XXTTIII.--On
Q o m NEWC O L ~ R I XMGA w E i t s , PRODUCED HY THE
A C T I O N OF r ) I A Z O - ( ' O M P O U N U S OX P H E N O L S .
BY JAS.H. S r r ~ n i mJ ~i i .. , B.S.
T h e study of the action of diazo-compounds on phenols dates back a good inany years, but i t is only withiii the last few years that it has nict wit,h any practical si~ccess,and 1 will now take the opportunity to givc a hrief sketch of some of t h e most intcwsting and valriahle comlmiinds, before entering on the tiescription o f my own results. In 1875, P. (+ricw made the discovery t,hat diazobenzofesulpho acid (froni sulphanilic avid), actiiig on phenols, produced a series of intel-esting compounds, which were characterized by more or lws' tinctorial power. In the spring of the following year, he sent a communication to t h e German (:hemic.al Society,* describing this reaction. l'hc great tinctorial power of these new conipounrls lead him to believe that they might be used with advantage in dyeing and printing, and several samples senb t o an expert on colors, proved that his theory was correct, as may now be seen by the great demand for Poirrier's oranges, Nos. 1 and 2, chrgsoine, tropaeoline, aeclit-roth, roccelline, etc. Among this group t h e following compoundst d t w r v r special att,ention, viz : I
I
1
4
P c t r a z o s u ~ ~ k u z y l b e i ~ z o l ~ ~ hC',H4(IIS0,) ei~ol, - N = x' - C,II,OH. This is prepared by the action of di:tzosiilp1ianilic acid on an alkaline solution of phenol, these two being t;tken i n equal rriolecules. T h e yellow-red liquid thus produced, is ; ~ l I o ~ v eto~ lrest for A short time, then heated to boiling, and saturated with acetic acid. On cooling, a large number of little ycllow leaflets crystallize out, and constitute the acid potassium salt. T h e w are thcri collected on a filter, dissolved i n water, and purified b y boiling a short tirne with a little animal black. The free ncG1 may bc obtained by treating a hot and concentrated solution c,f the acid potash salt with a large excess of strong hydrochloric acid. I t i s purified by washing with dilute HCl, and finally crystallized from an acidified aqueous solution. It crystallizes from its concentrated aqueous solution in yellow-red prisms, with a strong violet lustre. It is pretty soluble in alcohol, but nearly insoluble in ether or hydrochloric acid. _ _ ~
* H e r . (1. ti. clicm. Gescll., 9, 627. t I k r . d. d. cliem. Gcsell., I I, 2192.
237
ON SOME N E W COLORING M A l T E R S , ETC.
Nitric acid, even diluted with 3-4 times its bulk of water, decomposes it, with formation of yellow, oily drops, which, after a while, crystallize. This acid has the property of forming acid and neutral salts, with bases. T h e acid potassium salt, C,H,N,SO,R, may be prepared, besides the already mentioned method, by treating a hot solution of the acid with chloride of potassium. The following compounds are prepared in exactly the same manner as the previous one, and in their description I will only call your attention to some of the more particular differences. 1
4
1
MetazosuZpi~oxyZbenzoZephenoZ,CJI,(HS!O,) -N = N - C,H4(OH). This is prepared by the action of metadiazobenzolesalpho acid on an alkaline solution of phenol. It is easily soluble in water and alcohol, but insoluble in ether. 1 3 4 AzobenzoZesuZphoxyl33henol, C,H, - N = N - C,H3(HS03)(OH), prepared by the action of diazobenzole nitrate on an alkaline solution of orthophenolsulpho acid, The free acid is easily soluble in water and alcohol, but nearly insoluble in ether. 1
4
ParazosuZphoxyZbenzoZeorthonitrophenoZ,C,H,(HSO,) - N = N 2 4 - C6H3(N0,)(OH), prepared by the action of paradiazobenzolesulpho acid on orthonitrophenol ; crystallizes from alcohol in pretty, yellow needles. 1 Parnzosu~hox~Zbe~~~oZeresorcine,C,E14(H~0,) -N=N--C,II,( OH),, prepared from paradiazobenzolesulpho acid and an alkaline solution of resoruine. The free acid crystallizes in pointed leaflets. 3
1
~etazosu~hoxy~beiizo~eresorcine, ~,H,(HSO,)-~=~-~,H,(OI~),, prepared in the same way as the previous compound. 1
4
ParazosiclphoxyZbenzoZeorc~)ie,C,H,(HSO,) -N =N -C,lT,(OH),, crystallizes in sinall yellow-red needles. 4
1
Parazosu~hoxyZbenzoZesaZ~cyZic acid, C,H,(HS03)-N =N - C6H3 1 (OH) (COOH), pretty, yellow needles, soluble in alcohol. I should like to call your attention here, to the fact, that this is 2
the compound I meirtioned in my last paper and which is so similar t o the body I described as azobenzoleoxycarboxylbenzole (JOURNAL AMERICAN CHEMICAL SOCIETY, I , 466).
