Nitronate salt

Oxidation. Nitroparaffins are resistant to oxidation. At ordinary temperatures, they are attacked only very slowly by strong oxidi2ing agents such as potassium permanganate, manganese dioxide, or lead peroxide. Nitronate salts, however, are oxidi2ed more easily. The salt of 2-nitropropane is converted to 2,3-dimethyl-2,3-dinitrobutane [3964-18-9], acetone, and nitrite ion by persulfates or electrolytic oxidation. With potassium permanganate, only acetone is recovered. 

Determination of nitrate as nitron nitrate Discussion. The mono-acid base nitron, C20H16N4, forms a fairly insoluble crystalline nitrate, C20H 16N4,HN03 (solubility is 0.099 g L 1 at about 20 °C), which can be used for the quantitative determination of nitrates [see Section 11.11(E)]. The sulphate and acetate are soluble so that precipitation may be made in sulphuric or acetic (ethanoic) acid solution. Perchlorates (0.08 g), iodides (0.17 g), thiocyanates (0.4 g), chromates (0.6 g), chlorates (1.2g), nitrites (1.9 g), bromides (6.1 g), hexacyanoferrate(II), hexacyanoferrate(III), oxalates, and considerable quantities of chlorides interfere, and should be absent. The figures in parentheses are the approximate solubilities of the nitron salts in g L-1 at about 20 °C. 

In comparison to the chloro compounds the dibromophosphates are by far less thoroughly investigated. Grume et al. were the first to succeed in the isolation of the nitron salt of dibromophosphoric acid, by partial hydrolysis of POBr3 in cooled aceton solution 8). Later on it could be shown, that even CaO and MgO form solvatated... 

Treatment of the nitronate salt 397 (from nitroethane and methanolic sodium methoxide) with benzene in the presence of trifluoromethanesulphonic acid gives acetophenone oxime, which is obtained mainly as the (E)-isomer 398433. 

It should be mentioned that tetraphenylarsonium salts are soluble in alcohol and that the nitron salts dissolve in ethyl acetate. Thus, technetium as well as the organic reagents can be recovered. 

Nitronate salts can react with alkyl halides to yield polynitroaliphatic compounds with varying degrees of success. The main by-products of these reactions arise for competitive 0-alkylation. Alkyl nitrates are formed as by-products when the nitroform anion is used in these reactions. ... 

Poor to modest yields of trinitromethyl compounds are reported for the reaction of silver nitroform with substituted benzyl iodide and bromide substrates. Compounds like (36), (37), and (38) have been synthesized via this route these compounds have much more favourable oxygen balances than TNT and are probably powerful explosives." The authors noted that considerable amounts of unstable red oils accompanied these products. The latter are attributed to O-alkylation, a side-reaction favoured by an SnI transition state and typical of reactions involving benzylic substrates and silver salts. Further research showed that while silver nitroform favours 0-alkylation, the sodium, potassium and lithium salts favour C-alkylation." The synthesis and chemistry of 1,1,1-trinitromethyl compounds has been extensively reviewed. The alkylation of nitronate salts has been the subject of an excellent review by Nielsen." ... 

The addition of a-chloronitroalkanes to solutions of alkali metal hydroxide has been used for the synthesis of some 1,2-dinitroethylene derivatives (43)." " These reactions involve attack of the nitronate salt (40) on the aci-form (39) of the unreacted em-chloronitroalkane followed by formal loss of hydrogen chloride. 2,3-Dinitro-2-butene and 3,4-dinitro-3-hexene (45) are formed in this way from 1-chloro-l-nitroethane and 1-chloro-l-nitropropane (44) respectively. 

In a related reaction to that described above, nitronate salts have been reacted with a-chloronitroalkanes as a route to polynitroaliphatic compounds. 2,3-Dimethyl-2,3-dinitrobutane (48) is formed from the reaction of the nitronate salt of 2-nitropropane (46) with 2-chloro-2-nitropropane (47). A modification to the original process uses nitronate salts in the presence of iodine to form an a -iodonitroalkane in situP ... 

Nitronate salts and the tautomeric act-form of nitroalkanes, known as nitronic acids, are converted to gem-dinitro compounds on treatment with dinitrogen tetroxide. Novikov and co-workers synthesized phenyldinitromethane by treating phenylnitromethane with dinitrogen tetroxide in ether and later reported the synthesis of some substituted phenyltrinitromethanes from the direct nitration of the nitronate salts of phenylnitromethanes. 

The tautomeric nitronic acids of secondary nitroalkanes or their nitronate salts react with nitrous acid or alkali metal nitrites to yield pseudonitroles.These pseudonitroles are often isolated as their colourless dimers (78b) but are deep blue in monomeric form (78a). Primary nitroalkanes also form pseudonitroles (80b) but these rapidly isomerise to the nitrolic acid (80a).Reactions are commonly conducted by slowly acidifying a mixture containing the nitronate salt and the metal nitrite, during which, the nitronic acid reacts with the nitrite anion. These reactions, first discovered by Meyer, have been used to prepare 2-nitroso-2-nitropropane (78a) and acetonitrolic acid (80a) from 2-nitropropane (76) and nitroethane (22) respectively. ... 

