Relevant bibliographies by topics / Alkyl radical reactions

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  1. Journal articles
  2. Dissertations / Theses
  3. Book chapters
  4. Conference papers
  5. Reports

Academic literature on the topic 'Alkyl radical reactions'

Author: Grafiati
Published: 4 June 2021
Last updated: 1 February 2022

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Journal articles on the topic "Alkyl radical reactions"

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Kurandina, Daria, Padon Chuentragool, and Vladimir Gevorgyan. "Transition-Metal-Catalyzed Alkyl Heck-Type Reactions." Synthesis 51, no. 05 (February 7, 2019): 985–1005. http://dx.doi.org/10.1055/s-0037-1611659.

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The Heck reaction is one of the most reliable and useful strategies for the construction of C–C bonds in organic synthesis. However, in contrast to the well-established aryl Heck reaction, the analogous reaction employing alkyl electrophiles is much less developed. Significant progress in this area was recently achieved by merging radical-mediated and transition-metal-catalyzed approaches. This review summarizes the advances in alkyl Heck-type reactions from its discovery early in the 1970s up until the end of 2018.1 Introduction2 Pd-Catalyzed Heck-Type Reactions2.1 Benzylic Electrophiles2.2 α-Carbonyl Alkyl Halides2.3 Fluoroalkyl Halides2.4 α-Functionalized Alkyl Halides2.5 Unactivated Alkyl Electrophiles3 Ni-Catalyzed Heck-Type Reactions3.1 Benzylic Electrophiles3.2 α-Carbonyl Alkyl Halides3.3 Unactivated Alkyl Halides4 Co-Catalyzed Heck-Type Reactions5 Cu-Catalyzed Heck-Type Reactions6 Other Metals in Heck-Type Reactions7 Conclusion
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Guin, Joyram, Promita Biswas, and Subhasis Paul. "Synthesis of 3,3-Dialkylated Oxindoles by Oxidative Radical 1,2-Alkylarylation of α,β-Unsaturated Amides." Synlett 28, no. 11 (March 21, 2017): 1244–49. http://dx.doi.org/10.1055/s-0036-1588754.

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3,3-Dialkylated oxindoles (1,3-dihydro-2H-indol-2-ones), particularly those containing C3 quaternary stereogenic centers, occupy an important place in organic synthesis and drug discovery. The radical 1,2-alkylarylation of activated olefins with alkyl radicals has emerged as the most atom- and step-economical approach to 3,3-dialkylated oxindoles. This article covers important developments in the area of oxidative radical alkylation/cyclization cascade reactions of α,β-unsaturated amides toward the synthesis of alkyl-substituted oxindoles by employing a range of alkyl-radical precursors and various reaction conditions.
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Griesser, Markus, Jean-Philippe R. Chauvin, and Derek A. Pratt. "The hydrogen atom transfer reactivity of sulfinic acids." Chemical Science 9, no. 36 (2018): 7218–29. http://dx.doi.org/10.1039/c8sc02400f.

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Sulfinic acids are characterized to be very good H-atom donors to each of alkyl and alkoxyl radicals. In order to participate in useful radical chain reactions, the sulfonyl radicals must undergo fast propagating reactions to avoid autoxidation, which is surprisingly rate-limited by the reaction of sulfonyl radicals with oxygen.
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Baggott, J. E., H. M. Frey, P. D. Lightfoot, and R. Walsh. "Reactions of the formyl radical with alkyl radicals." Journal of Physical Chemistry 91, no. 12 (June 1987): 3386–93. http://dx.doi.org/10.1021/j100296a057.

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Elliot, A. John, Shahsultan Padamshi, and Jana Pika. "Free-radical redox reactions of uranium ions in sulphuric acid solutions." Canadian Journal of Chemistry 64, no. 2 (February 1, 1986): 314–20. http://dx.doi.org/10.1139/v86-053.

