Ironcyclopentadienyl mediated 2-alkyl-2-arylphenylsulphonylacetonitrile synthesis

1995 ◽  
Vol 73 (2) ◽  
pp. 289-295 ◽  
Author(s):  
Alaa S. Abd-El-Aziz ◽  
Christine R. de Denus ◽  
Harold M. Hutton
Keyword(s):  
Nucleophilic Substitution ◽  
Room Temperature ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Efficient Route ◽  
Cyclopentadienyliron Complexes ◽  
Formation Of Complexes

A unique route to the synthesis of 2-alkyl-2-arylphenylsulphonylacetonitriles via the nucleophilic aromatic substitution (SNAr) of chloroarene cyclopentadienyliron complexes with 2-alkyl phenylsulphonylacetonitriles has been investigated. Reactions of chloroarene complexes (1a–d) with 2-alkyl phenylsulphonylacetonitrile (2a,b) in the presence of K2CO3 in DMF at room temperature led to the formation of complexes 3a–d and 4a,c,d in good yields. The use of alkylated phenylsulphonylacetonitriles as nucleophiles in the reactions with the p-dichlorobenzene complex (1e) allowed the formation of the disubstituted complexes (5,6). Photolytic demetallation provided an efficient route to the liberation of the arylated phenylsulphonylacetonitriles 7a–d, 8a,c,d, 9, and 10. Keywords: chloroarene, phenylsulphonylacetonitrile, nucleophilic substitution.

Nucleophilic substitution of meso-nitrooctaethylporphyrins

1985 ◽  
Vol 63 (2) ◽  
pp. 406-411 ◽  
Author(s):  
Liang-Chu Gong ◽  
David Dolphin
Keyword(s):  
Nucleophilic Substitution ◽  
Nucleophilic Addition ◽  
Nucleophilic Aromatic Substitution ◽  
Redox Potentials ◽  
Aromatic Substitution ◽  
Halogen Atoms

Nitrooctaethylporphyrins readily undergo nucleophilic aromatic substitution in the presence of HCl or HBr. In the presence of methoxide, nucleophilic addition to give a porphodimethane occurs, followed by autoxidation to the methoxyporphyrin. Unlike the nitrated complexes, the chlorosubstituted porphyrins exhibit redox potentials similar to those of unsubstituted analogs. Meso-halogenated porphyrins do, however, show steric distortion due to the bulk of the halogen atoms.

How Does Nucleophilic Aromatic Substitution in Nitroarenes Really Proceed: General Mechanism

Synthesis ◽  
2017 ◽  
Vol 49 (15) ◽  
pp. 3247-3254 ◽  
Author(s):  
Mieczysław Mąkosza
Keyword(s):  
Ab Initio Calculations ◽  
Ab Initio ◽  
Nucleophilic Substitution ◽  
Experimental Studies ◽  
Secondary Reaction ◽  
Nucleophilic Aromatic Substitution ◽  
General Mechanism ◽  
Primary Process ◽  
Nucleophilic Substitution Of Hydrogen ◽  
Aromatic Substitution

On the basis of previously published experimental studies and ab initio calculations, a general corrected mechanism of nucleophilic aromatic substitution was formulated. It was shown that conventional nucleophilic substitution of halogens is a slow secondary reaction whereas nucleophilic substitution of hydrogen is the fast primary process. The general mechanism embraces both of these alternative and complementary reactions.

scholarly journals Utilizing the σ-complex stability for quantifying reactivity in nucleophilic substitution of aromatic fluorides

2013 ◽  
Vol 9 ◽  
pp. 791-799 ◽  
Author(s):  
Magnus Liljenberg ◽  
Tore Brinck ◽  
Tobias Rein ◽  
Mats Svensson
Keyword(s):  
Nucleophilic Substitution ◽  
Density Functional ◽  
Reaction Rates ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Functional Theory ◽  
Aromatic Substrates ◽  
Complex Approach ◽  
Mechanistic Analysis ◽  
Rate Limiting

A computational approach using density functional theory to compute the energies of the possible σ-complex reaction intermediates, the “σ-complex approach”, has been shown to be very useful in predicting regioselectivity, in electrophilic as well as nucleophilic aromatic substitution. In this article we give a short overview of the background for these investigations and the general requirements for predictive reactivity models for the pharmaceutical industry. We also present new results regarding the reaction rates and regioselectivities in nucleophilic substitution of fluorinated aromatics. They were rationalized by investigating linear correlations between experimental rate constants (k) from the literature with a theoretical quantity, which we call the sigma stability (SS). The SS is the energy change associated with formation of the intermediate σ-complex by attachment of the nucleophile to the aromatic ring. The correlations, which include both neutral (NH3) and anionic (MeO−) nucleophiles are quite satisfactory (r = 0.93 to r = 0.99), and SS is thus useful for quantifying both global (substrate) and local (positional) reactivity in SNAr reactions of fluorinated aromatic substrates. A mechanistic analysis shows that the geometric structure of the σ-complex resembles the rate-limiting transition state and that this provides a rationale for the observed correlations between the SS and the reaction rate.

