N-Nitro dimethylamine

Nitramines are known to photodissociate from their jt,jt state to give aminyl and nitric oxide radicals in the presence of an acid the aminyl radicals are protonated to give aminium radicals, which can initiate addition to olefins. As a synthetic reaction, photolysis of nitramines in the presence of acids can be conveniently run under oxygen to give oxidative addition similar to those shown in equation 145 indeed TV-nitrodimethylamine is photolysed with triene 299 under such conditions to give a mixture of 301 and 302, similar to results observed in the oxidative nitrosamine photoaddition169. To simplify the isolation, the crude products are reduced with LAH to form the open-chain amino alcohol 303. Some other oxidative photoadditions of N-nitro dimethylamine to other olefins are reported. As the photoreaction has to use a Corex filter and product yields are no better than those shown by nitrosamines, further investigations were scarcely carried out. 

Its trinitro deriv, 1,1 -Dinitramino-N-nitro dimethylamine, CH2NH.N02... 

MP 41, 364-68(1959) 1,l -Dinitramino-N-nitro-dimethylamine (called Trinitrodiaminodimethylamine by DiCerrione), 02N.N(CH2NHN02)2> mw 310.12, N 26.93%. A secondary product formed in the nitration of hexamethylenetetramine to trimethylenetrinitramine. Description of this compd is not given in the abstract (Ref 2) Refs 1) Beil — not found 2) A. DiCerrione, AnnChimApplicata 38, 255(1948) CA 43, 4633(1949) 3) Not found in later refs thru... 

Mix 0.25M substituted benzaldehyde, 0.3M nitroethane, 50 ml dry toluene and 5 ml n-butylamine (or other amine), and reflux 3 hours with a Dean-Stark trap (or prepare the nitro-propene as described elsewhere here). Add 50 g iron powder and 1 g FeCl3 optional) and reflux while adding 90 ml concentrated HCI over 3 hours. Reflux 1 hour more, add 2 liters of water and extract 3 times with ether, then dry and evaporate in vacuum (or steam distill until about 3.5 liters of distillate is obtained extract the distillate 3 times with toluene wash the toluene layers with 7 g NaHS03 in 225 ml of water, then 3 times with water and dry, evaporate in vacuum) to get the ketone. Mix 0.13M ketone, 28 g formamide (or dimethyl-formamide if the N.N-dimethylamine is desired) and 3 ml formic acid and heat at 160°. Add 3 more ml formic acid and heat 16 hours at 170-180° adding formic acid from time to time to keep the pH acid. Distill off the water formed (about 16 ml), cool and extract with 3X70 ml benzene. Distill off the benzene and reflux the residue 7 hours with 30 ml concentrated HCI. Chill, basify with 10% NaOH and extract with 3X70 ml ether. Dry and evaporate the ether in... 

Die Umwandlung des etwas weniger reaktiven l-Methoxy-4-nitro-benzols in N-Methyl-4-nitro- (54%) oder N,N-Dimethyl-4-nitro-anilin (65%) kann durch Reaktion mit waflriger Methylamin- bzw. Dimethylamin-Losung unter UV-Bestrahlung erreicht werden5. 

Bromo- (35, R = Br) with dimethylamine gave 4-dimethylamino-l,6-naphthyr-idine (35, R = NMe2) (neat reactants, 135°C, sealed, 16 h %)1057 but 4-chloro- (35, R = C1) gave 4-piperidino-l,6-naphthyridine [35, R = N(CH2)5] apparently under milder conditions (neat reactants, 95°C, 5 min %)1067 4-chloro-3-nitro-l,6-naphthyridine (36, R = C1) gave 3-nitro-l,6-naphthyridina-mine (36, R = NH2) (NH3/MeOH, 110°C, sealed, 4h 75%).819... 

Materials. 2-Carboxy-4-nitro-N,N-dimethylaniline (I) was synthesized from its chloro analog with dimethylamine (aqueous solution), mp 164°-166°C. p-Chloro-N,N-dimethylaniline (IVb) and N,N-di-methylaniline (IVa) were commercially available in the pure state and were used as supplied. p-Nitro-N,N-dimethylaniline (IVc) was prepared from p-nitrochlorobenzene and dimethylamine (9) mp 166°C. 

N, N Dime hyl-2,4,6-tr nitro m-phenylene-diaTnine, H2N.CgH(N02)g.N(CH3)2 crysts, mp 187° was prepd hy action of cold aq dimethylamine soln on 2,3,4,6-cetranitro-aniline, or by treating 2,3,4, 6 tetranitrodi-methylaniline with cold aq ammonia (Refs 3 5)... 

It is produced from furfuryl alcohol by sequential reaction with dimethylamine hydrochloride/formaldehyde, cysteamine and N-methyl-l>(methylthio) 2-nitro-ethenamine. The production of ranitidine in 1986 amounted to 2601. 

A soln. of an equimolar amount plus 25% excess dimethylamine borane in glacial acetic acid added slowly at ca. 20° to a suspension of ethyl N-benzyli-dene-p-aminobenzoate in glacial acetic acid, then refluxed 15 min. ethyl N-benzyl-p-aminobenzoate. Y 92.8%.—Other groups not affected by this reducing agent are carboxy, sulfonamido, nitro, chloro, methoxy, hydroxy. F. e. s. J. H. Billman and J. W. McDowell, J. Org. Ghem. 26, 1437 (1961). 

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