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The radiolytic reduction of uranyl ions in degassed sulphuric acid solutions containing various organic solutes was studied. It was shown that while ĊOOH, CO2−, and α-hydroxy-alkyl radicals reduced uranyl ions, the β-hydroxy-alkyl radicals and those derived from gluconic acid could not affect the reduction. The oxidation of uranium(IV) by hydrogen peroxide at pH 0.7 involves hydroxyl radicals in a chain mechanism but at pH 2.0 the oxidation proceeds by a non-radical reaction pathway. From the enhancement of the rate of oxidation of uranium(IV) by oxygen in the presence of 2-propanol, a mechanism involving the perhydroxyl radical, which reconciles earlier published data on kinetics and oxygen tracer studies, is proposed for the oxygen-uranium(IV) reactions.
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Murphy, John A. "Free radicals in synthesis. Clean reagents affording oxidative or reductive termination." Pure and Applied Chemistry 72, no. 7 (January 1, 2000): 1327–34. http://dx.doi.org/10.1351/pac200072071327.

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Neurotoxic organotin reagents currently play a key role in radical chemistry. As a result, this is an important area for development of new clean replacement reactions. The pharmaceutical industry in particular has had to avoid use of radical methodology for the formation of carbon_carbon bonds for this reason. With the current dawn in green chemistry, a host of new clean radical methods is beginning to flourish. Our aim has been to develop new nontoxic methodology for carbon_carbon bond formation by radical chemistry, which would provide either reductive termination (giving a hydrogen atom to the ultimate radical, as happens with tributyltin hydride), or oxidative functionalization, installing a useful polar group at the site of the ultimate radical. Two methods for effecting radical reactions in an environmentally friendly way are presented: (i) The tetrathiafulvalene (TTF)-mediated radical-polar crossover reaction converts arenediazonium salts to aryl radicals, which have sufficient lifetime to cyclize onto alkenes—the resulting alkyl radicals couple with TTF+• to afford sulfonium salts which, in turn, undergo solvolysis to alcohols, ethers or amides. The method provides the key step in a synthesis of (±)-aspidospermidine. (ii) Hypophosphite salts and hypophosphorous acid, on the other hand, form C_C bonds with reductive termination. These economical reagents afford radicals efficiently, starting from aryl iodides, alkyl bromides, and alkyl iodides, and give very easy separation of products from by-products.
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Renaud, Philippe, Alice Beauseigneur, Andrea Brecht-Forster, Barbara Becattini, Vincent Darmency, Sarkunam Kandhasamy, Florian Montermini, et al. "Boron: A key element in radical reactions." Pure and Applied Chemistry 79, no. 2 (January 1, 2007): 223–33. http://dx.doi.org/10.1351/pac200779020223.

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Boron derivatives are becoming key reagents in radical chemistry. Here, we describe reactions where an organoboron derivative is used as a radical initiator, a chain-transfer reagent, and a radical precursor. For instance, B-alkylcatecholboranes, easily prepared by hydroboration of alkenes, represent a very efficient source of primary, secondary, and tertiary alkyl radicals. Their very high sensitivity toward oxygen- and heteroatom-centered radicals makes them particularly attractive for the development of radical chain processes such as conjugate addition, allylation, alkenylation, and alkynylation. Boron derivatives have also been used to develop an attractive new procedure for the reduction of radicals with alcohols and water. The selected examples presented here demonstrate that boron-containing reagents can efficiently replace tin derivatives in a wide range of radical reactions.
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Fantin, Marco, Francesca Lorandi, Armando Gennaro, Abdirisak Isse, and Krzysztof Matyjaszewski. "Electron Transfer Reactions in Atom Transfer Radical Polymerization." Synthesis 49, no. 15 (July 4, 2017): 3311–22. http://dx.doi.org/10.1055/s-0036-1588873.

