Dinitromethane salts

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). 

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 ... 

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. 

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. 

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... 

Reaction at the C atom of nitronate salts is known with a variety of electrophiles, such as aldehydes (Henry reaction) and epoxides (191-193). Thus the incorporation of the nitro moiety and the cyclization event can be combined into a tandem sequence. Addition of the potassium salt of dinitromethane to an a-haloaldehyde affords a nitro aldol product that can then undergo intramolecular O-alkylation to provide the cyclic nitronate (208, Eq. 2.17) (59). This process also has been expanded to a-nitroacetates and unfunctionalized nitroalkanes. Other electrophiles include functionalized a-haloaldehydes (194,195), a-epoxyaldehydes (196), a-haloenones (60), and a-halosulfonium salts (197), (Chart 2.2). In the case of unsubstituted enones, it is reported that the intermediate nitronate salt can undergo formation of a hemiacetal, which can be acetylated in moderate yield (198). 

Its potassium salt, KCI(N02)2, mp (explodes violently at 154°) orange-yellow plates. It was first prepd by Villiers (Ref 2). Gotts Hunter (Ref 4) dissolved lOg of K dinitromethane in 300ml of water containing 4g of KOH (one equivalent), cooled the solution and slowly added powdered iodine (18g) to it with shaking. The solution was evaporated to a small bulk (50ml), which caused the separation of about... 

Iododinitromethane, CHI(N02)2. mw 231.9, N 12.1%. Its K-salt, prepd by slowly adding iodine to K-dinitromethane in aq KOH, orange-yellow platelets (from w) explodes violently at 154°. 

N)2C1C.CC1(N02)2 mw 278 96, N 20.09% snow-wh amor powd, sublimes at RT to form star-shaped crysts, mp - begins to decomp at 60-65° with evolution of N oxides, melts sharply at 107° volatile in steam with partial decompn very sol in org solvs with decompn slowly converted by boiling w into CO2, oxides of N, HC1 dichloro-dinitromethane forms with KOH or Kl, Dipotassium tetranitro-ethane, a yel cryst salt, explosion temp 268° was ptepd by bubbling Cl thru a soln of the dipotassium salt in the presence of Na acetate cooling the mixt (Refs 1 2)... 

Dinitromethane forms salts which are (generally speaking) unstable and decompose at temperatures not very much above 100°C. 

Alkali metal salts of dinitromethane have also been prepared (2) by nitrating methyl malonate to produce methyl dinitroacetate followed by saponification and decarboxalation as illustrated in Eq. 2 ... 

---