( N M R ) spectroscopy. The use of the contact shift reagent, Eu(fod)3-d27, greatly facilitated the interpretation of the N M R results. In aqueous media, the anionic form of OX-V is present virtually exclusively due to the low solubility of the neutral species; formation of the latter species occurs when ethanol or methanol solutions of OX-V From the Department ofchemistry (P.R. and B.S.C.) and the Johnson Research Foundation (J.C.S. and B.Fellow (1974)(1975)(1976). are acidiied. Both neutral and anionic dye forms can be detected in chloroform-ethanol solvents. The fluorescence intensity from excitation of the neutral species is an order of magnitude weaker than that from excitation of the anionic form and may result from the formation of excited anions due to the loss of a proton by the neutral species in the excited state.Polarization results indicate that the visible absorption of the dye is due to a single electronic transition. OX-V has been employed as a probe primarily in beef heart submitochondrial particles. reconstituted ATPase vesicles, and pigeon heart mitochondria. The energy-linked spectral changes of the probe in these preparations are described and mechanisms proposed for the spectral effects.M-540. The dyes MC-I, MC-11, and OX-V' (formerly MC-V) have also been used extensively as probes (Chance. 1975). A red shift in the absorption spectrum of these dyes is observed when submitochondrial particles stained with these dyes are energized. In particular, the dye OX-V has been given extensive use. Changes in the absorption and fluorescence spectrum of this dye have been demonstrated when R. rubrum chromatophores are energized with 860-nm light (Chance and Baltscheffsky, 1975). Cohen et al. (see Chance, 1975) havealso demonstrated that the fluorescence of OX-V undergoes changes similar to those observed with MC-I in squid axons, but the former dye is not as sensitive in this system as the latter ~ Abbreviations used: U MR, nuclear magnetic resonance; OX-V. (formerly ;MC-V), bis[3-phen> I-S-oxoisoxazol-4-yl]pentamethineoxonol: Eu( fod)i-d:T, tris( heptofluorodimethyloctanedion~~to)-il27-europium; T1.C. thin-layer chromatography: ir. infrared: uv, ultraviolet; SMP. submitochondrial particles: EDTA, ethylenediaminetetraacetic acid; NADH, reduced nicotinamide adenine dinucleotide; PHM, pigeon heart mitochondria: Mopes. 3-(,l'-morpholino)propanesulfonic acid.

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Section: Resultsmentioning

confidence: 99%

Synthesis, structure determination, spectral properties, and energy-linked spectral responses of the extrinsic probe oxonol V in membranes

Smith¹,

Russ²,

Cooperman³

et al. 1976

Biochemistry

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“…A synthesis sequence for the preparation of 3 and 4 was not previously reported. However, a similar type of mechanism, as depicted for the preparation of 2 , was established early28–30 (Scheme ). The kinetically less stable Z ‐isomer 2 Z upon absorption of light rapidly isomerizes to the more stable thermodynamic E ‐isomer 2 E together with the generation of an electrical pulse corresponding to a large cage in the molecular dipole moment upon photoexcitation.…”

Section: Resultsmentioning

confidence: 66%

Photochromic behavior of several new synthesized dyes via Zincke salts

Mahmoodi

Mamaghani

Ghanadzadeh

et al. 2009

J of Physical Organic Chem

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“…[17] A text book example of this class of reactions is given by Equation (2). That such reactions are also possible in C=CÀC=CÀC=N systems is known from experiment, [18] and have been studied in detail theoretically. [19][20][21][22] In our reaction of [RuA C H T U N G T R E N N U N G (C 6 H 6 )Cl 2 ] 2 with HL, we seem to have a case of a metal-assisted electrocyclic reaction in a C=N À N=C À C=N sequence.…”

Section: 101(2)mentioning

confidence: 99%

Metallo‐Organic Domino Reactions: CH versus CC Bond Breaking

Tocher

Drew

Nag

et al. 2007

Chemistry A European J

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HL and MeL are prepared by condensing benzil dihydrazone with 2-formylpyridine and 2-acetylpyridine, respectively, in 1:2 molar proportions. While in a reaction with [Ru(C(6)H(6))Cl(2)]2, HL yields the cation [Ru(C(6)H(6)){5,6-diphenyl-3-(pyridin-2-yl)-1,2,4-triazine}Cl]+, MeL gives the cation [Ru(C(6)H(6))(MeL)Cl]+. Both the cations are isolated as their hexafluorophosphate salts and characterised by X-ray crystallography. In the case of HL, double domino electrocyclic/elimination reactions are found to occur. The electrocyclic reaction occurs in a C=N-N=C-C=N fragment of HL and the elimination reaction involves breaking of a C-H bond of HL. Density functional calculations on model complexes indicate that the identified electrocyclic reaction is thermochemically as well as kinetically feasible for both HL and MeL in the gas phase. For a double domino reaction, similar to that operative in HL, to occur for MeL, breaking of a C-C bond would be required in the elimination step. Our model calculations show the energy barrier for this elimination step to be much higher (329.1 kJ mol(-1)) for MeL than that for HL (96.3 kJ mol(-1)). Thus, the domino reaction takes place for HL and not for MeL. This accounts for the observed stability of [Ru(C(6)H(6))(MeL)Cl]+ under the reaction conditions employed.

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Mechanism of the formation of phenylpyridium chloride from 1,7-diphenyl-1,7-diazahepta-1,3,5-triene

Cited by 11 publications

References 4 publications

Synthesis, structure determination, spectral properties, and energy-linked spectral responses of the extrinsic probe oxonol V in membranes

Synthesis, structure determination, spectral properties, and energy-linked spectral responses of the extrinsic probe oxonol V in membranes

Photochromic behavior of several new synthesized dyes via Zincke salts

Metallo‐Organic Domino Reactions: CH versus CC Bond Breaking

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