Methyl azide

Mercury Acetylenic compounds, chlorine, fulminic acid, ammonia, ethylene oxide, metals, methyl azide, oxidants, tetracarbonylnickel... 

Azidome thane (Methyl Azide), (called Azidome -than or Methylazid in Ger) CH3N3 mw 57.06, N 73.65% a colorl, mobile, ethereal liq with an unpleasant odor similar to hydrazoic acid (Ref 2) bp 20-1° d s,0.869g/ec (Ref 2) CA Registry No 624-90-8... 

The Adjacent Charge Rule and the Structure of Methyl Azide,... 

Methyl Azide.—In our earlier investigation of methyl azide2 it was concluded that the molecules contain a linear azide group with dimensions corresponding to resonance between the... 

Fig. 1.—Radial distribution curves for methyl azide, methyl nitrate, and fluorine nitrate.

The question as to whether or not hydrazoic add and nitric add are more closely related to the corresponding covalent compounds than to the ions could be answered by determining the configurations of the acids. From general information we would predict that the H-N and H-0 bonds are essentially covalent (with perhaps about one-third ionic character) and that the Ns and NOs groups in the acids have the same structures as in methyl azide and nitrates. This prediction is supported by the instability of the acids. 

The investigation of methyl azide, methyl nitrate, and fluorine nitrate by electron diffraction is shown to lead to configurations of the molecules corresponding in each case to resonance between two important valence-bond structures. The unimportance of a third otherwise reasonable structure for these molecules as well as for nitrous oxide is ascribed to instability due to the presence of electric charges of the same sign on adjacent atoms. It is shown that the differ-... 

Goubeau, J., E. Allenstein u. A. Schmid t)ber die Reaktion des Methyl-azids mit Antimon-(V)-chlorid und Chlorwasserstoff. Stabilisierung des Methylenimins durch Salzbildung. Chem. Ber. 97, 884 (1964). 

Presence of mercury in methyl azide markedly reduces the stability towards shock or electric discharge. 

In spite of extensive cooling and precautions, a mixture of methyl azide, methanol and dimethyl malonate exploded violently while being sealed into a Carius tube. The vapour of the azide is very easily initiated by heat, even at low concentrations. 

Neruda, B. et al., J. Organomet. Chem., 1976, 111, 241-248 In the exothermic reaction with trimethyl phosphite to give r/.v-dimethyl-bis(trimethyl phosphito)platinum, the azide must be added to the phosphite in small portions with stirring. Addition of the phosphite to the solid azide led to a violent explosion, probably involving the transitory by-product methyl azide. 

See Methyl azide, also 4-Chlorophenylisocyanate, also Nitrous acid A semicar-bazone, etc. 

Thermal decompositions of alkyl azides are advantageously studied in millimole quantities using a PE spectroscopically controlled flow system under low pressure ( ), thereby reducing the hazards involved in handling these explosive compounds in bulk. Our investigations started with methyl azide, which splits off nitrogen unexpectedly only at temperatures above 500° C (37) ... 

The known pentazoles are aryl derivatives which have the structure (3). They are obtained from the reaction of aryldiazonium ions with azide ion (Equation (2)). No alkylpentazoles are known and the reaction of diazomethane with HN3 which gives methyl azide has been shown by N-labelling not to pass through a pentazole intermediate <58HCA1823>. The parent NH-pentazole is unknown. The numbering system shown in (3) will be used in this chapter. 

Bellavia-Lund and Wudl (43) investigated the 1,3-dipolar cycloaddition of 2-(methoxyethoxy)methyl azide with [70]fuUerene (199) (Scheme 9.43). Three isomeric triazohnes 200-202 were obtained. Thermolysis of these triazolines gave the corresponding azafiilleroids and fulleroaziridines, as a mixture, respectively. 

These conclusions were anticipated by product studies. Alkyl azides are readily available and their thermal and photochemical decomposition reactions have been studied. In general, light and heat induced decomposition of methyl azide does not produce a MeN species that can be intercepted in respectable yields with a bimolecular trap. For example, attempts to trap MeN with cyclohexane as solvent produced only a 0.4% yield of adduct. Photolysis of CH3N3 or CD3N3 at cryogenic temperatures fails to produce an IR spectrum attributable to triplet methylnitrene. The IR spectrum of CH2=NH (or CD2=ND) is observed instead. " ... 

The structure of methyl azide, the simplest organic derivative of hydrazoic acid, is ... 

The asymmetric and symmetric vibrations of methyl azide have frequencies of 2141 cm-1 and 1351 cm-1 respectively (Eyster and Gillette [30]). For a number of aliphatic and aromatic azides Lieber et al. [31] found the figures 2114-2083 cm-1 for asymmetric vibrations and 1297-1256 cm-1 for symmetric ones. Among the other authors who have examined organic azides the investigations of Boyer [32] and Evans and Yoffe [33] are noteworthy. 

Reaction of ketones with tosyl-methyl azide, followed by hydrolysis... 

Azidomethane (Methyl Azide). See under Methane and Beil 1, 80 [48]... 

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