Relevant bibliographies by topics / Solvolytic Reactions

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

Academic literature on the topic 'Solvolytic Reactions'

Author: Grafiati
Published: 5 June 2025
Last updated: 24 June 2025

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Journal articles on the topic "Solvolytic Reactions"

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Kevill, Dennis N., Byoung-Chun Park, and Jin Burm Kyong. "Evidence for general base catalysis by protic solvents in a kinetic study of alcoholyses and hydrolyses of 1-(phenoxycarbonyl)pyridinium ions under both solvolytic and non-solvolytic conditions." Collection of Czechoslovak Chemical Communications 74, no. 1 (2009): 43–55. http://dx.doi.org/10.1135/cccc2008164.

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The kinetics of nucleophilic substitution reactions of 1-(phenoxycarbonyl)pyridinium ions, prepared with the essentially non-nucleophilic/non-basic fluoroborate as the counterion, have been studied using up to 1.60 M methanol in acetonitrile as solvent and under solvolytic conditions in 2,2,2-trifluoroethan-1-ol (TFE) and its mixtures with water. Under the non- solvolytic conditions, the parent and three pyridine-ring-substituted derivatives were studied. Both second-order (first-order in methanol) and third-order (second-order in methanol) kinetic contributions were observed. In the solvolysis studies, since solvent ionizing power values were almost constant over the range of aqueous TFE studied, a Grunwald–Winstein equation treatment of the specific rates of solvolysis for the parent and the 4-methoxy derivative could be carried out in terms of variations in solvent nucleophilicity, and an appreciable sensitivity to changes in solvent nucleophilicity was found.
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Popsavin, Velimir, Mirjana Popsavin, and Dusan Miljkovic. "S-O acetyl rearrangement in 6-thio-D-glucose derivatives." Journal of the Serbian Chemical Society 83, no. 12 (2018): 1297–303. http://dx.doi.org/10.2298/jsc180811075p.

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The solvolytic reaction of 1,2-O-isopropylidene-3,6-di-O-(p-toluenesulphonyl)- ?-D-glucofuranose (2), as well as that of 6-chloro-6-deoxy-1,2-O-isopropylidene-3-O-(p-toluenesulphonyl)-?-D-glucofuranose (3), in the presence of potassium thioacetate unexpectedly gave the 6-S-acetyl-5-O-acetyl derivative 5 as the main reaction product. A possible mechanism of these transformations was postulated whereby the main role was ascribed to a neighbouring group participation process, involving hydrogen thio-orthoester formation as an intermediate. The regiospecific monosubstitution of the 6-tosyloxy group in compound 2 was successfully achieved with potassium thioacetate, in presence of 2,3-benzo-15-crown-5 as a catalyst. The corresponding 6-S-acetyl derivative 7 was obtained representing a possible intermediate in the mentioned solvolytic reactions. Compound 7 was shown to be very reactive, since it fully transformed into the corresponding mercaptan 8 in the presence of silica gel. This transformation occurred via the same thio-orthoester 7a as in the mentioned solvolytic reactions of furanoses 2 and 3. The synthesized compounds are key intermediates in the planned synthesis of selected natural products and their analogues.
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Mollin, Jiří, Pavlína Staňková, and Oldřiška Staňková. "The evidence and applications of equilibria between hydroxide and alkoxide ions in aqueous-alcoholic systems." Collection of Czechoslovak Chemical Communications 55, no. 11 (1990): 2614–23. http://dx.doi.org/10.1135/cccc19902614.

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The composition of solvolysis products of butyl bromide, acetanhydride, and benzoyl chloride has been followed aqueous alcohol in alkaline and (except for butyl bromide) also in neutral regions. The results have been used as a piece of evidence of the existence of equilibrium between hydroxide and alkoxide ions and for evaluation of the possibility of calculation of the concentration ratio of hydroxide and alkoxide ions from the concentration ratios of the products as well as for evaluation of selectivities of the solvolytic reactions for mechanistic purposes.
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Creary, Xavier, Vincent P. Casingal, and Charlene E. Leahy. "Solvolytic elimination reactions. Stepwise or concerted?" Journal of the American Chemical Society 115, no. 5 (1993): 1734–38. http://dx.doi.org/10.1021/ja00058a018.

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Park, Kyoung-Ho, Chan Joo Rhu, Jin Burm Kyong, and Dennis N. Kevill. "The Effect of the ortho Nitro Group in the Solvolysis of Benzyl and Benzoyl Halides." International Journal of Molecular Sciences 20, no. 16 (2019): 4026. http://dx.doi.org/10.3390/ijms20164026.

