DIAZOHYDROXYLAMINO-COMPOUNDS, 767

LXXXVI II. -Diaxoh ydrox y la nzi9zo -conq3oz~r~ds and the Influence of Substituting G~oups 012 the Stability o j their Molecu.les.

Xy NORMAN LESLIE GEBIIARU and HERBERT BRYAN TIXOMPSON. TIIE action of P-arylhydroxylamines on diazonium salts has formed the subject of several papers (compare Bamberger, Ber., 1896, 29, 103; 1897, 30, 2280). When auch a hydroxylamine (or a P-alkyl- hydroxylamine, Ber., 1897, 30, 2282) reacts with a dinzonium salt under favourable conditions, a reaction takes place according t o the following equation :

Ar*NH*OH + ClN,*R = Ar*N(OH)*N:NIR + HCI, and a diazohydroxylamino-compound is formed (for other literature on this subject compare Walther, J. pr. Chem., 1896, [ii], 62, 144; Barr, Ber., 1887, 20, 1497 J 0. Pischer and Wacker, Ber., 1888, 21, 2609; 1889, 22, 622; Bamberger and Landsteiner, Be?.., 1893, 26, 483). These dinzohydroxylamino*compounds differ in several respecta

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768 GEBHAftD AND THOMPSON :

from the closely related diazoamines, chiefly in their behaviour towards reagents, for whilst the compound formed by the interaction of an amine and a diazonium salt reacts as if it existed in two tauto- meric forms, a similar phenomenon is not :shown by the substance resulting from a hydroxylamine and a diazonium salt ; thus the two forms :

R*NH-N:N*R, and R*N:N*N€I*R, are identical, and the imino-hydrogen atom is looked upon as being ‘ 4 mobile ” (Meldola and Streatfeild, Trans., 1887, 5 1, 102, 434 ; 1888, 53, 664; 1889, 55, 412; 1890, 57, 785). On the other hand, the two forms :

are quite distinct (Bamberger, Be?*., 1896, 29, 104). Only a limited number of these diazohydroxylamino-compounds

have been described, so tha t the preparat’ion of a further number was of interest; a t the same time the object of the research was widened considerably by the attempt to select such compounds as might lead to the determination of the influence of the various substituting groups on the general stability of the molecule.

R*N(OH)*N:N*R, and R*N:N*N(OH)*R,

Two methods are possible for carrying out this idea : (1) By using .the same /3-arylhydroxylamine throughout all the

experiments and acting on it with differeatly substituted diazonium salts, and

(2) By using the same diazonium salt throughout and acting on it with differently substituted P-arylhydroxylamines.

The former method has been adopted in the present paper, which deals only with those diazohydroxylamino-compounds resulting from the action of differently substituted Ldiazonium salts on the same P-arylhydroxylamine (compare Eamberger and Rising, Armalert, 190 1, 316, 257). The hydroxylamine chosen as typical of its class was p-toly lhydroxylamine (compare D’Orsa, Diss. FViesbccden, 1896), chiefly by reason of its ease of preparation.

The parent substance to be considered is benzenediazohydroxyl- amino-p-toluene,

C,H, N : N *N( OH) C6H4Me, obtained by the action of p-tolylhydroxylamine on benzenediazonium chloride; all the other substances described may be regarded as substitution products of this. Only mono-substituted derivatives have been considered, and those substituting groups only chosen which are commonly met with, namely : methyl, nitro-, bromo-, hydroxyl, sulphonic acid, and carbethoxyl groups.

Primarily, only the ortho-substituted compounds were prepared, and attempts were made to determine the influence of the substituting group on the pover of reactivity of the diazonium salt from con-

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DIAZOHY DROXYLAMINO-COMPOUNDS. 769

siderations of the various yields obtained (Bamberger and Rising Zoc. c i t . ) ; this method was found to be untrustworthy ; first, because of the immense difficulty in keeping the conditions OF the experiment identical €or all combinations, and secondly, because of the presence (due to secondary reactions) of substances other than the diazo- hydroxylamino-compounds, which might or might not influence the velocity of the various reactions. For these reasons, then, the pro- cedure of BLtmberger and Rising (Zoc. cit .) was not adopted. The best method of preparation for each individual diazohydroxylamino- compound was worked out, and the substances were obtained in the pure state in as good a yield as possible. The real influence of the substituting groups was then determined from experiments on the decomposition of the pure substances by specified means, and not from observations of the rate of formation of the compound in question. I n this way the infltience (if any) of any by-products formed during their preparation was entirely eliminated. The scope of the work was further increased by the inclusion of the other isomerides contain- ing substituting groups in the para- and meta-positions respectively, The re..ults of work on the decomposition of the various compounds described in this paper will form the subject of a future com-nunica- tion.

