610 MELDOLA AND HOLLELY : ALKYLATED

IIY1[l.-Alkylated P u r a - p h e n y l e n e d i a m i ~ e ~ and Deriva- t ives. Q u ino 11 eimid e- A m m o n iu m Compo u nds. By RAPHAEL M E L ~ O L A and WILLIAM FRANCIS HOLLELY.

THE well-known relationship between quinone, quinone-imide, and 0 K H N1I

quinone-di-imide points t o the possible existence of a class of compounds similarly related t,o the quinone-ammonium compounds which have formed the subject of numerous co,mmunications to the Society during the last three years:

0 N H

k. a. b. c. N k b . c . Quiiioneimide-ammonium compounds of the above type have long

The colouring matters classed been known in tinctorial chemistry.

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PARA-PHENYLENEDIAMINES AKD DERIVATIVES. 611

as indamines may, iiz fact, be regarded as derivatives of the hypo- thetical parent substance indicat'ed by the above formula, Bind- schedler's green (Bcr., 1883, 16, 865) being one of the first dis- covered coloured compounds of the group :

N*C6H,* lS(CH,), A

Although these indarnines may be referred to the quinoneimide- ammonium type, the analogy between these coloured compounds and the1 true quinone-ammonium derivatives is strictly valid only when a , b , c, in the above formula are all represented by organic radicles. The present research was undertaken with the object of preparing compounds of the true quinoneimide-ammonium type with special reference1 to those derivatives in which a, 6 , and c are represented by different radicles. Such compounds might be expected to be resolvable into optically active isomeridea. We have succeeded in obtaining one compound belonging t o the simpler type, in which a, b , and G all stand for CH,, but the preparation of derivatives containing an asymmetric quinquevalent nitrogen atom has presented great difficulties, and the results are as yet incon- clusive.

Quinoneimide-ammonium compounds of the required type may be regarded as inner anhydrides or condensation products of amino- ammonium hydroxides or salts :

The preparation of the parent amino-ammonium compounds could not, of course, be attempted by the direct alkylation of the

unsymmetrical dialkylated diamines, C6H4<E2b., since the unsub-

stituted aminorgroup would certainly be attacked by the alkylating agents. Two methods were therefore tried :

(1) The alkylation of pnitroaniline so as to prepare C6H4<x.ct.b.,

from which it was hoped to obtain C6H4<h>b.c.X by the usual

methods; the latter on reduction and removal of 'HX would give the required compounds.

(2) The acylation of the unsubstituted amino-group in the

dialkyl-diamine so as to obtain C6H4<i::tC which, by the addi-

N 0,

u

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61 2 MELDOLA AND HOTALELY : ALKYLATED

tion of alkyl iodides, might; be expected to give compounds of the

type c6H4<sz:2x, from which the required quinoneimide-

ammonium compounds might be prepared. The first of these methods has hitherto been unsuccessful, a fact

which is in itself of some interest, as the presence either of the para-nitro-group or the benzyl group appears to prevent the dialkylamino-group from alkylation into a quaternary (trialkyl) ammonium graup. The second method, on the other hand, has proved t o be quite successful, the para-acetylamino-group appear- ing to facilitate the formation of ammonium compounds by the nitrogen atom of the dialkylamino-group. It is obvious that by this method the synthesis of numbers of compounds containing an asymmetric quinquevalent nitrogen atom becomes posible, the addition of CX to the N.0.b-group giving rise to compounds con- taining the group N.a.b.c.S, in which a, b , and c may be dissimilar radicles .

The investigation of the dialkylphenylenediamines required for the present research has resulted in the discovery of certain new and interesting properties of these compounds which are described in the experimental part of this paper. Attention is directed more especially to the nitration products of the acetyl derivatives of the

NH-Ac a,l dialkylated diamines.

give on nitration the same product, the dinitronitrosoamine of the constitution :

Compounds of the type C6H4<N.,.b.