Azosu~hoxylxyloleresorciize,CsH8(HS0,)- N =N - CJ13(OH)2, pretty, yellow-red needles, soluble in alcohol.
238
ON SOME NEW COLORINQ MATI'ERS,
hTC.
h
Metazosulphoxylbenzole-a-naphthol,C,H,(H & ( ~ f ~ ) ~Ifj equal , mok?cules of diazosulphanilic acid and phlorogliicine arc allowed t o react on one another, the result is a heavy or:irige colored precipitate, aliich is collected on a filter, dissolve(1 i i i boiling water, and precipitated with coinnion salt, i i i the form of a s o d a salt. T h e sods salt is crystallized several times from hot w a w r , and is t l i c i i in a pretty pure state. 4
1
Soda salt, C,H,(NaSO,) - N = h' - C:,H,(OH),, fine orange wystalline powder, easily soluble in water. T h e free acid may be obtained from this by treating t h e concentrated aqueous solution with an excess of strong hydrochloric acid. 1
4
Free acid, C,',Z14(RS0,)--hT=N--0,FI,(OII),. Thin orange colored tables or leaflets, with a strong beetle green lustre. P r e t t y soluhle in water. Acid barium salt, (C,,H,N,SO,) Ea, obtained by treating a concentrated aqueous solution of the free acid with a strong soliitioii of baric chloride. Orange colored leaflets, less soluble in water tliaii the soda salt. If we look back a few steps and demand the structure of this compound, the answer will be found in its reduction products ; for, if the free acid be treated with tin slid hydrocliloric acid, arid the solution thus obtained is freed from tin by means of sulphuretted hydrogen, sulphanilic acid and aniidophloroglucine may be extracted from the mixture. T h e reaction t h a t takes place here is as follows : 1
1
C,€I4(HSO,) - K = K - C'JI~(OII)3 + eH,= Ci,H4(€ISO,)NII, + ('JI,( NH,) (OH),, Therefore, as t h e HSO, group in sulphanilic acid is in the para
ON SOME N E W COLORING MAITERS, W C .
241
position, it is evident that it must hold the same position in parazosulplioxylbenzolephloroglucine. This compound is of particular interest, as it is very similar to, and moreover, an isomere of azobenzolepyrogallol, the only difference being that the latter does not contain the HSOs group, while the former does.
Azobenzolesu~hocresole,C,H, -N = N - C,H,(HSO,)CH,(OH). If an alkaline solution of cresolesulpho acid be treated with an aqueous solution of diazobenzole nitrate, the result is a deep orange colored oily liquid. If this be allowed to stand for a short time, and then be treated with an excess of strong hydrochloric acid, the acid is by this means set free, and will after a short time crystallize in long brown needles, with a stroug metallic lustre. It is quite soluble in alcohol, less so in hot water, to which it imparts an orange color. When treated with reducing agents, it splits up into aniline and amidosulphocresole, viz :
+
C,H, - N N - C,H2(HSOs)CH3OH 2H2 C,H,NH, CeHZNHZ(HSO3)(CHS) (OH).
+
I have perhaps dwelt too long in the repetition of the compounds mentioned in my last paper, but there were certain points which I had omitted at first, and I therefore take this occasion of making them known. W e now come t o eome of m y new dyes, and among the first may be mentioned
-
DinitrozyazobenzoZeorth~y$~~hoz~Zbe~zoZe, C,H,( NO,),( OH) 1 2 N=N-C,Hs( HSO,) (OH), This compound lies intermediate between Griem’ azosulphoxylbenzoleorthonitrophenol and my azobenzoletrinitroxybenzole, and may be obtained by treating one molecule of diazodinitrophenol with an alkaline solution of one molecule of
phenolorthosulpho acid. The proportions used in the experiment were : IO grms of dinitroamidophenol were treated with 5 grms of strong HCl, and a solution of 3.5 grms of KNO, in 100 C.C. of water were added. The solution thus obtained is stirred for a short time, and then poured, little b y little, into a solution consisting of about 5 grms of phenolsulpho acid, 2.5 grms of KOH, and 100 C.C. of water. The mixture thus produced is allowed t o rest for an hour, and the deep yellow-brown liquid is heated to boiling, and then saturated with strong hydrochloric acid. On cooling, the free acid crystallizes out in the &ape of yellow-brown needles, with a metallic lustre. These are only sparingly soluble in hot and cold water.
