| Full text | |
| Author(s): |
Cruz, Gustavo N.
[1]
;
Lima, Filipe S.
[1]
;
Dias, Luis G.
[2]
;
El Seoud, Omar A.
[3]
;
Horinek, Dominik
[4]
;
Chaimovich, Hernan
[1]
;
Cuccovia, Iolanda M.
[1]
Total Authors: 7
|
| Affiliation: | [1] Univ Sao Paulo, Fac Filosofia Ciencias & Letras Ribeirao Preto, Dept Bioquim, Sao Paulo - Brazil
[2] Univ Sao Paulo, Dept Quim, Fac Filosofia Ciencias & Letras Ribeirao Preto, Sao Paulo - Brazil
[3] Univ Sao Paulo, Fac Filosofia Ciencias & Letras Ribeirao Preto, Inst Quim, Sao Paulo - Brazil
[4] Univ Regensburg, Inst Phys & Theoret Chem, D-93053 Regensburg - Germany
Total Affiliations: 4
|
| Document type: | Journal article |
| Source: | Journal of Organic Chemistry; v. 80, n. 17, p. 8637-8642, SEP 4 2015. |
| Web of Science Citations: | 2 |
| Abstract | |
The dediazoniation of aryldiazonium salts in mixed solvents proceeds by a borderline S(N)1 and S(N)2 pathway, and product distribution should be proportional to the composition of the solvation shell of the carbon attached to the -N-2 group (ipso carbon). The rates of dediazoniation of 2,4,6-trimethylbenzenediazonium in water, methanol, ethanol, propanol, and acetonitrile were similar, but measured product distributions were noticeably dependent on the nature of the water/cosolvent mixture. Here we demonstrated that solvent distribution in the first solvation shell of the ipso carbon, calculated from classical molecular dynamics simulations, is equal to the measured product distribution. Furthermore, we showed that regardless of the charge distribution of the initial state, i.e., whether the positive charge is smeared over the molecule or localized on phenyl moiety, the solvent distribution around the reaction center is nearly the same. (AU) | |
| FAPESP's process: | 14/06073-2 - Determining the origin of shape transitions in micellar systems at the atomic level: a computational study |
| Grantee: | Filipe da Silva Lima |
| Support Opportunities: | Scholarships abroad - Research Internship - Post-doctor |
| FAPESP's process: | 13/08166-5 - Interfacial chemistry: drugs, peptides and ezymes interactions with membrane models |
| Grantee: | Iolanda Midea Cuccovia |
| Support Opportunities: | Research Projects - Thematic Grants |