3198-23-0

Upstream product

• 13551-17-2 cyclohexanecarboxylic acid 4-nitrophenyl ester 
• 766-76-7 benzoate 
• 20396-49-0 t-butyl cyclohexanecarboperoxoate 
• 619-50-1 methyl p-nitrobenzoate radical anion 
• 105-07-7 4-cyanobenzaldehyde anion radical 

Downstream Products

• 473432-57-4 Zn(((CH₃)2NC₆H₄CH₂NHCH₂CH₂)2NCH₂CH₂NHCH₂(C₁₄H₉))(C₆H₁₁COO)⁽¹⁺⁾ 

Relevant academic research and scientific papers

Insights into the free-energy dependence of intramolecular dissociative electron transfers

To study the relationship between rate and driving force of intramolecular dissociative electron transfers, a series of donor-spacer-acceptor (D-Sp-A) systems has been devised and synthesized. cis-1,4-Cyclohexanedyil and a perester functional group were kept constant as the spacer and acceptor, respectively. By changing the aryl substituents of the phthalimide moiety, which served as the donor, the driving force could be varied by 0.74 eV. X-ray diffraction crystallography and ab initio conformational calculations pointed to D-Sp-A molecules having the cis-(cyclohexane) equatorial(phthalimido)axial(perester) conformation and the same D/A orientation. The intramolecular dissociative electron-transfer process was studied by electrochemical means in N,N-dimethylformamide, in comparison with thermodynamic and kinetic information obtained with models of the acceptor and the donor. The intramolecular process consists of the electron transfer from the electrochemically generated phthalimide-moiety radical anion to the peroxide functional group. The electrochemical analysis provided clear evidence of a concerted dissociative electron-transfer mechanism, leading to the cleavage of the O-O bond. Support for this mechanism was obtained by ab initio MO calculations, which provided information about the LUMO of the acceptor and the SOMO of the donor. The intramolecular rate constants were determined and compared with the corresponding intermolecular values, the latter data being obtained by using the model molecules. As long as the effective location of the centroid of the donor SOMO does not vary significantly by changing the aryl substituent(s), the intramolecular dissociative electron transfer obeys the same main rules already highlighted for the corresponding intermolecular process. On the other hand, introduction of a nitro group drags the SOMO away from the acceptor, and consequently, the intramolecular rate drops by as much as 1.6 orders of magnitude from the expected value. Therefore, a larger solvent reorganization than for intermolecular electron transfers and the effective D/A distance and thus electronic coupling must be taken into account for quantitative predictions of intramolecular rates.

Energetics of product formation during anaerobic degradation of phthalate isomers and benzoate

Methanogenic enrichment cultures grown on phthalate, isophthalate and terephthalate were incubated with the corresponding phthalate isomer on which they were grown, and a mixture of benzoate and the phthalate isomer. All cultures were incubated with bromoethanosulfonate to inactivate the methanogens in the mixed culture. Thus, product formation during fermentation of the aromatic substrates could be studied. It was found that reduction equivalents generated during oxidation of the aromatic substrates to acetate were incorporated in benzoate under formation of carboxycyclohexane. During fermentation of the phthalate isomers, small amounts of benzoate were detected, suggesting that the initial step in the anaerobic degradation of the phthalate isomers is decarboxylation to benzoate. Gibbs free energy analyses indicated that during degradation of the phthalate isomers, benzoate, carboxycyclohexane, acetate and molecular hydrogen accumulated in such amounts that both the reduction and oxidation of benzoate yielded a constant and comparable amount of energy of approximately 30 kJ mol-1. Based on these observations it is suggested that within narrow energetic limits, oxidation and reduction of benzoate may proceed simultaneously. Whether this is controlled by the Gibbs free energy change for carboxycyclohexane oxidation remains unclear. Copyright (C) 1999 Federation of European Microbiological Societies.

Photocontrol of Micellar Catalyses

The photoresponsive surfactants, C7H15CONHC6H4NNC6H4N+Me3MeOSO3- (1), C8H17OC6H4NNC6H4CH2N+Me3I- (2), and C16H33OC6H4NNC6H4CH2N+Me3I- (3), have been synthesised.The absorption spectrum of 2,6-dichlorophenolindophenol as a probe for micelle formation indicated that the aggregation mode of these photoresponsive surfactants is affected by photoinduced trans-cis isomerisation of the azobenzene head groups.The catalytic activities of these surfactant aggregates in base-catalysed proton abstraction from benzoin and alkaline hydrolysis of p-nitrophenyl cyclohexanecarboxylate were estimated in the dark and under photoirradiation.It was found that the rate constants in the micellar systems change sensitively in response to photoirradiation.The results imply that photoinduced isomerisation of the head groups leads to a change in the catalytic activity.This is the first example of photocontrol of micellar catalysis.