Abstract
The routine prediction of the reactivity of a complex, multifunctional molecule is a challenging and time-consuming procedure. In the last step of the synthesis of the well-known drug substance tenidap, a nonexpected difference was observed between the reactivities of two closely related carbamate moieties, the N-ethoxycarbonyl and the N-phenoxycarbonyl group. A detailed kinetic study, necessitating a significant computational effort, is described in the present paper for this reaction step. On the other hand, the systems chemistry concept, by analyzing the details of the electronic structure and the connections between functional groups in a fast and simple way, is also able to answer this question using various "-icity"? parameters (aromaticity, carbonylicity, olefinicity). The complete systems chemistry approach involves all these conjugativicity parameters, while its further simplified version is based on only one key parameter, which is carbonylicity in the present case. The above methods were compared in terms of their predictive power. The results show that the systems chemistry concept, even its one-parameter version, is applicable for the characterization of this challenging reactivity issue.
| Original language | English |
|---|---|
| Pages (from-to) | 7282-7290 |
| Number of pages | 9 |
| Journal | Journal of Organic Chemistry |
| Volume | 77 |
| Issue number | 17 |
| DOIs | |
| Publication status | Published - Sep 7 2012 |
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ASJC Scopus subject areas
- Organic Chemistry
Cite this
Application of the systems chemistry approach on the ammonolysis of 1-ethoxycarbonyl- and 1-phenoxycarbonyl-3-(2-thienyl)oxindoles. A method to predict reactivity. / Mucsi, Zoltán; Porcs-Makkay, Márta; Simig, Gyula; Csizmadia, I.; Volk, Balázs.
In: Journal of Organic Chemistry, Vol. 77, No. 17, 07.09.2012, p. 7282-7290.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Application of the systems chemistry approach on the ammonolysis of 1-ethoxycarbonyl- and 1-phenoxycarbonyl-3-(2-thienyl)oxindoles. A method to predict reactivity
AU - Mucsi, Zoltán
AU - Porcs-Makkay, Márta
AU - Simig, Gyula
AU - Csizmadia, I.
AU - Volk, Balázs
PY - 2012/9/7
Y1 - 2012/9/7
N2 - The routine prediction of the reactivity of a complex, multifunctional molecule is a challenging and time-consuming procedure. In the last step of the synthesis of the well-known drug substance tenidap, a nonexpected difference was observed between the reactivities of two closely related carbamate moieties, the N-ethoxycarbonyl and the N-phenoxycarbonyl group. A detailed kinetic study, necessitating a significant computational effort, is described in the present paper for this reaction step. On the other hand, the systems chemistry concept, by analyzing the details of the electronic structure and the connections between functional groups in a fast and simple way, is also able to answer this question using various "-icity"? parameters (aromaticity, carbonylicity, olefinicity). The complete systems chemistry approach involves all these conjugativicity parameters, while its further simplified version is based on only one key parameter, which is carbonylicity in the present case. The above methods were compared in terms of their predictive power. The results show that the systems chemistry concept, even its one-parameter version, is applicable for the characterization of this challenging reactivity issue.
AB - The routine prediction of the reactivity of a complex, multifunctional molecule is a challenging and time-consuming procedure. In the last step of the synthesis of the well-known drug substance tenidap, a nonexpected difference was observed between the reactivities of two closely related carbamate moieties, the N-ethoxycarbonyl and the N-phenoxycarbonyl group. A detailed kinetic study, necessitating a significant computational effort, is described in the present paper for this reaction step. On the other hand, the systems chemistry concept, by analyzing the details of the electronic structure and the connections between functional groups in a fast and simple way, is also able to answer this question using various "-icity"? parameters (aromaticity, carbonylicity, olefinicity). The complete systems chemistry approach involves all these conjugativicity parameters, while its further simplified version is based on only one key parameter, which is carbonylicity in the present case. The above methods were compared in terms of their predictive power. The results show that the systems chemistry concept, even its one-parameter version, is applicable for the characterization of this challenging reactivity issue.
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U2 - 10.1021/jo300715d
DO - 10.1021/jo300715d
M3 - Article
C2 - 22901033
AN - SCOPUS:84866113601
VL - 77
SP - 7282
EP - 7290
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 17
ER -