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Electrochemistry may seem an outsider to the field of polymer science and controlled radical polymerization. Nevertheless, several electrochemical methods have been used to determine the mechanism of atom transfer radical polymerization (ATRP), using both a thermodynamic and a kinetic approach. Indeed, electron transfer reactions involving the metal catalyst, initiator/dormant species, and propagating radicals play a crucial role in ATRP. In this mini-review, electrochemical properties of ATRP catalysts and initiators are discussed, together with the mechanism of the atom and electron transfer in ATRP.1 Introduction2 Thermodynamic and Electrochemical Properties of ATRP Catalysts3 Thermodynamic and Electrochemical Properties of Alkyl Halides and Alkyl Radicals4 Atom Transfer from an Electrochemical and Thermodynamic Standpoint5 Mechanism of Electron Transfer in ATRP6 Electroanalytical Techniques for the Kinetics of ATRP Activation7 Electrochemically Mediated ATRP8 Conclusions
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Sharma, Simmi, Shaista Sultan, Shekaraiah Devari, and Bhahwal Ali Shah. "Radical–radical cross coupling reactions of photo-excited fluorenones." Organic & Biomolecular Chemistry 14, no. 40 (2016): 9645–49. http://dx.doi.org/10.1039/c6ob01879c.

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Radical–radical cross coupling reactions of photoexcited 9-fluorenones have been accomplished for the first time, leading to the synthesis of 9-alkyl, pyrollidinyl and spiro-THF derivatives of 9-fluorenones.
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Eastwood, FW, RD Mifsud, and P. Perlmutter. "Acyclic Stereocontrol of Free Radical Reactions Involving Alkyl 2-(1-Hydroxyalkyl)propenoates." Australian Journal of Chemistry 47, no. 12 (1994): 2187. http://dx.doi.org/10.1071/ch9942187.

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The addition of cyclohexyl and t-butyl free radicals to silylated derivatives of alkyl 2-(1-hydroxyalkyl) propenoates was found to be stereoselective . In the case of the cyclohexyl radical the stereoselectivity was dependent upon the conditions used to generate the free radical and to quench the intermediate. Stereoselectivity in additions of the t-butyl radical was found to be temperature-dependent. In all cases stereoselectivity increased as the steric bulk of the group attached to the carbinol oxygen increased. A simple model which accounts for the stereoselectivity is proposed.
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Dissertations / Theses on the topic "Alkyl radical reactions"

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Brouard, M. "A flash photolysis study of atom plus reactions." Thesis, University of Oxford, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.371538.

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Sakurai, Shunya. "Development of Transformation Reactions with Alkylsilyl Peroxidesas Alkyl Radical Precursors under Cu Catalysis." Doctoral thesis, Kyoto University, 2021. http://hdl.handle.net/2433/263490.

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Sadeghipour, Mitra Jr. "Hydrocarbon Functionalization via a New Free Radical-Based Condensation Reaction." Diss., Virginia Tech, 1998. http://hdl.handle.net/10919/30627.

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A new free radical chain process for the allylation of hydrocarbons and some other substrates utilizing substituted allyl bromides (R-H + C=C-C-Br -> R-C-C=C + HBr) has been developed. Good to excellent yields were observed in all cases. Kinetic chain measurements and competition experiments were performed in order to elucidate the mechanism of the reaction. Overall, the results are consistent with a free radical chain process with bromine atom as the chain carrier. Substitution effects on the reactivity of the allyl bromides (CH2=C(Z)CH2Br) and their influence on the overall reaction rate were studied by conducting several competition experiments. The relative rate constants for addition of benzyl radical to CH2=C(Z)CH2Br are: Z=CN(180), COOEt(110), Ph(65), H(1.0). The trend of electronegativity/reactivity of these reactions was very similar to that reported for addition of benzyl radical to substituted alkenes. Other than alkyl aromatics (PhCH3, PhCH(CH3)2), other substrates (i.e., 2- propanol, phenyl cyclopropane) were also tested for this allylation reaction. The magnitude and scope of these reactions, and their synthetic utility is discussed.
Ph. D.
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Al-Niami, Kisma Hachim Ibrahim. "Unimolecular and bimolecular reactions of alkyl radicals." Thesis, University of Hull, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.328815.