T h e soda salt, C,H,(NO,),(O€I) - N == S - C,H,(i\'aSO,)OH, may be obtained from the free acid by treating it with carbonate or hydrate of soda. I t is somewhat more soluble i n water thaii the free acid. By reduction with strong redueing agents (a3 tin 2nd hydrochloric acid), dinitroamidophenol and o r t h v a i i i i d o s u l ~ ~ l i ~ ~ ~are ~ h eobtained, nol according t o the followii~gequation :
+
C,II,(h'O,),OH - S = N - C,II,(SaSO,)OII ZH, C,H,(NO,),(OH)?U'FI, C,€I,(NaSO,)(NH,)OH.
+
=
I n this reaction, as, in fact, in a11 t h e others of this kind, the azogroup, --S = N-, is split in two, each iiitrogen atom taking 111) t w o atoms of hydrogen, t o form the amido compound. T h e compounds obtained in this reaction are of particular interest, R S they clearly denionstrate the positions they hold. Thus, we found that by reduction of dinitroxyazobenzoleorthooxysulphoxylbenzole, that ort2ioariiitlosulpliophei~ol was obtained, this clearly showing that the sulplio group is in the ortho position. \Ve next come t o a compound I described a short time ago, but will here again mention, viz:
Uir/ethyluzobenzoledi~~itroamidooxylhenzole, C,I€,(CHJ, - N = N - C,H(NO,),(h'II,),OH. If equal molecules of diazoxylolchloridc and dinitroamidophenol are mixed together, and the solution be kept slightly alkaline, a deep red-brown liquid is thus obtained, which is then filtered t o separate it from a black resinous substance formed at the same time. T h e filtrate is then slightly heated, aiid saturated with strong IICl aq, which precipitates the coloring matter in the form of a red-brown crystalline powder, This is then collectcd on a filter ; washed and dried. It is sparingly soluble in cold, b u t more soluble in boiling water, and easily soluble in alcohol.
+
The aqueous solution is of a red-brown color, and t h e slightest trace of acid causes a marked change of color, namely, from redbrown t o straw yellow. Owing to this phenomenon, I think the dye might be used t o advantage as a test for acids. Its formation may be expressed according to the following equation :
+
C',H,(CII,), - N, - IICl C,fI,(NO,),(NII,)ONa = C',I%3(CI13)2 - N = S - C,H(NO,),(NH,)OH NaCl. T h e free acid may be obtained by saturating the soda salt with a large excess of strong HC1.
+
243
ON SOME NEW COLORING MATTERB, ETC.
