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Synthesis 2011(2): 265-272  
DOI: 10.1055/s-0030-1258353
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

A Convenient Synthesis and Some Characteristic Reactions of Novel Propiolamidinium Salts

Werner Weingärtnera, Willi Kantlehnerb, Gerhard Maas*a
a Institute of Organic Chemistry I, University of Ulm, Albert-Einstein-Allee 11, 89081 Ulm, Germany
Fax: +49(731)5022803; e-Mail: gerhard.maas@uni-ulm.de;
b Faculty of Chemistry, Organic Chemistry, University of Applied Research Aalen, Beethovenstraße 1, 73430 Aalen, Germany
Fax: +49(7361)5762250; e-Mail: willi.kantlehner@htw-aalen.de;
Further Information

Publication History

Received 8 September 2010
Publication Date:
07 December 2010 (online)

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Abstract

Starting from N,N,N′,N′,N′′,N′′-hexaalkylguanidinium chlorides and terminal alkynes, a series of new orthoamide derivatives of alkynecarboxylic acids were prepared. The orthoamides were converted into propiolamidinium chlorides by reaction with benzoyl chloride and into propiolamidinium triflates by reaction with triethylsilyl trifluoromethanesulfonate. Propiolamidinium salts undergo conjugate addition reactions with sec-amines and thiols­. Treatment of terminal alkyne chlorides with silver(I) oxide afforded a silver complex, which can apparently adopt the composition of either a bisalkynyl silver complex [Ag(CCC(NMe2)2)2]AgCl2 or a monoalkynyl silver complex [ClAgCCC(NMe2)2].

Key words

alkynes - amidinium salts - orthoamides - hexamethyl­guanidinium chloride - silyl triflates

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18

Details of the crystal structure analysis of 11b will be reported elsewhere. The bond lengths in the organic part of the complex suggest a rather small degree of electron delocalization toward the bond structure of a [bis(dimethylamino)allenylidene] silver(I) complex (compare lit.¹5).