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Seakins, Paul W. "Thermochemistry and reaction kinetics of alkyl radicals." Thesis, University of Oxford, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.276856.

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Basak, A. "Synthetic and biosynthetic studies based on radical and related processes." Thesis, University of Oxford, 1985. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.370310.

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Coleman, David Thornton III. "Involvement of radical intermediates in the reaction of alkyl halides with cuprates, the cannizzaro reaction, and the wittig reaction." Diss., Georgia Institute of Technology, 1986. http://hdl.handle.net/1853/27688.

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Patil, Shradha Vasant. "Radical additions of hydrocarbons, ethers and acetals to alkenes via allyl transfer reaction: A new chain reaction for C-H bond functionalization." Diss., Virginia Tech, 2013. http://hdl.handle.net/10919/50658.

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Functionalization of hydrocarbons via a free-radical based allyl transfer reaction using various allyl bromide substrates has been previously studied. The work described in this dissertation focuses on the replacement of Br by phthalimido-N-oxyl (PINO ) which helps make this chemistry environmentally friendly. To replace Br with PINO , replacement of previously used allyl-bromide substrates with new allyl-PINO substrates were necessary. Various allyl- PINO compounds were synthesized and the use of these allyl-phthalimido-N-oxyl (allyl-PINO) compounds for the functionalization of various alkyl aromatic hydrocarbons is demonstrated.
Kinetic studies were performed to observe the efficiency of the new chain reaction compared to the previously reported studies with allyl-bromides. We recently discovered that these allyl substrates are useful for the functionalization of ethers and acetals. The functionalization of various cyclic and acyclic ethers was performed using these allyl transfer reactions. This reaction was also performed in-solution, which allowed us to perform these reactions at low reagent concentrations. Kinetic chain lengths were measured for these reactions. High chain lengths were observed for all used ethers. Kinetic studies to investigate the rate of radical addition-elimination processes were performed using laser flash photolysis and competition kinetics. These experiments helped us to measure the reactivity and selectivity of PINO as a chain carrier in comparison with Br .
Additionally, a new competition experiment was designed to study the relative rate constant for
the 􀈕-fragmentation process. For this experiment a novel substrate that contains two leaving
groups, Br and PINO , was synthesized, and the relative rates of elimination of Br vs PINO
were compared.
Ph. D.
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Maury, Julien. "Nouveaux développements en chimie radicalaire des dialkylzincs : études mécanistiques et applications en synthèse." Thesis, Aix-Marseille, 2012. http://www.theses.fr/2012AIXM4351.

