Photo-CIDNP [chemically induced dynamic nuclear polarization] detection of transient intermediates.  Enol of acetophenone

Rosenfeld, Stuart M.; Lawler, Ronald G.; Ward, Harold R.

doi:10.1021/ja00784a065

Cited by 38 publications

(9 citation statements)

References 3 publications

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“…Individually, TTF and TCNQ are soluble in a variety of organic solvents, commercially available in bulk quantity, and are non‐conductive. The formation of the relatively insoluble charge‐transfer salt (Scheme ) occurs rapidly at room temperature, and preferentially forms the TTF‐TCNQ salt in a 1:1 molar ratio, even when TTF and TCNQ are not combined in equal amounts 16. Rapid and spontaneous generation of conductive TTF‐TCNQ via microcapsule delivery of solutions of its constituents could enable autonomous conductivity restoration.…”

Section: Introductionmentioning

confidence: 99%

Restoration of Conductivity with TTF‐TCNQ Charge‐Transfer Salts

Odom

Caruso

Finke

et al. 2010

Adv Funct Materials

137

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The formation of the conductive TTF‐TCNQ (tetrathiafulvalene–tetracyanoquinodimethane) charge‐transfer salt via rupture of microencapsulated solutions of its individual components is reported. Solutions of TTF and TCNQ in various solvents are separately incorporated into poly(urea‐formaldehyde) core–shell microcapsules. Rupture of a mixture of TTF‐containing microcapsules and TCNQ‐containing microcapsules results in the formation of the crystalline salt, as verified by FTIR spectroscopy and powder X‐ray diffraction. Preliminary measurements demonstrate the partial restoration of conductivity of severed gold electrodes in the presence of TTF‐TCNQ derived in situ. This is the first microcapsule system for the restoration of conductivity in mechanically damaged electronic devices in which the repairing agent is not conductive until its release.

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Section: Introductionmentioning

confidence: 99%

Restoration of Conductivity with TTF‐TCNQ Charge‐Transfer Salts

Odom

Caruso

Finke

et al. 2010

Adv Funct Materials

137

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“…For example, while pivalaldehyde has been detected by CIDNP as one of the products arising from the photolysis of di-t-butyl ketone (I), this aldehyde was not detected by means of 'Lonventionai product studies (2), presumably because the prolonged irradiation used for product studies decomposed the compound. More recently, CIDNP has been used to detect short-lived enols arising during the radiationinduced reaction of acetaldehyde (3) and acetophenone with phenol (4). The results of the acetaldehyde study are consistent with the conclusion that the main reaction path involves the transfer of the carbonyl hydrogen from one aldehyde molecule to a second one to give a radical pair consisting of an acetyl radical and an a-hydroxyethyl radical.…”

Section: Introductionmentioning

confidence: 54%

Photochemistry of Pivalaldehyde in Solution Studied by CIDNP

Chen¹,

Groen²,

Cocivera³

1973

Can. J. Chem.

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The n.m.r. spectruni observed during irradiation of pivalaldehyde dissolved in perfl~~oromethylcyclo-hexane indicates the formation of several compounds whose hydrogens are spin polarized. These compounds are 2-methylpropane, 2-methylpropene, and pivalaldehyde. A mechanism involving radical reactions which is consistent with these resillts is presented. According to this mechanism, the primary photochemical step is cleavage of the bond between the carbonyl carbon and the tertiary carbon of the t-butyl group. In contrast, this step does not appear to be important for acetaldehyde. As a test of the proposed mechanism CCI, is added to trap free radicals. In this case, one of the products is CC1,COH. A mechanism for the formation of this and the other products having nuclear spin polarization is presented.Le spectre r.ni.n. obtenu l o r~ de I'irradiation de la pivalaldChyde dissoute dans du perfluoroniethylcyclohexane, a lnontre qu'il se forniait plusieilrs produits. Ces coniposes sont le methyl-2 propane, le methyl-2 propene et la pivalaldehyde. On propose un niecanisme impliquant des reactions radicalaires qui serait en accord avec les ~esultats obtenus. Selon ce mecanisme, I'etape photochiniique fondanientale est la clivage de la liaison entre le carbone du carbonyle et le carbone tertiaire du groupe t-butyle. ALI contraire, cette Ctape ne senible pas importante en ce q i~i a trait 6 ]'acetaldehyde. Afin de prouver le micanisme propose, on ajouta du CCI, au melange rkactionnel pour isoler les radicaux libres: dans ce cas. I'un des produits isoles fut le CC1,COH. Un mecanisme est propose afin d'expliquer la formation de ce produit ainsi que des autres.[Traduit par le journal]Can. J. Chern., 51. 3032 (1973)

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“…The values for the carbon-13 chemical shifts of benzaldehyde (1), of the «-alkyl ketones from acetophenone (2) to heptanophenone (7), of the cycloalkyl phenyl ketones with cyclopropyl 8 up to cyclohexyl 11 groups, of isobutyrophenone (12), and of branched isomers of valerophenone 13-15 are given in Table I. As an example the dark and the photo-CIDNP spectra of propiophenone (3) are given in Figure 2.…”

Section: Resultsmentioning

confidence: 99%