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A kinetic study was carried out on the solvolysis of o-nitrobenzyl bromide (o-isomer, 1) and p-nitrobenzyl bromide (p-isomer, 3), and o-nitrobenzoyl chloride (o-isomer, 2) in a wide range of solvents under various temperatures. In all of the solvents without aqueous fluoroalcohol, the reactions of 1 were solvolyzed at a similar rate to those observed for 3, and the reaction rates of 2 were about ten times slower than those of the previously studied p-nitrobenzoyl chloride (p-isomer, 4). For solvolysis in aqueous fluoroalcohol, the reactivity of 2 was kinetically more reactive than 4. The l/m values of the extended Grunwald–Winstein (G–W) equation for solvolysis of 1 and 2 in solvents without fluoroalcohol content are all significantly larger than unity while those in all the fluoroalcohol solvents are less than unity. The role of the ortho-nitro group as an intramolecular nucleophilic assistant (internal nucleophile) in the solvolytic reaction of 1 and 2 was discussed. The results are also compared with those reported earlier for o-carbomethoxybenzyl bromide (5) and o-nitrobenzyl p-toluenesulfonate (7). From the product studies and the activation parameters for solvolyses of 1 and 2 in several organic hydroxylic solvents, mechanistic conclusions are drawn.
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Thibblin, Alf. "Mechanisms of solvolytic alkene-forming elimination reactions." Chemical Society Reviews 22, no. 6 (1993): 427. http://dx.doi.org/10.1039/cs9932200427.

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CREARY, X., V. P. CASINGAL, and C. E. LEAHY. "ChemInform Abstract: Solvolytic Elimination Reactions. Stepwise or Concerted?" ChemInform 24, no. 27 (2010): no. http://dx.doi.org/10.1002/chin.199327089.

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Meng, Qingshui, and Alf Thibblin. "Mechanisms of solvolytic elimination reactions of tertiary substrates: stereospecific 1,2-elimination reactions." Journal of the Chemical Society, Perkin Transactions 2, no. 7 (1999): 1397–404. http://dx.doi.org/10.1039/a901296f.

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Smith, Peter James, and Jyotsna Pradhan. "Solvolysis of 2-substituted-9-(otrho-substituted phenylmethyl)fluoren-9-yltrimethylammonium ions in various solvents. The effect of steric crowding on alkene formation." Canadian Journal of Chemistry 64, no. 6 (1986): 1060–71. http://dx.doi.org/10.1139/v86-178.

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The solvolytic reaction of several 9-(ortho-substituted phenylmethyl)fluoren-9-yltrimethylammonium salts has been investigated in several different solvents. Substitution and elimination products were found for the reactions in all the solvents studied, with the exceptions that reaction in both tert-butyl alcohol and chloroform led exclusively to the alkene product. The observed rate constants for alkene formation and the percent alkene were measured and it was found that the di-ortho compounds reacted at a faster rate but produced less alkene than the reaction of the corresponding mono-ortho salts. Hydrogen–deuterium isotope effects were also determined for the various reactions. The results are discussed in terms of the reaction proceeding by way of the E1 mechanism, where steric acceleration promotes the loss of the bulky ammonium leaving group to give the carbocation intermediate.
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Creary, Xavier, Holia N. Hatoum, Angela Barton, and Timothy E. Aldridge. "Solvolytic elimination reactions of tertiary .alpha.-CSNMe2-substituted systems." Journal of Organic Chemistry 57, no. 6 (1992): 1887–97. http://dx.doi.org/10.1021/jo00032a051.

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Dissertations / Theses on the topic "Solvolytic Reactions"

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Norman, S. J. "Solvent and structural effects in solvolytic reactions." Thesis, Swansea University, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.638338.