Preparation of the Diaxo~?ldrozylamino-com~oun~s. The method made use of in each case consisted in the addition of a

solution of p-tolylhydroxylamine in 90 per cent. alcohol, and cooled to about -5' to a similarly cooled solution of the diazonium salt in water, the proportions of the reacting substances being those dernanded by their equation of forma'ion. The concentr&Aon in each case was kept as near as possible the same. Considerable difficulty was initially experienced in preventing the reaction from proceeding in other than the desired direction, the two most important facttors affecting this being temperature and concentration. Increase of temperature and diminution of concentration both appeared to increase the reducing properties of the hydroxylamine, which generally caused nitrogen t o be evolved and p-azoxytoluene to be formed. This decomposition m2y be formnlated thus :

CH,*C6 K,.NH.OH - + CH3*C6H;N0 p-To'olylhgcl* ox ylaminc. p-Xitrosotolneiie.

On ncting as n reduciiig agent

4 i t h nriotlier molecule of / unchanged hydroxylamiue.

Ic CH;C,H,*N-N.C,Fi,.CH,

'\/ 0

p - Azoxytoluene,

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770 GEBHARD AND TlTOMPSON :

The experiments on the effect of temperature and concentration were carried out initially in the preparation of o-carbethoxybenzenediazo- hydroxylamino-p-toluene, and from the results obtained it was found possible t o prepare all the subsequent substances quite easily and without the formation of by-products in any quantity.

Attempts to prepare hydroxy- and sulphonic acid derivatives were not attended by success, I n the case of the phenols, all efforts to effect a direct coupling failed, a large amount of p-azoxytoluene only resulting (compare the experience of A. Wohl, Be?., 1903, 36, 4143, 0x1 the production of similarly substituted diazoamino-compounds, who accounts for their non-formation on theoretical grounds). Regard- ing the sulphonic acid derivatives, many direct coupling experiments were tried, but owing to the poorness of the yields and the extreme difficulty found in purifying the products, further work in this direction was abandoned.

General P.rope&es of the Di~xoiL?lc~roxylan.Lino-conapounds.

All the compounds prepared by us are finely crystalline solids, show- ing a tendency to become darker in colour on exposure to light, a fact particularly noticeable in the case of the more unstable ones: the unsubstituted benzenediazohydroxylamino-p-toluene and its methyl substituted derivatives coming first in this category, whilst the more &,able ones, the nitro-derivatives, for example, can be exposed to light and the atmosphere for an indefinite period without any deep-seated change taking place. Almost all are of a faint yellow colour, which is intensified only on the entrance of a ehromogenic group, for instance, the nitro-group into their molecule, and liere is to be observed, too, the fact that, of the three different nitro-substitution products prepared, the ortho-derivative is the most highly coloured, which is evidently occasioned by the closer proximity of the nitro- and azo-groups or the two chromogenic groups to one another in the ortho- than in the meta- and para-isomerides. The melting points should be better termed temperatures of decomposition, being always attended by frothing and gas evolution, Great care is necessary in the selection of solvents for the initial purification of these Substances, as, when they are in the impure state, they are particularly easily decomposed; in some cases the mere boiling of the impure substance with acetone or chloroform, or gentle warming with methyl alcohol, was sufficient to bring about a violent gas evolution ; on the other hand, when once in the pure state they may be crystallised from almost any solvent with impunity. Generally speaking, acids have R decomposing influence (Bamberger, Ber., 1897, 30, 2284). The action of hot or cold aqueous hydrochloric acid, dilute and concentrated, i s a moderately mild one ; when applied