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Le travail présenté dans ce mémoire de thèse concerne pour l'essentiel, l'utilisation des dialkylzincs en tant que médiateurs de réactions radicalaires. La particularité de ces organométalliques réside dans le fait qu'ils sont, d'une part, de très bons précurseurs de radicaux alkyle en présence d'oxygène, et d'autre part, qu'ils peuvent subir des réactions de substitution homolytique bimoléculaire permettant de passer au cours d'une même réaction d'une espèce radicalaire à une espèce organométallique. Ainsi, les dialkylzincs sont de très bons médiateurs de réactions radicalaires et polaires en cascade en milieu aérobie.Cette méthodologie a été appliquée à la synthèse one-pot stéréosélective de γ-lactones disubstituées et de pyrrolizidines à partir du fumarate de diéthyle. La synthèse inédite de dérivés fumariques tri- et tétrasubstitués a été réalisée, à partir de l'acétylènedicarboxylate de diéthyle. Des cétoesters ont également été préparés à partir du bromoacrylate d'éthyle et de cétones silylées. L'utilisation d'azoture d'alkyle comme accepteur de radicaux s'est révélée infructueuse mais a permis de détecter une réactivité originale des azotures d'alkyle, qui en présence d'iodure de tertiobutyle, sont convertis en iodures correspondants. Enfin, une étude fondamentale par RPE du mécanisme d'oxydation des dialkylzincs a été réalisée afin de mieux appréhender les différences de comportement observées pour les divers dialkylzincs à l'échelle préparative
The research work reported in this thesis is essentially concerned with the use of dialkylzincs in radical reactions. The peculiar behavior of these organometallic reagents resides in the fact that they are good precursors of alkyl radicals in the presence of oxygen and that they are good partners for bimolecular homolytic substitution reactions that enable to generate polar species from radical ones. Thereby, dialkylzincs are reagents of choice to perform radical-polar cascades in aerobic medium.This methodology has been applied to the one-pot stereoselective synthesis of disubstituted γ-lactones and pyrrolizidines from diethylfumarate and to the original formation of tri- and tetrasubstituted fumaric derivatives from diethylacetylene dicarboxylate. Ketoesters have also been prepared from bromoethylacrylate and sylilated ketones. The use of alkyl azide as radical acceptor in this process failed but a new reactivity of alkyl azides was detected during this study, i.e, their original conversion into the corresponding alkyl iodides in the presence of t-BuI.Finally, mechanistic studies have been achieved to investigate the mechanism of the oxidation of dialkylzincs. EPR experiments have been performed with the aim to gain a better understanding of the behavior observed for various dialkylzincs at preparative scale
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Risberg, Erik. "Lewis acid Mediated Aza-Diels-Alder Reactions and Asymmetric Alkylations of 2H-azirines." Doctoral thesis, KTH, Chemistry, 2004. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-3822.

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This thesis describes the use of 2H-azirines, three-membered unsaturatednitrogen-containing heterocycles, as reactive intermediates ina number of Lewis acid promoted alkylations and Diels-Alderreactions providing synthetically useful aziridines.

In order to carry out this investigation a new generalprocedure for the ring closure of vinyl azides, forming theresultant 3-substituted-2H-azirines, was developed applying low boiling solventsin closed reaction vessels at elevated temperatures.

The addition of organolithium reagents in the presence ofcommercially available chiral ligands, to the 3-(2-naphthyl)-2H-azirine was studied, which gave the correspondingaziridines.

Several Lewis acids were shown to catalyze the normalelectron-demand Diels-Alder reaction between 3-alkyl-,3-aromatic-, and 3-ester-substituted 2H-azirines and various dienes. These reactions gave theexpected cycloadducts in moderate yields.

Using a chiral auxiliary high diastereoselectivity wasobtained in the addition of alkyl radicals to a8-phenylmenthyl-substituted 2H-azirine-3-carboxylate. The alkyl radicals weregenerated from the corresponding trialkyl borane and molecularoxygen. Hydroborations and transmetallations were used toprepare these trialkylboranes. Catalytic amounts of CuClincreased the diastereoselectivity in the radical additionreactions.

Attempts were made to explain how the coordination of aLewis acid to the azirine nitrogen atom affects thereactivity/stability of the azirine. DFT calculations and NMRexperiments involving Lewis acid-azirine complexes wereperformed.

Keywords:Enantioselective, diastereoselective, vinylazide, 2H-azirines, aziridines, Lewis acid, chiral ligand,chiral auxiliary, organolithiums, Diels-Alder reaction, alkylradicals, triethylborane.

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Book chapters on the topic "Alkyl radical reactions"

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Kajiwara, Atsushi. "Electron Spin Resonance (ESR) Observation of Radical Migration Reactions in the Polymerization of Alkyl Acrylates." In ACS Symposium Series, 49–59. Washington DC: American Chemical Society, 2009. http://dx.doi.org/10.1021/bk-2009-1023.ch004.

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Russell, Glen A., and Rajive K. Khanna. "Reactions of Alkyl Radicals with Nucleophiles." In Advances in Chemistry, 355–68. Washington, DC: American Chemical Society, 1987. http://dx.doi.org/10.1021/ba-1987-0215.ch025.

