Nitromethane, III

Because of thek flash pokits, nitroparaftins are classified as flammable Hquids under DOT regulations (ha2ard class 3, PG III). Nitromethane and nitroethane tires can be extinguished with water, CO2, foam, or class ABC dry chemical extinguishers. Nitroparaftins should not be exposed to dry caustic soda, lye, or similar alkaline materials. 

A detailed study of spectra of compounds 1, 2, and 3 has been published as part of a general study of azolopyridines (84OMR209). The shifts are shown in Table III. The N shifts have been used to determine the structure of 7-amino-triazolopyridines 128 and 129 (89T7041). The shifts recorded were 56.8, 56.2 (Nl), 245.4, 246.3 (N2), 320.6, 316.8 (N7a), all from nitromethane as standard at 380 ppm the absorption for the amine was at 345.5, 350 ppm in accordance with the amino structure shown, rather than the imino forms 128a and 129a. 

IPN gave a ERDE gap test (Scale III) of 16 cards at ambient temp. A value of over 27 cards is indicative of positive sensy to the rifle bullet test. Refs as to gap sensy include ethylene oxide (10 cards), Nitromethane (24 cards) and ethyl nitrate (43 cards)... 

After eliminating (I), by-products (11) and (III) combusted. However, note that the presence of nitromethane/base is a factor of the accident in itseif as mentioned for nitrated derivatives on p.296. 

Some early studies [126] on the S-methyldithiocarbazate of 2-formylpyridine, 6, showed it to form low spin iron(III) species, [Fe(6-H)2]C104 and [Fe(6-H)2] [FeCm. The Mossbauer spectrum of the latter showed the presence of two different iron centers, and the compound was a 1 1 electrolyte in nitromethane. 

Besides complexes of thiosemicarbazones prepared from nitrogen heterocycles, iron(III) complexes of both 2-formylthiophene thiosemicarbazone, 26, and 2-acetylthiophene thiosemicarbazone, 27, have been isolated [155]. Low spin, distorted octahedral complexes of stoichiometry [Fe(26)2A2]A (A = Cl, Br, SCN) were found to be 1 1 electrolytes in nitromethane. Low spin Fe(27)3A3 (A = Cl, Br, SCN) complexes were also isolated, but their insolubility in organic solvents did not allow molar conductivity measurements. Infrared speetra indicate coordination of both via the azomethine nitrogen and thione sulfur, but not the thiophene sulfur. The thiocyanate complexes have spectral bands at 2065, 770 and 470 cm consistent with N-bonded thiocyanato ligands, but v(FeCl) and v(FeBr) were not assigned due to the large number of bands found in the spectra of the two ligands. 

Ge. Scandium(III) triflate-catalyzed allylation of carbonyl compounds with tetraallylgermane proceeded readily in aqueous nitromethane to afford homoallyl alcohols in excellent to good yields.175 The presence of H20 is indispensable for the allylation of aldehydes to proceed smoothly. Aldehydes were allylated exclusively in the presence of ketone moieties (Eq. 8.74). 

Very interesting transformations were reported in terminal alkynes RC=CH (R = alkyl, aryl, alkoxy, carboxylate, etc.). They react readily with nitric acid, in aqueous nitromethane (1 1) and in the presence of catalytic amounts of tetra-butylammonium tetrachloroaurate to give 3,5-disubstituted isoxazoles 15 in 35% to 50% isolable yield (92). The reaction might proceed via a nitrile oxide intermediate by attack of an electrophile (AuCh or H+) and of a nucleophile (N02 ) on the triple bond to form a vinyl nitrite, which is converted to a nitrile oxide by the action of gold(III) or of nitric acid (Scheme 1.8). 

The conductivities of thorium (III) and uranium (IV) halides in nitromethane are increased in the presence of a donor molecule from chloride to iodide and they also increase with increasing donicity of the neutral donor 49-53)... 

Complexes of the type Ln(TMSO)3 Cl3 are nonelectrolytes in nitromethane, indicating the coordination of all the chloride ions to the lanthanide ion (262). In methanol, however, these complexes behave as 1 1 electrolytes. The variation of molar conductance values with concentration of the Dy(III) complex in methanol was studied. The data indicate that at higher concentrations the complex behaves as a nonelectrolyte while at lower concentrations dissociation sets in and the complex behaves as a 1 1 electrolyte. 

The addition to alkenes of radicals derived from an a-nitroketone is also catalysed by manganese(III) [30]. During the reaction between a-nitroacetophenone 8 and m-but-2-ene, the stereochemical relationship between the methyl substituents is not preserved. The process terminates with the formation of a nitrone. A related process will generate nitromethyl radicals from nitromethane and these add to benzene to give phenyinitromethane [31],... 

The reduction of thienothiophene 2 with Na-K alloy produced a radical-anion (see Section III,D), and a radical-cation resulted from oxidation with AlCl, in nitromethane or SbCl, in methylene chloride (see Section IV,B 5). No such conversion was observed in the case of thienothiophene 1 this is explained by the extended conjugation throughout the thienothiophene 2 molecide, impossible in thienothiophene 1. 

Tris(dimethyl sulfoxide)indium(III) chloride is a white crystalline nonhygro-scopic compound, soluble in alcohols, ethyl acetate, and nitromethane. Decomposition occurs at 130°. The infrared spectrum and the results of thermal stability studies have been reported.6 The presence of dmso can be verified from the infrared spectrum,6 which shows C—H vibrations, and =0 at 945, 960, and 995 cm. ... 

Nitromethane can also be prepared by the action of sodium or potassium nitrite on the corresponding salt of monochloroacetic acid. (O. S., III., 83.)... 

In order to limit flexibility, three tridentate binding units similar to L3 have been connected to a covalent tri(2-aminoethyl)amine (TREN) tripod to give the nonadentate podand L4. Upon reaction with /J(III) (R = La-Eu, Yb, Lu, Y) in acetonitrile/nitromethane (1 1), the NMR spectra confirm the formation of the expected C3-symmetrical complexes [/ (L4)]3+ (Re-naud et al., 1999). The methylene protons are systematically diastereotopic at 298 K. For the diamagnetic cations R = Y, Lu, no coalescence is observed in the accessible temperature range (233-343 K), but the rate of helical interconversion increases with increasing ionic radii and [La(L4)]3+ shows coalescence at 323 K, thus pointing to a fast /J- Ea(L4)]3+ = M-... 

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