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DIAZOHYDROXYLAMINO-COMPOUNDS. 771

i n an organic solvent, however, its action is far more powerful. -4lkali hydroxides possess it slight solvent action, a faintly yellow solution generally !resulting, evidently attributable to salt formation owing to the presence of a hydroxyl group in the molecule. Tf the compound be initially dissolved in alcohol, the yellow colorat ion becomes more distinct on addition of alkali, and the yellow colour varies in depth with the substituting group contained in the molecule. The acidic nature of the hydroxyl group is further shown by the action of bases, like ammonia, methylamine, etc., which, when applied in absolute alcoholic solution in the cold, gradually deposit crystals of the salts; weaker bases, like aniline, do not give this reaction. It is further found that the reducing action of the hydroxylamine has not entirely disappeared, for when treated in alcoholic solution with cold ammoniacal silver nitrate, a yellow precipitate at first results (evidently due to salt formation), which gradually becomes darker and darker on slight warming, and a silver mirror is deposited, a gas evolution taking place, and an odour like that of a nitroso-compound becoming evident. Whether any reduction takes place with Fehling’s solution is extremely doubtful. One of the most characteristic reactions which these com- pounds shorn is that in alcoholic solution towards ferric chloride, when a coloration varying from a deep bluish-black to a bright grass-green is obtained (compare Bamberger, Ber., 1897, 30, 2280) ; whilst iq glacial acetic acid solution other colorations are almost invariably given with the two naphthylamines respectively.

E x P E B I M E N T A L.

p-Tolylhydroxylttmine was prepared according to the directions of D’Orsa (I1iss. Wiesbaden, 1896). On account of its tendency t o decompose, it was found necessary in all the experiments to prepare the compound immediately before use, otherwise it became so impure that it was practically insoluble in alcohol, and the yieid of the con- densation product prepared from it w a g very poor.

The following general method of preparation of the diazohydroxgl- amino-compounds was uniformly adopted. The amine, dissolved in water and hydrochloric acid, was diaxotised a t about -loo, and to it was slowly added with constant shaking a well-cooled solution of the calculated amount of p-tolylhydroxylamiue in alcohol and hydrochloric acid. The product of the reaction was immediately precipitated, and, after diluting with ice-water and keeping in the freezing mixture for a couple of hours, the liquid was filtered, the resulting solid dried on a porous plate, and recrystallised from suitable media until of constant melting point.

Benzeuediztzohydroxylarmino-p-toluene srptallises in short, flat

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772 GEBHARD AND THOMPSON :

needles, melting and decomposing at 125*5--126O (Bamberger, Ber., 1900, 33, 3508, gives 123*5--134O). It is sparingly soluble in alcohol or light petroleum, but very readily so in benzene, ether, acetone or chlorofoi m.

The substance is decomposed by warming with concentrated hydro- chloric acid. A yellow turbidity is produced by adding amrnoniacal silver nitrate t o the alcoholic solution, gentle warming cawing the deposition of a silver mirror, Ferric chloride gives an intense greenish-black coloration.

The glacial acetic acid solution gives with a-naphthylamine a faint pink, and with P-naphthylamine a yellow, coloration, both of which become deeper on wuming and eventually tnrbid. The substance is readily solitble in cold concentrated sulphuric acid to a deep yellow solution, which turns intense green on gentle warming.

0- To Zyldiaxohydrox?llamino-p-tol~ene, C6H,MeoN N*N( OH)*C,H,Me, crystallises in pale yellow, columnar, glassy prisms with domed ends, and melts a t 103.5'. The compound is rather unstable, particularly when in an impure state. It is spavingly soluble in cold methyl alcohol and light petroleum, more readily so in ethyl alcohol or ethyl acetate, and easily so in ether, chloroform or benzene; on warm- ing, however, it dissolves very readily in all these solvents :

0.1750 gave 0.4480 CO, and 0*1040 H,O. 0.1458 ,, 22.3 C.C. N, a t 20.5" and 764 mm. N = 17 54.

On warming the substance with 2N-sodium hydroxide, the solution turns yellow and a gas is evolved. The addition of ammoniacal silver nitrate to an alcoholic solution of the substance occasions a yellow precipitate, which rapidly darkens on warming, gas being evolved and a silver mirror deposited. Ferric chloride gives a deep bluish-black coloration, which assumes a green tinge on heating. a NaphthyI- amine gives a yellow coloration, turning a deep reddish-brown on warming ; with /3-naphthylamine the colour changes from very faint magenta t o red. The substance is soluble in cold concentrated sulphuric acid to a deep green solution, and its glacial acetic acid solution decomposes on warming. m-Tolyldiazohydroxylaccmino-p-toluene, C,H,~e.N:N*N(OH).C,H,Mc,

crystnllises in long, slender, yellow prisms, the domes a t t he ends of which are sharply defined ; it melts at 136.5".