Rapid Cesium Fluoride Catalyzed Synthesis of 5-Aryloxy-1-phenyl-1H-tetrazoles via Nucleophilic Aromatic Substitution

2020 ◽  
Vol 17 ◽  
Author(s):  
Syed Muhammad Saad ◽  
Shahnaz Perveen ◽  
Itrat Fatima ◽  
Khalid Mohammed Khan
Keyword(s):  
Reaction Time ◽  
Room Temperature ◽  
Nucleophilic Aromatic Substitution ◽  
Synthetic Approach ◽  
Aromatic Substitution ◽  
Short Reaction Time ◽  
Cesium Fluoride ◽  
High Yields

Abstract: A nucleophilic aromatic substitution via a new and facile cesium fluoride catalyzed synthetic approach to get 5-aryloxy-1-phenyl-1H-tetrazoles was developed. Dual usage of cesium fluoride as a nucleophilc catalyst as well as an elec-trophilic catalyst afforded the desired products at room temperature in a short reaction time without purification in high yields. This simple but useful reaction may be a rapid and reliable strategy for the synthesis of tetrazolyl ethers

Methylsulfone as a leaving group for synthesis of hyperbranched poly(arylene pyrimidine ether)s by nucleophilic aromatic substitution

RSC Advances ◽  
2015 ◽  
Vol 5 (17) ◽  
pp. 12821-12823 ◽  
Author(s):  
Yue Guan ◽  
Chunbo Wang ◽  
Daming Wang ◽  
Guodong Dang ◽  
Chunhai Chen ◽  
...  
Keyword(s):  
Nucleophilic Substitution ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Hyperbranched Poly ◽  
Leaving Group

Using a novel leaving group, methylsulfone activated by pyrimidine, 4,6-dichloro-2-(methylsulfonyl)pyrimidine was used to synthesize two new hyperbranched poly(arylene pyrimidine ether)s with diphenol via a nucleophilic substitution polymerization.

scholarly journals Microwave-assisted synthesis of azepines via nucleophilic aromatic substitution

2016 ◽  
Vol 81 (11) ◽  
pp. 1225-1230 ◽  
Author(s):  
Nina Bozinovic ◽  
Bogdan Solaja ◽  
Igor Opsenica
Keyword(s):  
Microwave Irradiation ◽  
Nucleophilic Aromatic Substitution ◽  
Irradiation Condition ◽  
Primary Amines ◽  
Microwave Assisted Synthesis ◽  
Aromatic Substitution ◽  
Microwave Assisted ◽  
Reaction Proceeds ◽  
Efficient Route

A novel and efficient route has been developed to afford 5H-dipyridoazepine derivatives from primary amines and 3,3'-(Z)-ethene-1,2-di-ylbis(4-chloropyridine). The procedure based on the double nucleophilic aromatic substitution provides a valuable synthetic tool for the synthesis of dipyridoazepines. The reaction proceeds without catalyst, under microwave irradiation condition.

scholarly journals Synthesis and nucleophilic aromatic substitution of 3-fluoro-5-nitro-1-(pentafluorosulfanyl)benzene

2016 ◽  
Vol 12 ◽  
pp. 192-197 ◽  
Author(s):  
Javier Ajenjo ◽  
Martin Greenhall ◽  
Camillo Zarantonello ◽  
Petr Beier
Keyword(s):  
Nucleophilic Substitution ◽  
Title Compound ◽  
Fluorine Atom ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Vicarious Nucleophilic Substitution ◽  
Direct Fluorination ◽  
Nitrogen Nucleophiles

3-Fluoro-5-nitro-1-(pentafluorosulfanyl)benzene was prepared by three different ways: as a byproduct of direct fluorination of 1,2-bis(3-nitrophenyl)disulfane, by direct fluorination of 4-nitro-1-(pentafluorosulfanyl)benzene, and by fluorodenitration of 3,5-dinitro-1-(pentafluorosulfanyl)benzene. The title compound was subjected to a nucleophilic aromatic substitution of the fluorine atom with oxygen, sulfur and nitrogen nucleophiles affording novel (pentafluorosulfanyl)benzenes with 3,5-disubstitution pattern. Vicarious nucleophilic substitution of the title compound with carbon, oxygen, and nitrogen nucleophiles provided 3-fluoro-5-nitro-1-(pentafluorosulfanyl)benzenes substituted in position four.

Nucleophilic aromatic substitution with dialkoxycarbenes

1997 ◽  
Vol 75 (10) ◽  
pp. 1331-1335 ◽  
Author(s):  
Joseph P. Ross ◽  
Philippe Couture ◽  
John Warkentin
Keyword(s):  
Nucleophilic Substitution ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Aromatic Rings ◽  
Aryl Group ◽  
Aryl Fluoride ◽  
Intramolecular Substitution

Dimethoxycarbene, generated at 110 °C by thermolysis of 2,2-dimethoxy-5,5-dimethyl-Δ3-1,3,4-oxadiazoline, displaces fluoride from aromatic rings that are activated with electron-withdrawing groups. Intermolecular substitution on Sanger's reagent and on hexafluorobenzene are reported, together with intramolecular substitution by a dioxycarbene with a tethered aryl group. Keywords: aromatic substitution, aryl(dimethoxy)fluoromethanes, aryl fluoride, dialkoxycarbene, nucleophilic substitution.

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