JAMES JONES AND LEWIS ACTION OF AMINES ETC. 1273 CXXXVI1.- The Action oJ’ Arniizes on Trinitrophenyl-methylnitroamine. By THOMAS CAMPBELL JAMES JAMES IVOR MORGAN JONES and ROBERT ILLTYD LEWIS. IT is a well-known propelrty of polynitro-aromatic aompoands that they form additive derivatives with various types of aromatic substanm such as hydrocarbons phenols amines etc. The most recent work on thesel derivatives has beten carried o a t by Sud-boroagh and his collaborators who1 have examined in detlail the €olrmat,ion and propertiea of a large series of the a,dditive com-pounds formed by s-trinitrobenzene. I n a review of the compounds prepared by them Sudborough and Beard (T. 1910 97 773) were leid to1 suggest a possible formula for the compound of trinitro-belnzenel with aniline relpreseating it as polsseesing a hemi-quinonoid The prewnt investigation was undertaken with a view to ascertain whether tlrinitropheiiylmethylnitro~arnine (tetryl) forms additive compounds of a similar type t o s-trinitrobenzene.It was olbselrveld that solutions of this subsLance in a variety of solvents belame deeply coloureld on tlhei addition of any amine primary, seaondary or tertiary except in such cases where the amine con-tlains strongly negative1 radicles and in a large number of cases it has been possible t o isolate from these solutions definite) crystalline aompounds which are without) exception compoands oh tebryl and the base united in equimolecular proportions. Owing to the fact that the additive1 compounds are1 largely dissociated in solution the separation of the pure! prolduct is difficult in oases whetre the constituents are less readily soluble than the additive product.The1 geaeral conclusions drawn by Sudborough and Beard (Zoc. c i t . ) regarding stability and depth of colour have been confirmed, altlhough the stability of this series of compounds is on the whole, less than $hat of the corresponding compounds of the trinitro-benzene series. Thus additive compounds of tetryl with phenols and tertiary amines have noti been isolated in a pure statq although evidence oif their formation is affordeid by the production of a red coloar wheln solutions of the components are mixeid and also i 1274 JAMES JONES AND LEWIS THE ACTION OF solrrie cases by ail iiivestjgation of tbs indting points of niixfures od the components.Hydrccarbon: and nitrophenols do not yield additive prolducts. The chied polintl od diffeIrelnm between t'hs additive compounds under consideration and those of the1 trinitroibenzelnei series is that, in many cases like the additjive compounds of picryl chloride with bases described by Sudbolrough and Piaton (T. 1906 89 583), they readily undergo a change to1 a condensed compound ; thus the' clompou nd o f t r i nit r oip heln y lme t h y lni t r o am inel and anilinel on storing in a sealed tube o r on slow crystallisation from a hotl solvent, yiedds 2 4 6-trinitrojdiphenylamine condensation appar-elntly ocaurring accolrding tot the equation C6H2(N02)3-NMel-N0,,N13,Ph = C,H,( NO,),*NHPh + NHMel-NO,. We have nolt succeeded in isolating the1 methylnitrofamine despite varioas attempts and itl is probably decomposed during the con-densatlion.The proiducts are idetntical with those formed by the action od picryl ohloridel on the aminel and in al numbw of cases exist in two olr mocel modifioations differing in crystalline1 form and mlour (compare Sudborolugh and Picton Zoc. c i t . ; Busch and Pungs J . p. Chem. 1909 [ii] 79 546; Hantzsch Bey. 1910 43 1678). It is of interest to1 nolte howelver thatl the1 first produotl is generally of a md aoIloIur whilst yelllaw or ocange mojdifications are obtained by the use of picryl ohloridel this beling duel to thei presence of hydrogen chloride which is instrumental in converting red forms into yedlow. Molle8ml ad - weight detelrmi na t i ons of the1 additive comp ounds indicate that noitwithst anding the delvellopmentl of deep1 collolur in the solutio'ns dissolaiation into tlhel compoaelnts is almost cmp1et.e in dilute solution.E x P E R I M E N T A L. The method olf work consisted in gefnelral in allowing a cold sattnrafleld solution of t,et,ryl in alcohol a,cet.one or be'nzene and t,realkld wit'h ra,thelr motre than o'ne molecular pro\portio:n of the aminel in the sa,rneI solvent1 or in ethe,r t o l remaJn untdl arystallisa-tioin took place. In many oa,ses oryst'als olf the a.dditive compojund were depoisited wit>h elasel ; in oitlhetrs condensation t,ook pla,m and t,he picry1 delrivative wa5 ob,taineld a,s first product. When the mixed sollutio8ns were helateid for some time o'n a water-bath or wheln the cryst,allisstioin was prolonged by leaving the solvent to evaporate slowly on a hot' plate t,hei coind,ensa8tioln cvrmpolund was usually deposited.Ammorn&z.