18938-14-2

Upstream product

• 28217-28-9 m-chlorophenyl β-D-glucopyranoside 
• 125357-85-9 3-chlorophenyl laurate 
• 75761-86-3 m-chlorophenyl fluorene-9-carboxylate 
• 16331-64-9 ethanolate 
• 13189-55-4 3-chlorophenyl benzoate 
• 626-60-8 3-Chloropyridine 
• 417708-17-9 3-chlorophenyl bis(4-methoxyphenyl) phosphate 
• 1122-54-9 methyl (4-pyridyl) ketone 
• 100-54-9 pyridine-3-carbonitrile 
• 288-32-4 1H-imidazole 
• 13031-39-5 3-chlorophenyl acetate 
• 110-89-4 piperidine 
• 108-43-0 3-monochlorophenol 
• 52200-04-1 3-chlorophenyl methanesulfonate 

Downstream Products

• 13031-39-5 3-chlorophenyl acetate 
• 18938-17-5 4-formylphenoxide ion 
• 60154-37-2 3,4-dinitrophenoxide ion 
• 30388-46-6 2-chloro-4-nitrophenolate 
• 108-43-0 3-monochlorophenol 
• 1163712-03-5 C₃H₉BP^(1-) 
• 69173-73-5 4-Chloro-2-nitro-phenol anion 
• 261172-44-5 4-acetylphenoxide 
• 20350-26-9 2,4-dinitrophenolate 
• 14609-74-6 p-nitrophenolate 
• 33104-33-5 3-chlorophenyl formate 
• 288-32-4 1H-imidazole 
• 32019-36-6 3-chlorophenyl diethyl phosphate 
• 33320-76-2 m-Chlorphenyl-diphenylphosphat 

Relevant academic research and scientific papers

Kinetic Study on Nucleophilic Substitution Reactions of O-Phenyl O-Y-substituted-Phenyl Thionocarbonates with 1,8-Diazabicyclo[5.4.0]undec-7-ene in Acetonitrile

Second-order rate constants (kN) for nucleophilic substitution reactions of O-phenyl O-Y-substituted-phenyl thionocarbonates (4a–4k) with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in MeCN at 25.0 ± 0.1°C are reported. The reactivity of 4a–4k decreases as basicity of the leaving group increases except O-2,4-dinitrophenyl O-phenyl thionocarbonate (4a), which is less reactive than O-3,4-dinitrophenyl O-phenyl thionocarbonate (4b) although the former possesses 2 pKa units less basic nucleofuge than the latter. The Br?nsted-type plot for the reactions of 4b–4k is linear with βlg = ?0.50, a typical βlg value for reactions reported to proceed through a concerted mechanism. The Hammett plot correlated with σY? constants for the reactions of 4b–4k results in a better linear correlation than that correlated with σYo constants. Besides, the Yukawa-Tsuno plot exhibits an excellent linear correlation with ρY = 2.12, r = 0.68 and R2 = 0.990, indicating that a negative charge develops partially on the O atom of the leaving group in the rate-determining step (RDS). Thus, the reactions have been concluded to proceed through a forced concerted mechanism. Effects of steric hindrance on reactivity and reaction mechanism are also discussed in detail.

Kinetic study on alkaline hydrolysis of Y-substituted phenyl picolinates: Effects of modification of nonleaving group from benzoyl to picolinyl on reactivity and reaction mechanism

Second-order rate constants (kOH-) for alkaline hydrolysis of Y-substituted phenyl picolinates (6a-6i) have been measured spectrophotometrically. A linear Bronsted-type plot is obtained with βlg = -0.34, which is typical for reactions reported previously to proceed through a stepwise mechanism with formation of an addition intermediate being the rate-determining step (RDS). However, σYo constants result in a much poorer Hammett correlation than σY- constants. Furthermore, the Yukawa-Tsuno plot exhibits an excellent linear correlation with ρY = 0.82 and r = 0.72, indicating that a negative charge develops partially on the O atom of the leaving group in the RDS. Thus, the reactions have been concluded to proceed through a forced concerted mechanism with a highly unstable intermediate 7. Comparison of the current kinetic data with those reported previously for the corresponding reactions of Y-substituted phenyl benzoates has revealed that modification of the nonleaving group from benzoyl to picolinyl causes not only an increase in reactivity but also a change in the reaction mechanism (i.e., from a stepwise mechanism to a forced concerted pathway).

Alkaline hydrolysis of Y-substituted phenyl phenyl thionocarbonates: Effect of changing electrophilic center from C=O to C=S on reactivity and mechanism

Second-order rate constants (kOH-) have been measured spectrophotometrically for reactions of Y-substituted phenyl phenyl thionocarbonates (4a-i) with OH- in 80 mol % H2O/20 mol % DMSO at 25.0 ± 0.1 °C. The ksu

Pitfalls in assessing the α-effect: Reactions of substituted phenyl methanesulfonates with HOO-, OH-, and substituted phenoxides in H2O

Toward resolving the current controversy regarding the validity of the α-effect, we have examined the reactions of Y-substituted phenyl methanesulfonates 1a-1l with HOO-, OH-, and Z-substituted phenoxides in the gas phase versus solu

