USRE12557E - of basel - Google Patents

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- 55; f irNITEn STATES PATENT OFFICE.

\THiLo "KROEBER AND (JARLJAGERSPACHER, OF BASEL, SWITZERLAND, 1 IFASSIGNORS TO THE FIRM OF soom'rY or CHEMICAL INDUSTRY IN I "BASLE, or BASEL', SWlTZERLAND.

Azo DYE AND PROCESS OF MAKING SAME.

To all'whom it may concern."

-Be it known that we, THILQ KROEBER,. chemist and do cto'r of hilosophy, a subjectof the Duke .of Sam-X1 I JAGERSPACHER-,Cheini8t and doctor ofphilos- Specification of Reissued Letters Patent. Reissued Nov. 13, 1906.

' Original Nc-'79 7 ,441, dated August 15, 1905. Application for reissue filed August '1, 1906 Serial No. 328.820-

o by, a subject of. the Em eror of Austria liner Ber,

ungary', both 'ifesidents Base], Switzerland, have invented new and useful Improvements in theManufactureof Monoazo Dyestuflafof the following is a specifica- Accordii% fiublished statements (Berformation of correspondin quinone alcidsthat is tosay, its action is t e same as that of nitric acid-'namely,',an oxidation. In German patent specification No. 155,083 it is 1 stated that '1 :2g4zamidonaphtholsulfonic acidfor exam 1c, in the presence of organic acidsmay bei iazotized and the diazo com pound. may be combined with resorcinol.

As a fact, in this case also the process leads to the formation in considerable proportion of quinoneacid as-can be gathered frOmthe 1 evolution ofred vapors and by the formation ofnap'hth'o uinoneanil when a sample of the dia;gtized l1 uidis heated with anilin, while 'thereis ro' uced 1n sma proportion with .I'esorcino a dyes'tufi' soluble in sodalye to a violet-colored solution. .Thus the existence of'a normal diazonaphtholsulfonic acid is.

'the'basicsodium salt' of, 1:2 :4-amidona hftholsulfonic acidis treated with the ca cu lated-pr'oportion .or with a slight excess of acetic anhydrid at a reduced or] at .ordinary I temperature aeetylization occurs, the acetyl group apparently attacking nearly exclusivgly the droxyl P- for Instanc the liquid containing the product ofvthe reaction (in case' an excess of anhydrid has been used a corresponding excess of alkali is .added, so thata-t the end of the acetyliz'ation all may be completely; dissolved and the re-' action to red litmus may be eyen -feebly alkaline) is mixed with'mineral acid and nitrite while cooling with ice until even after lengthy waiting iodin paper still shows a reaction,

tenburg, and GARL' s 23)"nitroi1s acid acts onthe sulfonic acids of ,1 :2-arnidoiiaphthol with there is obtained a d'iazocompound which separates as yellow crystals andmay be easily coupled with azo dyestuff component's. 'Fromits behavior it appears to be orthoacetoxydiazonaphthionic acid. It .c'o'mbines, for example, with b'eta-na hthol to form a red dyestufl, which gradual y or more quickly,=when warmed, passes to a greenishblued .estufif in consequence of the elimination .0 the acetyl group. This elimination occurs also when the said diaz'o compound is allowed to remain long-at rest. Already after the lapse of an hour it is found that a sample treated with anualkaline solution of beta-naphthol does not combine immediatel and-with'a red color, but more gradually wit a yellowisheen and, later,a blue color'a benaphtholsulfonic acid, which, indeed, is char-'- acterized by great stability toward heat. However, as was to be expected, it difiers by the more gradual cou ling'tendency from'the. corresponding acety derivative." The diazonaphtholsulf'onicacid is somewhat sparingly soluble in water containing mineral sa ts, but more easily soluble in pure water. It is easily obtained as beautiful small lustrons laminae by preparing the aforesaid dia'zoacetnaphtholsulfonic acid in a somewhat dilute solution, eliminating the acetyl group either by leaving thesolution to itself or quite gently warming it and mixing the clear solution with common salt or potassium chlorid. When a stronger solution is being worked, the separationoccurs even without common salt. The manufacture is illustrated by the following example:

23.9 kilos. of .1:2-amidonaphtol i-sulfonic.

acid are dissolved in two hundred-liters water with aid of twenty-nine kilos of soda-l e of thirtyper cent. NaOH and acetylized means of" eleven kilos of acetic a'nh dr1 d at av temperature below 0 centi gra e while good stirring ismaintained; Af-

ter a short time therezare addedto the .solution, which should have neutral orfeebl y alkaline reaction, seven kilos of solid sodium;ni-, trite, andthe whole is acidifiedat' 0 centie grade by addin all at once thirty kilos of ordinary hydrochloric acid, whereupon the mass, immediately solidifies without any evolution ,of gas to a yellow crystalline haviorwhic must be ascribed to the diazotoo , dioxynaphthalene.

magma. Thisdiazo compound is allowed I for the manufacture of 1-amido2-acetoxy to flow immediately into an aqueous solution of sixteen kilos of lzfi-dioxynaphthalene containing twenty-eight kilos of caustic soda-lye of thirty per cent. strmigtlr- At first a violet dyestufl is formed, which already after short stirring passes to a greenblue dyestufi'. To isolate it, the liquid is acidified with hydrochloric acid and mixed with common salt. The dyestufi may eventually be purified by redissolving. The dyestufi' thus obtained dissolves in water with a violet coloration and in concentrated sulfuric acid with a green-blue coloration. lt dyes unmordanted wool in an acid bath deep Bordeaux tints, which pass to deep greenish-black when subsequently treated with chromium compounds.

