Nitromethane preparation

Petroleum ether (30-60 deg C) Counter current chromatogFaphy in hexane/nitromethane Preparative TLC on Silica gel argentation TLC IR,GC-MS. GC (27,47)... 

Nitromethane, CH3NO2, the first member of the homologous series, can, however, be readily prepared by a special reaction. When equimolecular amounts of sodium nitrite and sodium monochloroacetate are heated together in aqueous solution, the chlorine in the monochloroacetate is replaced by the nitro group, and the sodium nitroacetate thus formed undergoes hydrolysis follow ed by decarboxylation ... 

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

Nitronium tetrafluoroborate was first prepared by adding a mixture of anhydrous hydrofluoric acid and boron trifluoride to a solution of dinitrogen pentoxide in nitromethane. Nitric acid can be used in place of dinitrogen pentoxide, and by replacing boron trifluoride by other Lewis-acid fluorides Olah and his co-workers prepared an extensive series of stable nitronium salts. ... 

Nitrofurantoin. The urinary tract antibacterial, l-[(5-nitro-2-furanyl)-methyleneamino]-2,4-imidazohdinedione, is prepared by reaction of 5-nitro-2-furancarboxaldehyde with l-anaino-2,4-imidazohdinedione (19,40). Crystallization of the material from nitromethane provides a macrocrystalline form (41) which continues to be employed clinically. 

This class was first reported in 1924 and was formed 62HC(17)l) by cyclization of a-bromo-/3-aryl-y-nitroketones. The direct synthesis by oxygenation of 2-isoxazolines has not been reported. To date only 3-substituted derivatives have been prepared. Aryl-nitromethanes react with nitrostilbene to form isoxazoline A-oxide by a nitrile ion displacement (Scheme 138) <62HC(17)1, 68TL3375). 

Anhalonine and Lophophorine. Spath and Gangl showed that each of these alkaloids contains a methylenedioxy group and that the quarternary iodide prepared from dZ-anhalonine is identical with lophophorine methiodide so that lophophorine must be N-methylanhalonine. Anhalonine was synthesised from 3 4-methylenedioxy-5-methoxybenzaldehyde by condensation with nitromethane, reduction of the product to the corresponding -ethylamine, the acetyl derivative (VII) of which, on treatment with phosphoric anhydride, condensed to 6-methoxy-7 8-methylenedioxy-l-methyl-3 4-dihydrofsoquinoline, m.p. 60-2°. This, on reduction, furnished the corresponding tetrahydrofsoquinoline, which proved to be anhalonine (VIII), and on conversion to the quaternary methiodide the latter was found to be lophophorine (IX) methiodide. The possible alternative, 8-methoxy-6 7-methylenedioxy-l 2-dimethyl-l 2 3 4-tetrahydrofsoquinoline, was prepared by Freund s method and the methiodide shown not to be identical with lophophorine methiodide. 

A mixture of nitromethane and hexafluorobenzene, when thermolyzed at 550 °C, yields pentafluorotoluene and pentafluorophenol as major products- The formation of nitrosyl and mtryl fluondes is probably a dnving force in this transfor-madon [705] A potential general preparative route to various perfluorovmyl amines is pyrolytic decarboxylation of potassium salts of perfluoro-2-(dialky-... 

Furoxan dialdehyde 105 has been prepared from the bisaldoxime 14 by des-oximation with nitrous acid. The bisaldoxime 14 was prepared by a two-step procedure from nitromethane [25LA7] (Scheme 55). The benzoylated oxime 106... 

All attempts failed to prepare 5-nitrotetrahydro-l,3-oxazine derivatives irom nitromethane, ammonia and formaldehyde, acetaldehyde, or isovaleraldehyde. ... 

C-Alkyldtkin takes place in the reaction of methyl nitroacetate with ilkyl h ilicles the products are useful intermediates for preparing amino acids fEq. 5.1 /The requisite nitro acetate is prepared by seif condensadon of nitromethane. ... 

Dithio-l-nitroalkenes are prepared by the reacdon of nitromethane v/ith CS and KOH followed by alkyladonv/ith alkyl halides CEq. 10.84. They are important reagents forsynthesis... 

Nitronium tetrafluoroborate has been prepared by interaction of nitric acid, hydrogen fluoride, and boron fluoride in nitromethane.5 However, mixtures of nitric acid and nitromethane are extremely explosive.6,7 The present modification of the procedure, in which the medium is methylene chloride instead of nitromethane, was developed to avoid this hazard. It has not been published before. 

A. Carbobenzoxy-L-asparaginyl-L-lewine Methyl Ester. A mixture of 2.024 g. (0.0080 mole) of A -ethyl 5 phenylisoxazolium-3 -sulfonate [Isoxazolium, 2-ethyl-5-(3-sulfophenyl)-, hydroxide, inner salt] (Note 1) and 20 ml. of nitromethane (Note 2) is prepared in a 50-ml., glass-stoppered Erlenmeyer flask at room temperature and stirred vigorously... 

The transformation of l-methylthio-l-(methylsulfonyl)alkanes (254) to methyl esters can be efficiently carried out by oxidation or by a-chlorination followed by methanolysis (equation 152)145. The lithium or the sodium salt of (phenylsulfonyl)nitromethane (256) is a very useful reagent for the preparation of higher homologues of nitromethanes by alkylation since the salts are air insensitive, non-hygroscopic, and easily handled without decomposition. The oxidation of the resulting secondary a-nitro sulfone (257) gives... 

Methyl nitroacetate has been prepared from nitromethane through the dipotassium salt of nitroacetic acid by the classical Steinkopf method3 but in lower yield. The dipotassium salt was obtained in 45% yield. The method has been improved by Matthews and Kubler4 but the salt must be recrystallized prior to esterification. 

The finding of preparatively available iminoboranes RB = NR some years ago opened exciting new possibilities not only in B—N chemistry, but also in coordination chemistry. The first examples of iminoborane-transition-metal complexes have now been published. The structurally completely characterized t-BuB = NBu-t adds, like its alkyne analog, to the 03(00)5 fragment as a bridging ligand. When Co2(CO)g and t-BuB = NBu-t are dissolved in pentane at 0°C, warming to RT and evaporation of unreacted iminoborane yields (t-BuBNBu-t)Co2(CO)5 (86%) as a black solid, which can be recrystallized from ether-nitromethane (1 3) ... 

A nitromethane/aluminium chloride complex had been prepared. A gaseous alkene was added to the complex the pressure reached 5.6 bar and the temperature 2°C. The medium had been stirred at the beginning of the operation and then intemupted. A temperature rise caused the autoclave to detonate and the medium to carbonise entirely. 

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. 

Olah, G. A. et al., J. Inorg. Nucl. Chem., 1960, 14, 295-296 Experimental directions must be followed exactly to prevent violent spontaneous explosions during preparation of the salt from silver oxide and boron trifluoride etherate in nitromethane, according to the earlier method [1], The later method [3] is generally safer than that in [2],... 

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