Nitro urethane

Nitramines show no basic properties whatever — indeed, primary nitramines have distinct acidic properties and can form salts with alkalis. Conversely, nitr-amides may be more strongly acidic than carboxylic acids, as, for example, nitro-urethane, which is a stronger acid than formic acid. 

Nitro- benzoate °C Phenyl- urethan °C 1- Hydrogen Naphthyl- 3-nitro-urethan phthalate °C °C O-Alkyl Other saccharin derivatives °C °C ... 

Alcohol B.P. M.P. 3 6>Dlnltro-benzoate p-NItro- benzoate Phenyl- urethane... 

Polymers. AH nitro alcohols are sources of formaldehyde for cross-linking in polymers of urea, melamine, phenols, resorcinol, etc (see Amino RESINS AND PLASTICS). Nitrodiols and 2-hydroxymethyl-2-nitro-l,3-propanediol can be used as polyols to form polyester or polyurethane products (see Polyesters Urethane polymers). 2-Methyl-2-nitro-l-propanol is used in tires to promote the adhesion of mbber to tire cord (qv). Nitro alcohols are used as hardening agents in photographic processes, and 2-hydroxymethyl-2-nitro-l,3-propanediol is a cross-linking agent for starch adhesives, polyamides, urea resins, or wool, and in tanning operations (17—25). Wrinkle-resistant fabric with reduced free formaldehyde content is obtained by treatment with... 

In one projected commercial modification of the process the phosgenation stage is replaced by one in which the nitro compounds are reacted with CO and an alcohol to form a urethane. This is then split to form an isocyanate in the second step. 

Alcohol B.P. Benzoate />-Nitro- benzoate S S-Dinitro- benzoate Phenyl- urethane a-Naphthyl. urethane Other Derivatives... 

Olsen and co-workers used a solution of nitronium tetrafluoroborate in acetonitrile for the V-nitration of acetamides and urethanes at —30°C. The following nitramides were obtained by this method V-nitroacetamide (13 %), V-nitro-2-chloroacetamide (55 %), V-nitro-n-butylacetamide (40 %), V-nitrobenzamide (53 %), ethyl V-nitro-n-butylcarbamate (91 %) and V-nitrosuccinimide (43 %). The low yield of V-nitroacetamide, a primary nitramide, is attributed to competing hydrolysis due to the release of tetrafluoroboric acid as the reaction progresses. The scope of the reaction is improved by moving to more basic solvents like ethyl acetate, 1,4-dioxane and trimethyl phosphate. ... 

PVC, polyamides, unsaturated crosslinked polyesters, ABS, and wood . Di- and tri-benzotriazole photostabilizers, such as (874) and (875) are synthesized from 2-nitro-benzenediazonium salts and an excess of 1,3-dihydroxybenzene or 1,3,5-trihydroxybenzene <85Mi 40i-0l>. The dibenzotriazole derivatives (874b and 875b) can be used as polymerizable acrylic UV absorbers <84PB237>. A few or/Ao-urethane and -trimethylsilane substituted 2-phenylbenzotriazoles (876 and 877) show similar photostabilization activity . Weather resistance of low-density polyethylene is improved by the addition of a benzotriazole-type photostabilizer <90M140i-04>. 

This is a powerful explosive, stronger than tetryl but weaker than cyclonite. It is, however, of no practical value chiefly because its preparation is too expensive, requiring first the conversion of methylamine into urethane and then into its nitro derivative. On hydrolysis the latter yields methylnitramine. Similarly, the hydrolysis of dinitrodimethyloxamide (p. 35) leads to the formation of methylnitramine. 

N.N -Bis(3-nitro-4-metbylpkenyl)-UTea, yel prisms (from ethyl acet), mp 251—52° si sol in eth benz sol in hot coned acetic acid hot ale. It was prepd by heating 2-nitro-4-aminotoluene with urethane at 210-20° (Ref 1, p999 Ref 2, p663)... 

Dlnltro-benzoate p-Nitro- benzcate Phenyl- urethane a-Naph- thyl- urethane Hydrogen 3-nitro- phthalate Other Derivatives... 

Nitroamide, the simplest of the nitroamines, is formed by the action of dilute acid on potassium nitrocarbamate, which itself results from the nitration of urethane and the subsequent hydrolysis of the nitro ester by means of alcoholic potassium hydroxide. 

Lithium aluminium hydride reduction of 235 followed by mesylation afforded 236. The latter was oxidized with osmium tetroxide and sodium metaperiodate to yield the cyclobutanone 237. Treatment of 237 with acid afforded in 48% yield the ketoacid (238), which was esterified with diazomethane to 239. The latter was converted to the ketal 240 by treatment with ethylene glycol and /7-toluenesulfonic acid. Compound 240 was reduced with lithium aluminium hydride to the alcohol 241. This alcohol had been synthesized previously by Nagata and co-workers (164) by an entirely different route. The azide 242 was prepared in 80% yield by mesylation of 241 and treatment of the product with sodium azide. Lithium aluminium hydride reduction of 242 gave the primary amine, which was converted to the urethane 243 by treatment with ethyl chloroformate. The ketal group of 243 was removed by acidic hydrolysis and the resulting ketone was nitro-sated with N204 and sodium acetate. Decomposition of the nitrosourethane with sodium ethoxide in refluxing ethanol afforded the ketone 244 in 65% yield. The latter had been also synthesized previously by Japanese chemists (165). The ketone 244 was converted to the ketal 246 and the latter to 247... 

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