NHAc A

NO,, I I ,NO,

CH,*N*NO

It thus appears that whatever radicles may be attached to the 4AT-atom, methyi alone is retained, the heavier radicles being expelled and replaced by the nitroso-group. This fact has been established for the dimethyl, methylethyl, and benzylmethyl com- pounds, all of which give the above nitrosoamine.

EXPERIMENTAL.

The discovery that all the dialkylated acetyl-pphenylenediamines gave the same product on nitration and the! determination of the constitution of this product resulted mainly from the detailed investigated of the methylethyl compound :

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PARA-PHENPLENEDI SMINES AND DERIVATIVES. 613

.Ue t?qlethylace ~yl-p-p?~.Pnylenedz'nnLine (11-Methtyle tkylnmin 0-

ace tcinizide), NHA~/--'w(cH,)-c,H,. \-/

Methylethylaniline was converted into its nitroso-derivative by adding the calculated quantity of sodium nitrite dissolved in water to a solution of the hydrochloride of the base cooled in ice. The nitroso-hydrochloride after purification was reduced by tin and hydrochloric acid, the tin removed as sulphide, and the solution containing the methylethyl-pphenylenediamine hydrochloride evaporated to, dryness after removing free hydrogen sulphide by passing a stream of carbon dioxide through the solution.* The hydrochloride forms a syrup, which solidifies partly t o a crystalline pulp on keeping. Acetylation was effected by heating the hydro- chloride with anhydrous sodium acetate and acetic anhydride on a water-bath. After decomposing the excess of acetic anhydride by hot water the base was precipitated by neutralising the solution of the acetate with ammonia; it separates as a resin, which solidi- fies to a crystalline mass on coding. The product was purified by crystallisation from dilute alcohol with the addition of animal charcoal, and consisted of colourless, silky needles, melting a t 92O :

0.0997 gave 12.7 C.C. N2 (moist) a t 1 8 O and 749.3 mm. N=14-50.

This acetylamino-compound combines readily with alkyl iodides to form quaternary ammonium iodides. Combination takes place a t the ordinary temperature after some hours, and more rapidly on heating. isoPropyl iodide is exceptional among the alkyl iodides experimented with, no combination taking place when this com- pound is used. The ammonium iodides are beautifully crystalline substances, soluble in water, and having all the properties pertain- ing to compounds of this group. The analytical results clearly indicated that dissociation of t.he iodides takes place on crystallisa- tion from alcohol or water, and no more stable salts have as yet been prepared. The bases formed by decomposing the iodides with moist silver oxide in the usual way are syrupy compounds which absorb carbon dioxide from the air, and form uncrystallisable carbonates on evaporation of their solutions.

I n view of the special interest attaching to the ammonium deriv- atives containing an asymmetric nitrogen atom the two compounds containing propyl and ally1 respectively have been prepared and studied in some detail.

C,,H,60N, requires N = 14.58 per cent.

These compounds are:

* This precaution is necessary in order to prevent) Ioss due to the formation of the homologue of methylene-blue by oxidation during the evaporation.

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614 MELDOLA AND HOLLELY : ALKYLATED

NHAc*C,H,*NI(CH3)(C,H5)*C3H,. Methylethylpropyl-4-acetylaminophenyl-

ammonium iodide. NHAc~C,H,~NI(CH~)(C,H,)*C,€I, Methylelhylallyl-4-a~et~ylaminophenyl-

ammonium iodide.

