Original Article:
Synthesis and Characterization of Geminal Diazido Derivatives Based on Diethyl Malonate
Harter, Alexander G., et al.
European Journal of Inorganic Chemistry, 2021, 23, 2241-2247.
10.1002/ejic.202100212
Diethyl malonate is a compound widely used in various reactions and synthetic processes in organic chemistry. In this work, various geminal diazide derivatives were synthesized starting from diethyl malonate. It is worth mentioning that organic azides have been extensively studied for use in various fields such as pharmaceuticals, precursors of click chemistry, agricultural chemicals, and energetic materials.
Scheme 1: Synthesis of diethyl 2,2-diazidomalonate from diethyl malonate
Diethyl malonate is iodized on the carbon atom between the ester groups in a slightly basic aqueous solution, followed by an iodine azide exchange, which leads to the desired geminal diazide.
Scheme 2: Synthesis of geminal diazide derivatives
A variety of geminal diazide derivatives can be synthesized by Bronsted acid-base chemistry, including the synthesis of ionic compounds (3-6) and neutral compounds (2). Hereby, the ethyl residue is cleaved by the basic reactants and the carboxylate-salt formation takes place. Diethyl 2,2-diazidomalonate (1) is mixed with water and is reacted with an equimolar amount of the respective base at slightly elevated temperatures. An exception is the guanidinium salt, which only reacts at higher temperatures. Under these conditions, CO2 is released from 1 and compound 6 is formed. Compound 2 is formed in a similar manner but acidified with sulfuric acid after formation of the potassium salt in order to form the dicarboxylic acid.
Chemicals Related in the Paper:
| Catalog Number | Product Name | Structure | CAS Number | Price |
|---|---|---|---|---|
| ACM53051813 | Diethyl malonate(1,2,3-13c3) |  |
53051-81-3 | Price |
| ACM4303495 | Diethyl malonate-d2 |  |
4303-49-5 | Price |
