Nitroxyl amide

W.C.Fernelius, ChemRevs 12, 67(1933) 20,413(1937) 3)Franklin(l935), 54-5 4)Inorg-Synth 1(1939) 74-7 2(1946), 128-35 Nitramide or Nitroxyl amide, 02N.NH2, raw 62.03, N 45.1755. Wh solid, mp 72-5° with de-compn puffs off on rapid heating. Sol in w (slowly dec) and in common solvents, except petr ether. Was first, prepd in 1890 by Mathieu-Plessy but not properly identified. Thiele Lachman prepd it in 1894(Refs 1,2 3) from nitrourethane,OaN.NHCOO.CaHs, and described its props. Since then nitramide was prepd by various investigators, mostly by hydrolysis and decarboxylation of potassium —N —... 

In 1894, J. Thiele and A. Lachman 10 prepared nitramide, nr nitroxyl amide, NH2.N02, i.e. H2N202, isomeric with hyponitrous acid. They found that by adding a soln. of potassium hydroxide to a cone. aq. soln. of nitrourethane, N02.NH.C00C2H5, at 0°, potassium nitrocarbamate, N02.NH.C00K, separates... 

P. Irwin, M. Sevilla and W. Chamulitrat, Homopolygalacturonan molecular size in plant cell wall matrices via paramagnetic ion and nitroxyl amide dipolar spin-spin interactions.Biophys. J., 54 (1988) 337. 

Another chemically more interesting spin labeled B12 derivative involves coordinate attachment of the nitroxyl function to the cobalt atom of a cobinamide. Fig. 22 shows a reaction in which an alkyl cobin-amide is mixed with 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl. The nitroxide displaces water from the 6th coordination position very slowly and therefore this reaction is usually allowed to proceed for a few days with a large excess of nitroxide. From the properties of the coordinated nitroxide derivative discussed below, it is certain that the cobalt is coordinated by the N—O functional group. An analogous compound to that shown in Fig. 22 can be made with a similar nitroxide in which the 4-hydroxyl-group is missing. In this case the N—O-function is the only basic site on the molecule and therefore must be the position of attachment to the cobalt 119). 

Nitrosamine formation is not the only conceivable fragmentation mechanism for compounds of structure I. By analogy to the nitrosative dealkylation reactions discussed above, one might predict that such compounds could also undergo cis elimination of nitroxyl in amide-forming reactions. Such a transformation has possibly been observed (14). During an attempt to synthesize the nitrosamino aldehyde VIII from immonium ion IX, Hecht coworkers were able to isolate only 5-10% of the desired product. The major product proved to be N-methyl-2-pyrrolidone, as shown in Fig. 10. We interpret this as evidence that an intermediate such as li can fragment not only by the Fig. 1... 

Treatment of polymer films by reactive gases or reactive volatil compounds allows to easily modify polymers containing alcohols, hydroperoxides, carboxylic acids (or acids halides), double bonds or piperidine groups. New functional groups as organic nitrites, nitrates, iodides, acid halides (Cl, F), amides, esters, peresters and nitroxyl radicals can be generated by a single reaction or by combination of two consecutive treatments. The reactions are very efficient on thin films (ca 50-100 pm) and can be controlled by transmission and reflexion 1R spectroscopy. 

Figure 4 Bleach oxidation of octan-2-ol using 1 mol% of nitroxyl catalyst (a) PIPO (3.19 mmol/g amine linker)15, ( ) MCM-41 TEMPO (0.60 mmol/g ether linker/2, ( ) Si02 TEMPO (0.87 mmol/g, amine linker/5, ( ) Si02 TEMPO (0.40 mmol/g, amide linker/, ( ) TEMPO...

The same TPP-acrylic add system was used by Eaton et al7 . Treatment of the acid chloride of Cu-TPP acrylic acid 52a with a nitroxyl resulted in the appropriate spin-labelled Cu-TPP derivatives 52b-f (Scheme 20). The extent of metal-nitroxyl interaction was investigated using EPR by varying the nature of the nitroxyl, the linkage (amide or ester), and the geometry of the complex (cis or trans). A similar study was carried out on a vanadyl porphyrin ... 

L. li, C.C. Chu, Nitroxyl radical incaporated electrospun biodegradable polyfester amide) nanofibo- membranes, J. Biomater. Sci. Polym. Ed. 20 (2009) 341-361. 

F. 32 Amide activation via bond-weakening PCET to nitroxyl species. Adapted with permission from [233], Copyright 2015 American Chemical Society... 

For less reactive 3-imidazoline derivatives containing no iV-oxide oxygen only a nitrosation reaction has been realized, and its results depend on the conditions under which the reaction is conducted. Slow addition of two equivalent amounts of amyl nitrite to nitroxides 13a,b or to 1-hydroxy-4-methyl-3-imidazoline (12a) in liquid ammonia in the presence of sodium amide produces nitroxyl oximes 52a,b. The immediate treatment... 

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