Similar t o Griess’ azosulphoxylbenz~leorthonitrophenolis : 4 1
A z o s u ~ h ~ y Z n a p h t h a Z ~ e o r t h o n i t r ~ y ~ eC,,H,(HSO,)-N ~zoZe,
1
=
2
N - C,H,(NO,)OH. This compound was produced b y treating one molecule of diazonaphthionic acid, with an equivalent amount of orthonitrophenol. T h e two substances were mixed slowly, under constant. stirring, and care was taken t o keep the solutioii #lightly alkaline until the end of the reaction. T h e deep red-brown solution, so obtained, was allowed t o rest for a few hours ; then heated to boiling, and saturated with strong HCI, which threw down the free acid in a crystalline state. Free acid. Red-brown microscopical needles, very soluble in water, with a red-brown color. 4 1 1 e Soda salt, ClOHB(NaSO,)- N = N - C,H,(NO,) - OH. Brown crystalline powder, easily soluble in water, and obtained from the foregoing by treating with NaOH aq. If we demand the constitution of this compound, the answer can readily be found in its reduction products ; for, if the dye be treated with reducing agents, as tin and hydrochloric acid, it Rplits up into paraamidosulphonaphthalene and orthoamidonitrophenol, thus showing that the sulpho group in the naphthalene nucleus, and the nitro group in the benzole nucleus, hold respectively the para (1 : 4) and the ortho (1 : 2) positions. Up to the present time no attempts had been made t o combine more than two sulpho groups in one compound, and these were either joined t o three nuclei, as in C,H,(HSO,) - N =N - C,H,(HSO,)OH, or, they were bound to one nucleus, as in C,oH, - N = N - C,oH,(HSO,),OH. Now, it occurred t o me that possibly three HSO, groups might be combined, and thus afford a new field for investigation. W i t h this point in view, the following compound was produced :
+
I’araazoszc~hoxyZ~enzoZe-~-~y~isu~hoxyZnaphth~e~e, C,€I,(H$O,) - = N -p-CloH,(HSO,),OH. This compound can be produced by several methods, giving oompounds isomeric with one another. For instance, it might be prepared by combining diazosulphanilic acid with betanaphtholdisulpho acid ; or, by treating diazodisulphobenzole with betanaphtholmonosulpho acid ; or, by treating diazobenzole nitrate with betanaphtholdisulpho acid, and then s u l e conjugating, or vice versa. All these methods would probably yield compounds similar to one another, as already stated, but the simplest method seemed t o be the
‘k
first one mentioned, namely, the combining of diazosulphanilic acid with betanaplitlioltlisulplio acid. If one molecule of dinzosulplixiiilic acid be treated with an equivalent aniourit of t~et:~~i:il)litlioltlisulpho acid (made slightly alkaline), and allowed t o rest for a few hours, tlic result is a deep orange-red solution. It is tIic,:i slightly heated and saturated with strong IIC1. On cooling, the free acid crystallizes out i n pretty, orange leaffcts, wit’li a beetle green lustrc. Thesc :we very soluble i n water with a fine orange color. ‘1‘11e sotla salt, c,H,(s~o,) - = N - /~-~,,lI,(NaSO,)OII, is an orniigcl ( d o 1 4 powder arid exceedingly soluble i n water. It can bc obtainctl from the free acid by treating it with sodic carbonate. A 1e:id salt was likewise produced by treating the free acid with plunibic acetate. Yellow powder, solublc iri water with an orange color. T i n and liytlrocfiloric acid redncc: this cornpound to paraamidobenzolesiilplio acid and arnidodisiilphoiiapl~tliol,thus showing the position held by the benzolesulplio group in the formula. This comporincl then goes t o prove that what we at first stated is possible, narncly, the combination of three sulplio groups in one compound. Isomeric with Griess’ ~iarazosulpl~oxylbenzolc-/~-naphtl~olsuI~~~ioacid, CJ14(IISOJ - h’-N - C~oI15(EIS0,)O€I, is nzobe?rzoZe tlisulphoq d i t k d , C&N = N - ~-C1,II,(IISO~,),OJI. This was obtained by treating an alkaline soliition of the soda salt of /3-1inphtholdisulpl1o acid with onc molecule of diazobenzole nitrate. ‘l’liesc two solutions were mixed under constant stirring, and t,hc heavy orange colored precipitate tliiis forrrietl, was collected on R filter, wished, dissolved in hot water, then precipitated with conirnon salt, i i i t h e form of a soda salt, alii1 finally dried. T l i c sotllt salt, C‘&X = S - /j-C,oI14(KaS0,)20H, consists of little, oraiigc colored leaflets, with strong green metallic lustre, and very soluhlc in water. ‘I’he t ’ i w acid, C,II,- N = ?; -- /~-C!loII~(HS0,)2011, is obtained from t h c soda salt by saturating an aqueous solution of the latter with an excess of strong HC1. Crystallizes in fern shaped leaflets, with strong metallic lustre; is very soluble in water and alcohol. ‘I’hc barium salt, C,H, - K = N - ~~-C,,H,Ba(SO,),OH,is obtained by treating a hot concentrated solution of the free acid with BaCI,; orange colored leaves, sparingly soluble in water. Reducing agents, as tin and hydrochloric acid, yicld aniline and amidodisulphonaphthol.
rt.
