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 The Truce–Smiles rearrangement and related reactions: a review

2017 ◽  
Vol 95 (5) ◽  
pp. 483-504 ◽  
Author(s):  
Anna R.P. Henderson ◽  
Joel R. Kosowan ◽  
Tabitha E. Wood
Keyword(s):  
Nucleophilic Aromatic Substitution ◽  
Future Research ◽  
Tandem Reaction ◽  
Aromatic Substitution ◽  
Smiles Rearrangement ◽  
Research Directions ◽  
Reaction Method ◽  
Design Variables ◽  
Leaving Group ◽  
Future Research Directions

The Truce–Smiles rearrangement is an X → C aryl migration reaction that is achieved by an intramolecular nucleophilic aromatic substitution pathway. The reaction exhibits a wide substrate scope with respect to a migrating aryl ring and leaving group, appearing in many different tandem reaction sequences, to achieve a wide variety of product outcomes. We present an extensive survey of reported examples of the Truce–Smiles rearrangement from the chemistry literature (1950s until present) organized by various substrate design variables or aspects of the reaction method. Present deficiencies in our understanding of the reaction are identified with recommendations for future research directions and useful developments in the application of the reaction are celebrated.

A new leaving group in nucleophilic aromatic substitution reactions (SNAr)

2008 ◽  
Vol 2008 (8) ◽  
pp. 432-433 ◽  
Author(s):  
Mehdi Bakavoli ◽  
Mehdi Pordel ◽  
Mohammad Rahimizadeh ◽  
Pooneh Jahandari
Keyword(s):  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Substitution Reactions ◽  
Leaving Group

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.

Mechanisms and models for homogeneous copper mediated ligand exchange reactions of the type: CuNu + ArX → ArNu + CuX

1985 ◽  
Vol 63 (1) ◽  
pp. 111-120 ◽  
Author(s):  
Christiane Couture ◽  
Anthony James Paine
Keyword(s):  
Molecular Design ◽  
Nucleophilic Aromatic Substitution ◽  
Common Mechanism ◽  
Aromatic Substitution ◽  
Exchange Reactions ◽  
Design And Synthesis ◽  
Alkyl Groups ◽  
Leaving Group ◽  
First Time ◽  
Redox Equilibria

The title reactions are an important class of copper mediated nucleophilic aromatic substitution processes, which constitute a useful tool in the molecular design and synthesis of small molecules. We report the results of extensive investigation of these processes, primarily focussing on cyanodeiodination (ArI + CuCN → CuI + ArCN). Among the interesting features of these processes are: (a) an unusual rate equation involving autocatalysis by CuI product; (b) retardation by both excess nucleophile (as KCN) and excess leaving group (as KI), which compete with ArX to complex with CuNu; (c) only cuprous nucleophiles are active (ligand exchanged products from cupric salts arise from prior redox equilibria which form CuNu); (d) the halogen effect is large (kI ~ 40–100 kBr ~ 300–5000kCl) but the Hammett ρ value is zero; (e) ortho-alkyl groups do not hinder the reaction (and actually cause mild acceleration by relief of steric strain). Finally, the introduction of an ortho-COO− group accelerates the reaction by a factor of 104–105, but the general features of the accelerated reactions are also the same, again indicating a common mechanism, with entropic acceleration by ortho-carboxylate. Both kinetic and thermodynamic factors were considered in detail, the latter apparently for the first time. Applications to practical syntheses are considered, and novel mechanistic models for these interesting processes are discussed.

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.

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