Instead of eliminating the acetyl group fi'ointhe dyestuffs the acetyl group may be split off from the diazoacetyloxynaphthalenesulfonic acid before it is combined with In the foregoing example the 1:2'-ami- .donaphthol-4-sulfonic acid maybe replaced by other sulfo'derivates of 1:2-amidonaphthol-as, for instance, 1:2-amidonaphthol- (i-sulfonic acid, 1:2-amidonaphtholl-fi disulfonic acid, 1 :2-amidonaphthol 3 6 disulfonicv acid, 850. Instead of 1:6-dioxynaphthalene other azo colorin -matter components may be em loyed. Thus, for instance, beta-naphthol or 1:5dioxynaphthalene gives a dyestuff which dissolves 1n water with a violet coloration and in concentrated sulfuric acid with a blue coloration anddyes wool in an acid-bath Bordeaux tints, passing by subsec uent treatment with chromium compoun s to blue-black. 1:8-dioxynaphthalene gives a-dyestrifi which dyes wool in an acid-oath blue tints, becoming black by treatment with bichromate.

What we claim is 1. The rocess for the manufacture of monoazo d yestuffs, which consists in acidylizing sulfonic acids of 1:2-amidonaphthol in the hydroxyl group, then diazotizing the lene'sulfonic acid and combining the resulting diazo compound matter component, as described.

2. The rocess for the manufacture of monoazo yestuffs, which consists in acet lizing 1:Q-amidonaphtholsulfonic acids 1n the hydroxyl group by treating their basic alkali salts in a ueous solutionwith acetic anhydrid, then iazotizing the so-obtained l amido 2 acetoxynaphthalenesulfonic acids and combining the resulting diazo compound with an azo coloring-matter component, substantially as described. Y

3. An improvement in the manufacture of monoazo dyestuffs, consisting in the process so-obtained acetylizing acidyl-oxynaphthawith an azo coloring-v 1mphthalenesulfonic acids, by treating the basic alkali salts of 1:2-amidonaphtholsulfonic acids with acetic anhydrid in an aqueone solution, substantially as described.

4 An improvement in the manufacture of monoazo dyestuffs, consisting in the manufacture of 1-amido-2-acetoxynaphthalene- 4-sulfonic acid, by treating the basic sodium salt of 1 :2amidonaphthol-4-sulfonic acid in an aqueous solution with acetic anhydrid.

4 5. The process for the manufacture of monoazo dyestuffs, which'process consists in acetylizing the basic sodium salt of 1:2ami do11aphthol-4-sulfonic acid, diazotizin the 1 amido 2 acetoxynap thalene-4-sulfonic acid, then combining the resulting diazo compound with an azo coloring-matter component, substantially as described.

6. The rocess for the manufacture of a monoazo yestufi, which process consists in the basic sodium salt of 1 :2-amidonaphthol-4-sulfonic acid, diazotizin the so-obtained 1 amido 2 acetoxynapi thalene-4-sulfonic acid, theneombining the resulting diazo compound with 1 :6dioxynaph thalene, substantially as described.

7. As new products the monoazo dyestuffs, containin sulfonic acids of 1 :2-diazonaph thol, whici dyestufi's dissolved in water with violet and in concentrated sulfuric acid with violet to blue colorations and which dye unmordanted wool in Bordeaux to violet tints which tints become on treatment with chromium compounds blue to black. a

8. As new roducts the monoazo dyestufi's containin t e 1 :2-diazonaphthol-4-sulfonic acid, whic li dyestuffs dissolved in water with violet and in concentrated sulfuric acid with violet to blue colorations and which-dye uninordanted wool in Bordeaux to violet tints which tints become on treatment with chromium compounds blue to black.

-' 9. Asa new product the monoazo dyestufl",

derived from '1:2-amidonalphthol-4-sulfonic acid and 1:6-dioxynaphtha ene which coloring-matter yields a violet a ueous solution, dissolves in concentrated su furic acid with greenish-blue coloration and dyes unmordantjed wool in Bordeaux shades, which shades .become greenish-black on treatment with chromium compounds, substantially as described.

In witness whereof we have hereunto signed our names, this 13th day of July, 1906,

in the presence of two subscri ing Witnesses.

THILO KROEBER. CA'RL JAGERSPAOHER.

Witnesses I GEO. GIFFoRD, AMAND BITTER.-