Dinitromethane

Rahman and Clapp decomposed dinitromethane derivatives in DMF in the presence of alkenes to obtain 2-isoxazolines. Without any alkene present, an acid and KNO2 were obtained. They proposed a mechanism which proceeded via a three-membered ring or a nitrocarbene which rearranged to a nitrile oxide (76JOC122, 75MI41612). 

The dinitromethane derivatives 135 and 136 were obtained by nitration of oximes of monoacyl furazans and furoxans with dinitrogen tetroxide [36G819, 37G518, 63T(S)143] or nitric acid (37G388, 97MI11, 97ROC1760) (Scheme 79). 

It is best prepd by the reduction of dibromo-dinitromethane with As trioxide in cold aq K hydroxide and isolated as the K salt (Ref 3). 

The stirring is contd for 5 hours, the pptd solid filtered off, and recrystd from w to give 8.4g of K dinitromethane, yield 23.3%, expln temp 208° (Ref 8). More recently it is conveniently prepd on a lab and comml scale by the interaction of NMe and Na nitrite with a Ag salt, most commonly the nitrate. This re- action, developed by Shechter and Kaplan of the Purdue Research Foundation, is called the Shechter-Kaplan reaction (Ref 14). The IR spectrum is given in Ref 13. The ionization constant in w at 25° is 2.26 0.01 (Ref 20). 

Reactions. For reactions see above under Dinitromethane and Bromodinitromethane Refs I) Bed 1, 78 [44] 2) S.M. Losa-... 

Ballistic Strength. 100% T NT (BuM ine s) Explosion Temperature. Does not expld or ignite at 360° or below Heat of Combustion. 8l8.1kcal/mole Hygroscopicity. Practically none Impact Sensitivity. Comparable to TNT Power. By Trauzl test, 103% TNT Rifle Bullet Test. No detonations from impact of. 30 cal bullet at 90 ft Thermal Stability. Unsatisfactory, loses 49% of wt in 48 hrs at 75° (International Test) Velocity of Detonation. No information Salts of (m-Nitrophenyll-dinitromethane. Milone and Massa (Ref 2) prepd several metallic salts and found that their expl power decreased with increasing atomic v/t of the metal Following are some of the expl salts K salt—yel crysts ... 

Figure 13. Isokinetic relationship for the reaction of substituted dinitromethanes with formaldehydes (57). The standard deviation is shown as function of the supposed isokinetic temperature (full curve).

Example 2. Equilibrium constants of the reaction of twenty substituted dinitromethanes with formaldehyde have been measured (57) in the range 10-50°C. The isokinetic relationship is valid for only nine of them, as revealed in a preliminary graphical treatment using the plot of log Kjo versus log Kio( 163) the pertinent values of logK are reproduced in Table I. The values of x = T" were transformed according to eq. (36a) with... 

Alkali-metal salts of of dinitromethane are sensitive to impact and should be handled remotely behind shields, in small quantity and with great care. 

This salt of acz-dinitromethane shows detonator properties. 

For example, the use of diazomethane makes it possible to synthesize the corresponding O-methyl nitronates from dinitromethane (18), trinitromethane (19), and two isomeric TV-methyltetrazolyldinitromethanes (20) (Scheme 3.8, Eq. 1)... 

In reactions of certain alkyl halides with salts of polynitromethanes, C-alkyla-tion can also be diminished and target O-nitronates can be prepared in satisfactory yields (21, 22) (Scheme 3.8, Eq. 2). Of special note is the study by Kim and Adolph (22), who prepared numerous nitronates by alkylation of salts of dinitromethane, cyanodinitromethane, and trinitromethane with a representative series of a-chloro-substituted (including functionalized) ethers. 

N. Levy and J. D. Rose, Quart. Rev., 1, 358 (1947). According to these authors, dinitromethane was first prepared ini 864, but they give no reference. 

Grakauskas, V. et al., J. Org. Chem., 1978, 43, 3485-3488 Trinitromethane ( nitroform ), dinitroacetonitrile, their salts and polynitroalkanes are all potentially dangerous, and must be carefully handled as explosive compounds [1], Many congeners and derivatives of dinitromethane are explosive and require careful and appropriate handling [2], Individually indexed compounds are ... 

The Ter Meer reaction has been used for the synthesis of the potassium salt of dinitromethane... 

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