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Relevant bibliographies by topics / Solvolysis. Chlorine

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Academic literature on the topic 'Solvolysis. Chlorine'

Author: Grafiati

Published: 4 June 2021

Last updated: 3 February 2022

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Journal articles on the topic "Solvolysis. Chlorine"

1

McLennan, Duncan J., Allan R. Stein, and Brian Dobson. "Chlorine isotope effects in the solvolysis of substituted 1-phenylethyl chlorides." Canadian Journal of Chemistry 64, no. 6 (1986): 1201–5. http://dx.doi.org/10.1139/v86-199.

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Kinetic chlorine isotope effects attending the solvolysis of several ring-substituted 1-phenylethyl chlorides in alcohol–water solvent mixtures are reported. The k35/k37 values are insensitive to the identity of ring substituents and to solvent composition. Results are interpreted in terms of an SN1 heterolytic process incorporating a significant amount of internal return. Theoretical calculations suggest that the incipient chloride ion in the transition state may be strongly hydrogen-bonded.

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2

D’Souza, Malcolm J., Jeremy Wirick, Osama Mahmoud, Dennis N. Kevill, and Jin Burm Kyong. "The Influence of a Terminal Chlorine Substituent on the Kinetics and the Mechanism of the Solvolyses of n-Alkyl Chloroformates in Hydroxylic Solvents." International Journal of Molecular Sciences 21, no. 12 (2020): 4387. http://dx.doi.org/10.3390/ijms21124387.

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A previous study of the effect of a 2-chloro substituent on the rates and the mechanisms of the solvolysis of ethyl chloroformate is extended to the effect of a 3-chloro substituent on the previously studied solvolysis of propyl chloroformate and to the effect of a 4-chloro substituent on the here reported rates of solvolysis of butyl chloroformate. In each comparison, the influence of the chloro substituent is shown to be nicely consistent with the proposal, largely based on the application of the extended Grunwald–Winstein equation, of an addition-elimination mechanism for solvolysis in the

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3

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 v

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4

Park, Kyoung Ho, Mi Hye Seong, Jin Burm Kyong, and Dennis N. Kevill. "Rate and Product Studies with 1-Adamantyl Chlorothioformate under Solvolytic Conditions." International Journal of Molecular Sciences 22, no. 14 (2021): 7394. http://dx.doi.org/10.3390/ijms22147394.

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A study was carried out on the solvolysis of 1-adamantyl chlorothioformate (1-AdSCOCl, 1) in hydroxylic solvents. The rate constants of the solvolysis of 1 were well correlated using the Grunwald–Winstein equation in all of the 20 solvents (R = 0.985). The solvolyses of 1 were analyzed as the following two competing reactions: the solvolysis ionization pathway through the intermediate (1-AdSCO)+ (carboxylium ion) stabilized by the loss of chloride ions due to nucleophilic solvation and the solvolysis–decomposition pathway through the intermediate 1-Ad+Cl− ion pairs (carbocation) with the loss

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5

D’Souza, Malcolm J., Zoon Ha Ryu, Byoung-Chun Park та Dennis N. Kevill. "Correlation of the rates of solvolysis of acetyl chloride and α-substituted derivatives". Canadian Journal of Chemistry 86, № 5 (2008): 359–67. http://dx.doi.org/10.1139/v08-028.

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Additional specific rates of solvolysis have been determined for acetyl chloride and diphenylacetyl chloride. These are combined with literature values to carry out correlation analyses, using the extended Grunwald–Winstein equation with incorporation of literature values for solvent nucleophilicity (NT) and solvent ionizing power (YCl). Parallel analysis are carried out using literature values for the specific rates of solvolysis of trimethylacetyl chloride, chloroacetyl chloride, phenylacetyl chloride, and α-methoxy-α-trifluoromethylphenylacetyl chloride (MTPAC). Chloroacetyl chloride and MT

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6

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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7

Bolton, R., RE Burley, and NJ Williams. "Stabilities of Carbonium-Ions. IV. Steric Effects in the Solvolysis of Substituted Diphenylmethyl Chlorides." Australian Journal of Chemistry 39, no. 4 (1986): 625. http://dx.doi.org/10.1071/ch9860625.