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Rate Constants for the solvolysis of standard compounds have been used as a measure of solvent polarity. The Grunwald and Winstein equation utilized <i>tert</i>-butyl chloride for the Y scale. Y<SUB>X</SUB> scales for the 1- and 2-adamantyl derivatives have been established to correlate various substrates with different leaving groups. This thesis presents Y<SUB>OMs</SUB> results for binary aqueous mixtures of acetonitrile and dioxane which are classified as dipolar aprotic solvents. Y<SUB>Cl</SUB> values have also been obtained. When compounds containing one aromatic ring such as <i>p</i>-methoxybenzoyl chloride are correlated against Y<SUB>Cl</SUB> the plot splits into separate lines for each binary mixture. It is shown that <i>p</i>-methoxybenzyl chloride eliminates this effect because positive charge can be delocalized onto the benzene ring. There is a notably good correlation with Z values: the solvent polarity scale based on the charge transfer absorption band of a pyridinium ion. Free energy relationships like rate-rate profiles can indicate a change in mechanism if a break occurs. This is observed for benzoyl chloride which reacts by a dissociative pathway in highly aqueous media and an addition-elimination pathway in less aqueous media. The compositions of acetonitrile and dioxane where the competing reaction channel contributes 50% to the overall rate have been located and the dissociative channel dissected. The benzhydryl system has been used to provide a rate ratio for tosylates and <i>p</i>-nitrobenzoate leaving groups. The reactive mesylate was prepared on a small scale and transferred to a conductivity cell without isolation. the <i>p</i>-nitrobenzoate was analysed by HPLC which is suitable for much slower reactions. The ratio obtained was compared to previous values for which steric and temperature considerations are important. Also studied were the solvolyses of bicyclo[2.1.1] hexyl and tricyclo[23.1.00<SUP>2,6</SUP>] hexyl tosylates which proceeded with anchimeric assistance. The corresponding ditosylates had rate constants 3 x 10<SUP>3</SUP> smaller in 80% ethanol-water at 25<SUP>o</SUP>C mainly due to inductive effects.
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Zeng, Xiaofeng. "Mechanisms for Solvolytic Elimination and Substitution Reactions Involving Short-lived Carbocation Intermediates." Doctoral thesis, Uppsala University, Organic Chemistry, 2002. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-2565.

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<p>Solvolysis reactions of a range of tertiary substrates in largely aqueous solvents were studied in such respects as β-deuterium kinetic isotope effects, linear free energy relationships and stereochemistry.</p><p>Solvolysis of the fluorene derivatives 9-methyl–9-(2´-X-2´-propyl)fluorene (<b>1-X,</b> X = Cl, Br, OOCCF<sub>3</sub>) involves a very short-lived carbocation intermediate. The fraction of alkene is increased by addition of general bases, which can be expressed by a Brφnsted parameter β = 0.07. The kinetic deuterium isotope effects vary with solvent composition in a way which is not consistent with a common carbocation intermediate which has time to choose between dehydronation and addition of a solvent water molecule. </p><p>In the absence of bases, the reaction of 4-chloro-4-(4´-nitrophenyl)pentan-2-one (<b>2-Cl</b>) proceeds through a short-lived carbocation intermediate yielding 4-(4´-nitrophenyl)-2-oxopent-4-ene (<b>2-</b><b>t</b>-ne)as the main elimination product. Addition of acetate ion and other weak bases results in the base-promoted E2 (or E1cb) reaction to give (<i>E</i>)-4-(4´-nitrophenyl)-2-oxopent-3-ene (<b>2-</b><b>E</b>-ne) and (<i>Z</i>)-4-(4´-nitrophenyl)-2-oxopent-3-ene(<b>2-</b><b>Z</b>-ne). There is no evidence for a water-promoted E2 (or E1cb) reaction.</p><p>The stereochemistry studies of elimination from (<i>R,S</i> and <i>S,R</i>)-[1-(3´-fluoro)phenyl-2-methyl]cyclopentyl-<i>p-</i>nitrobenzoate (<b>3-PNB</b>) and its (<i>R</i>,<i>R</i> and <i>S,S</i>)isomer <b>3´-PNB</b> and (<i>R,S</i> and <i>S,R</i>)-[1´-(3´´-fluoro)phenyl-2´-methylcyclopentyl]-2,2,2-trifluoroacetate(<b>3-OOCCF</b><b>3</b>) exclude the concerted pericyclic elimination mechanism for formation of the alkene 1-(3´-fluoro)phenyl-2-methylcyclopentene(<b>3-</b><b>m</b>-ne). The effects of added thiocyanate ion and halide ions on the solvolysis reaction are discussed.</p><p>Mass spectrometry analysis showed complete incorporation of the labeled oxygen from solvent water into the product 2-hydroxy-2-phenyl-3-butene (<b>4-OH</b>), confirming that it is the tertiary carbon-oxygen bond that is broken in the acid-catalyzed solvolysis of 2-methoxy-2-phenyl-3-butene (<b>4-OMe</b>). The mechanism for the dominant formation of the less stable <b>4-OH</b> is discussed.</p>
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Ussing, Bryson Richard. "Systematic examination of dynamically driven organic reactions via kinetic isotope effects." Texas A&M University, 2006. http://hdl.handle.net/1969.1/4877.

