Nitromethane: Methane, nitro

Glutaric dialdehyde Glutaraldehyde (8) Pentanedial (9) (111-30-8) Nitromethane Methane, nitro- (8,9) (75-52-5)... 

Hannum (Ref 12) patented mixts of fuels, consisting of NMe (Nitromethane), NEt (Nitro-ethane), and mono-, di-, or trinitropropane, with oxidants HNEt or TeNMe (Tetranitro-methane), stabilized by the addn of substituted ammonias in amts of 1 to 10% by wt. 

AI3-00111 CCRIS 1205 EINECS 200-876-6 HSDB 106 Methane, nitro- NM Nitrocarbol Nitrometan Nitromethane NSC 428 UN1261. Stabilizer for chlorinated solvents chemical intermediate solvent for cellulosic compounds, polymers, waxes rocket fuel, gasoline additive in coatings industry. Liquid mp = -28.5" bp = 101.1" d = 1.1371 soluble in H2O (10 g/100 ml), soluble in organic solvents LD50 (rat orl) = 1.44 g/kg. Grace W.R. Co. Whittaker Clark Daniels. 

CAUTION It is generally known that trinitrotoluene is a high explosive and that the treatment of glycerol, cellulose, and other carbohydrates with nitric acid/sulfuric acid leads to other explosives. The nitration of many other compounds may form products (or intermediates) which may be explosives, and precautions against detonations must be taken. Alkali salts of nitromethane or nitro-methane derivatives are sensitive to impact when dry [1]. In fact, the addition of bases or acids to nitromethane is said to render the compound susceptible to detonation according to a recent publication [2]. An explosion during the nitrolysis of an acetyl compound may... 

The simpler nitrop>arafIins (nitromethane, nitroethane, 1- and 2-nitroproj)ane) are now cheap commercial products. They are obtained by the vapour phase nitration of the hydrocarbons a gaseous mixture of two mols of hydrocarbon and 1 mol of nitric acid vapour is passed through a narrow reaction tube at 420-476°. Thus with methane at 476° a 13 per cent, conversion into nitro methane is obtained ethane at 420° gives a 9 1 mixture of nitroethane (b.p. 114°) and nitromethane (b.p. 102°) propane at 420° afifords a 21 per cent, yield of a complex mixture of 1- (b.p. 130-6°) and 2-nitropropane (b.p. 120°), nitroethane and nitromethane, which are separated by fractional distillation. 

Nitromethane is more easily prepared by heating together equimolecular amounts of sodium monochloroacetate and sodium nitrite in aqueous solution sodium nilroacetate is intermediately formed and is decomposed to nitro-methane and sodium bicarbonate. The latter yields sodium carbonate and carbon dioxide at the temperature of the reaction. 

Available from Aldrich Chemical Co. and used without further purification. Methylene chloride may be substituted for the nitro-methane. The checkers used reagent grade nitromethane available from Tokyo Kasei Kogyo Co. Ltd., Japan. 

It appears that gas-phase basicity of nitro compounds has been studied only scarcely. Thus, only the values of the parent compounds, nitromethane (179.2 kcalmol-1) and nitrobenzene (193.4 kcalmoD1), are found in the comprehensive listing given in Reference 39. The rather high PA values for nitro compounds suggest protonation by common chemical ionization reagent systems, such as hydrogen (H3+) and methane (CH5+). 

On treatment of glutaraldehyde with 2-hydroxy-3-nitropropionic acid, only 2-nitrocyclohexane-l,3-diol could be isolated in 10% yield, indicating that, under the conditions used, a retro-aldol degradation takes place with liberation of nitromethane. However, when using methyl 2-methoxy-3-nitropropionate, which cannot undergo a retro-nitro-methane addition", products (101) and (102) are obtained in yields of 7 and 13% respectively... 

Die Reaktion von Trimethylsilyl-methan (Tetramethyl-silan) mit einem Aquivalent Nitro-nium-tetrafluoroborat in Sulfolan zu Nitromethan wird in einem Druckreaktor bei 20-80° (2 h) durchgefiihrt (Ausbeute 80%)3 ... 

