Nitroacetaldehydes

The diethyl acetal of nitroacetaldehyde combines with (f )-2-(benzyloxy)-3-hydroxypropanal (Id) in the presence of tetrabutylammonium fluoride trihydrate to give an 89% yield of an 88 12 mixture of only two diastereomers17. 

It will form ac7-nitromethanoate salts, which are sensitive explosives when dry, and may form methazonates (salts of nitroacetaldehyde oxime) which are still more explosive. 

See Sodium acv-nitromethanide, 2-Nitroacetaldehyde oxime Alkylmetal halides... 

Made by dehydration of nitroacetaldehyde oxime, this is an explosion hazard. It is improbable that the nitrile is not, itself, detonable. 

Nitroacetaldehyde diethyl acetal is prepared by the reaction of nitromethane with triethyl orthoformate in the presence of ZnCl2 (Eq. 5.8).17 Jager and coworkers have used this reagent for the synthesis of amino sugars via nitro-aldol reaction.18 Preparation of this useful reagent is now described in volume 74 of Organic Synthesis.19... 

Interestingly, two of the other species in Table 3 are nitrolates, i.e. ethers of a-nitrooximes, an otherwise thermochemically unprecedented class of compounds. We already have briefly discussed one, 3-nitroisoxazoline, and the second is 1-nitroacetaldehyde 0-(l,l-dinitroethyl)oxime (ONo-ld-dinitroethyl acetonitronate), MeC (NOala—O—N=C(N02)Me. The latter acyclic species is a derivative of 1,1-dinitroethanol—we know of the enthalpy of formation of no other a-nitroalcohol or derivative. Nonetheless, we may ask if the two calorimetric data are internally consistent. Consider the condensed phase reaction 47, which involves formal cleavage of the O — bond in the nitroisoxazoline by the C—H bond of the dinitromethane. It is assumed that the isoxazoline has the same strain energy as the archetypal 5-atom ring species cyclopentane and cyclopentene, ca 30 kJ mol . ... 

Reaction 49 involves the isomerization of the 2,2-dinitro compound to its 1,1-isomer, which is of direct interest here. The latter is plausibly more strained and so its enthalpy of formation would be more positive. The phase change—from a liquid to a solid—would result in a more negative enthalpy of formation. If these two changes are assumed to cancel, we would predict an enthalpy of formation of 1-nitroacetaldehyde 0-(l,l-dinitroethyl)oxime of —151 kJmoU while the literature value is —165.5 kJmol . That these two values are close suggests that the two nitrolate enthalpy of formation values are at least self-consistent. 

Aliphatic nitro compounds are versatile building blocks and intermediates in organic synthesis,14 15 cf. the overview given in the Organic Syntheses preparation of nitroacetaldehyde diethyl acetal.16 For example, Henry and Michael additions, respectively, lead to 1,2- and 1,4-difunctionalized derivatives.14 18 1,3-Difunctional compounds, such as amino alcohols or aldols are accessible from primary nitroalkanes by dehydration/1,3-dipolar nitrile oxide cycloaddition with olefins (Mukaiyama reaction),19 followed by ring cleavage of intermediate isoxazolines by reduction or reduction/hydrolysis.20 21... 

COLORANTS FORFOOD, DRUGS, COSMETICS AND MEDICALDEVICES] (Vol 6) a-Nitroacetaldehyde [5007-21-6]... 

Nitro-l,2,4-triazolone, 0712 Nitroacetaldehyde, 0759 2-Nitroethanol, 0867 2-Nitroethanonitrile, 0707 Nitromethane, 0455 5-Nitrotetrazole, 0386 Potassium 1-nitroethoxide, 0802 Potassium 2,5-dinitrocyclopentanonide, 1841 Sodium 5-nitrotetrazolide, 0544... 

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