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Organic reactions are systematically examined experimentally and theoretically to determine the role dynamics plays in the outcome of the reaction. It is shown that trajectory studies are of vital importance in understanding reactions influenced by dynamical motion. This dissertation discusses how a combination of kinetic isotope effects, theoretical calculations, and quasiclassical dynamics trajectories aid in the understanding of the solvolysis of p-tolyldiazonium cation in water, the cycloadditions of cyclopentadiene with diphenylketene and dichloroketene, and the cycloaddition of 2- methyl-2-butene with dichloroketene. In the solvolysis of p-tolyldiazonium cation, significant 13C kinetic isotope effects are qualitatively consistent with a transition state leading to formation of an aryl cation, but on a quantitative basis, the isotope effects are not adequately accounted for by simple SN1 heterolysis to the aryl cation. The best predictions of the 13C isotope effects for the heterolytic process arise from transition structures solvated by clusters of water molecules. Dynamic trajectories starting from these transition structures afford products very slowly. The nucleophilic displacement process for aryldiazonium ions in water is determined to be at the boundary of the SN2Ar and SN1 mechanisms. The reaction of cyclopentadiene with diphenylketene affords both [4 + 2] and [2 + 2] cycloadducts directly. This is surprising. There is only one low-energy transition structure for adduct formation. Investigation of this reaction indicates that quasiclassical trajectories started from a single transition structure afford both [4 + 2] and [2 + 2] products. Overall, an understanding of the products, rates, selectivities, isotope effects, and mechanism in these reactions requires the explicit consideration of dynamic trajectories.
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Ebdon, D. N. "A mechanistic study of the solvolyis reactions of selected phosphoryl chlorides and p-anisoyl chloride." Thesis, Swansea University, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.636761.

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Throughout the 1990's several investigators have used a mechanistic theory based upon third order kinetics to explain the rates of the reactions of several substrates in aqueous mixtures of protic (e.g. methanol) an aprotic (e.g. acetone) solvents. Such substrates investigated have included <I>p</I>-nitrobenzoyl chloride and <I>p</I>-nitrobenzenesulfonyl chloride. Reactions of these substrates in aqueous alcohols yield two products; an acid (RCO<SUB>2</SUB>H and RSO<SUB>3</SUB>H) and an ester (RCO<SUB>2</SUB>R and RSO<SUB>3</SUB>R). Measurements of the relative amounts of the products obtained from these reactions has enabled investigators to calculate selectivity values, S (S = [Ester]/[Acid] x [Water]/[Alcohol]). Both the rates and products (selectivities) of these reactions have been successfully explained by this third order theory. This thesis (Chapters 1-5) is primarily concerned with testing the third order theory further by investigating the reactions of selected phosphoryl chlorides (e.g. diphenyl-chlorophosphate, (PhO)<SUB>2</SUB>POCl) in aqueous mixtures of protic and aprotic solvents. Some of the results obtained in this thesis strongly support the theory whilst some unexpected results have been explained by initial state solvation effects. Unexpected changes in selectivity in highly aqueous mixtures of methanol and ethanol (e.g. 10-30%) may be caused by complex solvent-solvent interactions in these solvents. Chapter six of this thesis is not concerned with the third order theory investigated in Chapters 1-5. Previous investigations of the solvolyses of <I>p</I>-methoxybenzoyl (anisoyl) chloride in aqueous methanol and ethanol have resulted in an S<SUB>N</SUB>1 type mechanism involving solvent separated ion pairs being postulated. Selectivities for these solvolyses are constant over the whole range of methanol-water and ethanol-water mixtures investigated (10-90%, % v/v) with the selectivity in ethanol being less than in methanol. These constant selectivities have provided an opportunity to investigate aqueous mixtures of other alcohols (e.g. propanols and butanols) and to discover whether effects such selective solvation of anisoyl chloride by alcohol occurs. Any changes in the pattern of selectivity might be due to such effects and not a change in mechanism because anisoyl chloride is reluctant to react via associative mechanisms even in solvents of low ionising power (e.g. ethanol).
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Firmino, Thiago Diamond Reis. "Reações de solvólise em fase gasosa do cátion +SiCl3: experimento e teoria." Universidade de São Paulo, 2010. http://www.teses.usp.br/teses/disponiveis/46/46132/tde-20072010-201222/.

