1523-21-3Relevant articles and documents
Binding Properties of 1-Pyrenesulfonic Acid in Water
Menger, F.M.,Whitesell, L.G.
, p. 3793 - 3798 (1987)
Experiments are described with 1-pyrenesulfonic acid (1-PSA), an unconventional surfactant of the type Arn-X where Arn is polycyclic aromatic and X is a water-solubilizing entity.Little is known about the properties of such compounds when dissolved in wat
MOLECULAR TETRAHEDRON NANOCAGE, ITS PREPARATION, AND USES THEREOF
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Paragraph 0175, (2021/12/15)
The present application is directed to a nanocage of Formula (I): wherein A and R are as described herein. The present application is also directed to a process for preparation of a nanocage of Formula (I). Methods of utilizing the nanocage for detecting an analyte in a fluid and for functionalizing a polymer are also described.
Size-Selective Catalytic Polymer Acylation with a Molecular Tetrahedron
Badireddy, Appala Raju,Campbell, Joseph P.,Dudkina, Natavan,Ivancic, Monika,Li, Jianing,McCarthy, Dillon R.,McKay, Kyle T.,Murphy, Kyle E.,Rajappan, Sinu C.,Schneebeli, Severin T.,Sharafi, Mona,Shen, Yuxiang
supporting information, p. 1469 - 1495 (2020/06/19)
Selective catalysis at the molecular level represents a cornerstone of chemical synthesis. However, it still remains an open question how to elevate tunable catalysis to larger length scales to functionalize whole polymer chains in a selective manner. We
Evidence for a catalytic six-membered cyclic transition state in aminolysis of 4-nitrophenyl 3,5-dinitrobenzoate in acetonitrile: Comparative Br?nsted-type plot, entropy of activation, and deuterium kinetic isotope effects
Um, Ik-Hwan,Kim, Min-Young,Bae, Ae-Ri,Dust, Julian M.,Buncel, Erwin
, p. 217 - 222 (2017/03/06)
A kinetic study for reactions of 4-nitrophenyl 3,5-dinitrobenzoate (1a) with a series of cyclic secondary amines in acetonitrile is reported. Plots of the pseudo-firstorder rate constant (kobsd) vs [amine] curve upward, while those of kobs
Aminolysis of Y-substituted-phenyl 2-methoxybenzoates in acetonitrile: Effect of the o-methoxy group on reactivity and reaction mechanism
Um, Ik-Hwan,Bae, Ae Ri
experimental part, p. 7510 - 7515 (2011/11/13)
Second-order rate constants (kN) were measured for aminolyses of Y-substituted-phenyl 2-methoxybenzoates 2a-i and 4-nitrophenyl X-substituted-benzoates 3a-j in MeCN at 25.0 °C. The Bronsted-type plot for the reactions of 2a-i with piperidine curves downward, indicating that a change in rate-determining step (RDS) occurs. The Hammett plot for the reactions of 3a-j with piperidine consists of two intersecting straight lines, which might be taken as evidence for a change in RDS. However, the nonlinear Hammett plot has been suggested not to be due to a change in RDS but rather to the stabilization of the ground state of substrates possessing an electron-donating group (EDG) (e.g., 3a-c) through a resonance interaction, since the corresponding Yukawa-Tsuno plot exhibits an excellent linear correlation with ρ = 0.54 and r = 1.54. The ρ value found for the reactions of 3a-j in MeCN is much smaller than that reported previously for the corresponding reactions in H2O (i.e., ρ = 0.75). It is proposed that the reactions of 3a-j in MeCN proceed through a forced concerted mechanism due to instability of T± in the aprotic solvent, while the reactions of 2a-i proceed through a stepwise pathway with a stabilized T ± through an intramolecular H-bonding interaction.