-The addition of an a,lcolholic solution of ammonia (one and two equivalents reapectively were used in differea A'RIINES ON TRINITROPHENYI,MET€IYIA~ITROAM~NE. 1275 elxperimeiits) t o a sat8iiratetl alcoholic sulutioii of tcltryl yielcletl a deep red solutioii olf an additive conipcmnd which i t was not possi6lel to isolate. The deep colour gradually disappeared on warming and from tlhe reisulting yellolw solution picramide (m. p. ISSO) in a yield corresponding with 53 per cent. of the1 theioretical, crystallised out. The1 filtrate on evapolration prolvided a further yield of crystals which pyoved t o bet axnmolnium picrate.When dry ammonia was passed into a sollution of tetryl in benzelne little aotion took place but 011 the1 addition of a small amountl of amtone a deep red sollution was produced from whiclh a fluorescentl green oil separated. This solidified on keeping to1 a deep green mass which when freshly prepared had a strong odolur of ammonia. It is soluble in wateir or alcohol giving orange-coloured solutlions but i t has not been olbtaineld in good crystallinel form and the melting point is indefinite the substance delcom-posing explosively on heating abolvve 100'. After elxcess of ammolnia is relmoved the substance oontains C =34*19 H = 3.61, and N=24.97 per cent. correapoading with the formula Methylamioae.-When treateld witah an alcoholio sollution of m&hylaminel tetryl givee a deep red-codoared solutlion which after slight warming deposits reddish-brolwn neeldles (m.p. 112O) con-sisting of 2 4 6-t4rinitromethylanilinel (Romburgh Rec. trav. chim. 1883 2 105). On remystallising from alcohol containing a small proportion oif acid purei yellow needles melting a t 114.8O are obtlained (Found N= 23.45. Calc. N =23*09 per cent.). Benzylamime.-This yields 2 4 6-tTz'nitrophenylb emzykamke, oonsisting of ohocolate-cdoured needles (m. p. 143*3O) which when crystallised from alcolhol containing a little acid becomes golden-yellow and melt8 at 144-8O (Found N=17*70 C13H100,N, requires N = 17-61 pelr cent.). 9 niZine.-Thel additive compound of tetryl with aniline was readily olbtlained from belnzenei solution and folrms orangel-red plates melting at 64O (Found N = 21.35.CI3Hl2O8NG relquires N = 22.11 per centl.). The1 substanael declomposes oln keeping in the1 air by treatmeat with acids and by treatment with. many solvents regenerahing teltryl (0.5425 treateld with acid gavel 0.4064 tetryl = 74.91. Calo. t&ryl= 75-48 per oent.). On keeping in a selaleld tuba folr several weelks the substarnoe became moist and the product on crystlallisartion proved to be 2 4 6-trinitrodiphenylamine~ This substance is also obtained by slow mystallisation od the original mixture from warm benzene, acetme o r alcohol solutions. Itl forms orange crystals melting a t C,OHl20*N6 1276 JAMES JONES AND LEWIS TIIE ACTJON OF 1 7 8 O corresponding with the descripthi of Bamberger and Muller (Ber.1900 33 188). ol-ToJaidhe .-An additive1 compo urLd with tetryl is readily obtained by adding a slight excess of the base to a hot solution ol tetryl in 'benzene solution and allowing t o crystallise. It consists of brick-red crystals melting a t 63O (Found N =21.18; tetryl= 72.7. C,,Hl,08N requires N = 21.32 ; tetryl= 72.8 per cent .). The substance decomposes on exposure t o the atmospherel and also on reorystallisation yiellding tettryl. It doe@ not however, yield a condeinsation product; and 2 4 6-trinitrolphenyl-o-tolyl-atmine( is not formeid even when thel mixture) of components is boiled for forty-eight hours in a reiflux apparatus using various solvents. m-Toluidine.