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Publication numberUSRE11078 E
Publication typeGrant
Publication dateMay 20, 1890
Filing dateFeb 6, 1890
Publication numberUS RE11078 E, US RE11078E, US-E-RE11078, USRE11078 E, USRE11078E
InventorsAlbert Herrmann
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Albert herrmann
US RE11078 E
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

UNITED STATES PATENT OFF-ICE.

ALBERT HERRMANN, OF HGCHST-ON-THE-MAIN, GERMANY, ASSIGNOR TO THE FARBWERKE, VORMALS MEISTER, LUCIUS & BRUNING, F SA E- PLACE.

COLORING-MATTER.

SPECIFICATION forming part of Beiesued Letters Patent No. 11,078, dated Kay 20, 1890.

Original 1T0. 412,814, dated October 8,1889. Aplicatioh for reissue filed February 6,1890. Serial No. 839,496. Pstontedin Belgium September 3, 1888, No. 83,650; in France September 5, 1888, No. 192,807; in Italy September 30, 1888, XLVII, 463: v in Germany October 13, 1888,10. 48,523; in England October 15, 1888, No. 14,822 in Spain December 7, 1888, Ho- 8,810,

and in Austrla-Hungarylay 4, 1889. No. 42,683 and No. 86,618.

To all whom it may concern.-

Be itknown that I, ALBERT HERRMANN, a citizen of the Empire of Germany, residing at Hoehst-on-the-Main, in the Empire of Ger- 5 many, have invented certain new and useful Improvements in Coloring-Matter, (the same having been patented in France, September 5, 1888, No. 192,807; in Belgium September 3, 1888, No. 83,650, and in Italy September 30, 1888, No. 463, Vol, 47 in Germany October 13, 1888, No. 48,523; in England October 15, 1888, No. 14,822; in Spain December 7, 1888, No. 8,810, and in Austria-Hungary May 4, l 889,N0. 42,683 and No. 65,518;) andIdo hereby declare r 5 the following to be a full, clear, and exact description of the invention, such as will enable others skilled in the art to which it apperains to make and use the same.

In two other applications (Serial Nos. 296,389 and 296,391) for Letters Patent I have described coloring-matters which are to be considered as derivatives of the metaoxydiamidotriphenyl methane and have put prominently forward that the sulphonio acids of the metaoxytetralkyldiamidotriphenyl carbinols acid. 1 Since I have discovered that also very" leuco bases of the generic formula fast coloring-matter may be obtained by direct sulphonatio'nof the meta-amido leuco bases prepared by the second operation and subsequent oxidation of the leuco sulphon'ic 5o acids. The identical acid coloring-matter may be obtained by oxidation of the metaamido leuco bases and subsequent sulpho-- nation of the formed basic coloring-matter.

I. PREPARATION OF SULPHONIC ACID OF ME- 'RAAMIDOTETRALKYLDIAMIDOTRIPHENYL METHANE.

The sulphonie acids of the meta-amide 6.

II B 4 2 8 are obtained by heating thei'bases with sulphuric acid, or, more-advantageously, with 5 fuming sulphuric acid. I proceed as'follows:

Example N 0. 1.Thi rty parts, by weight, of meta-amidotetraethyldiamidotriphenyl methane are dissolved in one hundred and fifty parts, by weight, of fuming sulphuric acid of twenty per cent. S0,. When the. solution 1 is slightly heated or left standing for a considerable time, there is first formed a sulphonie acid the ammoniacal. salt of which is with difiiculty soluble, and therefore gives a clear solution with hot diluted ammonia only. It is therefore more advantageous,

principally in view of the qualities of the. coloring-matter;resulting, to make use of a sulphonic acid the ammoniacal salt of which is easily soluble. To this efiect the liquid of the sulphonation-is heated to to cen-' tigrade until a sample gives a clear solution with cold ammonia of three per cent. The

mass of the reaction is converted then into 85 the calcium or sodium salt in a manner well knownis. -;The calcium salt is a powder easily soluble in water and in alcohol. In the same manner I proceed for the preparation of the sulphonic acids, respectivelhnf the calcium 9o salts of the same prepared from 'meta amidotetramethyldiamldotriphenyl methane, metameta amidotetrainethyldiamidodiorthoto]yl- I The manner in which the sulphonation of amidodimei'hyldiethyl d ia-m i d o t ri p h e n yl meththane symmetric,

G ILNI I, [C 11, NCII, 1

5J2, lneta-amidodimethyldiethyldiam idotriphenyl methane unsymmetri'c,

. C ,H N] l iJfi tt. o mmonn CII phenyl methane, and meta-amidotetraethyldiamidodiorthotolylphenyl methane.

