Methyl Hydrazinocarboxylate

(1; R = Me)

[6294-89-9]  · C2H6N2O2  · Methyl Hydrazinocarboxylate  · (MW 90.10) (2; R = Et)

[4114-31-2]  · C3H8N2O2  · Ethyl Hydrazinocarboxylate  · (MW 104.13) (3; R = t-Bu)

[870-46-2]  · C5H12N2O2  · t-Butyl Hydrazinocarboxylate  · (MW 132.19)

(used for conversion of ketones to nitriles, dehydrohalogenation of a-bromo ketones, and formation of azidoformates)

Alternate Name: methyl carbazate.

Physical Data: (1) mp 70-73 °C; bp 108 °C/12 mmHg. (2) mp 44-47 °C; bp 110 °C/22 mmHg. (3) mp 39-42 °C; bp 65 °C/0.03 mmHg.

Ketones to Nitriles.

Methyl and ethyl carbazate are used as derivatizing reagents for aldehydes and ketones.1 The methyl derivative is employed in the conversion of ketones to nitriles through the base-catalyzed decomposition of the intermediate diazene (eq 1).2 The procedure also works well for a-substituted ketones. If the diazene decomposition is conducted in aprotic medium (DME) in the presence of stoichiometric base (LiOMe), the resultant nitrile anion can be alkylated.


Ethyl carbazate is employed in the Kendall-Mattox dehydrohalogenation of a-bromo ketones (eq 2).3

t-Butyl Azidoformate.

Nitrosation converts t-butyl carbazate into t-Butyl Azidoformate, a reagent for the protection of amines as their Boc derivatives.4

Related Reagents.

2,4-Dinitrophenylhydrazine; Hydrazine; Semicarbazide; p-Toluenesulfonylhydrazide; p-Tolylsulfonylmethyl Isocyanide; 2,4,6-Triisopropylbenzenesulfonylhydrazide; Trimethylaminoacetohydrazide Chloride.

1. Rabjohn, N.; Barnstorff, H. D. JACS 1953, 75, 2259.
2. (a) Ziegler, F. E.; Wender, P. A. JACS 1971, 93, 4318; JOC 1977, 42, 2001. Wender, P. A.; Eissenstat, M. A.; Sapuppo, N.; Ziegler, F. E. OSC 1988, 6, 334.
3. (a) Joly, R.; Nominé, G. BSF 1956, 1381. (b) Kirk, D. N.; Petrow, V. JCS 1959, 1691.
4. Carpino, L. A.; Carpino, B. A.; Crowley, P. J.; Giza, C. A.; Terry, P. H. OSC 1973, 5, 157.

Frederick E. Ziegler & Anders K. Petersen

Yale University, New Haven, CT, USA

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