Preparation of 3-(trimethylsilanyl)propynoic acid N-(hydroxyalkyl)amides

Alevtina Medvedeva,Galina Sarapulova,Michael Andreev,Andrey Afonin,Lyubov’ Safronova,Joachim Schantl

doi:10.3998/ark.5550190.0002.917

Abstract

New 3-(trimethylsilanyl)propynoic acid N-(hydroxyalkyl)amides were synthesized by the reaction of silyl-protected aminoalcohols with 3-(trimethylsilanyl)propynoyl chloride in high yields. The reaction of unprotected ethanolamine with 3-(trimethylsilanyl)propynoyl chloride caused N,O-bisacylation and the formation of 2-(3-(trimethylsilanyl)propynoyl)aminoethyl 3- (trimethyl-silanyl)propynoate.

Highlights

Amides of propynoic acid feature a variety of pharmacological profiles;[1,2,3,4,5,6,7,8] they have been used for the synthesis of rapamycin,[9] an immunosuppressant, and they serve as building blocks in organic chemistry, in particular, for the formation of heterocyclic systems which may be of special interest as biologically active compounds
We have described the synthesis of 3-(trimethylsilanyl)propynoic acid N,Ndialkylamides,[11,12] their fragmentation under electron impact[2] and the determination of their basicity by an IR method.[13]
The goal of this investigation is the synthesis of new amides of 3-(trimethylsilanyl)propynoic acid containing an N-hydroxyalkyl group by the reaction of 3-(trimethylsilanyl)propynoyl chloride 1 with hydroxyalkylamines H2NCR1R2CH2OH 2-4 [R1 = R2 = H (2), R1 = H, R2 = Et (3), R1 = R2 = Me (4)] and 1,3-diamino-2-propanol 5

Summary

Introduction

Amides of propynoic acid feature a variety of pharmacological profiles;[1,2,3,4,5,6,7,8] they have been used for the synthesis of rapamycin,[9] an immunosuppressant, and they serve as building blocks in organic chemistry, in particular, for the formation of heterocyclic systems which may be of special interest as biologically active compounds.Silicon-substituted propynoic acid amides have received little attention. 3-(Trimethylsilanyl)propynoic acid N-benzylamide has been prepared from lithiated 2-propynoic acid amide and chlorotrimethylsilane; its reaction with arylisocyanates in the presence of triethylamine has been reported to afford Z-trimethylsilydenehydantoin.[10]Previously, we have described the synthesis of 3-(trimethylsilanyl)propynoic acid N,Ndialkylamides,[11,12] their fragmentation under electron impact[2] and the determination of their basicity by an IR method.[13]. Selective N-acylation of O-silylated ethanolamine with 3-(trimethylsilanyl)propynoyl chloride (1) gave 3-(trimethylsilanyl)propynoic acid N-(2-hydroxyethyl)amide (7) in high yield.

Results

Conclusion