These substances are no doubt resolvable into optically active isomerides, but the rmearch has not yet been developed in this direction as all the salts with optically active' acids so far studied appear t o be non-crystalline syrups o r resins. The acetyl group is readily removed by acid hydrolysing agents, with the formation of Salk of the aminophenylammoniunl bases. Attempts to prepare quinoneimide-ammonium compounds and their nitrederivatives from these last bases have so far been unsuccessful, but this branch of the research will be continued. These aminophenylammonium compounds may also1 serve as starting p i n t s for the synthesis of quinoneammonium derivatives containing an asymmetric nitrogen atom, preliminary experiments having shown that the amino-group is readily diazotisable. The removal of the acetyl group can be effected by boiling tihe base with dilute sulphuric acid or by repeated evaporation with concentrated hydrobromic acid. The compound containing methyl, ethyl, and propyl, when submitted to this last treatment, left a dzbromide,

HBr,NH2*C6H4*NBr (CH,) (C2H,)*C3H,, crystallising in colourless tlablets :

0.2463, dried a t looo, gave 0.2619 AgBr. Br=45'26. C,,H2,N,Br,HBr requires Br = 45.16 per cent.

N i t rn t io IZ of t h e Uicrlliylace t yl-p-phetcyleizediamines.

The three compounds : NHAc NHAc NHAc

as already stated, all give the same product on nitration. I n order to prepare this compound the dialkylacetyl derivative is dissolved in a small quantity of glacial acetic acid, the solution cooled in ice, and fuming nitric acid dilut'ed with twice its volume of glacial acetic acid added in small portions. The nitric acid acts very energetically at first, but more sluggishly as the quantity is increased. In order t-o complete the nitration an excess of nitric acid is required, and the solution must be taken from the ice-bath and allowed 60 remain a t the at'mospheric temperature for about an hour. The nitro-derivatlve partly separates in a crystalline

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PARA-PHENYLESEDIAM1N ES A XD DERIVATIVES. G1 Ti

form from the acetic acid solution, and is completely precipitated on stirring the solution into water. The course of the nitration can be followed by withdrawing a drop of the solution from time t o time, and diluting with water on a watch-glass; as long as the nitration is incomplete the produc,t which separates on applying this test is resinous, but becomes white and crystalline when the nitration is complete. Attempts to isolate definite intermediate products resulting from the action of nitric acid have been unsuc- cessful. By the actrion of nitrous acid on the dimethylacetyl deriv- ative a definite crystalline compound (red, stumpy prisms, m. p. 132-133O; N=19*31) has been obtained, but the study of this substance, 1;hich does not appear t o be a nitrosoamine, has not been completed.

3 : 5-Dinitro-1-ace tylaminophee.ny1-4-m e t h ylnitrosoamine, NO,

\-/ NO,

NHA~/-\N(cH~)-NO.

The product of nitration obtained as described has been proved to have the above constitution by methods described later in this paper. It crystallises from alcohol, in which it is readily soluble, in stumpy prisms, in tablets, or in scales, according to' the rate of deposition. The compound is colourleas, and melts a t 152-153O. It gives the Lieibermann reaction for the nitroso-group with sulphric acid and phenol. The identity of the product from all three sourcee was proved by analysis, melting point, and mixed melting points :

0.1042 gave 0.1450 CO, and 0.0310 H,O. C =37*95 ; H = 3-30. 0'1004 ,, 0.1400 CO, ,, 0'0305 H,O. C=38.03; H=3*37. 0.0936 20.3 C.C. N2 (moist) a t 15.5O and 746.9 mm.

0.1322 gave 28.0 C.C. N, (moist) a t 16.5O and 761.3 mm.

,, N = 24-89.

N = 24-67. C,H,O,N, requires C = 38.15 ; H = 3-20 ; N = 24.74 per cent.

The evidence on which the above constitutional formula is based is summarised in the scheme on p. 616.

The diriitronitrosoamine on boiling f o r about half-an-hour with absolute phenol loses its nitroso-groap, and is converted into the dinitrom&bylacetyl-pphenylenediamine (11). This last compound crystallises from alcohol in small, scarlet needles, melting at 196-197O :

0.1041 gave 0.1610 CO, and 0.0385 H,O. 0.0885 ,, 17 C.C. N, (moist) a t 21*5O and 769.9 mm. N=22.11.

C =42'18; H=4*11.

C,H,,O,N, requires C = 42-5 ; H = 3'97 ; N = 22.05 per cent.