-The additive compound in this casel has not.bee111 obtained in a pure form as it is rapidly changed even a t the ordinary teimpraturel to a coindenseid derivativel. The productl obtained from a mixture1 otf the components in benzene solution clonsists od deep reld needles melting at about SOo which on treatr ment with acid regenerate hltryl. On warming this product with benzene o r with a' mixturel of chloroform and light petroIeum and allolwing to crystallise bright scarlet needles are1 deposited which melt a t 118.5O (Found N = 17.37. C,,H,,,O,N requires N = 17.73 per cent.). This substance wheln first prepared oould be recrystallised from alcohol1 without changel but ofn the additJon of a drop of acid to a saturated solutioa in alcohol orangepyellow prismatJc crystqals separa,ted.These1 melt at 129O and correspond with 2 :4 6-tri-nitrolphenyl-m-tolylamine as describeid by Busch and Pungs ( J . pr. Chern. 1909 [ii] 79 550). Theee autholrs state) that the sub-stance occurs in two forms an orange1 modification (m. p. 129.5") and a pure yellow form (m. p. 130'). The forms obtained by us are1 readily soluble in alkali hydroxide yielding deep red solutions, which on acidifying yield a pure yellow form melting at 1 3 9 O . We have been unablel so far t o reconvert the stable yellow form into the labile scarlet form melting a t 1 1 8 . 5 O . pToZuidime.-In the case of this amine an additive compound with t rini trop hen ylme thylnit ro amins is reladil y obtained by cry st al-lising a mixture1 olf the componeats from benzene or alcohol.It consists of deep red needles melting at 54" which are1 readily decaniposed by acids regenerating tetryl (Found N = 20.82 ; tetryl= 72.1. C14H1408N6 requires N = 21.32 ; tetryl = 72.8 per mnt.). The1 coadensation compound 2 4 6-trinitrophenyl-p-tolylaniine, was obtained in the manner described above and was isolateld i AWNES ON TRlNI!l!ROPHENYLMETHYLNI!L’ROAMINE. 1277 the two forms described by Busoh and Pungs (Zoc. cit. p. 548) a8 orange-yellow needles (m. p. 163-164O) and b l d - r e d prisms (m. p. 165O). m-XyZidine.-This base yields with tetryl a very unstable additive compound which undergoes condensation very readily to form 2 4 6-trinitrophenyl-m-xyZyhine, this crystallises in orange-yellow needles melting at 157O (Found : N*= 17.11.C,,H,,O,N re-quirea N= 16-86 per oent.). o-Anisidine.-We were unable to isolate an additive compound in this case although the colour of the solution indioated that suoh a compound is formed. From a warm solution in aleohol red crystals of 3/ 4/ 6/-trinitrc~2-methoxydiphenylamine separated, melting a t 143O (Busch and Pungs Zoc. c i t . p. 552 give 1 4 2 O ) . p-Anisidine.-In this case again no additive compound was isolated for 2/ 41 6’-trinitrc4-4-methoxydiphenylamine wits obtained even when cold solutions of the components were mixed. This consists of orange-red needles melting a t 172-5O (Found: N=16*75. Calc. N=16-77 per cent.). Busch and Pungs (loc. cit. p. 552) describe this compound as melting at 138O. We have repeated their preparation of the aub-stance from picryl chloride and p-anisidine and find that the product melts a t 172*5O as given above.p-A?~zinopher~oZ.-The additive compound in this case has not been obtained pure and readily passes into the condensed deriv-ative 2/ 4/ 6/-trinitro-4-hydroxydiphenylamine which consists of brick-red needles melting a t 174O (Turpin T. 1891 59 718). a-Naphthylaminc-The additive compownd of this base is readily obtained by crystallising a mixture of the components in equivalent amounts from benzene. It consists of well-defined black prisms melting at 94O. Tho compound is of considerably greater stability than the additive compounds previously described, but is partly decomposed by crystallisation from many solvents, and completely by warming with acids (Found N = 19.73 ; tetryl= 66.46.C,7H,,0,N6 requires N = 19.53 ; tetryl= 66-73 per aent.). N o condensation product is formed even after prolonged boiling of the additive compound or of a mixture of the components in a variety of solvents. P-Naphthy1amine.