Amine nitroalkane

Wick, C.D., Stubbs, J.M., Rai, N., Siepmann, J.I. Transferable potentials for phase equilibria. 7. Primary, secondary, and tertiary amines, nitroalkanes and nitrobenzene, nitriles, amides, pyridine, and pyrimidine, J. Phys. Chem. B 2005,109(40), 18974-82. 

While nitroparaffins are resistant to oxidation, they are easily reduced to the corresponding amine. Nitroalkanes can be added across an activated double bond structure in the presence of a basic catalyst [II]. The reader should check the references cited in [IG] for several review articles that detail the scope of the nitroalkane reactions also, Kass [12] outlined many of the nitroalkane reactions along with the literature references. 

While nitroparaffins are resistant to oxidation, they are easily reduced to the corresponding amine. Nitroalkanes can be added across an activated double bond structure in the presence of a basic catalyst. 

CAUTION - The lower nitroalkanes form shock and/or temperature sensitive EXPLOSIVE compounds with amines and hydroxides. BE CAREFUL, DAMNIT You have been warned. 

Simple ketones and esters are inert. On the other hand, nitroalkanes react smoothly in r-butyl alcohol as a solvent with butadiene, and their acidic hydrogens are displaced with the octadienyl group. From nitromethane, three products, 64, 65, and 66, are formed, accompanied by 3-substituted 1,7-octadiene as a minor product. Hydrogenation of 65 affords a fatty amine 67 which has a primary amino function at the center of the long linear chain[46,61]. 

Many of these reactions are reversible, and for the stronger nucleophiles they usually proceed the fastest. Typical examples are the addition of ammonia, amines, phosphines, and bisulfite. Alkaline conditions permit the addition of mercaptans, sulfides, ketones, nitroalkanes, and alcohols to acrylamide. Good examples of alcohol reactions are those involving polymeric alcohols such as poly(vinyl alcohol), cellulose, and starch. The alkaline conditions employed with these reactions result in partial hydrolysis of the amide, yielding mixed carbamojdethyl and carboxyethyl products. 

CH—NHOH) to oxime (C=NOH) and ultimately to the nitroalkane (CH—NO2). Hydrogen peroxide generates amine oxides from tertiary cycloaUphatic... 

A number of disinfectants apparentiy owe their activity to formaldehyde, although there is argument on whether some of them function by other mechanisms. In this category, the dmg with the longest history is hexamethylenetetramine (hexamine, urotropin) [100-97-0] which is a condensation product of formaldehyde and ammonia that breaks down by acid hydrolysis to produce formaldehyde. Hexamine was first used for urinary tract antisepsis. Other antimicrobials that are adducts of formaldehyde and amines have been made others are based on methylolate derivations of nitroalkanes. The apphcations of these compounds are widespread, including inactivation of bacterial endotoxin preservation of cosmetics, metal working fluids, and latex paint and use in spin finishes, textile impregnation, and secondary oil recovery (117). 

Condensadon of glyoxalic acid, nitroalkanes, and amines provides a simple method for fi-nitro-ct-airino acids fEq 4 116 ... 

Light and permanent gases, low molecular weight acids, alcohols, glycols, ketones, hydrocarbons, esters, nitriles and nitroalkanes. Amines, amides, alcohols, aldehydes, hydrazines and ketones. 

Acidic substances, glycols, nitriles and nitroalkanes. Amines and glycols. 

Dendritic molecules with a single triethylene amine core surrounded by hyperbranched polyether sectors catalyze the nitro-aldol reaction between aromatic aldehydes and nitroalkanes (Eq. 3.5).15 The activity of the catalysts decreases when the generation number increases. No significant changes in stereo-control are observed on passing from lower- to higher-generation dendrimers. 

In general, base-catalyzed reactions of aromatic aldehydes with nitroalkanes give nitroalkenes directly (Knoevenagel reaction).54 The reaction is very simple heating a mixture of aromatic aldehydes, nitroalkanes, and amines in benzene or toluene for several hours using a Dean-Stark water separator gives the desired nitroalkenes in good yield, as shown in Eqs. 3.31-3.34.54-58... 

The addition of alkoxides to 2-nitro-l-phenylthio-l-alkenes affords P-nitro-aldehyde acetals.276 The reaction of the same nitroalkenes with amines gives nitroenamines.270 They are important intermediates for organic synthesis and are generally prepared by the reaction of nitroalkanes with triethylorthoformate in the presence of alcohols or secondary amines.2"1 0 The methods of Eqs. 4.20 and 4.21 have some merits over the conventional methods, for variously substituted (3-nitro-aldehydes acetals or nitroenamines are readily prepared by these methods. 

The cycloaddition, reduction and oxidation reactions emanating from a,/J-unsatu-rated nitroalkenes provide easy access to a vast array of functionalities that include nitroalkanes, N-substituted hydroxylamines, amines, ketones, oximes, and a-substi-tuted oximes and ketones [73-75], Consequently, there are numerous possibilities of using these in situ generated nitroalkenes for the preparation of valuable building blocks and synthetic precursors. 

The most characteristic reaction of butadiene catalyzed by palladium catalysts is the dimerization with incorporation of various nucleophiles [Eq. (11)]. The main product of this telomerization reaction is the 8-substituted 1,6-octadiene, 17. Also, 3-substituted 1,7-octadiene, 18, is formed as a minor product. So far, the following nucleophiles are known to react with butadiene to form corresponding telomers water, carboxylic acids, primary and secondary alcohols, phenols, ammonia, primary and secondary amines, enamines, active methylene compounds activated by two electron-attracting groups, and nitroalkanes. Some of these nucleophiles are known to react oxidatively with simple olefins in the presence of Pd2+ salts. Carbon monoxide and hydrosilanes also take part in the telomerization. The telomerization reactions are surveyed based on the classification by the nucleophiles. 

Alternatively, Ballini devised a new strategy to synthesize tri-alkylated pyrroles from 2,5-dialkylfurans and nitroalkanes <00SL391>. This method involves initial oxidation of 2,5-dimethylfuran with magnesium monoperoxyphthalate to cA-3-hexen-2,5-dione (6). Conjugate addition of the nitronate anion derived from the nitro compound 7 to 6 followed by chemoselective hydrogenation of the C-C double bond of the resulting enones 8 (obtained by elimination of nitrous acid from the Michael adduct) completes the conversion to the alkylated y-diketones 9. Final cyclization to pyrroles 10 featured improved Paal-Knorr reaction conditions involving reaction of the diketones with primary amines in a bed of basic alumina in the absence of solvent. 

Nitromethane is a detonable explosive, nitroethane can be detonated if both hot and under strong confinement, other nitroalkanes are mild oxidants under ordinary conditions, but precautions should be taken when they are subjected to high temperatures and pressures, since violent reactions may occur [1], Explosives are described consisting of nitromethane stabilised for transport by admixture with nitroethane or nitropropane, then resensitised by addition of an amine [4], The polynitroalkanes, being more in oxygen balance than the mono-derivatives, tend to explode more easily [2], and caution is urged, particularly during distillation [3], See also POLYNITROALKYL COMPOUNDS... 

Nltro compounds are reduced to amines by passing hydrogen gas In the presence of finely divided nickel, palladium or platinum and also by reduction with metals In acidic medium. Nitroalkanes can also be similarly reduced to the corresponding alkanammes. 

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