Nitrolic

Dissolve a few drops of nitromethane in 10% sodium hydroxide solution. Add a few crystals of sodium nitrite and shake. Now add dilute sulphuric acid drop by drop. A brownish-red coloration develops, but fades again when an excess of acid is added. The sulphuric acid has thus liberated nitrous acid, which has in turn reacted with the nitromethane to give a nitrolic acid, the sodium salt of which is CH3NO2 + ONOH = CH(N02) N0H + HgO reddish-brown in colour, probably owing to mesomeric ions of the type ... 

O NCH NO 0 N CHN 0 An excess of sulphuric acid then converts the coloured sodium salt back to the almost colourless nitrolic acid. 

Note.—A secondary nitro-paratfin, such as a nitropropane, (CH3)2CHN02, when similarly treated gives a pseudo-nitrol, which dissolves in chloroform,... 

Primary nitro compound intense red colour, disappearing upon acidification. The colouration is that of the alkali salt of the nitrolic acid (nitro oxime) -... 

Reaction with nitrous acid can be used to differentiate primary, secondary, and tertiary mononitroparaffins. Primary nitroparaffins give nitrolic acids, which dissolve in alkali to form bright red salts. 

Furoxan nitrolic acid 34 was converted into isoxazoline 36 (96% yield) on storage in CH2CI2 solution in the presence of water (93CHE1099, 93KGS1283) (Scheme 12). The intermediate 35 could be trapped as [3 + 2] cycloaddition product 37. Reaction of nitrolic acid 34 with an excess of N2O4 also occurred via 35, giving 3-cyano-4-nitrofuroxan 38. 

Treatment of nitrolic acid 34, which is in turn available from hydroximino malonaldehyde dioxime (N2O4 in CH2CI2, 20 min, 10-15°C), with TFA gives furoxan-4-carboxylic acid in 35% yield (93CHE952, 93KGS1117) (Scheme 39). 

Eraciioii Ihfj" to lb-5" had a pronounced ini pene odour. S iecific grayicy 0-S695 at 1.5 optical rotation ap — - 16 10. The uitro-so-chloridc of iho melting-point 102 to 10.3 , and the nitrol beu2ylamine icclting at 122 to 123, oblalin-d froin the former, proved the presence [Pg.138]

Pinene-nitrosochloride forms a series of compounds with various bases, such as propylamine, amylamine, benzylamine, etc., known as pinene-nitrolamines. If two molecules of benzylamine in alcoholic solution be allowed to act on one molecule of pinene-nitrosochloride, pinene nitrol-benzylamine separates on the addition of water, and on recrystallisation from a mixture of ether and alcohol, forms beautiful... 

When the last-described body is warmed with benzylamine, in alcoholic solution, sylvestrene nitrol-benzylamine... 

No crystalline hydrochlorides eould be obtained from either santalene. tt-Santalene forms a liquid dihydrochloride of optical rotation -n 6°, when dry hydrochloric acid is passed through its ethereal solution. It also forms a crystalline nitrosochloride melting with decomposition at 122°, and a nitrol-piperidide melting at 108° to 109°. /3-santalene forms corresponding compounds, the dihydrochloride having a rotatory power -H 8°. It forms, however, two isomeric nitrosochlorides, CigHj NOCl. They may be separated by fractional crystallisation from alcohol. One melts at 106°, the other at 152°. The corresponding nitrol-piperidides melt at 105° and 101° respectively. 

It yields the following crystalline derivatives, which are suitable for its identification nitrosochloride melting at 103°, nitrol-piperidine melting at 108°, nitrol-anilide melting at 110°, and phenyl-urethane melting at 85°. 

Compared to the chemical modification reactions of PS, alkylation and acylation reactions are preferred to other reactions, such as halogenation, nitrolation, sulfo-nation, amination, and chloromethylation, etc. because the obtained polyfunctional PS has higher physico-me-chanical properties. 

Nitrol. Early Brit plastic safety expl, patented by O. Silberrad in 1912 (Ref 2). A typical formulation is Nitrol 10, highly. nitrated benzene hydrocarbons 20, collodion cotton 0.5, and AN 69.5%. Under the same name, O. Silberrad took... 

Peroxybenzoic Acid, p-Nitrol, 1,4,4-Tetramethyl-tetramethylene ester. See 2,5-Bis(p-nitrobenz-oylperoxy-2,5-Dimethylhexane in Vol 2, B135-R... 

Pyruvonitrolic Acid. See under Acetylmethyl-nitrolic Acid in Vol 1, A84-L... 

If the presence of unreduced nitrol>enzene is suspected (odour and/or hi b.p. residue), treat nil the product with excess of dilute hydrochloric acid and remove the nitrobenzene either by steam distillation or by ether extraction render the residue alkaline with sodium hydroxide solution and isolate the aniline as before. 

Isolated salts of nitrolic acids , produced by action of nitrous acid on 1-nitroalka-nes, are explosive. 

Nitrile oxides generated under neutral conditions by thermal fragmentation of nitrolic acids 32, were trapped in situ with alkenes to afford isoxazolines 33 in 53-97% yields <00TL1191>. Nitrile oxides were also produced by treating O-silylated hydroxamic acids 34 with triflic anhydride and TEA . ... 

Z-Acetonitrolic acid rapidly loses N02 to form unstable acetonitrile oxide, which could be detected by monitoring its subsequent reactions (86). Arylnitrolic acids 12 (X = />-Cl. m-N02, o-N02) exist in the -configuration and undergo slow loss of N02 to give nitrile oxides. Subsequently it was shown (87) that nitrolic acids are converted to nitrile oxides in practically quantitative yields under neutral conditions (heating in THF). 

Nitrogen tribromide, 4 319 Nitrogen trifluoride, 22 830 production of, 22 845 Nitroglycerin[e] (NG), 9 47, 48 10 730 molecular formula and structure, 5 110t pharmacokinetics, 5 115 processes, 27 164 production of, 27 174 Nitro group, 27 157-158 Nitroguanidine, 20 734 Nitrol, molecular formula and structure, 5 1 lOt... 

Nitrous acid converts -primary nitroparaffins into nitrolic acids and the secondary ones into so-called pseudonitroles, which latter, being nitroso-compounds, are coloured green or blue ... 

The nitrolic acids are colourless, hut dissolve in alkalis with a deep red colour because in addition to the chromogenic nitroso-group the aci-nitro-group is formed. The following formula is ascribed to the... 

If an aromatic compound contains saturated aliphatic side chains nitration carried out under the above conditions takes place always in the benzene nucleus and not in the side chain. Since the carbon atoms of benzene are each united directly to only one hydrogen atom, the nitro-derivatives obtained are tertiary and therefore incapable of forming salts, nitrolic acids, or pseudonitroles, as do the primary and secondary nitro-compounds. 

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