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616 MELDOLA A N D IIOLLELY : hT,RYLATED

I

CH,*NH (IV.)

NHAc

f- NO1 /NO, CH,*N*NO,

(111.)

/\

2\./

The bright red colour of this compound suggests, in accordance with our former conclusions concerning the relationship between colour and constitution (T., 1914, 105, 414), that its constitution is that of an inner salt:

NHAc i\ NO,I,:NO I

I c I€, k-0 H TI.)

NH, /\

N02!,,!:T0

N--O H

( V I I . ) The dinitronitrosoamine dissolves in funling nitric acid (cooled

to 0.) with the formation of the corresponding nitroamine (111). The oxidation of the nitroso-group was effected by dissolving 3 grams of the nitrosoamine in 25 C.C. of cooled fuming nitric acid, removing the solution from the ice-bath, and allowing to remain a t the atmospheric temperature for an hour. The product was isolated by precipitation with water, collecting and washing and crystallising from alcohol, from which i t separates in t u f t s of white needles forming fern-like groups, melting a t 183-184O :

0.10 gave0.1312 CO, and 0.0274 H,O. C=35-78; H=3*04. Oa1O05 ,, 20.5 C.C. N, (moist) a t 1 6 O and 751.4 mm. N=23*51,

C,H90,NS requires C = 36.1 1 ; H = 3-03 ; N = 23.42 per cent.

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PARA-PHENYLENEDIAMINES AND DERIVATIVES. 617

The compound has all the properties of a nitroamine; boiling phenol converts it into the dinitromethylaoetyl-pphenylenediamine melting a t 196-197O. A solution of the substance in glacial acetic acid containing a little a-naphthylamine develops a reddish-violet colour o n heating with a fragment of zinc (Franchimont-Bamberger reaction). The substance dissolves in concentrated sulphuric acid, and the solution, after being kept, a t the atmospheric temperature for an hour, gives the original nitrosoamine (m. p. 152-153O) on dilution with water (Reverdin’s reaction).

3 : 5-Dinitromethyl-p-phenylenediamine (IV) was obtained from its acetyl derivative by heating the latter with concentrated sulphuric acid diluted with a few drops of water until a drop of the solution remained clear on dilution with water. A t this stage hydrolysis is complete, and on pouring the solution into water the sulphate of the base remains dissolved. The free base is precipi- tated as a deep purple, flocculent substance on neutralisation of the acid solution with ammonia. After being collected, washed with water, and crystallised from dilute alcohol, the compound consists of dark purple needles, having a green lustre by reflected light, and inelting a t 186-187O:

0.1128 gave 0.1637 CO, and 0.040 H,O. 0.1074

C = 39.58 ; H = 3.94. ,,

N = 26.28. 24.7 C.C. N, (moist) a t 20’5O and 761.2 mm.

C7H804N4 requires C = 39.6 ; H = 3.8 ; N = 26-42 per cent. The compound is distinctly basic, and displays remarkable colour

changes under various conditions. The intense colour of the free base is in harmony with the view that, like its acetyl derivative (VI), i t has the “inner salt,” structure (VII). It dissolves in dilute acids with a yellow colour, the solution a t this stage probably containing the di-acid salt. On dilution with water the solution becomes pink, probably owing t o the formation of the mono-acid salt by dissociation. The addition of alkali causes the immediate development of the intense purple colour of the free base. The colour change is strikingly sharp, and the compound would, no doubt, be useful as an indicator.

The constitution of this dinitromethyl-p-phenylenediamine was determined by replacing the amino-group by hydrogen by the diazo-method, as described in the following section, the product being 2 : 6-dinitromethylaniline (V).

Dime thyla.ce tyl-p-phen ylan Pdirrmin e (Dimet hylamino-p-rr cetanilide).

