Amines compds

Dinitro N-nitroso-2- chloro-N me thy laniline or (4,6-Dinitro-2 chlorophe nyl) methylnitros-amine, compd not recrystd because it decompd when petr eth was added to its benz soln at RT was obtd by treating an ice-cold soln of 2-chloro-N-merhylaniline with HN03 NaN02 (Ref 3)... 

A variety of reducing agents have been used hut the usual ones are -sodium methoxide in MeOH or sodium arsenite. The azoxy compd results from the condensation of the nitroso and the hydroxylamine compds produced during the reduction. The nitroso and hy-droxyi amine compds can be prepd separately and condensed together to give the azoxy compd. Even when the nitroso and the hydroxylamine compds contain different substituted groups, with only one or two exceptions sym azoxy compds (R = R ) are formed, and not the unsym azoxy compd, as expected. Another method for prepg azoxy compds is by the oxidn of azo compds ... 

Chem. Descrip. Sillitin Z 86 (quartz-kaolinite) coated with stearic acid/ stearyl amine compd. 

NFPA Health 3, Flammability 3, Reactivity 2 Uses Intermediate in prep, of chloromethyl derive, which are subsequently converted to amine compds. for use as ion exchange resins, water repellents, and other industrial polymers chloromethylation reagent ion exhange membrane in prod, of grapefruit juice protective agent... 

It forms a complex with dioxane contg 2 moles of TNMe to one of dioxane, mp 44—4.5°, bp at 8mm, 61—2° (Ref 19a, p 33). It reacts with aromatic dlazonium salts to give compds of the type ArN NC(N02)3. The compds are relatively unstable and their expl props have not been examined (Ref 12). It reacts with N-hydroxymethyl compds to form adducts of the type RNHCH2C(N02)3. The same compds are formed from TNMe, formaldehyde, and the amine or from trinitroethanol and the amine (Ref 31). It forms complexes with N-contg heterocyclics whose expl props have not been examined (Ref 42). It forms complexes with benzene and methylbenzenes. The formation constants for these complexes vary from 8.46 for the benzene complex to 279.4 for the hexa methylbenzene complex (Ref 49)... 

Pure samples are best prepd by the methylation of acetanilide or benzanilide to the N-methyl compds followed by acid hyd. It has been prepd commercially by the action of methyl ale on aniline in an autoclave under press and by the action of methyl amine on halobenzenes. For a summary of prepns see Refs 6 9. It may be separated from aniline and dime thy laniline by treatment of the mixt with benzenesulfonyl chloride. Dimethylamline fails to react and is extd out with dil acid. Aniline forms benzenesulfonanilide which is acidic and is removed by washing with dil base, leaving the N-methylbenzenesulfonanilide. Purified N-methylaniline is obtd by acid hyd (Ref 8). N-Methylaniline is used as an additive to raise the octane no of motor fuels (Ref 6), as a dyestuff intermediate (Ref 3), in the prepn of Tetryl (see below), and in the prepn of Methylcentralite (Encycl, Vol 2, C137-R)... 

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)... 

Nitroaminocompounds or Nitroamines. Compds containing both —N02 and —NH2 radicals attached to different C atoms, eg, nitroaniline, 02N.C6H4.NH2, etc. Nitroamines can be prepd either by the nitration of amines, or by partial reduction of nitrocompounds contg several —N02 groups. Another method is to treat a chloronitrocompound with ammonia, as in the prepn of dinitroaniiine... 

DNPh forms low mp additive compds with ammonia or amines (aniline, toluidine, naphthyl-amine, etc), which on intimate mixing with oxidants (AN, K nitrate, Na nitrate, K chlorate,... 

These compds can be prepd, in general, by dissolving the respective organic compds (hydrocarbons, nitrohydrocarbons, amines, phenols, etc) in warm ale solns of PA, boiling the mixt, and then cooling it to cryst out the resulting picrate... 

Styrene C6H5CH=CH2. Alkali Peroxy compds Vap in Air 1.1 to 6.1% > Ambient > Ambient Inhibitor—Methyl Ether of Hydroquinone—10-15 ppm, Phenol Subst-Hydroxyl Amine, etc. Store below 70°F. Avoid sparks in. vap/air mixt 17.4-17.8 490 Soln polymerization catalyzed with w or Ti tetrachloride. Also self polymerization... 

Vinyl Acetate CH3COOCH=CH2 OH compds, HCN, Halides, Halogens, Mer-cap tans, Amine, Silanes Oxygen Vap in Air 2.6 to 13.4% > Ambient > Ambient Inhibitor—Methyl Ether of Hydroquinone or 3-5ppm Diphenylamine. Store in a dry, cool place shield from light impurities 20.9-21.5 402 427 Free-radical polymerization initiated by Benzoyl Peroxide... 