-The additive coml?ou?td is similar to the above and is obtained in black prisms melting at 90° (Found: N = 19.72. C,,H,,08N requires N = 19.53 per cent.). The mnipoiind is fairly stable and does not yield a condensed derivative. C,H,( NO,),*NH* C,H,M% 1278 JAMES JONES AND LEWIS THE ACTION OF m-Phe.12y~e~e~~~?n~ne .-Thel additive compo.tcnd od this base is madily obtaineld by crystallisation from benzene solution and colnsists of silky brolwn netedles melting at 84O whidh are moderateily stable[ but are partly decomposed by recrystallisation and completeily by warming with acids (Found N=24*94.C,,H,,O,N relquirea N = 24.81 per cent(.). The1 condetnsa,tion compound 2 4 6-triiiitro-nz-aminodiphenyl-amine is olbtainetd by slow crystallisation from hot acetone and folrms al deep red crystlalline powder mellting a t 207O (compare Jaubert Ber. 1898 31 1182). MethyZarlziZ&tze .-This base yields an additive cornpm~rlznd with trinitlrophenylmelthylnitroamine which consists of deep reld plates meltling a t 86O (Found N = 21.86. C,,H,,O,N require6 N = 21.32 per cent.). The condensation compound has not been obtained by our general methold. Dimelthylanilinei elthylanilinel and diethylanilinel all yietld deeply collolureld sollutions when mixed with solutions of tetryl but pure1 additive compoands have1 nolt yetl been olbtained in these cams.Moreolver condensatioln to1 picryl derivatives does notl occur elven aftler prolonged boiling in alcohol or acetonel solutions. Similarly nz-nitroaniline m d p n i troaiiilinel yietld slightly coloured solutions with tetryl but t>he separation of pure additive compounds has not been achieived. An investigation of the freezing-point curvels of mixturm of these bases with tetryl indicates that unsta,bls modecular compounds can exist. Halogen-substituted axnines give oaly feeble1 colorations with solutions of tettryl and form no additlive1 compounds ; condelnsation is also1 not possible. Su,mmary and Cowclusion~. Trinitrophenylmelthylnitroamine ( teltryl) reladily f olrms q u i -molecular additive1 compounds with the siinplelr arninm which in many cams readily condemse t o form pimylamines.The presence of alkyl substituelnts in the ortho-position in the1 amins does not affect the forniation of the1 additive compound but inhibits the colndeinsatioa The1 presence of the meltholxy-group in tho olrtho. position does not howevelr prevent the condeasation (oompare o-talixidinel and o-anisidinel). On the1 other hand sitbstitution in the meta-position renders the molecular compoiind unstable and it readily pashes iiito tfie corresponding picrylaminel. Thet naphthylaminels and the! secondary amines yield stablet additiv AMINES ON TRI~ITROPHENYLMETHYLNITROBMINE. 1279 CoinpoIunds which do notl pass intot condensatlion derivatives (colmpam Sudborough and Picbn Zolc.c i t . p. 589). According to Werner the components of molecular compounds Percentage of tetryl. Freezing-point curves of tstryl-m-nitroaniline (I) and totryl-p-nitroaniline mixtures (11). of this type are to be repraenteid as united by the residual or auxiliary valencies of the1 nitro- and amino-groups (I) 1280 MAXTED THE INFLUENCE OF HYDROGEN SULPHIDE ON It may be pointed ofut howelver that a representation in accord-ancel with Sudbolrough and Beard’s suggestion (p. 1273) brings the nitroaminel group into close proximity with the amino-group. If the amine be represented as possessing a hemi -quinonoid structure, the1 intense coilour of the1 molecular compounds and the1 comparative stability of the derivativels of secondary amines may also1 be explaineld. Thus the molecular compound with methylaniline might be representeld as (11). The influence of substituents in the1 phenyl grolup of the) amine on the ease with which condensation can take1 place1 is not4 obvious in a formula of this type whereas in tIhe case olf the Werner formula such substituents may be represented as modifying tho amount of residual valency whereby the aminel is attached to1 the ni troLgroup . We desire1 to thank Mr. Talfryn James f o r assistance in the1 preiparatioa oE some1 of the substances described. THE EDWARD DAVIES CHEMICAL LABORATORIES, ABERYSTWPTH. [Rcccived September 13th 1920.