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Íons polihalogenados de Si, X3Si+ (X = F, Cl), são fragmentos facilmente gerados em espectrometria de massas por ionização eletrônica de compostos de silício polihalogenados. Estes cátions possuem um elevado caráter eletrofílico e desempenham um papel importante como intermediários em processos de corrosão auxiliados por plasma utilizados na fabricação de dispositivos em microeletrônica. Esta dissertação apresenta um estudo sobre a reatividade dos íons +SiCl3, em fase gasosa, perante uma série de substratos neutros simples como água, alcoóis, amônia, aminas e algumas bases doadoras de elétrons &pi;. As reações íon-molécula em fase gasosa foram caracterizadas do ponto de vista experimental por espectrometria de massas de ressonância ciclotrônica de íons por transformada de Fourier (FTICR) a pressões da ordem de 10-8 Torr. As reações foram acompanhadas em função do tempo de reação na cela do espectrômetro, o que permitiu a elucidação de uma série de reações sequenciais. O perfil de energia das reações e as estruturas dos íons silicênios formados nestas reações foram também caracterizados por métodos de química computacional, usando métodos ab initio e métodos baseados na teoria do funcional da densidade, a fim de elucidar o mecanismo das reações. Observou-se que o cátion +SiCl3 reage rapidamente em fase gasosa com os diversos substratos neutros através de processos semelhantes a reações de solvólise que resultam na adição do neutro seguida de eliminação de HCl. Em vários dos casos, foi possível observar a solvólise total do cátion com substituição dos três átomos de cloro. Os cálculos revelam que estas reações se processam inicialmente pela adição do eletrófilo aos centros ricos em densidade eletrônica dos substratos neutros e que estes adutos são mais estáveis que os reagentes isolados. O estado de transição destas reações envolve uma migração 1,3 de um hidrogênio e a energia calculada para o estado de transição é consideravelmente menor que a energia dos reagentes, fato este comum para reações rápidas íon/molécula em fase gasosa. Os cálculos para a espécie correspondente +CCl3 revelam que este tipo de reação não é favorável para os cátions metílicos substituídos e experimentalmente reações semelhantes não são observadas para +CCl3. No caso dos íons ClnSi(OH)3-n+ (n=1, 2 e 3), oriundos das reações de hidrólise do íon +SiCl3, observou-se reações secundárias de condensação com SiCl4 que levam a formação de espécies iônicas com ligações tipo siloxanas (-Si-O-Si-). Os cálculos teóricos sugerem que estas reações se processam inicialmente através de um intermediário tipo clorônio, R1-Cl+-R2 seguida de uma transferência formal de um átomo de Cl e rearranjo para uma estrutura tipo siloxana.<br>Polyhalogenated silicenium ions, X3Si+ (X = F, Cl), are common fragment ions in the mass spectra of polyhalogenated silanes obtained by electron ionization. These ions are powerful electrophiles and are believed to play a role in plasma enhanced corrosion processes and plasma enhanced chemical vapour deposition processes. In this dissertation, we present some new results on the gas-phase reactivity of the +SiCl3 ion with a number of simple n electron donor bases such as water, alcohols, ammonia, amines and some &pi; electron donor bases. Ion-molecule reactions were characterized experimentally by Fourier transform ion cyclotron resonance mass spectrometry (FTICR) at pressures in the 10-8 Torr range. Reactions were followed as a function of trapping time of the ions in the cell of the spectrometer and this allowed for the identification of subsequent reactions of the primary product ions. The energy diagram and structure of the different silicenium ions were also characterized by computational chemistry using both ab initio and density functional theory methods in order to understand the mechanism of these reactions. +SiCl3 reacts rapidly in gas phase with various neutral substrates through processes similar to solvolysis in which the neutral substrate adds onto the silicenium ion followed by elimination of HCl. In some cases, complete solvolysis is observed with substitution of all three chlorine atoms. The calculations show that reactions proceed by initial addition of the electrophile onto the electron center of the neutral substrates giving rise to stable adducts. The transition state for these reactions involve a 1,3 hydrogen migration and the calculated energy for these transition states is less than the energy of the isolated reactants, a fact that is common to fast gas-phase ion-molecule reactions. Similar calculations for +CCl3 reveal similar solvolysis reactions to be energetically unfavourable, and in fact these reactions are not observed experimentally. Secondary reactions have been observed for the product ions ClnSi(OH)3-n+ (n = 1, 2 and 3), obtained from successive hydrolysis of +SiCl3, with the parent SiCl4 neutral. These secondary condensation reactions yield ionic species containing a siloxane type linkage (-Si-O-Si-). The theoretical calculations suggest that is that these secondary condensation reactions initially proceed via chloronium ion intermediate, R1-Cl+-R2 , followed by formal Cl transfer and rearrangement to a siloxane type structure.
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Quteishat, Laith. "Contribution à la synthèse totale de la céphalotaxine." Thesis, Paris 11, 2013. http://www.theses.fr/2013PA114846/document.