2 15
ON SOME NEW COLORING MATTERS, F;TC. 1
'
4
Parazotoluole-P-nuphtKoZ~s~~ho acid, C,H,(CH,) - N = N /3-CloH,(HS03),0€I. This pretty, scarlet dye was produced by combining equal molecules of diazotoluole nitrate and fi-naphtholdisulpho acid together, the solution being kept slightly alkaline until the end of the reaction. T h e heavy red precipitate thus formed was collected on a filter, washed, dissolved in water, and precipitated again with common salt, in the form of a soda salt. T h e soda salt, C,H4(CH,) - N =N - /3-Cl0H,(NaS0,),OH, is produced as already stated. Red-brown crystalline powder, soluble in water with a fine scarlet color. T h e free acid is obtained from this by treating with an excess of strong HCI. R e d colored leaves, with strong beetle green lustre, and very soluble in H,O. T h e barium salt, C,H4(CH,) - N = N - p-Cl0H4(SO,),BaOH, is obtained from the free acid by treating with BaCl,. Red crystalline po.wder, sparingly soluble in water. Treated with reducing agents, paratoluidine and amidodisulphonaphthol are formed. I have likewise produced the ortho (1: 2) and meta (1 : 3) azotoluole0-naphtholdisulpho acid in the same way as the previous compound, and it will not be necessary to describe the method of preparation. They all resemble the para conipound, more or less, and differ mostly in their shades ; one being yellower and the other redder. They are, likewise, pretty, scarlet dyes, and are easily soluble in water. On reduction, they yield respectively ortho and meta-toluidine and amidodisulphodaphthol. Similar in nature to Griess' parazosulphoxylbenzoleresorcine, and differing only in the color, is: I
:
1
Purazosu~hozyZ?2uphthuZe~~resorc~~e, Cl0& (HSO,) - N C6H3(gE
=N
-
This is produced by treating one molecule of diazo-
naphthionic acid with an equivalent amount of an alkaline solution of resorcine. T h e mixture thus obtained is allowed to stand for an hour, then heated to boiling and saturated with strong HCl. On cooling, the free acid crystallizes out, and may be purified by recrystallizing from water. 4 : 1 O H crystallizes in T h e free acid, C,,&(HSO,) - N =N -C6H3(oH, dark brown needles, with metallic lustre, and is very soluble in water, with a fine red-brown color.
246
ACTION O F LIGHT AND DARKNESS ON AMMONII'M CIILORIDE, ICTC.
T h e soda salt, C,,H,(NaSO,)
- N = N - C6H1(gE, is prepared
from the foregoing by treating with NaOH. Brown crystalline powder, soluble in water. T h e constitution of t h e above named compound can bc found i n its reduction products, which are rraphtliionic acid and arnidoresorcinv. 1
1
PtrrurutZibi~r~.tc,r~c~iho.cylbe~~zole-f~-tit-c)~hthol, C6I-I&r2(HS0,) - N = N - /J-C,0116011. This interesting compound was obtained h y allowing equal molecules of paradi:i~obibrornb~iizolesulphoacid and P-naphthol to rcact oii one another ; the solution being kept slightly alkaline until tlie e n d of the reaction. The mixture t h u s ohtairied
was then heated slightly atid saturated with HC'I, which precipitated the free acid i n the shape of an amorphous, orange-red niass. This was then washed, arid crystallized from water. T h e free acid is pretty soluble in hot water, less so in cold. T h e soda salt can he obtained from the acid by treating with NaOII. Reducing agents i'orni amidotribrombenzolesulp~io acid arid amidonaphthol. In concluding, I would say, that I hope next fall t o be able to give a much fuller account of these compounds, with the analytical data.
XX1X.-Ox THE ACTION OF LIGHTANI) DAKKNESS ON STANDARD AmroNruv CHLORIDEA N D TANNIN SOLUTIONS. BY A . R. LEEDS,PH.D.
In the December number of the PROCEEDINGS OF T H E AMERICAN CHEM~CA SOCIETY, L for 1578, in a paper '' On the Alteration of Standard Ainmonium Chloride Solution, when kept in the Dark," I have given a brief resumi! of tlie labors of MM. Schloesing and Muntz on the dependence of nitrification upon the presence of an organized ferment, and of the researches of Mr. R. Warington upon the necessity of darkness t o the developrnent of the nitrifying body. A standard ammonium chloride, kept in the dark, was found t o contain a determinable amount. of nitrites, and the titre of the solution t o have diminished by an amount sufficient t o unfit it for employment in Nesslerizing. These results were connected, by the author, with the transformation of the elements of ammonia into nitrous acid, under influence of fungoid growth in the dark. At the close of this article, i t was stated that t w o methods of avoiding the change were naturally suggested : '(1st. Keeping the ammonium solutions, not in