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Nielsen, O. J., M. Donlon, H. W. Sidebottom, and J. J. Treacy. "Reactions of OH Radicals with Alkyl Nitrates." In Physico-Chemical Behaviour of Atmospheric Pollutants, 309–14. Dordrecht: Springer Netherlands, 1990. http://dx.doi.org/10.1007/978-94-009-0567-2_47.

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Meyerstein, Dan. "Reactions of Alkyl Radicals in Aqueous Solutions*." In Alkane Functionalization, 73–103. Chichester, UK: John Wiley & Sons, Ltd, 2018. http://dx.doi.org/10.1002/9781119379256.ch4.

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Pedersen, Steen Uttrup, Torben Lund, Kim Daasbjerg, Mihaela Pop, Ingrid Fussing, and Henning Lund. "Investigation of the Coupling Reaction between Aromatic Radical Anions and Alkyl Radicals." In Novel Trends in Electroorganic Synthesis, 283–86. Tokyo: Springer Japan, 1998. http://dx.doi.org/10.1007/978-4-431-65924-2_85.

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Heicklen, Julian. "The Decomposition of Alkyl Nitrites and the Reactions of Alkoxyl Radicals." In Advances in Photochemistry, 177–272. Hoboken, NJ, USA: John Wiley & Sons, Inc., 2007. http://dx.doi.org/10.1002/9780470133446.ch4.

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Isemer, S. J., and K. Luther. "Shock tube studies on the high temperature chemical kinetics of allyl radicals: reactions with C2H2, CH4, H2 and C3H5 at 1000–1400 K." In Shock Waves, 609–14. Berlin, Heidelberg: Springer Berlin Heidelberg, 2005. http://dx.doi.org/10.1007/978-3-540-27009-6_91.

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André-Joyaux, E., L. Gnägi, C. Melendez, V. Soulard, and P. Renaud. "1.11 Generation of Radicals from Organoboranes." In Free Radicals: Fundamentals and Applications in Organic Synthesis 1. Stuttgart: Georg Thieme Verlag KG, 2021. http://dx.doi.org/10.1055/sos-sd-234-00224.

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AbstractRadicals can be generated by the cleavage of the C—B bond of alkylboranes or boronic acid derivatives. The fragmentation process may result from a nucleohomolytic substitution process or from a redox process. The nucleohomolytic substitution is ideal for the generation of alkyl radicals and is usually part of a chain-reaction process. Redox processes (mainly oxidative reactions) have been used to generate both alkyl and aryl radicals. The use of stoichiometric oxidizing agents can be avoided by employing photoredox catalysis. A broad range of synthetic applications such as radical cascade processes, multicomponent reactions, and cross-coupling reactions in the presence of suitable metal catalysts are now possible. In their diversity, organoboron compounds represent one of the most general sources of radicals. The merging of radical chemistry with the classical chemistry of organoboron derivatives opens tremendous opportunities for applications in organic synthesis.
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Zhang, J., D. Liu, and Y. Chen. "1.9 Oxygen-Centered Radicals." In Free Radicals: Fundamentals and Applications in Organic Synthesis 1. Stuttgart: Georg Thieme Verlag KG, 2021. http://dx.doi.org/10.1055/sos-sd-234-00177.

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AbstractOxygen-centered radicals (R1O•) are reactive intermediates in organic synthesis, with versatile synthetic utilities in processes such as hydrogen-atom transfer (HAT), β-fragmentation, radical addition to unsaturated carbon–carbon bonds, and rearrangement reactions. In this review, we focus on recent advances in the generation and transformation of oxygen-centered radicals, including (alkyl-, α-oxo-, aryl-) carboxyl, alkoxyl, aminoxyl, phenoxyl, and vinyloxyl radicals, and compare the reactivity of oxygen-centered radicals under traditional reaction conditions with their reactivity under visible-light-induced reaction conditions.
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Calvert, Jack G., John J. Orlando, William R. Stockwell, and Timothy J. Wallington. "Mechanisms of Reactions of HO2 and RO2 Radicals." In The Mechanisms of Reactions Influencing Atmospheric Ozone. Oxford University Press, 2015. http://dx.doi.org/10.1093/oso/9780190233020.003.0008.