Polynitroamines. A series of compds developed by Frankel and Klager (Ref) as expls and O donors in proplnt fuels. These compds are prepd by condensing j3-geminal polynitro alcohols with ammonia or polynitro amines. The compds produced are of the type,... 

In studying the reactions betw nitroso-acylamines and diazo esters several expl compds were prepd. Some reactions involved explosion hazards) 4) F. Bucci, AnnChim (Rome), 41, 587-93(1951) CA 47, 3443 (1953) (Reactions of alkali nitrites with some otg amines, such as urea may result in explns) 5) G. Armistead, ChemEngt-Progress 48, 5-10(1952) CA 46, 2298 (1952) (A review of expln hazards)... 

N20.09%, yel ndl(w/alc), mp 196°, sol in 20% HC1 dil alkali. Prepd by boiling with IN NaOH the triethylamine salt of HO2C CH(2,4-dinitroaniline) CH2(2,4-dinitrophenol) - the amine salt of 0,N-bis(2,4-dinitrophenyl)-serine — and then acidifying. The compd may actually be N-vihyl-2,4-dinitroaniline, but the authors made no attempt to find out... 

It easily forms double compds, such as boron trifluoride etherate. Another compd, boron tri fluoride-mono ethyl amine, BFa— C2H6NH2 is wh to pale tan flakes, melting at 88—90°. It released BFa above 110° and is used for elevated temp cure of epoxy resins Refs 1) Gmelin-Kraut Syst Number 13(1954), 168 2) CondChemDict (1961), I661L R ... 

Diomides. These compds are the dibasic acid derivs of ammonia or amines, and contain two -CONH2 groups. Numerous combinations of diacids, diamines, and amino acids have been interacted. Copolymers contg various proportions of two or more diacids have been prepd (Ref 2). The diamide of carbonic acid is called urea, H2NCONH2. It is a product of animal metabolism and is prepd industrially by reaction of CO2 with excess NH3 at high temp, or by an older method involving the hydrolysis of cyanamide (Ref 5)... 

Compds of the general structure RC(0)N(N02)A.CH2.C(N02)2CH2.Ar N(N02)-C(0)R where R is alkyl and A is alkalene, were also patented by Frankel Sc Klager (Ref 4) for use as HE chges or proplnt additives. These nitramides are prepd by heating the appropriate dinitrodi-amines with acyl anhydrides and treating the product with HNO - Thus, the following N-nitro nitramides were prepd cited ... 

Diazocompounds. A group of very reactive org compds, many of which are explosive, containing the bivalent radical -N N- or N N-. They are formed when nitrous acid acts at low temp on the salts of primary amines. The process of prepg diazocompds Is called diazo-tization and was discovered about I860 by P. Griess (Ref 4)... 

Diazotization. This is a reaction by which a diazo compd is obtd from a primary amine. The reaction is as follows ... 

Azido-l dimethylbenzene or 4 Azido m-xylene, compd prepd by Smolinsky (Ref 6) by a procedure which converts the amine to the corresponding azide, but no details of its props are given... 

N, N -Dime thy l-methanedi amine, (H.3C)HN.CH2.NH(CHa) mw 74.13, N 37.80% may be considered as the parent compd of its dinitro deriv, although not used to prep it N,N -Dinitro-N/N1-dimethylmethanediamine or 2,4-Dinitro-2,4-diazapentane, (H3C)(02N)N.CH2.N(N02XCH3) mw 164.13, N 34.14% crysts (from chlf-hexane), mp 49—51° was prepd by treating paraformaldehyde in 90% sulfuric acid at —2 to —6° portionwise with methylnitramine, the mixe stirred, poured on a large amt of ice, and the solid combined with product from ether extraction (Ref 3). No expl props are repotted Refs 1) Beil, not found (DMMDA) 2) Beil, not found (Dinitro DMMDA) 3) L. Goodman, JACS 75, 3020(1953) CA 49, 4630(1955)... 

Di(metbylol)-amine N, N -Bis( ft-hydroxy-. metbyl)-amine, or Di(methanol)-amine, HN(CH2OH)2 mw 77.08, N 18.17% may be considered as the parent compd of its nitrated deriv, although not used to prep it Di(methylol)-nitromine Dinitrate or Nitro-imino-dimethanol Dinitrate,. ... 

Ref 2). It can be prepd by treating N,N-di-(j3 propylol)-amine with 98% nitric acid at below 15°(Ref 1), It was used by Blomquist St Fiedorek for prepn of the compd listed below Refs Same as under next compd... 

Bakerbond Chiral DNBPG (ionic or covalent).4 r-BuOH, 2-PrOH, Butyl methyl ether, hexane, CHC13, and phases below. Chiral mixts of alcohols, acids, amines, variety of enantiomeric compds... 

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