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Depuis plus de 40 ans des chimistes se sont intéressés à l’extraction, à l’activité biologique et à la synthèse de l’homoharringtonine (HHT), un ester naturel de la céphalotaxine, qui est un puissant antileucémique utilisé pour le traitement des leucémies résistantes aux inhibiteurs de tyrosine kinase. Ces alcaloïdes sont extraits de Cephalotaxus, des conifères originaires du sud de la Chine à croissance extrêmement lente et menacés d’extinction. Leur synthèse est donc nécessaire. L’homoharringtonine utilisée en thérapeutique est obtenue à partir de (-)-céphalotaxine d’origine naturelle, par greffage d’une chaîne latérale acide suivie de purifications longues et coûteuses. L’objectif de ce travail consiste à développer une synthèse concise de la (-)-céphalotaxine, afin de s’affranchir de la ressource naturelle, de ce fait de garantir un approvisionnement d’HHT de qualité constante et de développer des analogues de seconde génération.Les stratégies développées dans ce travail ont consisté à développer une synthèse très concise de la céphalotaxine, d’une part en valorisant un synthon ABC nitrile pour y introduire les deux atomes de carbone manquant au squelette de la céphalotaxine, et d’autre part à améliorer l’accès à une synthon analogue ABC ester pour en étudier la réactivité. Ces travaux ont conduit à décrire un nouveau complexe arène chrome pentacarbonyle analogue de céphalotaxine, une méthode originale et efficace de cyclisation anionique d’imide formant un squelette 3-benzazépine à l’aide d’une nouvelle combinaison de bases, le tert-butylate de potassium et le carbonate de potassium agissant en synergie, et une nouvelle méthode de solvolyse de nitrile aliphatiques ou aromatiques sous micro-ondes qui a été exemplifiée<br>For over 40 years, chemists are interested in the extraction, biological activity and synthesis Homoharringtonine (HHT ), a natural cephalotaxine ester, which is a potent antileukemic used therapeutically, especially leukemias resistant against tyrosine kinase inhibitors. These alkaloids are extracted from Cephalotaxus, evergreen trees from southern China having extremely slow growth and are in extinction. Their synthesis is thus necessary. Homoharringtonine used therapeutically is obtained from (-)-cephalotaxine of natural origin, by grafting an acidic side chain followed by lengthy and expensive purifications. The objective of this work is to develop a concise synthesis of (-)-cephalotaxine to get rid of the natural resource, thereby ensuring a supply of constant quality and develop similar second generation of HHT.The strategies developed in this work has been to develop a very concise synthesis of cephalotaxine , firstly by enhancing an ABC nitrile synthon to introduce the two carbon atoms missing to the backbone of cephalotaxine , and secondly to improve access to similar ABC ester synthon to investigate its reactivity. This work led to describe a new arena complex chromium pentacarbonyle cephalotaxine analog, an original and efficient method of anionic cyclization of imide forming a 3-benzazepine skeleton using a new combination of bases , potassium tert -butoxide and potassium carbonate acting synergistically, and a new method of aliphatic or aromatic nitrile solvolysis under microwave which was exemplified
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Chamseddine, Yssam. "Sondes mecanistiques chirales et/ou regioselectivement deuteriees : application a l'etude de quelques processus de substitution nucleophile." Paris 6, 1988. http://www.theses.fr/1988PA066133.

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Lin, Yen-Shyi, and 林岩錫. "Studies on the Solvolytic Reactions of 9-fluorenyl Derivatives and Related Substrates." Thesis, 1997. http://ndltd.ncl.edu.tw/handle/43650832084025097631.

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秦建譜. "Studies on Solvolytic Reactions of Secondary Benzylic、Benzhydryl and Highly Hindered Tertiary Benzylic Substrates." Thesis, 1996. http://ndltd.ncl.edu.tw/handle/41899122152091917139.

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Chang, Chih-Wei, and 張志偉. "Studies on the Solvolysis Reactions of Highly Hindered Benzhydryl and 9-Fluorenyl Substrates." Thesis, 1998. http://ndltd.ncl.edu.tw/handle/12571597271252574433.

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碩士<br>國立臺灣大學<br>化學系<br>86<br>In chapter 1, we use 2-naphthyl-2-adamantyl p-nitrobenzoate to measure the solvolysis rate constant and to show the necessary that develop the YxBnX scales. In chapter 2 and chapter 3，we use Grundwald-Winstein equation correlation analysis ortho-methyl substituted of benzhydryl and 9-aryl-9-fluorenyl substrates. For benzhydryl substrates，we can know the different effect by means of solvolysis when the increase of ortho-methyl group. The log k value of 9-aryl-9-fluorenyl derivatives handles correlation analysis with different Y scales，When the aryl ring have nonsubstituted or monosubstituted group，9-aryl-9-fluorenyl cation can extensive charge delocalization throughout the aryl ring and 9-fluorenyl ring。The more methyl group increase on aryl ring，the higher crowded reaction center. The phenomenon of electrophilic pull will be obvious to leaving group
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Book chapters on the topic "Solvolytic Reactions"

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Zingaro, R. A. "O-Sb Bonds by Solvolytic Reactions." In Inorganic Reactions and Methods. John Wiley & Sons, Inc., 2007. http://dx.doi.org/10.1002/9780470145197.ch114.