Recently Lee et al (Ref 3) re-examined the behavior of PETN under 10 to 50 kbars of external pressure. They also find a reduction in decomposition rate with increasing applied pressure. HMX behaves similarly to PETN. TNT whose explosion products contain a high proportion of solid carbon, as expected from LeChatelier s Principle, shows little pressure effect on its thermal decomposition. Nitro-methane, however, appears to decompose more rapidly under an external pressure of 50 kbars than 10 kbars. This effect is not completely understood but Lee et al suggest that high pressure may favor the formation of the thermally less stable aci form of Nitromethane ... 

The solvent affects the chemical equilibria of reactions. Second-order rate constants and equilibrium constants have been determined for the benzoate ion promoted deprotonation reactions of (m-nitrophenyl)nitromethane, (p-nitrophenyl)nitromethane, and (3,5-dinitrophenyl)nitromethane in methanol solution. The pKa values for the arylnitromethanes in methanol are the following pKa = 10.9, 10.5, and 9.86 for m-nitrophenyl)nitromethane, (p-nitrophenyl)nitromethane, and (3,5-dinitrophenyl)nitro-methane, respectively, relative to benzoic acid (pKa = 9.4). A Bronsted B value of... 

Abb. 9. Absorbtionsspektrum 3,0 x 10 4 molarer Losungen von / -Naphthol in Nitro methan/n-Heptan-Mischungen. Nitromethan-Konzentrationen 1) Null, 2) 0,104, 3)... 

A Bronsted fl]t value of 0.5 and occh value of 1.31 have been calculated for deprotonation reactions of (3,5-dinitrophenyl)nitromethane promoted by substituted benzoate ions and of substituted (3-nitro-, 4-nitro- and 3,5-dinitro-)phenyhiitro-methanes promoted by benzoate ion, respectively, in methanol.146 The intrinsic rate constants are (2.0-6.3)x 104 tunes lower than for the same reactions in acetonitrile solution, and this has been attributed to commensurate reduction of strength of the hydrogen bond between the carbon acid and benzoate ion in the imbalanced transition state. The transfer activity coefficient (logMyAN) from methanol to acetonitrile solution have been calculated for (// -nitrophenyl)nitromcthyl anion (3.6) and (m-nitrophenyl)-nitromethane (—1.0). 

Mixtures of sodium (or its alloy with potassium) and nitromethane, trichloronitro-methane, nitrobenzene, dinitrobenzene, dinitronaphthalene, ethyl nitrite, ethyl nitrate or glyceryl nitrate are shock-sensitive, the sensitivity increasing with the number of nitro groups. 

The largest group of organic molecular compounds, in which hydrogen bond formation plays no part, are the compounds, usually in the ratio 1 1, between on the one hand aliphatic and aromatic nitro compounds (nitromethane, tetranitro-methane, chloropicrin CC13N02, nitrobenzene, s-trinitrobenzene, picric acid), quinones, anhydrides (phthalic acid-and maleic acid anhydride) and ketones with on the other hand especially aliphatic and aromatic amines (aniline, pyridine), unsaturated aliphatic and aromatic hydrocarbons, ethers etc. 

DMSO-DMF-nitromethane. In the last example nitromethane acts merely as an inert diluent. In the P-NMR spectra of the system BeCl2 -hexamethylphosphoramide-water and in the A1-NMR spectra of the systems Al(C104)3-DMF-DMS0-nitro-methane and Al(C104)3-trimethylphosphate-DMSO-nitromethane all different solvates could be observed as separate lines. 

Benzyl chloride can be converted into bcnzaldehyde by treatmeni with nitromethane and base. The reaction involves initial conversion ot nitro-methane into its anion, followed by S 2 reaction of the anion with benzyl chloride and subsequent E2 reaction. Write the mechanism in detail, using cursed arrows to indicate the electron flow in each step. 

Several 4-deoxy-4-nitro ketose derivatives have been synthesized. Three crystalline 2,7-anhydro-4-deoxy-4-nitro-/3-D-heptulopyranoses arose by nitromethane cyclization92 of the dialdehyde (74) produced by periodate oxidation of sedoheptulosan (73), and were assigned93 the D-alio (75), D-gulo (76), and D-altro (77) configurations by nuclear magnetic resonance spectroscopy of the corresponding, peracetylated amino sugars. When the cyclization of 74 was performed in methan-olic medium, a solid mixture of stereoisomeric nitronates was obtained in almost quantitative yield, and it could be partially separated into the individual nitronates, which furnished 75 and 76. The isomer 77... 

---