It is sparingly soluble in hot or cold ether or light petroleum, more readily so in alcohol, benzene or acetone, and very readily so in chloroform :

0.1691 gave 0.4342 CO, and 0,0959 H,O. 0.1351 ,, 20.3 C.C. N, at 18" and 756 mm. N=17*26.

C = 69.81 ; H = 6.60.

C,,H,,ON, requires C = 69-72 ; H = 6-32 ; N = 17.43 per cent.

C='70*01; H ~ ~ 6 . 3 0 .

C,,H,,ON, requires C = 69 *72 ; H I- 6.22 ; N = 17.43 per cent,

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DIAZO€IYDROXYLAMINO-CORIPOU NDS. 773

The substance is readily decomposed on warming with hydrochloric acid, both concentrated and dilute. Ammoniacal silver nitrahe is rapidly reduced, a fine silver mirror baing deposited.

Ferric chloride, produces a beautiful bluish-black coloration. a-Naphthylamine causes a magenta, arid /3-naphthylarnine a yellow,

coloration. Cold concentrated sulphuric acid dissolves the substance, forming a fine green solution, which turns brown on warming.

p- ~~ZylJia/xoh~drox~/Iccmi.rzo-p-toZ~ene, C,H,Mo*N: N*N(O R)*C,H,Me, crystdlises in long, slender, can my-yellow prisms, melting a t 130.5'. It is sp:tringly soluble in light petroleum, alcohol, glacial acetic acid or ether, dissolving more readily in acetone or chloroform :

0.1950 gave 0.4960 CO, and 0.1 136 H,O. 0.1320 ,, 19.6 C.C. N, a t 16Oand 757 mm. N=17*26.

The substance is rapidly decomposed by warming with hydrochloric acid. Ammoniacal silver nitrate is reduced with deposition of a silver mirror. Ferric chloride gives a greenish-blne-black coloration ; a- and P-naphthyhmines produce magenta and deep yellow colorations respec ti vel y.

C = 69.44 ; H = 6.47.

Cl,Hl,0N3 requires C = 69-72 ; H = 6.22 ; N = 17.43 per cent.

o-C~P'bet~oxybertxe~aeclia~oZL~drox~Ianaino-p-toZue~ae, COaEt*C,H;N:N*N(OII)9C~H~~e,

-This cmpound was the first of the series prepared in the course of the present investigation, and many experiments were carried out with the view of ascertaining the most suitable conditions of tmipcrature and concentration. The former is apparently a most important factor, since, at a temperature of about lo", the hydroxylamine exerts a reducing action on the diazo-compound, and is thereby oxidiied to p-azoxytoluene, very little, if any, of the diazohydroxylamino-coni- pound being formed.

On carrying out the experiment, however, a t - 5", the diazohydroxyl- amino-compound was obtained i n long, slender, pale yellow prisms melting a t 122.5O. It is sparingly soluble in cold light pet'roleum or alcohol, more readily so in ether, and very easily so in benzene, chloro- form or acetone :

0.1362 gave 0.31'75 GO, and 0.0720 H,O. C = 64.31 ; H = 5.S7 0.1764 ,, 22.3 C.C. N, a t 13" and 745 mm. N = 14.02. C1,H1103NY requires C = 64.21 ; H = 5-69 ; N = 14.05 per cent.

Hydrochloric acid is apparently without action on the substance, and ammoniacal silver nitrate is only reduced to a very slight extent even on boiling. Ferric chloride gives a dark greenish-blue coloration, whilst a-naphthylamine produces a pink, and P-naphthylamine a red, colour. Concentrated sulphuric acid dissolves the substance in the cold to a deep yellow solution.

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774 GEBHARD AND THOMPSON :

m-Cai.6et~oxybernxened~a~o~~y~roxykto-p- toZuene, C02Et* C6H4*N:N*N( OH) C,H,Me.

-This compound is almost identical in appearance with the corre- sponding ortho-derivative, and melts a t 149-150". I t is sparingly soluble in all the common organic solvents with the exception of chloroform ; on warming, it dissolves readily in glacial acetic acid, benzene or alcohol :

0.1395 gave 0.3289 CO, and 0 0711 H,O. 0.1239 ,, 15-7 C.C. N, at 2l0 and 756 mm. N = 14.35.