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Gallego, Mar Gómez, and Miguel A. Sierra. "Level 3 - Case 35 Solvolysis of Vinyl Iodonium Salts." In Organic Reaction Mechanisms. Springer Berlin Heidelberg, 2004. http://dx.doi.org/10.1007/978-3-642-18788-9_35.

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Gallego, Mar Gómez, and Miguel A. Sierra. "Level 3 - Case 40 Solvolysis of 8-Deltacyclyl Brosylates." In Organic Reaction Mechanisms. Springer Berlin Heidelberg, 2004. http://dx.doi.org/10.1007/978-3-642-18788-9_40.

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Gallego, Mar Gómez, and Miguel A. Sierra. "Level 1 — Case 9 Solvolysis of Electron-Deficient Norbornyl Triflates." In Organic Reaction Mechanisms. Springer Berlin Heidelberg, 2004. http://dx.doi.org/10.1007/978-3-642-18788-9_9.

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Zingaro, R. A. "From Solvolysis of the As-N or the As-P Bond." In Inorganic Reactions and Methods. John Wiley & Sons, Inc., 2007. http://dx.doi.org/10.1002/9780470145197.ch105.

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Okuyama, Tadashi, and Howard Maskill. "Rearrangement Reactions involving Polar Molecules and Ions." In Organic Chemistry. Oxford University Press, 2013. http://dx.doi.org/10.1093/hesc/9780199693276.003.0022.

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This chapter focuses on the [1,2] sigmatropic rearrangements. It shows how 1,2-shifts in carbenium ion intermediates in solvolytic reactions, for example, can be considered as [1,2] sigmatropic rearrangements, and (consequently) related to concerted sigmatropic rearrangements of nonpolar compounds. The MO description of these simple 1,2-shifts in carbenium ions can be extended to describe the rearrangement steps in more complicated multistep heterolytic reactions. The chapter also details the catalysed rearrangement of carbonyl compounds involving 1,2-shifts, then investigates the 1,2-shifts from carbon to oxygen and nitrogen. Finally, the chapter covers the stepwise rearrangements via cyclic intermediates formed by neighbouring group participation. It also looks at the rearrangements involving carbenes and nitrenes or their precursors.
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Henderson, Richard A. "Catalysed substitution reactions." In The Mechanisms of Reactions at Transition Metal Sites. Oxford University Press, 1993. http://dx.doi.org/10.1093/hesc/9780198557463.003.0006.

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This chapter shows how the rates of substitution reactions at a variety of metal sites can be accelerated by base, acid, or electron transfer. It mentions Werner-type complexes of cobalt(III), chromium(III), ruthenium(III), rhodium (III), and iridium(III), which are the most extensively studied system showing base catalysis. What generated interest in these reactions was the apparent anomaly in the reaction of hydroxide that appears to be an exception to the general rule that the rate of substitution at cobalt(III) complexes show the characteristics of a dissociative mechanism. In addition, reactions with hydroxide were faster than the corresponding rates of solvolysis typically studied in acidic solution. The chapter explains that the main feature of this mechanism is the deprotonation of an anime ligand which generates the conjugate base of the complex.
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Richard, John P., Tina L. Amyes, Maria M. Toteva, and Yutaka Tsuji. "Dynamics for the reactions of ion pair intermediates of solvolysis." In Advances in Physical Organic Chemistry. Elsevier, 2004. http://dx.doi.org/10.1016/s0065-3160(04)39001-5.

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Jolivet, Jean-Pierre. "Water and Metal Cations in Solution." In Metal Oxide Nanostructures Chemistry. Oxford University Press, 2019. http://dx.doi.org/10.1093/oso/9780190928117.003.0005.