This compound was prepared from nitrosodimethylaniline by reduction and acetylation of the hydrochloride of the base in the same way as described for the methylethyl derivative. The pure

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618 MELDOLA AND HOLLELY : ALKYLATED

substance crystallised from water consisted of slender, white needles melting a t 132-133O (130°, Beilstein, IV, 588). Combination with methyl iodide takes place when the compound is covered with methyl iodide and allowed t o remain a t the ordinary temperature in a closed vessel for three t o four days.

NHAc*C,HH,*NI( CH,), (4-acetylaminophenyltr~methylammonium iodide), crystallises from water in dense, colourless prisms, which have the usual tendency to dissociate on crystallisation. The ammonium hydroxide base pre- pared by means of silver oxide in the usual way is an alkaline syrup which carbonates on exposure to the air. A picrate,

N HAC*C,H,*N(C'H~)~*O*C,H,(N~,)~, was prepared by adding an alcoholic solution of picric acid to an aqueous solution of the base. The salt separates in yellow scales melting a t about 206-208° with a considerable range of prelimin- ary softening : 0.1373 gave 20.5 C.C. N, (moist) a t 16.5O and 729.6 mm. N=16*65.

C,,H,90,N, requires N = 16-63 per cent. A definite ferrocyunide was obtained by dissolving the meth-

iodide in water, adding a solution of potassium ferrocyanide in excess, and acidifying with hydrochloric acid. A crystalline pulp of slender, whito needles formed after some hours. This salt, after being collected, washed with water, and dried at looo, had the compoeition [ NHAc* C,H,-N( CH,),],,H$e ( CN),,2H20 :

The methiodide,

0.1053 gave 0.2037 CO,, 0.0569 H,O, and 0-0134 Fe,O,.

0.3046 gave, on ignition in air, 0.0384 Fe,O,. Fe = 8.83. 0.0842 ,, 16 C.C. N2 (moist) a t 17O and 761.5 mm. N=22*09. (C',,H,,0N,),,H,Fe(CN),,2H20 requires C = 52.8 ; H = 6.33 ;

N = 22-02 ; Fel= 8-77 per cent. The salt does not lose water a t looo, and a t higher temperatures

decomposition takes place, resulting in a loss of weight greater than that required theoretically for the expulsion of two molecules.

C=52.76; H=6*0; Fe=8.91.

A ction of Alcoholic Hydrochloric 9 c i d oxt t h e Diizitro- nztrosoamzne.

A supply of the nit'rosoamine having been prepared from dirnethylacetyl-p-phenylenediamine by nitration in the way previ- ously described, an attempt was made t'o remove the nitroso-group by boiling the compound with alcoholic hydrochloric acid. The study of the ensuing reaction led t o the discovery that every possible change takes place, the nitroso- and acetyl groups being eliminated, and the amino-group a t the same t ime being replaced

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PARA-PHENYLEKEDIAMINES AND DERIVATIVES. 619

by hydrogen, the final product being 2 : 6-dinitromethylaniline, melting a t 106O (Bamberger, Uer., 1897, 30, 1257):

NlIRc NH, /\

NO,/ lNOz NO2!,) N 0, NO,(,NO, I CH,*N*NO A. !'+ CH,*NH '\ I+ NH*CH, \/

This result determines the constitution of the dinitronitrosoamine and nitroarnine, and of the dinitromethyl-pphenylenediamine. The reaction results in the removal of acetyl and the nitroso-group, the diazotisation of the dinitromethyl-p-phenylenediamine by the latter, and the decomposition of the diazonium salt by alcohol. The intermediate stages are passed through rapidly under the con- ditions imposed, namely, the heating of the solution of the nitroso- amine in absolute alcohol with the addition of a little concen- trated hydrochloric acid until the decomposition commences. The reaction then continues spontaneously with brisk evolution of nitrogen and the formation of aldehyde, and is completed by boiling the solution f o r about an hour with reflux condensation. On diluting the cold solut.ion with water the dinitromethylaniline separates in dull orange needles, which are purified by crystallisa- tion from hot water, and then melt a t 106-loro:

0.0866 gave 15.9 C.C. N, (moist) a t 1 7 O and 761.6 mm. N=21*34. C,H,O,N, requires N = 21.33 per cent.

