Amination Nitric acid

Copper alloys Ammonia/amines Nitric acid/nitrate fumes... 

N-Methyl-N-f2-Nitroxy propyl) Nitramine. (Me2NENA N-(2-NitroxypropyI) methyl nitramine. (02N)N(CH3).(CH2CH(0N02).CH3, mw 179.16, N 23.46%, OB to C02 -66.80%, pale yellow oil, mp 22—23°, d 1.320g/cc at 25/4°, RI 1.478 at 25°. Prepn from 2-hydroxy-propylamine after nitration with 98% nitric acid at 10° by reaction of the amine-nitric acid mixt with acetic anhydride acetyl chloride at 35°. Reaction mixt poured on ice. Yield is 74%. No expl properties listed Reft 1) Beil - not found 2) Blomquist, OSRD 4134, 45 119 (1944)... 

HEXONE (108-10-1) Forms explosive mixture with air (flash point 62°F/17°C). Able to form unstable and explosive peroxides on contact with air and/or when in contact with hydrogen peroxide. Reacts violently with strong oxidizers, aldehydes, aliphatic amines, nitric acid, perchloric acid, potassium fert-butoxide, strong acids, reducing agents. Dissolves some plastics, resins, and rubber. 

Other work with tertiary amine nitric acid systems with generally similar results... 

CCls CHO. A colourless oily liquid with a pungent odour b.p. 98°C. Manut actured by the action of chlorine on ethanol it is also made by the chlorination of ethanal. When allowed to stand, it changes slowly to a white solid. Addition compounds are formed with water see chloral hydrate), ammonia, sodium hydrogen sulphite, alcohols, and some amines and amides. Oxidized by nitric acid to tri-chloroethanoic acid. Decomposed by alkalis to chloroform and a methanoate a convenient method of obtaining pure CHCI3. It is used for the manufacture of DDT. It is also used as a hypnotic. 

Nitromethane Acids, alkylmetal halides, hydroxides, hydrocarbons, organic amines, formaldehyde, nitric acid, perchlorates... 

Nitration. Direct nitration of aromatic amines with nitric acid is not a satisfactory method, because the amino group is susceptible to oxidation. The amino group can be protected by acetylation, and the acetylamino derivative is then used in the nitration step. Nitration of acetanilide in sulfuric acid yields the 4-nitro compound that is hydroly2ed to -rutroaruline [100-01-6]. 

The y -phenylenediamiaes are easily obtained by dinitrating, followed by catalyticaHy hydrogenating, an aromatic hydrocarbon. Thus, the toluenediamiaes are manufactured by nitrating toluene with a mixture of sulfuric acid, nitric acid, and 23% water at 330°C which first produces a mixture (60 40) of the ortho and para mononitrotoluenes. Further nitration produces the 80 20 mixture of 2,4- and 2,6-dinitrotoluene. Catalytic hydrogenation produces the commercial mixture of diamiaes which, when converted to diisocyanates, are widely used ia the production of polyurethanes (see Amines, aromatic, DIAMINOTOLUENES) (22). 

Ammonia is used in the fibers and plastic industry as the source of nitrogen for the production of caprolactam, the monomer for nylon 6. Oxidation of propylene with ammonia gives acrylonitrile (qv), used for the manufacture of acryHc fibers, resins, and elastomers. Hexamethylenetetramine (HMTA), produced from ammonia and formaldehyde, is used in the manufacture of phenoHc thermosetting resins (see Phenolic resins). Toluene 2,4-cHisocyanate (TDI), employed in the production of polyurethane foam, indirectly consumes ammonia because nitric acid is a raw material in the TDI manufacturing process (see Amines Isocyanates). Urea, which is produced from ammonia, is used in the manufacture of urea—formaldehyde synthetic resins (see Amino resins). Melamine is produced by polymerization of dicyanodiamine and high pressure, high temperature pyrolysis of urea, both in the presence of ammonia (see Cyanamides). 