C = 64.30 ; H = 5-66,

C,,Kl7O3N3 requires C = 64.21 ; H =.5.69 ; N = 14.05 per cent. -The substance is decomposed by warming with dilute hydrochloric acid, and ammoniacal silver nitrate suffers reduction in the cold, a faint silver mirror being formed on warming. Ferric chloride pi-oduces a fine blue coloration, and a- and P-naphthylamines give pink and yellow ones respectively. The substance undergoes decomposition on warming with alkalis.

p- Carbethoxp benxeneclic~xol~~droxylamino- p-tolzcene, C 0,Et C,H;N : N* N( 0 H) C,H,Me.

--This compouiid crystallises in canary-yellow, long, slender, hair-like needles with glistening, silky lustre, and melts a t 144-145'. It is very sparingly soluble i n light petroleum, more readily so in alcohol or ether, and very easily so in chloroform, benzene or ethyl acetate :

0.1494 gave 0,3497 CO, and 0*0'771 H,O. 0.1543 ,, 19.8 C.C. N, at 25' and 767 mm. N = 14.45.

C = 63*S3 ; H = 5.73.

C1,H1703N, requires C = 64-22 ; H = 5.69 ; N = 14.05 per cent. -Hydrochloric acid is without action on the substance, and ammoniacal silver nitrate shows only a trace of reduction even on boiling. Perric chloride gives a blackish-green precipitate, a i d a-naphthylamine produces a pink, and P-naphthylamine a yellow, coloration. The substance is readily soluble i n cold concentrated sulphuric acid. 0- Nitrobenxenediaxohydrox~~am,i~o-p-tolue?ae,

NO,*C,H,* N:N*N( OH)*C,H4&le, was obtained as a brilliant, golden-orange-colonrod substance, crystal- lising in fine, apparently monoclinic, plates melting a t 1 $3-173*5O. It is very sparingly soluble in ether or light petroleum, more readily so in alcohol, acetone, bonzene or glacial acetic acid, and dissolves easily in chloroeorrri :

0.1583 gave 0,3319 GO, and 0.0659 H20. C = 5'7.19 ; H = 4.62. 0.1320 ,, 23.2 C.C. N, at 11' and 743 nun. N = 20-48.

C1,H,,O,N, requires C = 57.34 ; H = 4.41 ; N = 20.58 per cent. The substance is unacted on by hydrochloric: acid, but ammoniacal

silver nitrate suffers reduction slowly on heating. Ferric chloride produces a greenish-yellow coloration, turmixig brown on warming.

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DIAZOHYDROXYLAMINO-COMPOUNDS. 775

The naphthylamines give no colour reaction in the cold, but, on warming, a very deep red is produced in both cases. On warming with alkalis, a deep red coloration is obtained, which on the addition of alcohol becomes a very deep crimson. The sulphuric acid solution possesses a deep red colour.

m- I~ii lrobe~axenediuzohydroxyZa~~no-p-toluene, N0,*C6H,*N:N=N(OH)*C,H,Me,

crystnllises in long, slender, sharply pointed, bright yellow needles melting at 1S4", much resembling masses of thorns in their manner of grouping.

Tn the cold i t is very sparingly soluble in the conmion organic solvents ; on warming, how-ever, it dissolves rather more readily i u glacial acetic acid, benzene, toluene or chloroform :

0.1377 gave 0.2880 CO, and 0,0589 H,O. 04925 ,, 16.4 C.C. N, a t 21' and 763 mm. N=2098.

The substance suffers slight decomposition on heating with con- centrated hydrochloric acid. It; is questionable whether ammoniacsl silver nitrate undergoes reduction, the yellow precipitpte initially formed gradually turning brown on prolonged boiling. Ferric chloride gives a dark green coloration, which assumes a violet tinge on warming. The naphthylamines produce no coloration in the cold ; on warming, a reddish-brown colour is developed in both cases.

C = 57.03 ; H = 4.75.

C,,H,,O,N, requires C = 57.34 ; I3 = 4.41 ; N = 20.58 per cent.

p -i2'itrobenneer~edine07~y~roxylamino-p-t0 Zuene, NO,*C,H,*N :N*N (OH) *C6H4Me,

crystnllises in long, sharply pointed, bright yellow needles and melts a t 1 SS", the melting-point being, however, rather dependent 011 the rate of heating. It is very sparingly soluble in the cold in the usual organic solvents, but dissolves fairly readily on warming in chloroform, glacial acetic acid or benzene :

0.1567 gave 0.3282 CO, and 0.0625 H,O. C = 57.13 ; H = 4.43. 0 0954 ,, 17.1 C.C. N, at 2 2 O and 766 mm. N = 20.48.

