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Synthesis 2011(7): 1037-1044  
DOI: 10.1055/s-0030-1258457
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

2-Azido-1,3-dimethylimidazolinium Salts: Efficient Diazo-Transfer Reagents for 1,3-Dicarbonyl Compounds

Mitsuru Kitamura*, Norifumi Tashiro, Satoshi Miyagawa, Tatsuo Okauchi
Department of Applied Chemistry, Kyushu Institute of Technology, 1-1 Sensuicho, Tobata, Kitakyushu, 804-8550, Japan
Fax: +81(93)8843304; e-Mail: kita@che.kyutech.ac.jp;
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Publication History

Received 6 January 2011
Publication Date:
02 March 2011 (online)

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Abstract

We have developed the diazo-transfer of 2-azido-1,3-dimethylimidazolinium salts to 1,3-dicarbonyl compounds. 2-Azido-1,3-dimethylimidazolinium chloride (ADMC) was prepared by N-nitrosation of N-aminoguanidine or by the reaction of 2-chloro-1,3-dimethylimidazolinium chloride (DMC) and sodium azide. The corresponding phosphate, ADMP, was isolated as a crystal, and was found to be a stable and safe reagent. Both ADMC and ADMP reacted with 1,3-dicarbonyl compounds under mild conditions to give 2-diazo-1,3-dicarbonyl compounds in high yields, which are easily isolated because the by-products are highly soluble in water.

Key words

azides - diazo compounds - diazonium salts - diazo-transfer - heterocycles

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13

The prepared hydrochloride salt of 4 was very hygroscopic. The amount of HCl in the salt was estimated to be 2 by elemental analysis (see the experimental section).

14

Initially, methanol was added as a co-solvent to dissolve sodium azide in the reaction mixture; however, its use did not increase the yields of diazotized compounds.

16

Recently, we reported the preparation of ADMP (3b) and its diazo-transfer to primary amines as a communication (see ref. 11a).

18

Impact sensitivity was determined to be >25 [Nm] by the German Federal Institute for Materials Research and Testing (BAM) procedure.

19

Friction sensitivity was determined to be >360 [N] by the German Federal Institute for Materials Research and Testing (BAM) procedure.