Structure-reactivity correlations in nucleophilic substitution reactions of Y-substituted phenyl X-substituted benzoates with anionic and neutral nucleophiles
Um, Ik-Hwan,Lee, Ji-Youn,Fujio, Mizue,Tsuno, Yuho
, p. 2979 - 2985 (2008/02/11)
A kinetic study is reported for the reactions of 4-nitrophenyl X-substituted benzoates (1a-l) and Y-substituted phenyl benzoates (2a-l) with two anionic nucleophiles (OH- and CN-) and three amines (piperidine, hydrazine, and glycylglycine) in 80 mol% H2O-20 mol% dimethyl sulfoxide (DMSO) at 25.0 ± 0.1 °C. Each Hammett plot exhibits two intersecting straight lines for the reactions of 1a-l with the anionic nucleophiles and piperidine, while the Yukawa-Tsuno plots for the same reactions are linear. The Hammett plots for the reactions of 2a-l with hydrazine and glycylglycine demonstrate much better linear correlations with σ- constants than with σ° or σ constants, indicating that the leaving group departure occurs at the rate determining step (RDS). On the contrary, σ- constants result in poorer Hammett correlation than σ° constants for the corresponding reactions with OH- and CN-, indicating that the leaving group departure occurs after the RDS for the reactions with the anionic nucleophiles. The large ρX value (1.7 ± 0.1) obtained for the reactions of 1a-l with the anionic nucleophiles supports the proposal that the reactions proceed through an addition intermediate with its formation being the RDS. The Royal Society of Chemistry 2006.
Kinetics of the reaction of 4-nitrophenyl benzoates with 4-chlorophenol in the presence of potassium carbonate in dimethylformamide
Os'kina,Vlasov
, p. 865 - 872 (2007/10/03)
The effect of the substituent in the benzoyl group on the relative rate and activation parameters of transesterification of substituted 4-nitrophenyl benzoates with 4-chlorophenol in dimethylformamide in the presence of potassium carbonate was studied by the competing reaction technique. The whole series of benzoates showed the enthalpy-entropy compensation effect. 4-Nitrophenyl benzoates having electronacceptor substituents give rise to isokinetic relationship with an isokinetic temperature β of 382 K. The mechanism of the transesterification process is discussed. Pleiades Publishing, Inc., 2006.
Kinetics and mechanism of phosphate-catalyzed hydrolysis of benzoate esters: Comparison with nucleophilic catalysis by imidazole and o-iodosobenzoate
El Seoud, Omar A.,Ruasse, Marie-Francoise,Rodrigues, Wagner A.
, p. 1053 - 1058 (2007/10/03)
Phosphate-catalyzed hydrolysis of 2,4-dinitrophenyl 4-X-benzoate, and 3- or 4-Y-phenyl 3,5-dinitrobenzoates, where X and Y are substituents, has been studied spectrophotometrically. The following conclusions are based on catalytic rate constants, solvent
Nucleophilic displacement at the benzoyl centre: A study of the change in geometry at the carbonyl carbon atom
Colthurst, Matthew J.,Williams, Andrew
, p. 1493 - 1497 (2007/10/03)
The second-order rate constants for the reaction between hydroxide ion and phenoxide ion with 4-nitrophenyl esters of substituted benzoic acids in 10% acetonitrile-water (v/v) solution obey Hammett σ correlations. The values of the Hammett ρ of 1.67 (κArO) and 2.14 (κOH) are consistent with a large change in hybridization at the central carbon by comparison with the ρ value for a standard reaction where a full sp2 to sp3 change occurs. The transition state for the concerted reaction thus has a substantially tetrahedral geometry. The observation of the anti-Hammond effect whereby the ρ value for the hydroxide ion exceeds that of the less reactive phenoxide ion is consistent with a concerted, ANDN, mechanism for these reactions. A stepwise mechanism, AN + DN, is unlikely to yield a measurable break in the Hammett correlation for a change in the benzoyl substituent if the partitioning of the putative tetrahedral intermediate involves forward and reverse reactions with Hammett correlations possessing similar ρ values.
