Nucleophilic Aromatic Substitution Reactions in Water Enabled by Micellar Catalysis

2015 ◽  
Vol 17 (19) ◽  
pp. 4734-4737 ◽  
Author(s):  
Nicholas A. Isley ◽  
Roscoe T. H. Linstadt ◽  
Sean M. Kelly ◽  
Fabrice Gallou ◽  
Bruce H. Lipshutz
Keyword(s):  
Micellar Catalysis ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Substitution Reactions

ChemInform Abstract: Nucleophilic Aromatic Substitution Reactions in Water Enabled by Micellar Catalysis.

ChemInform ◽  
2016 ◽  
Vol 47 (7) ◽  
pp. no-no
Author(s):  
Nicholas A. Isley ◽  
Roscoe T. H. Linstadt ◽  
Sean M. Kelly ◽  
Fabrice Gallou ◽  
Bruce H. Lipshutz
Keyword(s):  
Micellar Catalysis ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Substitution Reactions

Micellar catalysis of nucleophilic aromatic substitution reactions between anionic nucleophiles and aromatic substrates containing anionic substituents

1981 ◽  
Vol 34 (5) ◽  
pp. 969 ◽  
Author(s):  
TJ Broxton
Keyword(s):  
Micellar Catalysis ◽  
Nucleophilic Aromatic Substitution ◽  
Organic Substrates ◽  
Aromatic Substitution ◽  
Substitution Reactions ◽  
Nitrite Ion ◽  
Aromatic Substrates ◽  
Anionic Nucleophiles ◽  
Aqueous Micellar Solution ◽  
Order Of Magnitude

Rate constants for SNAr reactions between anionic nucleophiles and aromatic substrates bearing anionic substituents in the presence and absence of micelles of cetyltrimethylammonium bromide (ctab) have been measured. Micellar catalysis of this class of reaction seems to be of the same order of magnitude as for SNAr reactions between anionic nucleophiles and dipolar organic substrates. Micellar catalysis ofSNAr reactions of the ambident nitrite ion has also been studied. The magnitude of catalysis of SNAr reactions of sodium nitrite by micelles of ctab is large compared to that for SNAr reactions of hydroxide ions or azide ions. This suggests that nitrite ion is well solubilized by micelles of ctab and some consequences of this in biological systems are discussed. The ambident behaviour of nitrite ion in aqueous micellar solution towards organic substrates seems to mirror that in methanolic solution.

scholarly journals The use of bisphthalonitriles in the synthesis of side-strapped 1,11,15,25-tetrasubstituted phthalocyanines

1996 ◽  
Vol 74 (3) ◽  
pp. 307-318 ◽  
Author(s):  
Clifford C. Leznoff ◽  
David M. Drew
Keyword(s):  
Key Words ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Substitution Reactions ◽  
Pure Compounds

Nucleophilic aromatic substitution reactions of 3-nitrophthalonitrile yield 3-hydroxyphthalonitrile and 3-neopentoxyphthalonitrile, the latter of which condensed to 1,8,15,22-tetraneopentoxyphthalocyanine as a mixture of isomers. Bisphthalonitriles such as 1,3-bis(2′,3′-dicyanophenoxy)-2,2-dipentylpropane, 1,3-bis(2′,3′-dicyanophenoxy)-2,2-diethylpropane, 1,3-bis(2′,3′-dicyanophenoxy)-2,2-dioctylpropane, and 1,3-bis(2′,3′-dicyanophenoxy)-2-methyl-2-trityloxymethylpropane all gave bis-crown-like 1,11,15,25-tetrasubstituted phthalocyanines as pure compounds when treated with lithium octoxide in 1-octanol at 196 °C. A host of nine other bisphthalonitriles including 1,5-bis(2′,3′-dicyanophenoxy)-3-oxapentane, 1,1-bis(2′,3′-dicyanophenoxymethyl)cyclohexane, 1,2-bis(2′,3′-dicyanophenoxymethyl)benzene, and 2,5-bis(2′,3′-dicyanophenoxymethyl)furan did not dimerize to mononuclear phthalocynaines. The "gem dimethyl" effect was suggested as a reason for the successful macrocyclizations. Key words: nucleophilic aromatic substitution, phthalonitriles, bisphthalonitriles, 1,11,15,25-tetrasubstituted phthalocyanines.

scholarly journals Synthesis and fluorescent properties of N(9)-alkylated 2-amino-6-triazolylpurines and 7-deazapurines

2019 ◽  
Vol 15 ◽  
pp. 474-489 ◽  
Author(s):  
Andrejs Šišuļins ◽  
Jonas Bucevičius ◽  
Yu-Ting Tseng ◽  
Irina Novosjolova ◽  
Kaspars Traskovskis ◽  
...  
Keyword(s):  
Nucleophilic Aromatic Substitution ◽  
Secondary Amines ◽  
Acetonitrile Solution ◽  
Quantum Yields ◽  
Cell Labelling ◽  
Aromatic Substitution ◽  
Fluorescent Properties ◽  
Substitution Reactions ◽  
Low Cytotoxicity ◽  
Electron Donating Groups

The synthesis of novel fluorescent N(9)-alkylated 2-amino-6-triazolylpurine and 7-deazapurine derivatives is described. A new C(2)-regioselectivity in the nucleophilic aromatic substitution reactions of 9-alkylated-2,6-diazidopurines and 7-deazapurines with secondary amines has been disclosed. The obtained intermediates, 9-alkylated-2-amino-6-azido-(7-deaza)purines, were transformed into the title compounds by CuAAC reaction. The designed compounds belong to the push–pull systems and possess promising fluorescence properties with quantum yields in the range from 28% to 60% in acetonitrile solution. Due to electron-withdrawing properties of purine and 7-deazapurine heterocycles, which were additionally extended by triazole moieties, the compounds with electron-donating groups showed intramolecular charge transfer character (ICT/TICT) of the excited states which was proved by solvatochromic dynamics and supported by DFT calculations. In the 7-deazapurine series this led to increased fluorescence quantum yield (74%) in THF solution. The compounds exhibit low cytotoxicity and as such are useful for the cell labelling studies in the future.

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