Photolysis of Nitrate Esters: Part I. Photonitration of Diphenylamine

Hayward, L. D.; Kitchen, R. A.; Livingstone, D. J.

doi:10.1139/v62-069

Cited by 14 publications

(3 citation statements)

References 22 publications

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“…Purification was monitored by t.1.c. (26) and by the u.v., c.d., n.m.r., (27) and i.r. (24) spectra which agreed with the constitutional assignments.…”

Section: Methodsmentioning

confidence: 98%

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Circular Dichroism of Nitrate Esters: A Planar Symmetry Rule for the Nitrato Chromophore

Barton¹,

Hayward²

1972

Can. J. Chem.

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Conformational analysis of nitrate esters based on X-ray and spectroscopic data showed the nitrato group to be coplanar with the a carbon atom and, in the preferred rotamer, the nitro moiety to be antiperiplanar to the /I carbon atom. Three optically active absorption bands not apparent in the isotropicelectronic spectra were resolved in the circular dichroism spectra. Band I (270 nm) reflected nitrato group libration changing sign and magnitude with changes in temperature and solvent polarity. Differences in rotatory strength of band 111 (210 nm) for cis-and trans-dinitrates indicated transition moment coupling. A planar symmetry rule for chromophores in the C, point group correlated the molecular geometry and sign of band I1 for 42 nitrate esters: when the lowest-energy rotamer of the nitrate ester is viewed down the 0-C bond with the nitro group uppermost rotatory contributions to band I1 (230 nm) are positive for perturbing atoms to the right and negative for those to the left of the nitrato symmetry plane.L'analyse conformationnelle des esters nitriques, baste sur les donntes de la spectroscopie et des rayons-)<, montre que le groupe nitrate est coplanaire avec I'atome de carbone en a et que, dans le rotamere priviltgit, le fragment nitro est antiptriplanaire a I'atome de carbone en /I. Trois bandes d'absorption optiquement actives, non apparentes sur le spectre tlectronique isotrope, ont t t t rtsolues dans le spectre de dichroisme circulaire. La bande I (270 nm) reflete la vibration du groupe nitro et change de signe et d'amplitude lorsque la temptrature et la polaritt du solvant changent. Les differences dans le pouvoir rotatoire de la bande I11 (2i0 nm) pour les dinitrates ci.s et trat1.s indiquent un couplage du moment de transition. Une rtgle de symttrie plane pour les chromophores du groupe C, relie la gtomttrie moltculaire au signe de la bande 11 pour 42 esters nitriques: lorsque le rotamtre de plus basse energie de I'ester nitrique est regard6 le long de la liaison 0-C avec le groupe nitro, les contributions rotatoires decisives pour la bande I1 (230 nm) sont positives lorsque les atomes sont situes a droite du plan de symttrie du nitrate et negatives lorsqu'ils sont a gauche.

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“…Purification was monitored by t.1.c. (26) and by the u.v., c.d., n.m.r., (27) and i.r. (24) spectra which agreed with the constitutional assignments.…”

Section: Methodsmentioning

confidence: 98%

“…0.5 Torr) or chromatography on columns of silica gel developed with chloroform (26). Purification was monitored by t.1.c.…”

Section: Methodsmentioning

confidence: 99%

Circular Dichroism of Nitrate Esters: A Planar Symmetry Rule for the Nitrato Chromophore

Barton¹,

Hayward²

1972

Can. J. Chem.

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“…Most of these studies used excitation wavelengths >290 nm, a region of very weak absorption . For nitrate esters excited at λ>290 nm, photolysis involves cleavage of the O–NO 2 bond to form NO 2 and an alkoxy radical. − …”

Section: Introductionmentioning

confidence: 99%

UV Resonance Raman Investigation of Pentaerythritol Tetranitrate Solution Photochemistry and Photoproduct Hydrolysis

2017

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Ultraviolet resonance Raman spectroscopy (UVRR) is being developed for standoff trace explosives detection. To accomplish this, it is important to develop a deep understanding of the accompanying UV excited photochemistry of explosives, as well as the impact of reactions on the resulting photoproducts. In the work here we used 229 nm excited UVRR spectroscopy to monitor the photochemistry of pentaerythritol tetranitrate (PETN) in acetonitrile. We find that solutions of PETN in CDCN photodegrade with a quantum yield of 0.08 ± 0.02, as measured by high performance liquid chromatography (HPLC). The initial step in the 229 nm UV photolysis of PETN in CDCN is cleavage of an O-NO bond to form NO. The accompanying photoproduct is pentaerythritol trinitrate (PETriN), (CHONO)CCHOH formed by photolysis of a single O-NO. The resulting UVRR spectra show a dominant photoproduct band at ∼1308 cm, which derives from the symmetric stretch of dissolved NO. This photoproduct NO is hydrolyzed by trace amounts of water, which downshifts this 1308 cm NO Raman band due to the formation of molecular HNO. The dissociation of HNO to NO in the presence of additional water results in an intense NO- symmetric stretching UVRR band at 1044 cm.

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A new strategy to design a graphene oxide supported palladium complex as a new heterogeneous nanocatalyst and application in carbon–carbon and carbon‐heteroatom cross‐coupling reactions

Bahrami

Targhan

2019

Applied Organom Chemis

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The palladium nanoparticles were successfully stabilized with an average diameter of 6–7 nm through the coordination of palladium and terpyridine‐based ligands grafted on graphene oxide surface. The graphene oxide supported palladium nanoparticles were thoroughly characterized and applied as an efficient heterogeneous catalyst in carbon–carbon (Suzuki‐Miyaura, Mizoroki‐Heck coupling reactions) and carbon–heteroatom (C‐N and C‐O) bond‐forming reactions. The catalyst was simply recycled from the reaction mixture and was reused consecutive four times with small drop in catalytic activity.

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Photolysis of Nitrate Esters: Part I. Photonitration of Diphenylamine

Cited by 14 publications

References 22 publications

Circular Dichroism of Nitrate Esters: A Planar Symmetry Rule for the Nitrato Chromophore

Circular Dichroism of Nitrate Esters: A Planar Symmetry Rule for the Nitrato Chromophore

UV Resonance Raman Investigation of Pentaerythritol Tetranitrate Solution Photochemistry and Photoproduct Hydrolysis

A new strategy to design a graphene oxide supported palladium complex as a new heterogeneous nanocatalyst and application in carbon–carbon and carbon‐heteroatom cross‐coupling reactions

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