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The peroxy radicals are an important link in the reaction chain that develops ozone in the atmosphere through their reactions with NO. This chapter explores the kinetics and mechanisms of these RO2 reactions. In Chapters III and IV, the kinetics and mechanisms of the reactions of organic compounds with the major atmospheric oxidants [HO, NO3, and O3] were discussed. The organic radicals formed in these reactions add O2 to form organic peroxy radicals (RO2). The rate coefficient for these reaction is typically of the order of (10−12–10−11) cm3 molecule−1 s−1 under tropospheric conditions. One atmosphere (1 atm) of air contains 5 × 1018 molecule cm−3 of O2, and the lifetime of organic radicals with respect to addition of O2 to give peroxy radicals is 10–100 nanoseconds. Addition of O2 is essentially the sole atmospheric fate of the organic radicals formed during the oxidation of organic compounds. As examples, consider the HO-initiated oxidation of ethane and acetone (M is a third body, such as N2, which collisionally deactivates the nascent peroxy radical): . . . HO + CH3CH3 → CH3CH2 + H2O . . . . . . CH3CH2 + O2 + M → CH3CH2O2 + M . . . . . . HO + CH3C(O)CH3 → CH3C(O)CH2 + H2O . . . . . . CH3C(O)CH2 + O2 + M → CH3C(O)CH2O2 + M . . . Because of the rapidity and exclusivity of the O2 addition to alkyl radicals, the organic peroxy radicals (CH3CH2O2 and CH3C(O)CH2O2) can be thought of as the primary products of the initial oxidation step. HO2 radicals are formed in reactions of O2 with alkoxy radicals (e.g., CH3O) and by the association reaction of H atoms with O2: . . . CH3O + O2 → CH2O + HO2 . . . . . . H + O2 + M → HO2 + M . . . Peroxy radicals (HO2 and RO2) have a rich atmospheric chemistry and undergo reactions with NO, NO2, HO2, and other peroxy radicals (R′O2). Unimolecular isomerization is also an important fate for larger organic peroxy radicals where the peroxy radical can abstract a hydrogen atom from another part of the organic moiety (the peroxy radical bites its own tail). Reactions of peroxy radicals with NO3 radicals at night, and ClO and BrO radicals in maritime environments, can also be of importance on local scales.
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Conference papers on the topic "Alkyl radical reactions"

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Gokulakrishnan, Ponnuthurai, Casey C. Fuller, and Michael S. Klassen. "Experimental and Modeling Study of C1 to C3 Hydrocarbon Ignition in the Presence of Nitric Oxide." In ASME Turbo Expo 2017: Turbomachinery Technical Conference and Exposition. American Society of Mechanical Engineers, 2017. http://dx.doi.org/10.1115/gt2017-65001.

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Nitric oxide produced during combustion will be present in vitiated air used in many devices with exhaust gas recirculation. An experimental and modeling investigation of the effect of nitric oxide on the ignition of C1 to C3 hydrocarbon fuels, namely, CH4, C2H4, C2H6 and C3H6, is presented. These molecules are important intermediate species generated during the decomposition of long-chain hydrocarbon fuel components typically present in jet fuels. Moreover, CH4 and C2H6 are major components of natural gas fuels. Although the interaction between NOx and CH4 has been studied extensively, limited experimental work is reported on C2H4, C2H6 and C3H6. NOx, even in very low concentrations, has previously been shown to effectively enhance the ignition of CH4. As a continuation of previous work with C3H8, ignition delay time measurements were obtained using a flow reactor facility with the alkanes (CH4 and C2H6) and olefins (C2H4 and C3H6) at 900 K and 950 K temperatures with 15 mole% and 21 mole% O2. Based on the experimental data, the overall effectiveness of NO in promoting ignition is found to be: CH4 > C3H6 > C3H8 > C2H6 > C2H4. CSE’s detailed kinetic mechanism, developed for natural gas fuel components, is used for model predictions as well as for sensitivity and species flux analyses. As expected, the reaction between HO2 and NO plays a critical role in promoting the ignition by generating the OH radical while converting NO into NO2. In addition, various important fuel-dependent reaction pathways that promote the ignition of these fuels are identified. H-atom abstraction by NO2 has significant contribution to the ignition of C2H4, and C2H6 whereas the reaction between NO2 and allyl radical (aC3H5) is an important route for the ignition of C3H6.
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2

