How Do Aromatic Nitro Compounds React with Nucleophiles? Theoretical Description Using Aromaticity, Nucleophilicity and Electrophilicity Indices

被引：7

作者：

Blaziak, Kacper ^{[1
,2
]}

Danikiewicz, Witold ^{[3
]}

Makosza, Mieczyslaw ^{[3
]}

机构：

[1] Univ Warsaw, Fac Chem, PL-01224 Warsaw, Poland

[2] Univ Warsaw, Biol & Chem Res Ctr, PL-01224 Warsaw, Poland

[3] Polish Acad Sci, Inst Organ Chem, Kasprzaka 44-52, PL-01224 Warsaw, Poland

来源：

MOLECULES | 2020年 / 25卷 / 20期

关键词：

nucleophilic aromatic substitution; reaction mechanism; DFT; SUBSTITUTION; HYDROGEN; MECHANISM; NITROBENZENE; NITROARENES; COMPLEXES; CARBANION; PROCEED; STEP;

D O I：

10.3390/molecules25204819

中图分类号：

Q5 [生物化学]; Q7 [分子生物学];

学科分类号：

071010 ; 081704 ;

摘要：

In this study, we present a complete description of the addition of a model nucleophile to the nitroaromatic ring in positions occupied either by hydrogen (the first step of the SNAr-H reaction) or a leaving group (SNAr-X reaction) using theoretical parameters including aromaticity (HOMA), electrophilicity and nucleophilicity indices. It was shown both experimentally and by our calculations, including kinetic isotope effect modeling, that the addition of a nucleophile to the electron-deficient aromatic ring is the rate limiting step of both SNAr-X and SNAr-H reactions when the fast transformation of sigma(H)-adduct into the products is possible due to the specific reaction conditions, so this is the most important step of the entire reaction. The results described in this paper are helpful for better understanding of the subtle factors controlling the reaction direction and rate.

引用

页数：11