Amine Mediated Photoreduction of Aryl Ketones in <i>N</i>-Heterocyclic Ionic Liquids: Novel Solvent Effects Leading to Altered Product Distribution

Jones, Paul B.; Reynolds, Jhon L.; Brinson, Robert G.; Butke, Ryan L.

doi:10.1021/bk-2003-0856.ch030

Cited by 3 publications

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“…The classical example of Type II photoinitiators is benzophenone (BPh). Its photoreduction by amines (a typical Type II radical formation process; reaction 2a) has been investigated in N ‐heterocyclic ILs . Unlike the analogous reaction in organic solvents, the photoreduction of BPh in ILs by amines produces mainly the corresponding benzhydrol instead of benzpinacol.…”

Section: Photochemical Reactions In Ionic Liquidsmentioning

confidence: 99%

“…Unlike the analogous reaction in organic solvents, the photoreduction of BPh in ILs by amines produces mainly the corresponding benzhydrol instead of benzpinacol. The ratio of benzhydrol to benzpinacol is a function of the reduction potential of the intermediate ketyl radical . The possible explanation was a shift of equilibrium between pinacol radical–aminoalkyl radical pair and pinacol anion–aminoalkyl cation pair towards the ion pair; the latter is responsible for benzhydrol formation.…”

Section: Photochemical Reactions In Ionic Liquidsmentioning

confidence: 99%

“…The possible explanation was a shift of equilibrium between pinacol radical–aminoalkyl radical pair and pinacol anion–aminoalkyl cation pair towards the ion pair; the latter is responsible for benzhydrol formation. Interestingly, in non‐imidazolium‐based ILs only benzpinacol was obtained, which indicates the essential role of the 1‐butyl‐3‐methylimidazolium cation (its salts were found to be efficient electron acceptors). It is still not known whether such behaviour will have an impact on the initiation process; however, this photoinitating system should work because photoreduction of BPhs by amines in ILs was found to be efficient.…”

Section: Photochemical Reactions In Ionic Liquidsmentioning

confidence: 99%

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Photoinitiated polymerization in ionic liquids and its application

Andrzejewska

2016

Polymer International

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Ionic liquids (ILs) are low-melting organic salts often liquid at room temperature, whose unique properties are the reason of increasing interest for their applications as solvents, reaction media and functional additives. The exceptional properties of ILs have proved to be particularly useful in polymer science giving the potential to produce polymeric materials with improved properties or to immobilize ILs in polymer matrices while keeping their special characteristics. One of the possibilities is polymerization in ILs which can also affect positively polymerization reactions. An especially attractive technique is photopolymerization due to the ease of process control, short reaction time and ambient working temperature. This review gives a literature survey of developments in photopolymerization processes carried out in ILs as well as applications of these processes. It covers both the photopolymerization in ILs as well as photopolymerization of IL monomers. The first part presents a short overview of physicochemical and photochemical properties of ILs; it includes also photochemical reactions and photoinitiation of polymerization in ILs. The second part covers both the basic research (kinetics of photopolymerization including polymerization rate coefficients and polymerization of IL monomers) as well as applications of UV-induced polymerization in ILs.

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Section: Photochemical Reactions In Ionic Liquidsmentioning

confidence: 99%

Section: Photochemical Reactions In Ionic Liquidsmentioning

confidence: 99%

Section: Photochemical Reactions In Ionic Liquidsmentioning

confidence: 99%

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Photoinitiated polymerization in ionic liquids and its application

Andrzejewska

2016

Polymer International

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“…9 are very similar to those obtained upon photolysis of 1 and 2 in their crystalline states over similar temperature ranges (17). Because of the large differences expected between the reaction cavities afforded by the neat crystals and the 1P14BF4 salt (43–45), the effects observed in Fig. 9 cannot be ascribed solely to the ionic environment perceived by the oxoamides during photoreaction.…”

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Medium Effects on Zwitterionic-Biradicaloid Intermediates from Two Phenyl--α-oxoamides. Irradiations in Fluid and Solid Protic Media, Neat Solid Phases, and the Solid, Smectic and Isotropic Phases of a Completely Saturated Phosphonium Salt at Different Te

Chesta

George²,

Luo³

et al. 2007

Photochemistry and Photobiology

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The photochemical processes of two N,N-dialkyl phenyl-alpha-oxoamides, N,N-diisopropyl phenyl-alpha-oxoamide (1) and N,N-dibenzyl phenyl-alpha-oxoamide (2), are investigated at different temperatures in methanol and ethylene glycol (to probe the influences of H-bonding and viscosity), in the solid phase of D-sorbitol at room temperature (to compare with the results in the liquid alcohols and to assess the influence of a poorly organized "stiff" environment), in the neat solid phase (to probe the influence of well-ordered, "stiff" matrices), and in the solid, smectic A2 and isotropic phases of methyl-tris-tetradecylphosphonium tetrafluoroborate (1P14BF4) (to assess the ability of the intermediates to respond to subtle changes in the order and polarity of their local environments). From differences between the activation parameters for product pathways from irradiations in methanol and in 1P14BF4, we conclude that the zwitterionic pre-product intermediate from 1 is much more sensitive to the polarity, viscosity and order of its local environment than is the isomeric pre-product biradicaloid intermediate or either of the pre-product intermediates from 2. A very sensitive balance among the medium parameters, as well as internal steric and electronic factors of 1 and 2, controls the reactive pathways of the photochemically generated intermediates.

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Ionic liquid soluble photosensitizers

Hubbard

Jones

2005

Tetrahedron

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Amine Mediated Photoreduction of Aryl Ketones in N-Heterocyclic Ionic Liquids: Novel Solvent Effects Leading to Altered Product Distribution

Cited by 3 publications

References 0 publications

Photoinitiated polymerization in ionic liquids and its application

Photoinitiated polymerization in ionic liquids and its application

Medium Effects on Zwitterionic-Biradicaloid Intermediates from Two Phenyl--α-oxoamides. Irradiations in Fluid and Solid Protic Media, Neat Solid Phases, and the Solid, Smectic and Isotropic Phases of a Completely Saturated Phosphonium Salt at Different Te

Ionic liquid soluble photosensitizers

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