Carr, Matthew A., Patrick A. Caton, Leonard J. Hamilton, Jim S. Cowart, Marco Mehl, and William J. Pitz. "An Experimental and Modeling-Based Study Into the Ignition Delay Characteristics of Diesel Surrogate Binary Blend Fuels." In ASME 2011 Internal Combustion Engine Division Fall Technical Conference. ASMEDC, 2011. http://dx.doi.org/10.1115/icef2011-60027.

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Abstract:
This study examines the combustion characteristics of a binary mixture surrogate for possible future diesel fuels using both a single-cylinder research engine and a homogeneous reactor model using detailed chemical reaction kinetics. Binary mixtures of a normal straight-chain alkane (pure n-hexadecane, also known as n-cetane, C16H34) and an alkyl aromatic (toluene, C7H8) were tested in a single-cylinder research engine. Pure n-hexadecane was tested as a baseline reference, followed by 50%, 70%, and 80% toluene in hexadecane blends. Testing was conducted at fixed engine speed and constant indicated load. As references, two conventional petroleum-based fuels (commercial diesel and US Navy JP-5 jet fuel) and five synthetic Fischer-Tropsch-based fuels were also tested. The ignition delay of the binary mixture surrogate increased with increasing toluene fraction and ranged from approximately 1.3 ms (pure hexadecane) to 3.0 ms (80% toluene in hexadecane). While ignition delay changed substantially, the location of 50% mass fraction burned did not change as significantly due to a simultaneous change in the premixed combustion fraction. Detailed chemical reaction rate modeling using a constant pressure, adiabatic, homogeneous reactor model predicts a chemical ignition delay with a similar trend to the experimental results, but shorter overall magnitude. The difference between this predicted homogeneous chemical ignition delay and the experimentally observed ignition delay is defined as the physical ignition delay due to processes such as spray formation, entrainment, mixing, and vaporization. On a relative basis, the addition of 70% toluene to hexadecane causes a nearly identical relative increase in both physical and chemical ignition delay of approximately 50%. The chemical kinetic model predicts that, even though the addition of toluene delays the global onset of ignition, the initial production of reactive precursors such as HO2 and H2O2 may be faster with toluene due to the weakly bound methyl group. However, this initial production is insufficient to lead to wide-scale chain branching and ignition. The model predicts that the straight-chain alkane component (hexadecane) ignites first, causing the aromatic component to be consumed shortly thereafter. Greater ignition delay observed with the high toluene fraction blends is due to consumption of OH radicals by toluene. Overall, the detailed kinetic model captures the experimentally observed trends well and may be able to provide insight as to the relationship between bulk properties and physical ignition delay.
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Reports on the topic "Alkyl radical reactions"

1

Neckers, D. C. Tetramethylammonium Phenyltrialkylborates in the Photoinduced Electron Transfer Reaction with Benzophenone. Generation of Alkyl Radicals and Their Addition to Activated Alkenes. Fort Belvoir, VA: Defense Technical Information Center, June 1995. http://dx.doi.org/10.21236/ada296065.

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2

Kelley, D. Kinetics and mechanisms of the reactions of alkyl radicals with oxygen and with complexes of Co(III), Ru(III), and Ni(III). Office of Scientific and Technical Information (OSTI), October 1990. http://dx.doi.org/10.2172/6454295.

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