[70-25-7]  · C2H5N5O3  · 1-Methyl-3-nitro-1-nitrosoguanidine  · (MW 147.12)

(precursor to diazomethane1)

Alternate Names: MNNG; N-methyl-N-nitro-N-nitrosoguanidine.

Physical Data: mp 118 °C (dec).

Solubility: sol alcohol, chloroform, acetone.

Form Supplied in: orange-yellow powder; commercially available.

Handling, Storage, and Precautions: shelf life of several years (somewhat longer than that of N-Methyl-N-nitroso-p-toluenesulfonamide); store in brown bottle, refrigerated; severe irritant, carcinogen, potent mutagen;2 contact may lead to sensitization, so contact by all routes must be avoided; handle in a fume hood.

General Discussion.

This reagent reacts to generate Diazomethane upon treatment with aqueous sodium hydroxide at rt. For the generation of small quantities of diazomethane (e.g. less than 1 mmol), this compound is probably the reagent of choice. A convenient apparatus (Figure 1) has been reported by Fales et al;3,4 the following procedure is representative.

1 mmol (133 mg) of the reagent is placed in the inside tube through its screw-cap opening along with 0.5 mL of water to dissipate any heat generated. 3 mL of ether is placed in the outside tube and the two parts are assembled with a butyl O-ring and held with a pinch-type clamp. The lower part is immersed in an ice bath and about 0.6 mL of 5 N sodium hydroxide is injected through the silicone rubber septum via a syringe with a narrow-gauge (No. 22) needle to prevent leakage around the shank.1,3 Diazomethane is collected in ether.

The alkali injection must be dropwise and very slow to control the volume of gas produced. At least 45 min are required for acceptable yields (over 50%). Solvents other than ether can be used for the collection of diazomethane. It is generally desirable to dissolve the substrate for reaction with diazomethane in the solvent in the outer tube prior to the generation, so that the reagent is consumed as it is produced.

1. McKay, A. F.; Wright, L. F. JACS 1948, 70, 1974.
2. A large number of papers have also reported biological use of this reagent as mutagen and carcinogen. For example: (a) Druckrey, H.; Preussmann, R.; Ivankovic, S.; Schmahl, D. Z. Krebsforsch. 1967, 69, 103. (b) Sugimura, T.; Fujimura S.; Baba, T. Cancer Res. 1970, 30, 455. (c) Fujimura, S.; Kogure, K.; Oboshi, S.; Sugimura, T. Cancer Res. 1970, 30, 1444. (d) Takayama, S.; Kuwabara, N.; Azama, Y.; Sugimura, T. J. Natl. Cancer Inst. 1971, 46, 973. (e) McCann, J.; Choi, E.; Yamasaki, E.; Ames, B. N. PNA 1975, 72, 5135.
3. Fales, H. M.; Jaouni, T. M.; Babashak, J. F. Anal. Chem. 1973, 45, 2302.
4. Available from Aldrich Chemical Company, Inc.

Yoshiyasu Terao & Minoru Sekiya

University of Shizuoka, Japan

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