Example No. 2.Son1ewhat different is the manner of preparing the sulphonic acids of those leuco bases that are still aromatic in the amido group, and are therefore apt to be sulphonated, such as benzyl or phenyl. The compounds appertaining to this class are the following, viz: ineta-ainidodibenzyldiinethyl diamidotriphenyl methane,

. C I-I,1\*H GIL-C 11, ()I'I (CJI ginN on (0,1 1,)

meta amidodibenzyldiethyldiamidotri'phenyl methane, meta-amidodiphenyldiniethyldiamidotriphenyl methane, and meta-amidediphcnyldiethyldiamidotriphenyl methane.

these leueo bases is carried out I explain by the folio-wing example: Thirty parts, by weight, of meta-amidodiethyldibenzyldiamidotriphenyl methane are dissolvedin one hundred and fifty parts,by weight, of fuming sulphuric acid of twenty per cent. S0,. At.

ordinary temperature a sulphonic acid soluhis in Water with difliculty is formed. Af- 1 .lward the solu tion is heated for several hours to centigrade, until a sample dissolves easily in water, and also gives with diluted ammonia a clear solution of violet tint. Now the mass of the reaction is poured into water and converted into the calcium or sodium salt. in manner Well known.

11. oxinA'rion on THE LEUCO s LPHoNIo ACID. 1

From the calcium salts of the leuco sulphonic acids mentioned hereinbefore is prepared the corresponding.coloring-matter by oxidation with. peroxidessuch as mangan peroxide, lead peroxide, or barium peroxide in the presence of the calculated quantity of amineral acid. The oxidation is carried out p in the manner described in the following example: Ten parts, by weight, of the calcium. salt of the sulphonic acid prepared from meta am idotetraethyldiamidotriphenyl m ethane are dissolved in about three hundred parts, by weight, of water. Then there are added the calculated quantities of diluted sulphuric acid and superoxide 'of lead filtered ofli from the precipitated sulphate of lead,

- tion.

and the blue solution of coloring-matter is evaporated to dryness.

The new-coloring-matter is in the form of a'copper-red powder of metallic luster, dissolving quite easily in water, with blue tint.

The aqueous solution comports rgaiilst mineral acids and against alkalies in quite the same manner as the acid coloring-matter deriving from inetaoxytetralkyldiamidotriphenyl methane. By the addition. of at.

of mineral acids the solution is colored green. The blue coloring does not disappear on the addition of cold soda-lye, neither on being boiled with diluted ammonia or soda soluwhen boiled with soda-lye. The new coloring-matter dyes wool and silk in acid bath a level green-blue shade, and the shades excel by great fastn ess.'

III. CONVERSION OF META-AMIDOTETRALKYL- DIAMIDOTRIPHENYL CARBINOL INTO ACID COLORING-MATTER.

The 1neta-amidotetralkyldiamidotriphenyl earbinols are green coloring-matters which, according to E. ((5 O. Fischer, (Berichte cZer (Zeutschen chem-ischen G esellschaft, 12,803,) are obtained by oxidation of the corresponding meta-amidotetralkyldiamidotriphenyl methanes. These coloring-matters-viz., the sulphates or chlorhydrates of m'eta-amidotetramethyldiamidotriphenyl carbinol, meta-amidotetraeihyldiamidotriphenyl carbine], meta-' aniidodimethyldiethyldiain dotriphenyl" earbinol symmetric,

I O H NH finimdmon-I, ,3

metaamidodiniethyldiethyldiamidotriphenyl -carbinol unsymmetric,

The blue solution turns violet only moniaa clear solution of pure blue coloring.

The mass of the reaction is then converted into the calcium or sodium salt in manner well known.

What I claim as new, andwish to secure by t ls Iatent, is

1. As a new article, blue-green coloring-matter, the sulphonic acid of meta-amidotetralkyldizunidotriphenyl carbinol, a. copper-red powder with metallic luster, dissolving in Wa- 5 ter with blue color, dyeing Wool and silk bluegrecn tints, and prepared according to the process herein described, or by any other process giving similar results.

2. The process of marking fast blue-green colorbydissol'vingmeta-amidotctralkyldiaiui- -dotriphcnyl methane in fuming sulphuric acid, heating the solution until a sample gives a clear solution with cold ammonia, convert- ALBERT HERRMANN. Witnesses:

JosEF REVERDY, HEINRICH HAHN.

Referenced by
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US5194390 *Jul 5, 1988Mar 16, 1993Miles Inc.Composition for the assay of albumin