The Ever-surprising chemistry of boron: Enhanced acidity of phosphine·boranes

The gas-phase acidity of a series of phosphines and their corresponding phosphine·borane derivatives was measured by FT-ICR techniques. BH 3 attachment leads to a substantial increase of the intrinsic acidity of the system (from 80 to 110 kJ mol-1). This acidity-enhancing effect of BH3 is enormous, between 13 and 18 orders of magnitude in terms of ionization constants. This indicates that the enhancement of the acidity of protic acids by Lewis acids usually observed in solution also occurs in the gas phase. High- level DFT calculations reveal that this acidity enhancement is essentially due to stronger stabilization of the anion with respect to the neutral species on BH3 association, due to a stronger electron donor ability of P in the anion and better dispersion of the negative charge in the system when the BH3 group is present. Our study also shows that deprotonation of ClCH2PH2 and ClCH 2PH2·BH3 is followed by chloride departure. For the latter compound deprotonation at the BH3 group is found to be more favorable than PH2 deprotonation, and the subsequent loss of Cl- is kinetically favored with respect to loss of Cl - in a typical SN2 process. Hence, ClCH2PH 2·BH3 is the only phosphine·borane adduct included in this study which behaves as a boron acid rather than as a phosphorus acid.

Analysis of linear free-energy relationships combined with activation parameters assigns a concerted mechanism to alkaline hydrolysis of X-substituted phenyl diphenylphosphinates

A kinetic study is reported for alkaline hydrolysis of X-substituted phenyl diphenylphosphinates (1a-i). The Bronsted-type plot for the reactions of 1a-i is linear over 4.5 pKa units with βlg= -0.49, a typical βlg value for reactions which proceed through a concerted mechanism. The Hammett plots correlated with σo and σ- constants are linear but exhibit many scattered points, while the corresponding Yukawa-Tsuno plot results in excellent linear correlation with ρ= 1.42 and r=0.35. The r value of 0.35 implies that leaving-group departure is partially advanced at the rate-determining step (RDS). A stepwise mechanism, in which departure of the leaving group from an addition intermediate occurs in the RDS, is excluded since the incoming HO - ion is much more basic and a poorer nucleofuge than the leaving aryloxide. A dissociative (DN + AN) mechanism is also ruled out on the basis of the small βlg value. As the substituent X in the leaving group changes from H to 4-NO2 and 3,4-(NO2)2, ΔH≠ decreases from 11.3 kcal mol-1 to 9.7 and 8.7 kcal mol-1, respectively, while ΔS≠ varies from -22.6 cal mol-1 K-1 to -21.4 and -20.2 cal mol-1 K-1, respectively. Analysis of LFERs combined with the activation parameters assigns a concerted mechanism to the current alkaline hydrolysis of 1a-i.

Aminolyses of aryl diphenylphosphinates and diphenylphosphinothioates: Effect of modification of electrophilic center from P=O to P=S

(Chemical Equation Presented) A kinetic study is reported for aminolysis of aryl diphenylphosphinothioates (2a-i). The phosphinothioates 2a-i are less reactive than aryl diphenylphosphinates (1a-i), the oxygen analogues of 2a-i, regardless of the basicity

Aminolysis of Y-substituted phenyl X-substituted benzoates with piperidine: Effect of nonleaving group substituent

The title reaction has been suggested to proceed through a zwitterionic tetrahedral intermediate with a change in the rate determining step on the basis of the curved Bronsted-type plots obtained. The curvature center of the curved Bronsted-type plots is at pKa = 6.4 regardless of the electronic nature of the substituent X in the benzoyl moiety.

Alkaline phosphatase mono- and diesterase reactions: Comparative transition state analysis

Enzyme-catalyzed phosphoryl transfer reactions have frequently been suggested to proceed through transition states that are altered from their solution counterparts. Previous work with Escherichia coli alkaline phosphatase (AP), however, suggests that thi

Mechanistic change in the reactivity of substituted phenyl acetates over phenyl thiolacetates toward imidazole in aqueous phase

The kinetics of aminolysis of several substituted phenyl acetates by imidazole is studied in aqueous medium at 20°C and an ionic strength of 0.1 M (KCl). By following the leaving groups spectrophotometrically (λ max = 272-401 nm), under excess free imidazole, pseudo-first-order rate constants (κobs) are obtained. For the esters with good nucleofuges, the reaction follows clean second-order kinetics and the plots of (κobs - κH) against free imidazole concentration are linear at constant pH. The macroscopic nucleophilic substitution rate constants (κN) are obtained as the slopes of these plots and found to be pH independent. For the esters with poor nucleofuges, a rate dependence on more than first power of the free imidazole and a linear dependence of κ′2 on free imidazole is observed. Accordingly, the microscopic rate constants for the assisted paths viz. κga and κgb have been disseminated besides for simple bimolecular attack. The Broensted-type plots and Hammett plots were constructed whose slope values are consistent with a stepwise mechanism through a bipolar tetrahedral addition intermediate whose formation or breakdown being rate determining for various paths. Comparison of this reaction of oxyesters with the earlier reported works on similar reaction of analogue thiolesters under identical reaction conditions showed remarkable mechanistic differences which are discussed in detail. The discussion is extended to include the details on previously studied ammonolysis of these two types of esters wherein thiolesters showed differed reactivity than that reported in the present study.