Nitroacetone

Nitric acid in preparation of nitromum tetrafluoroborate, 47, 57 Nitroacetone, 45, 3... 

Nitroacetone (237 g) was generated in dichloromethane-ethyl acetate solution by treating its dicyclohexylamine aci-salt with sulfuric acid. Towards the end of concentration of the solution by rotary vacuum evaporation at 40-50°C, a small explosion occurred. Extreme caution and small scale handling of a-nitroketones are urged [1], If exact neutralisation of the dicyclohexylamine salt had not been achieved, presence of excess sulfuric acid (or of some undecomposed aci-salt) may have reduced the stability of the nitroacetone [2],... 

The modified Hantzsch condensation of nitroacetone, 2,l,3-benzoxadiazol-4-carboxaldehyde 253, and ( S,ZR)-Z-(3,5-dinitrophenylcarbonylamino)-2-methoxycarbonyl-l-methylethyl 3-aminocrotonate afforded a mixture of the two diastereomers that differ in configuration (S or R) at the C-4 position of the 1,4-DHP ring (DHP - dehydropeptidase) (Equation 49) <2004JME254>. 

H)-Naphthalenone, 4,4a,5,6,7,8-HEXAHYDRO-, 46, 80 Nitroacetone, 46, 3 />-Nitrobenzaldehyde, 46, 36 Nitrosation of N-phenylglycine, 46, 96 N-Nitroso-N-phenylglycine, 46, 96 reaction with acetic anhydride to yield 3-phenylsydnone, 46, 96 Nitrosyl chloride, addition to bicyclo [2.2.1]hepta-2,S-diene, 46, TS Nonane, 1,1,3-trichloro-, 46,104 Noriricvclanol, 46, 74 oxidation by chromic acid, 46, 78 NortricyclanOne, 46, 77 Nortricyclyl acetate, 46, 74 from bicyclo[2.2.1]hepta-2,5-dlene and acetic acid, 46, 74 saponification of, 46, 75... 

More recently, Tietze s group adapted the well-known domino Knoevenagel-Hetero-Diels-Alder MCR to the efficient synthesis of the deoxyaminosugar (-l-)-D-Forosamine starting from nitroacetone, aqueous formaline, and ethyl vinyl ether (Scheme 65) [169]. The expected racemic dihydropyran was obtained in 37% yield and further transformed to the optically pure product in eight steps in chiral resolution with chiral HPLC. 

It was claimed by Henry(Ref 2) that 0. de Battice prepd nitroacetone in 1895 in Belgium by oxidation of nitroisopropanol with chromic mixture. Henry described the compd as a coi, mobile liq with a sharp odor, a 1.070 at 14°, bp 152° at 767 mm and insol in w. Lucas c]aimed(Ref 3) that the compd described by Henry was not nitroacetone, but this statement was disputed by Henry(Ref 4). Harries also claimed(Ref 5) that the compd described by Henry is not nitroacetone More recently, Hass Hudgin(Ref 7) claimed that they had isolated some nitroacetone from the high-boiling fraction of the vapor-phase nitration of acetone but it is not clear from their paper whether the substance was liq or solid. Hurd NilsonfRef 8) prepd nitroacetone as pale-green crysts, mp 47°, by oxidizing 1—nitro—2—propanol with sodium dichromate and sulfuric acid. The yield was (5% of theoretical. The explosifcility of this compd was not mentioned... 

If a C6-unsubstituted DHPM derivative needs to be synthesized, the corresponding 3-oxopropanoic ester derivative in which the aldehyde function is masked as an acetal can be employed [116]. Apart from ester-derived CH-acidic carbonyl compounds, nitroacetone also serves as a good building block, leading to 5-nitro-substituted DHPM derivatives in generally high yields [117]. 

The complexes of zinc and cadmium with Schiff bases derived from salicylaldehyde and propan-2-olamine or 2-aminomethylpropanol have been reported,57 as well as their complexes with ethanolamine and propan-2-olamine.58,59 Zinc complexes of stoicheiometry ZnL2X2 have been obtained where L = benzoyl- and salicyl-hydra-zones of vanilline. furfural, and cinnamaldehyde. Zinc complexes of several substituted o-bydroxybutyrophenones and their oximes have been reported.60-62 Complexes of stoicheiometery ZnL2U have been reported where L = the a-nitroketonato-anion obtained from nitroacetone, 3,3-dimethyl-l-nitrobutan-2-one or 3-nitrocam-phor and L — bipyridyl or 1,10-phenanthroline.63... 

The following represent the resonance forms of the nitroacetone anion ... 

Isatin has been reported to yield 3-nitrocinchoninic acid (92 R = C02H) with nitromethane in aqueous KOH.83 Although this seems like the use of a type 1 synthon, it is more appropriate to regard it as another example of a methazonic acid reaction. The reaction of nitroacetone with o-aminobenz-aldehyde leads to 2-methyl-3-nitroquinoline derivatives.84... 

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