Micellar catalysis of organic reactions. Part 34. Nucleophilic aromatic substitution reactions in micelles with bulky head groups

1993 ◽  
Vol 6 (9) ◽  
pp. 535-538 ◽  
Author(s):  
Trevor J. Broxton ◽  
John R. Christie ◽  
Dorothy Theodoridis
Keyword(s):  
Micellar Catalysis ◽  
Organic Reactions ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Substitution Reactions ◽  
Head Groups

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

Micellar Catalysis of Organic Reactions. XXXVIII A Study of the Catalytic Effect of Micelles of 3-Hydroxymethyl-1-tetradecylpyridinium Bromide on Amide Hydrolysis and Nucleophilic Aromatic Substitution

1998 ◽  
Vol 51 (7) ◽  
pp. 541 ◽  
Author(s):  
Trevor J. Broxton
Keyword(s):  
Catalytic Effect ◽  
Micellar Catalysis ◽  
Aryl Halides ◽  
Organic Reactions ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Rate Determining Step ◽  
Amide Hydrolysis

The preparation of 3-hydroxymethyl-1-tetradecylpyridinium bromide and its use as a catalyst of nucleophilic aromatic substitution and also amide hydrolysis are reported. It was found that the hydroxydehalogenation of nitro-activated aryl halides was much faster in these micelles than in the presence of cetyl(2-hydroxyethyl)dimethylammonium bromide. It was concluded that the increased catalysis of nucleophilic aromatic substitution by this micelle was due to a faster decomposition of the aryl micellar ether which must occur before the phenolate product is released. No such difference in the two micelles was found for amide or thioamide hydrolysis since in these reactions the product amine is produced in the first step of the reaction and decomposition of the acylated micelle is not required in the rate-determining step of the reaction.

Micellar catalysis of organic reactions. IX. The reaction of sodium azide with activated aromatic halides and the subsequent decomposition of the initially formed aryl azide

1982 ◽  
Vol 35 (12) ◽  
pp. 2557 ◽  
Author(s):  
TJ Broxton ◽  
AC Jakovljevic
Keyword(s):  
Sodium Azide ◽  
Substitution Reaction ◽  
Cetyltrimethylammonium Bromide ◽  
Micellar Catalysis ◽  
Organic Reactions ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Aryl Azide ◽  
Snar Reaction ◽  
Subsequent Decomposition

The effect of micelles of cetyltrimethylammonium bromide on the SNAr reaction of azide ions with 1-halogeno-2,4-dinitrobenzenes and on the subsequent decomposition of the aryl azide product has been measured. The nucleophilic aromatic substitution reaction is shown to be subject to significant micellar catalysis whereas the subsequent decomposition of the aryl azide is not.

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.

Sign in / Sign up

Export Citation Format

Share Document