Note
Thesis (M.S.)--Florida Atlantic University, 1976.
Member of
Contributors
Publisher
Florida Atlantic University
Date Issued
1976
Description
The acid-catalyzed N-alkylation of an amide by an alcohol or an alkene
occurs successfully if the intermediate carbenium ion is highly stabilized
and therefore readily formed. This is because carbenium ion formation
must compete successfully with protonation and consequent deactivation
of the amide. The carbenium ion will N-alkylate the amide unless steric
requirements preclude such attack. In boiling glacial acetic acid acetamide is N-alkylated readily by ferrocenylmethanol, a-hydroxyethylferrocene and vinylferrocene but slowly by triphenylmethanol. Triphenylnmethylation is accelerated by a small amount of sulfuric acid. Reaction
of acetamide with diphenylmethanol in boiling glacial acetic acid yields
N-diphenylmethylacetamide in the presence of sulfuric acid, diphenylmethyl acetate in the ascence of sulfuric acid. Under both these conditions
the reaction of acetamide with benzyl alcohol fails, benzyl acetate
being the sole product. Nicotinamide is triphenylmethylated and ferrocenylmethylated only on the amide nitrogen, not on the pyridine nitrogen.
N-methylacetamide, a secondary amide, can be N-ferrocenylmethylated.
occurs successfully if the intermediate carbenium ion is highly stabilized
and therefore readily formed. This is because carbenium ion formation
must compete successfully with protonation and consequent deactivation
of the amide. The carbenium ion will N-alkylate the amide unless steric
requirements preclude such attack. In boiling glacial acetic acid acetamide is N-alkylated readily by ferrocenylmethanol, a-hydroxyethylferrocene and vinylferrocene but slowly by triphenylmethanol. Triphenylnmethylation is accelerated by a small amount of sulfuric acid. Reaction
of acetamide with diphenylmethanol in boiling glacial acetic acid yields
N-diphenylmethylacetamide in the presence of sulfuric acid, diphenylmethyl acetate in the ascence of sulfuric acid. Under both these conditions
the reaction of acetamide with benzyl alcohol fails, benzyl acetate
being the sole product. Nicotinamide is triphenylmethylated and ferrocenylmethylated only on the amide nitrogen, not on the pyridine nitrogen.
N-methylacetamide, a secondary amide, can be N-ferrocenylmethylated.
Language
Type
Form
Extent
187 p.
Subject (Topical)
Identifier
13786
Additional Information
Thesis (M.S.)--Florida Atlantic University, 1976.
Charles E. Schmidt College of Science
FAU Electronic Theses and Dissertations Collection
Date Backup
1976
Date Text
1976
Date Issued (EDTF)
1976
Extension
FAU
FAU
admin_unit="FAU01", ingest_id="ing1508", creator="staff:fcllz", creation_date="2007-07-19 01:37:23", modified_by="staff:fcllz", modification_date="2011-01-06 13:09:02"
IID
FADT13786
Issuance
monographic
Organizations
Attributed name: Florida Atlantic University
Person Preferred Name
BROWN, PATRICK MARTIN.
Graduate College
Physical Description
187 p.
Title Plain
N-ALKYLATION OF AMIDES USING ALCOHOLS OR ALKENES
Use and Reproduction
Copyright © is held by the author, with permission granted to Florida Atlantic University to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder.
http://rightsstatements.org/vocab/InC/1.0/
Origin Information
1976
monographic
Boca Raton, Fla.
Florida Atlantic University
Physical Location
Florida Atlantic University Libraries
Place
Boca Raton, Fla.
Sub Location
Digital Library
Title
N-ALKYLATION OF AMIDES USING ALCOHOLS OR ALKENES
Other Title Info
N-ALKYLATION OF AMIDES USING ALCOHOLS OR ALKENES