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The replacement of ortho-hydrogen atoms by methyl groups in diphenylmethyl chloride has three distinguishable results upon the rate of solvolysis . Firstly, the alkyl groupactivates by its electronic effect; secondly, steric interactions diminish all observed substituent effects regardless of the position of the substituent in the aryl system; and thirdly, steric acceleration of the solvolysis can be seen in the rate of reaction of bis (2,6-dimethylphenyl)methyl chloride. The ortho-methyl substituents inhibit the formation of the planar transition state necessary to allow the greatest resonanc

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8

D'Souza, Malcolm J., Anthony M. Darrington, and Dennis N. Kevill. "On the Importance of the Aromatic Ring Parameter in Studies of the Solvolyses of Cinnamyl and Cinnamoyl Halides." Organic Chemistry International 2010 (June 29, 2010): 1–9. http://dx.doi.org/10.1155/2010/130506.

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In solvolysis studies using Grunwald-Winstein plots, dispersions were observed for substrates with aromatic rings at the α-carbon. Several examples for the unimolecular solvolysis of monoaryl benzylic derivatives and related diaryl- or naphthyl-substituted derivatives have now been reported, where the application of the aromatic ring parameter (I) removes this dispersion. A recent claim suggesting the presence of an appreciable nucleophilic component to the I scale has now been shown, in a review of the solvolysis of highly-hindered alkyl halides, to be unlikely to be correct. Attention is now

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9

Mclure, FI, RK Norris, and K. Wilson. "Nucleophilic Substitution Reactions of Thienyl Neopentyl Substrates." Australian Journal of Chemistry 40, no. 1 (1987): 49. http://dx.doi.org/10.1071/ch9870049.

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The reaction of the chlorides (4)-(6), which are both neopentylic and thenylic , were studied. The chloride (4), unlike its analogue (13) in the benzene series, undergoes ready solvolysis with alcohols to give the corresponding ethers, e.g. (7)-(9). The chlorides (5) and (6) react more slowly than (4) but undergo methanolysis to give the methyl ethers (11) and (12) respectively. In the dipolar aprotic solvents, dimethyl sulfoxide and dimethylformamide, the reactions of the chlorides (4), (5) and (6) with the thiolate salt (16) appear to proceed by an SN1-like, an SN(AEAE) and an SRNl process r

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10

Kevill, Dennis N., and Malcolm J. D'Souza. "Concerning the Extents of Nucleophilic Participation in Solvolyses of p-Methoxybenzyl Halides." Journal of Chemical Research 23, no. 5 (1999): 336–37. http://dx.doi.org/10.1177/174751989902300520.

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The solvolyses of p-methoxybenzyl chloride (1) in 39 solvents are well correlated using an extended form of the Grunwald-Winstein equation; a claim that nucleophilic participation is greater than in the solvolyses of the corresponding bromide 2 is discussed.

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Dissertations / Theses on the topic "Solvolysis. Chlorine"

1

Brogdon, Brian N. "Effects of ethanol media on chlorine dioxide and extraction stages for kraft pulp bleaching." Diss., Georgia Institute of Technology, 1997. http://hdl.handle.net/1853/7014.

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2

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

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3

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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4

I, Chen Hung, and 陳宏亦. "Studies on the Solvolysis of Hindered Benzylic Substrates and Substituted Acyl Chlorides." Thesis, 1999. http://ndltd.ncl.edu.tw/handle/74439635431443202438.

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博士<br>國立臺灣大學<br>化學研究所<br>87<br>In the solvolysis of the 1-aryl-2,2-dimethylpropyl substrates (I-T-X，I-B-X，I-C-X), the effect of ortho-methyl group on the reaction center could be reflected in two aspects. One was electron-donating effect and the other was steric hindrance. Introduction of two ortho-methyl groups in the phenyl ring, the steric hindrance will cause the deviation from the coplanarity of the aryl ring and the reaction center, and will change the extent of solvation between solvents and leaving groups (electrophilic pull). From the rate data, the deviation from the coplanarity w

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Book chapters on the topic "Solvolysis. Chlorine"

1

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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