Diazomethane

Title: Diazomethane
CAS Registry Number: 334-88-3
Additional Names: Azimethylene
Molecular Formula: CH2N2
Molecular Weight: 42.04
Percent Composition: C 28.57%, H 4.80%, N 66.64%
Line Formula: CH2=N+=N-
Literature References: Prepd from chloroform and hydrazine by reaction with potassium hydroxide: Staudinger, Kupfer, Ber. 45, 501 (1912); McManus et al., J. Org. Chem. 33, 4272 (1968); from KOH and nitrosomethylurea: Dessaux, Durand, Bull. Soc. Chim. Fr. 1963, 41. These methods yield gaseous diazomethane. The following procedures yield ether solns of diazomethane. From N-nitroso-b-methylaminoisobutyl methyl ketone in ether and isopropanol by reaction with sodium isopropoxide or from the same ketone in ether by reaction with sodium cyclohexoxide: Redemann et al., Org. Synth. 25, 28 (1945). By KOH saponification of nitrosomethylurea in ether: Arndt, Org. Synth. coll. vol. II, 165 (1943), or of nitrosomethylurethan in ether: von Pechmann, Ber. 27, 1888 (1894); 28, 855 (1895); Meerwein, Burneleit, Ber. 61, 1845 (1928). In the laboratory diazomethane may be prepd most simply by the action of alkali on the commercially available N-methyl-N-nitroso-N¢-nitroguanidine, cf. McKay, J. Am. Chem. Soc. 70, 1974 (1948); McKay et al., Can. J. Res. 28, 683 (1950); Fieser and Fieser, Organic Chemistry (Reinhold, New York, 3rd ed., 1956) p 176. Alternate intermediate: p-tolylsulfonylmethylnitrosamide ("Diazald" Aldrich Chemical Co.), see De Boer, Backer, Org. Synth. coll. vol. IV, 250 (1963).
Properties: Very toxic yellow gas. Explosive! Use safety screen. Insidious poison, a well-ventilated hood is absolutely necessary, avoid vapor. mp -145°; bp -23°. Undil liq and concd solns may explode violently, especially if impurities are present. Gaseous diazomethane may explode on heating to 100° or on rough glass surfaces. Ground glass apparatus and glass stirrers with glass sleeve bearings where grinding may occur, should not be used. Alkali metals also produce explosions with diazomethane. Sol in ether, dioxane. Such solns dec only slowly at low temps. Decompn is more rapid if alcohols or water are present. Copper powder causes active decompn with the evolution of nitrogen and the formation of insol white flakes of polymethylene (CH2)x. Solid calcium chloride or boiling stones have the same effect. This phenomenon appears to occur always during the action of diazomethane on solid substances.
Melting point: mp -145°
Boiling point: bp -23°
CAUTION: Potential symptoms of overexposure are eye irritation; coughing, shortness of breath; headache; fatigue, flushing of skin, fever; chest pain, pulmonary edema, pneumonitis; asthma; direct contact with liquid may cause frostbite. See NIOSH Pocket Guide to Chemical Hazards (DHHS/NIOSH 97-140, 1997) p 92. May act as a respiratory sensitizer. See Patty's Industrial Hygiene and Toxicology vol. 2A, G. D. Clayton, F. E. Clayton, Eds. (Wiley-Interscience, New York, 3rd ed., 1981) pp 2784-2786.
Use: Powerful methylating agent for acidic compds such as carboxylic acids, phenols, enols. For syntheses with diazomethane see the reviews by Smith, Chem. Rev. 23, 193 (1938); Eistert, Z. Angew. Chem. 54, 99, 124 (1941) translated by Spangler in Newer Methods of Preparative Organic Chemistry (New York, 1948) p 513; J. S. Pizey, Synthetic Reagents vol. 2 (John Wiley, New York, 1974) pp 65-142.
Diazoxide Dibekacin Dibenzalacetone Dibenzepin Dibenzoylmethane

Diazomethane
Diazomethane
Diazomethane
Identifiers
CAS number 334-88-3 YesY
PubChem 9550
ChemSpider 9176 YesY
KEGG C19387 N
ChEBI CHEBI:73716 N
Jmol-3D images Image 1
Properties
Molecular formula CH2N2
Molar mass 42.04 g/mol
Appearance Yellow gas
Density 1.4 (air=1)
Melting point -145 °C
Boiling point -23 °C
Solubility in water hydrolysis[1]
Structure
Molecular shape linear C=N=N
Dipole moment polar
Hazards
R-phrases R12 R19 R22 R66 R67
S-phrases S9 S16 S29 S33
Main hazards toxic and explosive
Related compounds
Related compounds R2CN2 R = Ph, tms, CF3
 N (verify) (what is: YesY/N?)
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
Infobox references

Diazomethane is the chemical compound CH2N2, discovered by German chemist Hans von Pechmann in 1894. It is the simplest diazo compound. In the pure form at room temperature, it is an extremely sensitive explosive yellow gas; thus, it is almost universally used as a solution in diethyl ether. The compound is a popular methylating agent in the laboratory, but it is too hazardous to be employed on an industrial scale without special precautions.[2]