77614-06-3

Upstream product

• 100-02-7 4-nitro-phenol 
• 35086-79-4 p-chlorocinnamoyl chloride 
• 27019-24-5 p-nitrocinnamoyl p-nitro-phenyl ester 
• 18736-43-1 4-nitro-phenyl cinnamate 
• 105650-19-9 C₁₆H₁₃NO₄ 
• 71255-82-8 C₁₆H₁₃NO₅ 

Downstream Products

• 461704-24-5 C₁₅H₁₀Cl₂O₂ 
• 27019-24-5 p-nitrocinnamoyl p-nitro-phenyl ester 
• 100-02-7 4-nitro-phenol 
• 18736-43-1 4-nitro-phenyl cinnamate 
• 105650-19-9 C₁₆H₁₃NO₄ 
• 71255-82-8 C₁₆H₁₃NO₅ 

Relevant academic research and scientific papers

Structure-reactivity correlations in nucleophilic displacement reactions of Y-substituted-phenyl X-substituted-cinnamates with Z-substituted-phenoxides

Second-order rate constants (kN) have been measured spectrophotometrically for the nucleophilic displacement reactions of 4-nitrophenyl X-substituted-cinnamates (4a-4e) and Y-substituted-phenyl cinnamates (5a-5e) with Z-substituted-phenoxide anions in 80 mol % H2O/20 mol % DMSO at 25.0 ±0.1 °C. The Hammett plot for the reactions of 4a-4e with 4-chlorophenoxide (4-ClPhO.) consists of two intersecting straight lines, which might be taken as a change in the rate-determining step (RDS). However, it has been concluded that the nonlinear Hammett plot is not due to a change in the RDS but is caused by stabilization of the ground state of substrates possessing an electron-withdrawing group in the cinnamoyl moiety through resonance interactions, since the Yukawa-Tsuno plot exhibits an excellent linear correlation with ρX = 0.89 and r = 0.58. The Bronsted-type plot for the reactions of 4-nitrophenyl cinnamate (4c) with Z-substituted-phenoxides is linear with βnuc = 0.76. The Bronsted-type plot for the reactions of Y-substituted-phenyl cinnamates (5a-5d) with 4-chlorophenoxides (4-ClPhO.) is also linear with βlg =.0.72. The Hammett plot correlated with σ-. constants for the reactions of 5a-5d results in a much better linear correlation than that correlated with σo constants, indicating that a partial negative charge develops on the O atom of the leaving aryloxide. Thus, the reactions have been concluded to proceed through a concerted mechanism.

The α-effect in nucleophilic substitution reactions of Y-substituted-Phenyl X-substituted-cinnamates with Butane-2,3-dione monoximate

Second-order rate constants (kOx-) have been measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl X-substituted-cinnamates (7a-7e) and Y-substituted-phenyl cinnamates (8a-8e) with butane-2,3-dione monoximate (Ox-) in 80 mol % H2O/20 mol % DMSO at 25.0 ± 0.1 °C. The Hammett plot for the reactions of 7a-7e consists of two intersecting straight lines while the Yukawa-Tsuno plot exhibits an excellent linearity with ρX = 0.85 and r = 0.58, indicating that the nonlinear Hammett plot is not due to a change in the rate-determining step but is caused by resonance stabilization of the ground state (GS) of the substrate possessing an electron-donating group (EDG). The Bronsted-type plot for the reactions of Y-substituted-phenyl cinnamates (8a-8e) is linear with βlg = - 0.64, which is typical of reactions reported previously to proceed through a concerted mechanism. The a-nucleophile (Ox-) is more reactive than the reference normalnucleophile (4-ClPhO-). The magnitude of the α-effect (i.e., the kOx-/k4-ClPhO- ratio) is independent of the electronic nature of the substituent X in the nonleaving group but increases linearly as the substituent Y in the leaving group becomes a weaker electron-withdrawing group (EWG). It has been concluded that the difference in solvation energy between Ox- and 4-ClPhO - (i.e., GS effect) is not solely responsible for the α-effect but stabilization of transition state (TS) through a cyclic TS structure contributes also to the Y-dependent a-effect trend (i.e., TS effect).

Influence of electronically and sterically tunable cinnamate ligands on the spectroscopic, kinetic, and thermodynamic properties of bis(triphenylphosphine) palladium(0) olefin complexes

A detailed study of the influence of electronic and steric characteristics of cinnamic acid esters on the spectroscopic, kinetic, and thermodynamic properties of bis(triphenylphosphine)palladium(0) cinnamic acid ester complexes is presented (51 different new complexes included). These complexes show a dynamic behavior on the NMR spectroscopic time scale. Therefore, the rotational barriers of the olefin about the metalolefin bond as well as the dissociation entropy and enthalpy of the olefin and the dissociation mechanism could be determined. These findings are interpreted together with the NMR spectroscopic, IR spectroscopic, and X-ray structural data (7 new structures included) concerning the influence of the different olefin ligands on the complex properties by means of Hammett plots. DFT calculations were performed to support the mechanistic conclusions.