US957683A - Dichlor-dibrom-indigo and process of making same. - Google Patents

Description

- and, the other,

t a blue solution in cold concentrated sulfuric I which are fast against the action of washing, 1

circumstances.

To all whom 'it may concern:

dichlor-dibrom-indigo in which the four new product symmetrical L.4.5.5-dichlor- UNITED STATES PATENT OFFICE.

PAUL vIK'ron VILLIGER, Ann PAUL NAWIASKY,2 ornnnwresHArEn-onran-mums, GERMANY, ASSIGNO'BS r0 BAmsoHE' ANILINUG: isone. EABBIK, or LUDWIGSHAFEN-ON-THE-RHINE, GERMANY, A ooRronA'rrort or GERMANY.

nrcnr-onrmnnon-mmco AND rnocnss or time sAmE.

Ho Drawing. Serial no; 528,563.

Application filed November 17, 1909.

The followinexample will serve to illustrate further tie nature of this invention and how it can' be carried into practical effect, but our invention is not confined to this example. The parts are by weight. In this example, we first, for the sake ,of convenience, describe the production of the methyl ester of chlor-brom-indoxyl carb'oxylic acid used in carrying out the process of the example. Introduce, :while stirring, three hundred and thirty-seven parts of the methyl ester of 3.4-hlor-brom phenyl= glycin-Q-carboxylic acid or of Bat-bromchlor-phenyl-glycin-2-carl)oxylic acid into a solution of twenty-three parts of sodium in one thousand parts of methyl alcohol, and maintain the whole at seventy degrees centigrade for thirty minutes. Distil ofl the methyl 'alcohol,'d ige'st the residue with one thousand parts'of water and two hundred parts of thirty per -c entaacetic acid, and filter off, and wash and dry the chlor-bro'm- Be it known that we, PAUL J nuns, Ph. D., Vixron VILLIGER, Ph. 1)., and PAUL NAwI- ASKY, Ph. D., chemists, subjects the first and third of the Emperor of Austria, the second.a citizen of the Swiss Republic, residing at Ludwigshafemon-the-Rhine, Germany, have invented new and useful Improvements in Dichlor-Dibromslndigo and Processes of Making Same, of Which the following is a specification.

Our invention relates to the production of halogen atoms are in the positions 4.4.5.5.

\Ve have invented a process for the .pro-' duction of our dichlor-dibrom-indigo by the saponification and oxidation of an ester of the corresponding chlor-brom-indoxyl carboxylic acid. Thus, upon operating in thisway upon the methyl ester of 4,5-chlor-bromv indoxyl carboxylic acid, or of 4:.5-bromchlor-indoxyl carboxylic acid, we obtain the soluble in water and is diflicultly soluble in. most of the common organic solvents. can be converted into the corresponding indigo coloring matter dred and five parts of it with six thousand parts of water and five hundred and eleven parts of caustic while passing a current of the so'lution. Then add twelve thousand parts of boiling water to the mixture, and

dibrom-indigo, of a constitution corresponding to the formula I NH NH fifth in which Hal and Hal are, the one, chlorin, bromin, It consists when dry ofa greenish blue powder which. yields hundred degrees cent-i rade, until the oxidation is complete. If esired, the saponificaacid and a blue solution in hot dimethyl tion-can be carried out in the absence of coal anilin. It differs from all known dichlors. dib'rom-indigoes in that it dyes cotton from a. Now what we claim is a v vat exceptionally greenish shades of blue, 1. The process of producing symmetrical dichlor-dibrom-indigo, in which the four halogen atoms are in the positions 4.4:.55, by saponifying and oxidizing an ester of the *eorresponding chlor'brom-indox vl carboxlight, and chlorin. Moreover, the said shades when viewed by artificial light retain theirgreenish tint, whereas the other tetrahalogen indigoes hitherto described assume a reddish or violet-black tint under similar ylic acid substantially as described.

2. As a new article of manufacture, symmetrical dichlor-dibrom1ndigo, in which the 'indoxyl carboxylic acid ester, which is 1nby boiling three hunpotash for thirty minutes, coal gas through four Quiet-:3

outside suction heads through Said diffusion eel; 1 the 'piieseuce of two subhalo en atoms are in the positions .1 rihingi J i 4415.5, which consists when (Try of a greenir'll blue powder cold concentratec Sulfuric acid and a blue solution in hot dimethyl, aniling dyes cotton particularly greenish shades of blue and contains both ch-lorin and br0n1in..

In testimony whereof We have hereunto ion in Letters Patent No. 957,683.

Correct k 'PAUL JULIUS. I

- VIKTOR VILLIGER PAUL NAWIASKY.

i I W] i yields a blue solution in lVii'uesses J. Amie. LLOYD, W. W. SHMTDT.

, It is hereby certified that in Letters Patent No. 957,683, granted May 10, 1910,

upon the application of PaulJuliu-s, Viktor Viiiiger, eusi Paul Nawiasky, of Ludwigshafen-on-the-Rhine, Germany, for an improvement in Diehloi Dibrom-Indigo and ,Processes of Making Same, an error appears in the printed specification requiring I correction as follows: Page 2, line 1, the words. outside suction heads through said difl'usion, should be erased; and that the said Letters Patent shouldbe read with this correction therein that the same may conform to the record of the case in the Patent Oflice. I

Signed and sealed this 5th day of July, A 1)., 1910.

[SEAL F. A. TENNANT,

Acting Obmmz'ssz'omr of Patents..

ion in Letters Patent No. 957,683.

Correct Quiet-:3

set

1 ghe urzseuce of two subin the positions yields a blue solution in lVitnesses J. Amie. LLOYD, W. W. Sruwror.

testimony whereof We have hereunto It is hereby certified that in Letters Patent No. 957,683, granted May 10, 1910,

upon the application of PaulJuliu-s, Viktor Viiiiger, exosi Poul Nawiasky, of Ludwigsbafen-on-the-Rhine, Germany, for an improvement in Diehloefiibrom-Indigo and ,Processes of Making Same, an error appears in the printed specification requiring I correction as follows: Page 2, line 1, the words. outside suction heads through said dif i'usion, should be erased; and that the said Letters Patent shouldbe read with this correction therein that the same may conform to the record of the ease in the Patent Oflice. I

Signed and sealed this 5th day of July, A 1)., 1910.

[SEAL F. A. TENNANT,

Acting Commissioner of Patents..

Correction in Letters Patent No. 957,683.

It is hereby certified that in Letters Patent No. 957,383, granted May 10. 1910,

upon the application of Pan! Julius, Viktor Viiiigrfii :Eui Paul Nawiusk u of Ludwigshafen-on-the-Rhine, Germany, for an improvement; in l ishIor-Dibromlndigc and Processes of Making Same, an error appears in the r-i mm specification requiring correction as follows: Page line 1, the word; outside suction heads through said diifusion. should be erased; and that the said Letters Patent should'he read with this correction therein that the same may conform to the record of the ease in the Patent Office.

Signed and sealed this 5th day of July, A. D., 1910.

[SEAL] F. A. TENNANT,

Acting Commissioner of Patents.