Diethyl azodicarboxylate
From Wikipedia, the free encyclopedia
| Diethyl azodicarboxylate | |
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| IUPAC name | Diethyl diazenedicarboxylate |
| Other names | Diethyl azidoformate, DEAD, DAD |
| Identifiers | |
| CAS number | [1972-28-7] |
| SMILES | O=C(/N=N/C(=O)OCC)OCC |
| Properties | |
| Molecular formula | C6H10N2O4 |
| Molar mass | 174.15 g/mol |
| Density | 1.106 g/cm³ |
| Boiling point |
106 °C at 13 mm Hg |
| Hazards | |
| MSDS | External MSDS |
| Flash point | 85°C |
| Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) Infobox disclaimer and references |
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Diethyl azodicarboxylate, often abbreviated DEAD, is the organic compound CH3CH2O2CN=NCO2CH2CH3. As indicated with this formula, the molecule consists of a central azo functional group, RN=NR, flanked by two ethyl ester groups. This red orange liquid is a valuable reagent but also quite dangerous.
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[edit] Preparation
Although widely available, diethyl azodicarboxylate can be prepared in the laboratory. A two-step synthesis starts from hydrazine, first by alkylation with ethyl chloroformate. followed by treating the resulting ethyl hydrazodicarboxylate with chlorine.[1]
- 2 CH3CH2O2CCl + N2H4 → CH3CH2O2CN(H)N(H)CO2CH2CH3 + 2 HCl
- CH3CH2O2CN(H)N(H)CO2CH2CH3 + Cl2 → CH3CH2O2CN=NCO2CH2CH3 + 2 HCl
Red fuming nitric acid can also be used in the second step.[2]
[edit] Applications
DEAD is an efficient component in Diels-Alder reactions and in click chemistry, for example the synthesis of Bicyclo[2.1.0]pentane, which originates from Otto Diels.[3]
DEAD is an important reagent in the Mitsunobu reaction where it forms an adduct with phosphines. In one study[4] the compound together with triphenylphosphine and a chalcone formed a pyrazoline:
[edit] Safety
DEAD is toxic, shock sensitive, and thermally unstable. It is handled as a solution, rarely as the pure compound. This safety hazards have resulted in DEAD usage rapidly declining and being replaced with DIAD (Diisopropyl azo dicarboxylate).
[edit] References
- ^ Rabjohn, N.. "Diethyl azodicarboxylate". Org. Synth.; Coll. Vol. 3: 375.
- ^ Kauer, J. C.. "Diethyl azodicarboxylate". Org. Synth.; Coll. Vol. 4: 411.
- ^ Gassman, P. G.;Mansfield, K. T.. "Bicyclo(2.1.0)pentane]". Org. Synth.; Coll. Vol. 5: 96.
- ^ A Novel Reaction of the “Huisgen Zwitterion” with Chalcones and Dienones: An Efficient Strategy for the Synthesis of Pyrazoline and Pyrazolopyridazine Derivatives Vijay Nair, Smitha C. Mathew, Akkattu T. Biju, and Eringathodi Suresh Angew. Chem. Int. Ed. 2007, 46, 2070 –2073 doi:10.1002/anie.200604025
