122935-06-2

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• 103-63-9 1-phenyl-2-bromoethane 
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• 122058-04-2 (3-Phenyl-propyl)-phosphoramidic acid diethyl ester 
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Relevant academic research and scientific papers

New protocol for converting alcohols into amines

The reactions between diethyl N-(t-butoxycarbonyl)phosphoramidate 1, diisopropyl azodicarboxylate (DIAD), triphenylphosphine (TPP) and primary or secondary alcohols lead to the corresponding diethyl N-alkyl-N-(t-butoxycarbonyl)phosphoramidates 2a-o. Deprotection of crude 2 by refluxing with p-toluenesulfonic acid monohydrate in ethanol affords ammonium tosylates 3a-o in moderate to good overall yields. The N-alkylation of 1 proceeds stereoselectively with complete inversion of the configuration of the alkyl group.

An optimized version of Gabriel-type nucleophilic amination

N-Alkylation of primary alkyl bromides with diethyl N-sodio-N-(t- butoxycarbonyl)phosphoramidate 1 carried out in boiling acetonitrile in the presence of 10mol% of tetrabutylammonium bromide as catalyst leads to the corresponding N-alkyl derivatives 2a-I. Deprotection of 2 by refluxing with p-toluenesulfonic acid in ethanol-affords ammonium tosylates 3a-I in reasonable yields.

Optimized procedures for one-pot conversion of alkyl bromides into amines via the Staudinger reaction

New optimized procedures for transforming primary and secondary alkyl bromides into the corresponding primary amine salts have been elaborated. Essential modifications of azidation and deprotection of intermediate triethoxyphosphine alkylimides resulted in substantial improvement of the overall yields. Conversion of ammonium tosylates and hydrochlorides into free amines in a nonaqueous medium is described.

THE REACTION OF ETHYL-FORMIMIDATE WITH GRIGNARD REAGENTS: A NEW APPROACH TO ELECTROPHILIC AMINATION

Addition of Grignard reagents to ethyl-N-(diethoxyphosphoryl)formimidate, 3 followed by aqueous workup and treatment of the resultant diethyl phosphoramidates with p-toluenesulfonic acid in ethanol gives, depending upon the organomagnesium reagent used, the corresponding tosylates of primary or secondary amines in moderate to good yields.The diethoxyphosphoryl moiety remains unchanged upon treatment of 3 with Grignard reagents.Key words: Diethyl-(N-alkylphosphoramidates); Grignard reagents; ammonium tosylates; substitution-addition; substitution-reduction; electrophilic amination.