This dinitromethylaniline when acted on by nitrous acid (sodium nitrite) in cooled acetic acid solution forms a nitromamine (2 : 6-di- n.itrophe.,zyl-l-met/l.ylnitrosocrnzilze), which crystallises from alcohol in white needles melting at 115-llSo:

0.0892 gave 19.4 C.C. N, (moist) a t 2 l 0 and 761.5 rrini. N =24.8. C,H,O,N, requires N = 24.79 per cent.

That the above interpretation of the action of alcoholic hydro- chloric acid on the dinitronitroeo,amine is correct was proved by diazotising dinitromethyl-pphenylenediamine in dilute sulphuric acid solution, and boiling the diazonium sulphate with alcohol. The solution, on completion of the re'action, gave on dilution with water the 2 : 6-dinitromethylaniline described.

Be 12 zyln~ethylnce t yl-p-phenzylenediamine (p-Benz y l m e th yla-mino- acetanilide).

p-Nitroaniline was converted into its monobenzyl derivative by the method described in 1888 (Meldola and Salmon, T., 53, 774), and the product methylated by heating with excess of methyl sulphate a t looo f o r two hours. After removing the excess of methyl sulphate by heating the solution alternately with dilute

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620 MELDOLA A N D HOLLELY : ALICYLA'I'EI)

hydrochloric acid and alkali and washing with water the resulting compound was obtained pure by crystallisation from methyl alcohol.

Ifenz?/lnzethyl-p-~Eitrocrnil.ine crystallises in silky, yellow needles, melting a t 68-69O:

0.1144 gave0.2915 CO, and 0.0630 H,O.

&4ll attempts t o prepare ammonium derivatives from this com- pound led tot negative results. Methyl and ethyl sulphates leave the benzylmethylamino-group unchanged, and heating with alkyl iodides results in the detachment of benzyl.

The base, benzylmet?~pl-p-phenylenediamine, was obtained from the foregoing compound by reduction with tin and hydrochloric acid in the usual way. The1 hydrochloride separatles in white needles on concentrating the solution after removal of the tin as sulphide. I n order to characterise the compound a toluene- sulphonamide was prepared by agitating a hot aqueous solution of the hydrochloride with alkali and toluenesulphonyl chloride. A product insoluble in alkali was finally obtained, and this on analysis proved to be the di-derivative (I):

C = 69-49 ; H = 6.12. C14H1402N2 requires C=69.37; H=5*8; N=11-57 per cent.

~ ( so ,~c , H ,*CH, jz /\

NHAc /\

i I I 1

This compound crystallises from glacial acetic acid in colourless

0.1626 gave 7.7 C.C. N, (moist) a t 14O and 767 mm. N=5-62. 0.2016 ,, 0-1806 BaSO,. S=12*30.

C2,€I,,04N2S, requires N -5.39 ; S = 12.34 per cent. The acetyl derivative (11) was prepared from the hydrochloride

by the action of acetic anhydride and sodium acetate in the usual way. It crystallises from dilute alcohol in slender, white, silky needles, melting a t 110-11lo :

0.1564 gave 15.1 C.C. N, (moist) a t 19'5O and 772 mm. N=11.25. C,6€I,,0N2 requires N = 11.02 per cent.

This acetyl derivative, unlike those containing methyl and ethyl, fails to give quaternary ammonium iodides with alkyl iodides, the presence of the benzyl group apparently preventing the formation of these compounds. I f heated with alkyl iodides to temperatures above 100° benzyl is split off. Negative results were obtained with propyl and ally1 iodides, both of which combine readily with the dialkylacetyl derivatives previously described. Benzylmet8hylacetyl-

scales melting a t 217O:

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PARA-PHENYLENEDIAMINES AND DERIVATIVES. G21

p-phenylenediamine can be nitrated in acetic acid solution with the formatioll of the same dinitrophenylmethylnitrosoamine as that obtained from the other dialkyl derivatives. The benzyl is split off as benzaldehyde, the nitric acid acting also as an oxidising agent.

