<b>Photolysis of Nitrite Esters in Solution. III. Photochemistry of Primary, Secondary and Tertiary Alkyl Nitrites</b>

Kabasakalian, Peter; Townley, Edward R.; Yudis, Milton D.

doi:10.1021/ja00873a015

Cited by 23 publications

(14 citation statements)

References 2 publications

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“…All of the analyzed alcohols led to the detection of the forecasted radical species, i.e., those observed when the corresponding nitrites ,, are photolyzed. Unexpectedly, the 1,4-anhydroerithritol (tetrahydro-3,4-furandiol) ( 6 ) and the 2-methylcyclopentanol ( 7 ) enabled us to detect (see Table ) the corresponding δ-valerolactam-1-oxyl-type radicals, respectively 8 (see Figure ) and 10 (see Figure ). Detection had failed when the pure nitrites were investigated.…”

Section: Resultsmentioning

confidence: 99%

A New Synthesis of Alkyl Nitrites: The Reaction of Alkyl Alcohols with Nitric Oxide in Organic Solvents

Grossi

Strazzari

1999

J. Org. Chem.

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In a nonaqueous solvent, alkyl nitrites can be easily achieved through the reaction of alkyl alcohols and gaseous NO. In the presence of air, the nitric oxide can in fact be oxidized to nitrous anhydride, which acts as a nitrosating agent. A quantitative study conducted on cycloalkyl alcohols has shown conversion yields to nitrites within the range 65-90%. This result has been validated by ESR spectroscopy experiments on several alkyl alcohols/NO mixtures, which lead to the detection of the same radical species detectable when a solution of the corresponding nitrites is photolyzed.

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Section: Resultsmentioning

confidence: 99%

A New Synthesis of Alkyl Nitrites: The Reaction of Alkyl Alcohols with Nitric Oxide in Organic Solvents

Grossi

Strazzari

1999

J. Org. Chem.

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“…Higher molecular weight nitrites have been explored to inhibit styrene and butadiene polymerization during distillation, generally requiring low concentrations (0.0001–0.1%) to be effective . Although alkyl nitrite photolysis has been extensively investigated, , their use as photoinhibitors has been limited to an examination of butyl nitrite (BN) as a UV-activated inhibitor of thermally initiated, radical-mediated chain-growth polymerization . The photochemical decomposition of organic nitrites results in the formation of nitric oxide, an efficient inhibitor of radical-mediated polymerizations, and alkoxide radicals capable of polymerization initiation.…”

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confidence: 99%

Volumetric Photopolymerization Confinement through Dual-Wavelength Photoinitiation and Photoinhibition

2019

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Conventional photolithographic rapid prototyping approaches typically achieve reaction confinement in depth through patterned irradiation of a photopolymerizable resin at a wavelength where the resin strongly absorbs, such that only a very thin layer of material is solidified. Consequently, three-dimensional objects are fabricated by progressive, two-dimensional addition of material, curtailing fabrication rates and necessitating the incorporation of support structures to ensure the integrity of overhanging features. Here, we examine butyl nitrite as a UV-active photoinhibitor of blue light-induced photopolymerizations and explore its utilization to confine in depth the region polymerized in a volume of resin. By employing two perpendicular irradiation patterns at blue and near-UV wavelengths to independently effect either polymerization initiation or inhibition, respectively, we enable three-dimensional photopolymerization patterning in bulk resin, thereby complementing emergent approaches to volumetric 3D printing.

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“…8–10,20–22 On the other hand, studies of larger condensed-phase radicals indicate that reaction r 4 becomes less important once RO radicals reach the size at which unimolecular isomerization is facile (i.e., in which a 1,5 H-atom shift from a secondary or tertiary carbon can occur), with decreases in observed ROH yields and increases in the yields of isomerization products. 23 While such studies suggest the dominance of reaction r 1 over r 4 for large RO radicals, they were carried out under oxygen-free conditions, with high concentrations of radicals, and so results may not be representative of radical reactivity in the atmosphere. Thus the relative importance of unimolecular and bimolecular reactions of large RO radicals is poorly constrained under relevant atmospheric conditions.…”

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confidence: 99%

“…23,32 Studies that instead showed the dominance of bimolecular reactions focused almost entirely on small (C 1 – C 4 ) radicals, 19 for which the 1,5-isomerization cannot occur, and for which fragmentation is known to be slow. Further, most previous studies were conducted under high concentrations (1 – 10%) of radical precursors, which may promote alkoxy disproportionation (RO + RO) reactions that form ROH and carbonyl species.…”

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confidence: 99%

Radical Reactivity in the Condensed Phase: Intermolecular versus Intramolecular Reactions of Alkoxy Radicals

Carrasquillo

Daumit

Kroll

2015

J. Phys. Chem. Lett.

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Condensed-phase alkoxy (RO) radicals can undergo unimolecular (e.g., intramolecular H-atom abstraction) reactions as well as bimolecular (intermolecular H-atom abstraction) reactions, though the competition between these two channels is not well constrained. Here we examine this branching, by generating RO radicals from the photolysis of a large alkyl nitrite (C20H41ONO) in hexanes, and nebulizing the mixture into an aerosol mass spectrometer for analysis. Product ions associated with unimolecular (isomerization) reactions were observed to increase upon photolysis. However, no formation of the C20 alcohol (C20H41OH, the expected product from RO + RH reactions) was observed, suggesting that bimolecular reactions are at most a minor channel for this condensed-phase system (involving saturated hydrocarbons). This result, combined with previous studies of condensed-phase RO radicals carried out at higher concentrations, suggests that when 1,5-H-atom abstraction reactions are facile (i.e., in which a 1,5-H-atom shift from a secondary or tertiary carbon can occur), this channel will dominate over bimolecular reactions.

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Photolysis of Nitrite Esters in Solution. III. Photochemistry of Primary, Secondary and Tertiary Alkyl Nitrites

Cited by 23 publications

References 2 publications

A New Synthesis of Alkyl Nitrites: The Reaction of Alkyl Alcohols with Nitric Oxide in Organic Solvents

A New Synthesis of Alkyl Nitrites: The Reaction of Alkyl Alcohols with Nitric Oxide in Organic Solvents

Volumetric Photopolymerization Confinement through Dual-Wavelength Photoinitiation and Photoinhibition

Radical Reactivity in the Condensed Phase: Intermolecular versus Intramolecular Reactions of Alkoxy Radicals

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