C,,H,,O,N, requires C = 57-34 ; H = 4.41 ; N = 30.68 per cent. Hydrochloric acid has no action on the substance, and nnimoniacal

silver nitrite produces a bright scarlet. precipitate, permanent on boiling. The naphthylamines give no coloration even on warming, but ferric chloride gives a sage-green coloration, wliicli turns brown on heating. On warming with alkalis, the solution becomes pink and eventually dark red, almost chocolate.

o-Uromobenxe.nediaxohyclroxylclniino-p-tolue~aze!, C,H,Br*N :N*N(OB)*C,H 4M.e.

-0-Bromoaniline was prepared by the reduction of the corresponding nitro-compound according t o Fittig and 1pfager's method (Ber., 1874,

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776 DIAZOHY DROXYLAMINO-COMPOUNDS.

7, 1175). A departure from this method was, however, made in order to isolate thO pure substance, dry hydrogen chloride being passed into the dry ethereal solution of the arnine, whereby its hydrochloride wag precipitated as a pure white solid in an almost theoretical yield.

The diazohydroxylarnino-compound crystallises in slender, faintly yellow needleg melting at 92". It is very readily soluble in all the Common organic solvents with the :exception of alcohol and light petroleum, in which it dissolves rather more sparingly :

0.1455 gave 18.1 C.C. N, a t 14" and 729 mm. 0,1279 ,, 0.0'780 AgBr. Br=25*95.

C13H120N,Br requires N = 13.73 ; Br = 26.14 per cent.

The substance undergoes slight decomposition on heating with concentrated hydrochloric acid. Amuaoniacal silver nitrate is rapidly reduced on warming. Ferric chloride gives a very intense green coloration, and a- and P-naphthylamines magenta and pinkish- yellow ones respectively.

N = 14.03.

m- Bromo benxenediaxoh ydroxy ?amino-p-toluerta, CGH4Bi *N :N*N( OH) C,H,Me,

crystallises in very pale yellow, long, striated needles melting a t 173'. It is very sparingly soluble in light petroleum or glacial acetic acid, rather more readily so in alcohol, acetone, benzene or ether, and dissolves very easily in chloroform :

0.1480 gave 17.45 C.C. N, at 13" and 758 mm. 0 1361 ,, 0.0836 AgBr; Br=26*14.

The substance is unaff ectetl by hydrochloric acid, but ammonixcd silver nitrate gives a yellow precipitate, which darkens rapidly on warming. Ferric chloride gives a greenish-black coloration, but a- and P-naphthylamines are without action in the cdd, although, on warming, rose-pink and p de yellow colorations are produced, which ultimately become turbid.

N = 13.90.

C,,H,20X3Br reqiiires N = 13.73 ; Br = 26.14 per cent.

p-Bromo benzmediazo?h y droxylami no- p-t olzcene, CGH,&Br*N :N *N(OH)*CGH4Me,

crystallises in fine hair-like, pale yellow needles melting at 162' It is vary sparingly soluble in light petroleum, alcohol, ether o r glacial acetic acid, more readily so in benzene or acetone, and very easily in chloroform :

0.1536 gave 18.1 C.C. N, a t 13' and 763 mm. 0-1868 ,, 0,1153 AgBr. Br = 26.26.

C13H,,0N3Rr requires N = 13.73 ; Br = 26.14 per cent. Hydrochloric acid is without action on the siibstarice, but ammoni

acal silver nitrate gives a yellow precipitate, which rapidly darkens on

N=13*98.

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EXPERIMENTS ON ?'HE WALDEN INVERSION. PART 11. 777

heating. Ferric chloride gives an intense bluish- black coloration; a-napbthylamine gives a faint pirik colour, which deepens on warming, whilst P-naphthylamine on warming produces a pale yell ow color- ation,

Work on the stability of these various compounds is approaching completion, and will, it is hoped, form the subject of a further com- munication at an early date. I n conclusion, the authors desire to express their indebtedness to the Research Fund Committee OF the Chemical Society for a grant which has partly defrayed the expenses of this investigation.

CHEMICAL LABORATORY, TECHNICAL COLLEGE,

DE~UKY.

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