High molecular weight primary, secondary, and tertiary amines can be employed as extractants for zirconium and hafnium in hydrochloric acid (49—51). With similar aqueous-phase conditions, the selectivity is in the order tertiary > secondary > primary amines. The addition of small amounts of nitric acid increases the separation of zirconium and hafnium but decreases the zirconium yield. Good extraction of zirconium and hafnium from ca 1 Af sulfuric acid has been effected with tertiary amines (52—54), with separation factors of 10 or more. A system of this type, using trioctylarnine in kerosene as the organic solvent, is used by Nippon Mining of Japan in the production of zirconium (55). 

Acetylene, fulminic acid (produced in ethanol - nitric acid mixtures), ammonia Acetic acid, acetone, alcohol, aniline, chromic acid, hydrocyanic acid, hydrogen sulphide, flammable liquids, flammable gases, or nitratable substances, paper, cardboard or rags Inorganic bases, amines Silver, mercury... 

This leaction is lesorted to for the reason that naphthalene forms only the n-nitro-compound with niti icacid. The method, similar to that used for prepaiing aniline from nitiobenzene, cannot, therefore, be employed for the production of /3-n.tphtliyl-.amine. u-Naphthol is mainly used foi the manufacture of yellow and orange colours (Martins and naphthol yellow) by the action of nitric acid, and are similai m constitution to picric acid (see Prep. 107). 

NMe is now commercially available and is prepd by the vapor phase nitration of methane at a ratio of 9 moles of methane to I mole of nitric acid at 475° and a residence time of 0.18sec (Ref 12) or by the similar nitration of aliphatic hydrocarbons (Ref 8). Other prepns are from Me sulfate and Na nitrite (Ref 26) by the oxidn of Me amine with dinitrogen trioxide in the gas phase or in methylene chloride, yield 27%... 

It is prepd by the action of methylamine on 4-chloro-l-nitrobenzene (Ref 5) by the action of methyl iodide (Ref 6), or methyl sulfate on 4-nit roaniline (Ref 7) or by the hydrolysis of 4-nitro-N-methylformanilide with hot coned aq HC1 (Ref 8). In a study of the effect of nitric acid concn on the prods of the nitration of N,N-dimethylaniline to form Tetryl, it was isolated in low yield by the action of nitric acid, d 1.046g/cc, plus Na nitrite on N,N-dimethylaniline (Ref 10). A eutectic mixt with N-ethyl-4-nitroaniline has been patented as a stabilizer for NC (Ref 12). Studies at NPF indicate that 4-nitro-N-methyl-aniline is superior to Centralite, 2-nitrodiphenyl-amine, or Acardite in stabilizing. NC Refs 1) Beil 12, 586, (295) 1125 ... 

Trinitro-N-methylaniline (N-methyl picra-mide), yellow needles from EtOH contg acid, mp /l4.8° (Refs 4 7) the UV spectrum has a peak at 340 and a shoulder at 410—20m (Ref 19) CA Registry No 1022-07-7. It is prepd by the hydrolysis of the N nitroso compd (see below) at 70—80° (Ref 5) by the action of coned sulfuric acid (Ref 8) or UV light (Ref 12) on Tetryl by the action of methyl amine on Ethyl Picrate (Ref 18) or Tetryl (Ref 7) or by the action of nitric acid (d 1.42g/cc) at 0° on N,N-dimethylaniline (Ref 10). It is present in crude Tetryl and is the active der-matitic agent in the latter (Ref 12). It can be isolated from crude Tetryl and identified by thin layer chromatography (Ref 21)... 

The formation of chloramine as an intermediate, followed by reaction with nitric acid to produce the corresponding nitramine and HOC1, may explain the catalytic action of HC1 in the nitration of amines... 

The fact that practically all aromatic amines are readily converted into diazo compounds contributed greatly to Griess s success. The original method (Griess, 1858) by which he diazotized picramic acid (1.1 see Scheme 1-1) consisted of passing nitrous gases, prepared by the reduction of nitric acid with starch or arsenious acid, into an alcoholic solution of the amine. 

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