After numerous experiments leading to negative results the above compound has been obtained as the first representative of the true quinoneimide-ammonium derivatives. The simpler unsub- stituted compounds of this type have not yet been isolated, and unsatisfactory results have been obtained with derivatives con- taining radicles other than methyl. We hope to be able to extend the research in the required direction so as t o obtain compounds containing an asymmetiric quiTiquevalent nitrogen atom.

I n order t o prepare tl10 above compound, dimethylacetyl-p- phenylenediamine was converted into its methiodide, and the latter into the nitrate by decomposition with silver nitrate. The tri- metliylanimonium nitrate, NHAC*C,H,*N(CH~)~*NO,, crystallises from alcohol, in which it is extremely readily soluble, in flat, colour- less needles decomposing over a wide range of temperature reach- ing finally 225O. Partial dissociation takes place during crystal- lisation (Found, N = 17.26. Calc., N = 16.47 per cent.). The nitrate was nitrated by dissolving in a cold mixture of fuming nitric and concentrated sulphuric acid, and testing the solution from time to time by diluting a drop with water on a watch-glass. The appearance of a yellow, crystalline deposit indicates that the nitra- tion is complete, the process requiring for its completion about three or four hours a t the ordinary atmospheric temperature. If the solution is allowed to stand too long the yield of nitro-deriv- ative decreases. The product is isolated by pouring the nitrating solution on ice, and collectirug the precipitate, washing with water, and finally with alcohol, in which the compound is practi- cally insoluble. It crystallises in small, golden-yellow scales having no definite melting point, but decomposing a t ZOOo to 220°:

0.1003 gave 0.1386 CO, and 0.0312 H,O. C = 37-66 ; H= 3-45. 3.3191 ,, 0.4398 CO, ,, 0-1096 H,O. C=37*59; H=3*82. 0'1502 ,, 0.2066 CO, ,, 0-0534 R,O. C=37*51; H=3'95. 0'1101 ,,

N = 24.44. 23.7 C.C. N, (moist) a t 20'5O and '756.5 mm.

C9H,,0,N, requires C = 37.88 ; IT = 3.89 ; N = 24-57 per cent.

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622 DURRANT: THE ACTION OF STANNOUS CELORIDE ON

Tlie compound has the properties attributable to a quinoiieimide derivative, but a inure detailcd study will be necessary in order t o confirm the coiisti Lution assigned. Tlie only doubtful position is that given to the third nitro-group which is assumed to be in position 5 (instead of 6,) by virtue of the analogy t o the product of nitration of the dialkylacetyl derivatives previously sliown to have the nitrocgroups in positions 3 and 5. The quinoneimide-ammon- ium compound dissolves in cold hydrochloric acid with the forma- tion of a salt of the hype shown in the above formula. The solution of the salt is colourless, and the yellow quinoneimide crystallises out unchanged on neutralisatioii with alkali. This quinoneimide is unstable, and no definite derivatives have as yet been obtained. The acid solution if 1ieat)ed t o near it6 boiling point decomposes with the evolution of gas, and the formation of a crystalline substance volatile in steam. These products have not yet been examined in detail, as the original compound is difficult to prepare in quantity, and the yield of decomposition products is etxtremely small. There can be no doubt, however, that the decomposition of the quinoneimide by heatIng with acids is the result of the complete disruption of the benzene ring. The ring-system appears to break down also when the nitro-groups are camplstely reduced by tin and hydrochloric acid.

I n carrying out the foregoing research we have received valuable assistance from Mr. H. S. Foster, t'o who'm we desire to express our thanks. We are indebted also t o the firm of Read Holliday and Sons, Ltd., of Huddersfield, f o r supplies of many of the maberials required for our work.

CITY AND GUILDS TECHNICAL COLLEGE, FINSBURY. [Received, ApriE 21st, 1915.1

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