Pseudonitrole or nitrolic acid formation can be a side-reaction during the acidification of nitronate salts, particularly if the acid addition is slow. This process has been studied, optimized, and patented as a route to these compounds. " ... 

Oxidative nitration, a process discovered by Kaplan and Shechter, is probably the most efficient and useful method available for the synthesis of em-dinitroaliphatic compounds from the corresponding nitroalkanes. The process, which is an electron-transfer substitution at saturated carbon, involves treatment of the nitronate salts of primary or secondary nitroalkanes with silver nitrate and an inorganic nitrite in neutral or alkali media. The reaction is believed ° °° to proceed through the addition complex (82) which collapses and leads to oxidative addition of nitrite anion to the nitronate and reduction of silver from Ag+ to Ag . Reactions proceed rapidly in homogeneous solution between 0 and 30 °C. 

A major drawback of the Kaplan-Shechter reaction is the use of expensive silver nitrate as one of the reagents, which prevents scale up to an industrial capacity. Urbanski and co-workers modified the process by showing that the silver nitrate component can be replaced with an inorganic one-electron transfer agent like ferricyanide anion. In a standard procedure the nitroalkane or the corresponding nitronate salt is treated in alkaline media with potassium... 

Feuer and co-workers extended their studies to the alkaline nitration of a,Nitration with potassium ferf-butoxide and amyl nitrate in THF at —30 °C yields the corresponding dipotassium salt of the a,induced precipitation from the aqueous reaction liquors, a process which also separates the product from impurities. These salts undergo hydrolysis on treatment with aqueous potassium hydroxide, and subsequent acidification yields the corresponding Q, y-dinitroalkane. This route has been used to synthesize 1,4-dinitrobutane (27) from apidonitrile (95) in 30 % overall yield. 

Kaplan and Shechter found that certain oxidants react with the nitronate salts of secondary nitroalkanes to yield vic-dinitroalkanes (111) in a reaction referred to as oxidative dimerization. These reactions are believed to involve transfer of an electron from the secondary alkyl nitronate to the oxidant with the production of a nitroalkyl radical. The radical can then dimerize to the corresponding vtc-dinitroalkane (111) (Equation 1.2) or lose nitric oxide to form a ketone via the Nef reaction (Equation 1.3). Unfortunately, formation of the ketone is a major side-reaction during oxidative dimerization and is often the major product. 

Shackelford and co-workers studied the 1,2-addition of 2,2-dinitropropanol, 2,2,2-trinitroethanol, and 2-fluoro-2,2-dinitroethanol across the double bonds of vinyl ethers. These reactions are Lewis acid catalyzed because of the weak nucleophilic character of alcohols which contain two or three electron-withdrawing groups on the carbon p to the hydroxy functionality. Base catalysis is precluded since alkaline conditions lead to deformylation with the formation of formaldehyde and the nitronate salt. 

Michael reactions are base catalyzed and reversible, and so it is common to use either the nitronate salt of the nitroalkane substrate or the nitroalkane in the presence of a catalytic amount of alkali metal hydroxide, alkoxide or amine base. 

Polynitroaliphatic alcohols are invaluable intermediates for the synthesis of energetic materials (see Section 1.11). The most important route to /i-nitroalcohols is via the Henry reaction where a mixture of the aldehyde and nitroalkane is treated with a catalytic amount of base, or the nitronate salt of the nitroalkane is used directly, in which case, on reaction completion, the reaction mixture is acidified with a weak acid. Reactions are reversible and in the presence of base the salt of the nitroalkane and the free aldehyde are reformed. This reverse reaction is known as demethylolation if formaldehyde is formed. 

Many of the nitronate salts of polynitroaliphatic compounds, particularly salts of gem-nitronitronates, exhibit properties similar to known primary explosives. Consequently, the storage of such salts is highly dangerous. Treatment of these nitronate salts with formaldehyde yields the corresponding methylol derivative via the Henry condensation. These methylol... 

The furoxan ring is more susceptible to nucleophilic attack and reduction than it is to reaction with electrophiles or oxidation. Grignard reagents react with disubstituted furoxans primarily at C-3 and, in most cases, the resulting adduct fragments to a nitrile and a nitronate salt which affords a ketone on workup. 

An alternative to activating the nitro moiety by forming the nitronate salt is the activation of an oxygen leaving group under Mitsunobu conditions (Eq. 2.15) (155,156). Treatment of methanol with diethyl azodicarboxylate and triphenyl-phosphine in the presence of ethyl nitroacetate provides the nitronate 85 in good yield. Unfortunately, only methanol has been demonstrated to be compatible with this procedure. 

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). 

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