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Nitrosations in Anhydrous Trifluoroacetic Acid Media: A Modification for Insoluble or Deactivated Amine and Amide Precursors.

ADA212276

Publication Date	1988
Personal Author	Kanakarajan, K.; Haider, K.; Czarnik, A. W.
Page Count	5
Abstract	The nitrosation of amines with sodium nitrite to afford the corresponding diazonium salts is one of the most versatile reactions in organic chemistry. Over the past several years, we have found that some amines are not amenable to nitrosation using the conditions found most commonly in the literature e.g. sodium nitrite in aqueous mineral acids. Problems of this type are seen when the starting amine is either deactivated by strongly electron - withdrawing groups at adjacent or conjugated positions. Or when the starting amine is extraordinarily insoluble. Especially vigorous nitrosation conditions have been used previously with deactivated amine starting materials; such variations include the use of concentrated sulfuric acid, mixtures of sulfuric and acetic or phosphoric acids, concentrated nitric acid, and the use of organic cosolvents. We now report the nitrosation reactions can be accomplished cleanly in anhydrous trifluoroacetic acid (TFA) solvent, and that this reaction medium allows the use of both deactivated and insoluble amines and amides as starting materials. Reprints. (KT)
Keywords	Amides Amines Nitration Organic chemistry Acetic acid Diazo compounds Reaction kinetics Electrons Minerals Nitric acid Phosphoric acids Precursors Reprints Response Salts Sodium nitrite Sulfuric acid Water Nitrosation Trifluoroacetic acid
Source Agency	Army Non Paid Reprints
NTIS Subject Category	99D - Basic & Synthetic Chemistry
Corporate Authors	Ohio State Univ., Columbus. Dept. of Chemistry.; Army Research Office, Research Triangle Park, NC.
Supplemental Notes	Pub. in Synthesis, 1988.
Document Type	Journal Article
NTIS Issue Number	199002
Contract Number	DAAG29-85-K-0200

Nitrosations in Anhydrous Trifluoroacetic Acid Media: A Modification for Insoluble or Deactivated Amine and Amide Precursors.

Nitrosations in Anhydrous Trifluoroacetic Acid Media: A Modification for Insoluble or Deactivated Amine and Amide Precursors.
ADA212276

Publication Date	1988
Personal Author	Kanakarajan, K.; Haider, K.; Czarnik, A. W.
Page Count	5
Abstract	The nitrosation of amines with sodium nitrite to afford the corresponding diazonium salts is one of the most versatile reactions in organic chemistry. Over the past several years, we have found that some amines are not amenable to nitrosation using the conditions found most commonly in the literature e.g. sodium nitrite in aqueous mineral acids. Problems of this type are seen when the starting amine is either deactivated by strongly electron - withdrawing groups at adjacent or conjugated positions. Or when the starting amine is extraordinarily insoluble. Especially vigorous nitrosation conditions have been used previously with deactivated amine starting materials; such variations include the use of concentrated sulfuric acid, mixtures of sulfuric and acetic or phosphoric acids, concentrated nitric acid, and the use of organic cosolvents. We now report the nitrosation reactions can be accomplished cleanly in anhydrous trifluoroacetic acid (TFA) solvent, and that this reaction medium allows the use of both deactivated and insoluble amines and amides as starting materials. Reprints. (KT)
Keywords	Amides Amines Nitration Organic chemistry Acetic acid Diazo compounds Reaction kinetics Electrons Minerals Nitric acid Phosphoric acids Precursors Reprints Response Salts Sodium nitrite Sulfuric acid Water Nitrosation Trifluoroacetic acid
Source Agency	Army Non Paid Reprints
NTIS Subject Category	99D - Basic & Synthetic Chemistry
Corporate Authors	Ohio State Univ., Columbus. Dept. of Chemistry.; Army Research Office, Research Triangle Park, NC.
Supplemental Notes	Pub. in Synthesis, 1988.
Document Type	Journal Article
NTIS Issue Number	199002
Contract Number	DAAG29-85-K-0200