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Water has an exceptional ability to dissolve minerals. It is safe and chemically stable, and it remains liquid over a wide temperature range. Thus, it is the best solvent and reaction medium for both laboratory and industrial purposes. Water is able to dissolve ionic and ionocovalent solids because of the high polarity of the molecule (dipole moment μ = 1.84 Debye) as well as the high dielectric constant of the liquid (ε = 78.5 at 25°C). This high polarity allows water to exhibit a strong solvating power: that is, the ability to fix onto ions as a result of electrical dipolar interactions. Water is also an ionizing liquid able to polarize an ionocovalent molecule. For example, the solvolysis phenomenon increases the polarization of the HCl molecule in aqueous solution. Finally, owing to the high dielectric constant of the liquid, water is a dissociating solvent that can decrease the electrostatic forces between solvated cations and anions, allowing their dispersion as H+solvated and Cl−solvated through the liquid. (The attractive force F between charges q and q′ separated by the distance r is given by Coulomb’s law, F = qq′/εr2.) These characteristics are rarely found together in common liquids. The dipole moment of the ethanol molecule (μ = 1.69 Debye) is close to that of water, but the dielectric constant of ethanol is much lower (ε = 24.3). Ethanol is a good solvating liquid, but a poor dissociating one; consequently, it is considered a bad solvent of ionic compounds. Dissolution in water of an ionic solid such as sodium chloride is limited to dipolar interactions with Na+ and Cl− ions and their dispersion in the liquid as solvated ions, regardless of the pH of the solution. Cations with higher charge, especially cations of transition metals, retain a fixed number of water molecules, thereby forming a true coordination complex [M(OH2)N]z+ with a well-defined geometry. In addition to the dipolar interactions, water molecules behave as true ligands because they are Lewis bases exerting an electron σ-donor effect on the empty orbitals of the cation.
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Lambert, Tristan H. "Functional Group Interconversion." In Organic Synthesis. Oxford University Press, 2015. http://dx.doi.org/10.1093/oso/9780190200794.003.0004.

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Chaozhong Li of the Shanghai Institute of Organic Chemistry reported (J. Am. Chem. Soc. 2012, 134, 10401) the silver nitrate catalyzed decarboxylative fluorination of carboxylic acids, which shows interesting chemoselectivity in substrates such as 1. A related decarboxylative chlorination was also reported by Li (J. Am. Chem. Soc. 2012, 134, 4258). Masahito Ochiai at the University of Tokushima has developed (Chem. Commun. 2012, 48, 982) an iodobenzene-catalyzed Hofmann rearrangement (e.g., 3 to 4) that proceeds via hypervalent iodine intermediates. The dehydrating agent T3P (propylphosphonic anhydride), an increasingly popular reagent for acylation chemistry, has been used (Tetrahedron Lett. 2012, 53, 1406) by Vommina Sureshbabu at Bangalore University to convert amino or peptide acids such as 5 to the corresponding thioacids with sodium sulfide. Jianqing Li and co-workers at Bristol-Myers Squibb have shown (Org. Lett. 2012, 14, 214) that trimethylaluminum, which has long been known to effect the direct amidation of esters, can also achieve the direct coupling of acids and amines, such as in the preparation of amide 8. The propensity of severely hindered 2,2,6,6-tetramethylpiperidine (TMP) amides such as 9 to undergo solvolysis at room temperature has been shown (Angew. Chem. Int. Ed. 2012, 51, 548) by Guy Lloyd-Jones and Kevin Booker-Milburn at the University of Bristol. The reaction proceeds by way of the ketene and is enabled by sterically induced destabilization of the usual conformation that allows conjugation of the nitrogen lone pair with the carbonyl. Matthias Beller at Universität Rostock has found (Angew. Chem. Int. Ed. 2012, 51, 3905) that primary amides may be transamidated via copper(II) catalysis. The conditions are mild enough that an epimerization-prone amide such as 11 undergoes no observable racemization during conversion to amide 13. A photochemical transamidation has been achieved (Chem. Sci. 2012, 3, 405) by Christian Bochet at the University of Fribourg that utilizes 385-nm light to activate a dinitroindoline amide in the presence of amines such as 15, which produces the amide 16. Notably, photochemical cleavage of the Ddz protecting group occurs at a shorter wavelength of 300 nm.
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Conference papers on the topic "Solvolytic Reactions"

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Singh, Anil Kr. "Kinetics Investigation of Solvent Polarity on Reaction Rate for Solvolysis of Ethyl Caprylate Ester in Binary Solvent System." In 2021 10th International Conference on System Modeling & Advancement in Research Trends (SMART). IEEE, 2021. http://dx.doi.org/10.1109/smart52563.2021.9676306.

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Reports on the topic "Solvolytic Reactions"

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Braun, Andre M. Enhanced Oxidation and Solvolysis Reactions in Chemically Inert Microheterogeneous Systems. Defense Technical Information Center, 1986. http://dx.doi.org/10.21236/ada191248.

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Braun, Andre M. Enhanced Oxidation and Solvolysis Reactions in Chemically Inert Microheterogeneous Systems. Defense Technical Information Center, 1985. http://dx.doi.org/10.21236/ada191250.

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Braun, Andre M. Enhanced Oxidation and Solvolysis Reactions in Chemically Inert Microheterogeneous Systems. Defense Technical Information Center, 1987. http://dx.doi.org/10.21236/ada191251.

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Braun, Andre M. Enhanced Oxidation and Solvolysis Reactions in Chemically Inert Microheterogeneous Systems. Defense Technical Information Center, 1987. http://dx.doi.org/10.21236/ada191252.

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