465
80ME NEW AZO-COLORS.
Tlie following papers hy H. A. Mott, Jr., were announced f o r the next meeting : 1. “ A1,sorption of S u g a r by Bone Black.” 2. “ Practical Determination of t h e S u g a r of Coinnierce.” Tlie meeting adjourned.
F. CA4SAMAcTOR,
Reco)w?:iugSecretary, pro tern. XXXIV.--SOME NEWAZO-COLORS. BY JAMES H. STEBBINS. JR.. B. S When I first began the study of the azo-com1)OuiidP, I selected aH m y starting point the action of diazoheiizole upon the amine$, amides, and phenolls, reserving the privilege of e x p e r i m e n h g with the higher diazo-compoundn at some future period. T h e following compounds are the result- of my experiments : AzohenzoZe-trirLitroo~~ybei/zoZe. -(:,H,N=NC,H(
NO,),OH.
This compound was obtained by treating an alcoholic solution of picric acid with an aqueous solution of one molecule of diaxobrnzole nitrate. After standing a short time the liquid became filled with long, brown needles These had then t o he filtered rapidly, an only a short contact with the mother liquor was sufficient to decompose them. T h e y were then washed several times with cold alcohol, and dried in the air pump, over sulphuric acid. W h e n dry, they appear as long, brown, prismatic: needles, with a strong metallic lustre. They are very explosive, a temperature of about i o ” C. being sufficient t o explode thein. T h e melting point could not be obtained, owing t o this circumstance. T h e y are insoluble in cold, but slightly soluble in boiling water, under partial decomposition. On the other hand, they are readily dissolved in warm alcohol, with a pretty yellow color. T h e analysis of the above compound leads t o the following result : THEORY.
C l 2 . ,. . 1 4 4 . . .. H, .... 7 . . . . N, . . . . 70 . . . . 0, .... 112 ....
43.21 2.10 21.02 33.67
FOUND.
. . . . . . . . . . . . . . . . . . . . . . . . . 43.83 ........................... 2.59 ........................... 20.93 .............................
-
-
333
100.00
-
? I
1liese figures prove the correctness of the assumed formula, viz. (:J~~-X=N-(-)JI
:
(~o,)~oii.
1zobe?l d c - p y r q pr N d .-4‘61 I,- -S =S -C6 11, ( 0€1):,. I his was obtained by t r u t i n g an d k l t l i i i c solution of pyrogallol, a
- 1
with an aqueons solution of I mol. hf diazoijc~iizolcnitrate. Tmmediately a brick-red precipitate is formetl, which iticreascs on standing. It was then collectecl on ii tilter, w a s l i d with :i little aicoliol, and dried. I t dissolves i n glacial acetic: a(4d and nitroheirzolr, f i w m which it crystallizes in dark, rid-brown needles. An alcolialic~solution of these dyes silk and wool of a pretty old-gold c:olor, without mordants. T h e analyses gave the following results : ’rrl ~o R Y.
POL XI).
Anal. 1.
Anal. 2. . , 1 4 4 , . . . ~ 2 . 6 0 .. .. . . . . . . . . . . . . . . . . e 2 . x HIO.. . . I O . . . . 4.34 . . . . . . . . . . . . . . . . . . . 5.2:3
c12.. N, . . .
2 8 , . . . 20.Hb:.
os . . . .
481..
..
-
.............
.-
. . . . - --
-
___
.___
230
....
_-
12.20
100.00
These figures evitleritly I
d to the following forniula
(‘,I is-X=X-(-’eIIz(
:
OH)*
~.izo6enzolt.-~,syccrrho~~yZbe~~zoZ~,.--C’,Ii,--N--i‘--C’,H,~~00H /OH .
‘ h i s pretty orange dye was obtained by the action of diazo1)eiizole nitrate, on an alkaline solution of salicylic acid. It crystallizes in orange-red needles, which a r e insoluble in water, hut easily soluble in alcohol or ether. If this compound Ire treated with strong sulphuric acid it dissolves, forming a sulpho-acid which, to me, has all the appearances of t h e compound obtained by P. Griess from diazosulphanilic anti salicylic: acids. ~
Izosrs~kosylhei(zole-(,hloroyZ~cc.iiL.
This was produced by the action of diazosiilphanilic acid on a n alkaline solution of phloroglucin. A heavy orange precipitate is thus formed, which is collected on a tilter, dissolved in water, and precipitated as a soda salt, by means of cornmon salt. T h e compound thus obtained has the appearance of an orange crystalline powdey, and is easily soluble in water. T h e free acid may be obtained by treating a concentrated aqueous solution of
467
ROME N E W AZOCOLORG.
t h e soda salt with an excess of strong hydrochloric acid. lizes in thin, orange tablets, with a beetle-green lustre. Animal fibre is dyed a tine orange with these.
It crystal-
Azoberizo2e-dior~~i~otol~cole Nitrute.
This pretty orange dye stuff is obtained b y treating an aqueous solution of diazobenzole nitrate with a solution of alpha taluylendianiirie, m. pt., 99'. Immediately the mixture assumes an orange-red color, and, after an hour's standing, the liquid becomes tilled with fine, rcd needles. These are then thrown on a tilter and allowed to drain ; they are then dihuolved in boiling water, and the base is set free with ammonia, in the form of a yellow colored, crystalline precipitate. These crystals a r e then washed, and dried a t 100'. T h e analysis leads to the following formula : CaHb-N=N--C'aHg ( X H 2 ) g CHP c,, . . . . . . . . . . . . . . . . . . . . .68.35 per cent.
HI,. . . . . . . . . . . . . . . . . . . . . . . . . N, . . . . . . . . . . . . . . . . . . . . . . .
5.61 .21.60
"
''
T h e base unites readily with acids to forni salts ; but the best form of salt is the chloride, as it is by far the most easily soluble and cow venient to handle. If a concentrated solution of the chloride be treated with an aqueous solution of zinc chloride, a heavy, crystalline, orange-red precipitate of the zinc double salt is formed. Platinic chloride produces a precipitate of beautiful crimson needles, which constitute the platinum salt. If this dye be dissolved in strong H,SO,, and heated for a short time, and then thrown in cold water, a heavy precipitate is formed, which constitutes the sulpho-acid. This dissolves i n water readily, but has a browner tinge than the previous dye. Reducing agents decolorize the solution, regenerating toluylendiamine. I)ia,iLick,nzoicrrj~if~(~let~e Hydrochlorate.
C,,H;N=N-C,,H,(hTH,).,HCI. I obtained this brown dye by the action of diazoiiaphbhaleiie hydrochlorate in aqueous solution, oil a solution of iiaphthalene diamine dissolved in alcohol. If a little of the solution be evaporated, the coloring matter will crystallize out in long, brown needles. These are insoluble in water, but quite readily soluble in alcohol.
