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Publication numberUS412615 A
Publication typeGrant
Publication dateOct 8, 1889
Filing dateJan 15, 1889
Publication numberUS 412615 A, US 412615A, US-A-412615, US412615 A, US412615A
InventorsAlbert Herrmann
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Albert herrmann
US 412615 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)




SPECIFICATION forming part of Letters Patent No. 412,615, dated October 8, 1889.

Application filed January 15, 1889. Serial No. 296,391. (Specimens) Patented in Germany August 18, 1888; in Belgium September 3, 1888, No. 83,115 i in France September 5. 1888, No. 192,807, and in Italy September 30, 1888, XLVII, 176.

To all whom it may concern..-

Be it known that I, ALBERT HERRMANN, doctor of philosophy, a citizen of the Empire of Germany, residing at Hochst-on-the-Maine, in the Empire of Germany, have invented certain new and useful Improvements in Coloring-Matter, (patented in Germany August 18, 1888, F. 3,757; in Belgium September 3, 1888, No. 83,115; in France September 5, 1888, No. 192,807, and in Italy Vol. 47, No. 176, September 30, 1888;) and I do hereby declare 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 appertains to make and use the same.

My invention relates to the production of coloring-matters obtained from the etherized compounds of metaoxytetralkyldiamidotri phenyl methane or, rather, from metamethoxy or metaethoxy tetralkyl diamido triphenyl carbinol. The sulphonic acid of these compounds dyes greenblue tints which are very fast.

In carrying out my invention I proceed as follows:


A. The methyl and ethylethers of the leuco bases O H OAlk (meta) O 4 e 4 2)2 rnethoxybenzaldehyde three to twenty-four hours to 130 centigrade. The product of the reaction is supersaturated with alkali and heated by a current of steam, and the remaining leuco base is boiled and finally dried. In a similar manner is obtained the ethoxidized leuco base by means of metaethoxybenzalde- .hyde

/OO H xcnofif,

which forms at the boiling-point, which is about 245 centigrade, a colorless fluid. For the production of the corresponding leuco bases are used, in the place of the diethylaniline in the same process, dimethylaniline, methylethylaniline, methylbenzylaniline, ethylbenzylaniline, dimethyl-orthotoluidine, diethyl orthotoluidine, methyl diphenylamine, or ethyldiphenylamine.

B. The ether compounds obtained by the process just described may also be produced by methylizing or ethylizing of the metaoxytetralkyldiamido triphenyl methane. These oxy leuco bases are to this elfect heated for several days in a close vessel in a Water-bath with three or four times their quantity of alcohol,caustic soda, (one molecule,) and an excess of chloro, bromo, or iodo methyl or chloro, bromo,or iodo ethyl. Thus, for example, thirty parts, by weight, of metaoxytetraethyldiamr dotriphenyl methane, twenty parts, by weight,

of bromo-ethyl, one hundred parts, by weight,

of alcohol, and the calculated quantity of canstic soda are heated in a vessel in a water bath for forty-eight hours. Afterward the alcohol and the excess of bromo-ethyl are distilled OE, and the residue is boiled with water and dried. The me'tamethoxidized and ethoxidized tetralkyldiamidotriphenyl methanes are, when hot, semiliquid. When cold they are brittle, pulverizable resinous bodies which show but little inclination to crystallize, andin consequence of these qualities it is rather difficult to obtain them in a perfectly pure state. *The one relatively most easy to be obtained in small colorless crystals is the metaethoxydiethyldibenzyldiamidotriphenyl methane. The bases dissolve readily in ether, benzol, and toluolles's readily in alcohol. 'Ag'ainst diluted mineral acids they behave in the same way as the corresponding non-alkylized bases. Those bases deriving from dimethylaniline, diethylaniline, ethylmethylaniline, dimethyl-orthotoluidine, and diethyl-orthotoluidine are relatively stronger bases, which dissolve readily in diluted mineral acids, whereas the bases deriving from methyl and ethyl benzylaniline and from methyl and ethyl diphenylamine show scarcely any basic qualities.


A. The metamethoxydized andmetaethoxidized leuco bases of the generic formula.

/C PLOAlk(meta) s H4NA1k can be converted into the sulphonic acid by heating them with concentrated sulphuric acid; but, principallyin consideration of the purity of the product to be obtained, it is more advantageous to use fuming sulphuric acid instead of the ordinary acid. The process is as follows:

Example N0. 1.Thirty parts, by weight, of metamethoxytetraethyldiamidotriphenyl methane are dissolved in one hundred and fifty parts, by weight, of fuming sulphuric acid of ten percent. S0 and the solution left standing at ordinary temperature until a sample gives with diluted ammonia a clear solution. Now the product of the reaction is poured into water and the solution converted into the calcium salt in well-known manner. The calcium salt is a powder very easily soluble in alcohol and in water. In the same manner is carried out the production of the sulphonic acids respectively of their calcium salts of metaethoxytetraethyldiamidotriphenyl' methane, metamethoxy and metaethoxy tetramethyldiamidotriphenyl methane, metamethoxy and metaethoxydimethyldiethyldiamidotriphenyl methane symmetric, metamethoxy and metaethoxy dimethyldiet-hyldiamidotriphenyl methane unsymmetric-,1netamethoxy and metaethoxy tetramethyldiorthotolylphenyl methane, metamethoxy and metaethoxy tetraethyldiorthotolylph en'yl methane.

Example N0. 2.-Somewhat different is the process for the preparation of the sulphonic acids of those leuco bases which in the amido group still contain aromatic residues, (capable of being sulphonated,) such as benzyl or phenyl. The compounds belonging to this class are the following: metamethoxy and metaethoxy dibenzyldiethyld ia midotriphenyl methane, metamethoxy and metaethoxy di= benzyldimethyldiamidotriphenyl methane, metamethoxy and metaethoxy diphenyldiethyldiamidotriphenyl methane, metametlr oxy and metaethoxy diphenyldimethyldiamidotriphenyl methane.

In the following example is described the way in which is carried out the sulphonation of these leuco bases: Thirty parts, by weight,

of metamethoxydibenzyldiethyldiamidotrt phenyl methane are dissolved in one hundred and iiftyparts, by weight, of fuming sulphuric acid of twenty per cent. 80,. At ordinary temperature is formed a sulphonic acid scarcely soluble in water. Then the solution is heated for several hours to about centigrade, until a sample dissolves easily in water with blue coloring and gives with diluted ammonia a pure blue solution having the shade of a diluted ammoniacal solution of oxide of copper. N ow the product of the reaction is poured into water and converted into the calcium salt in manner well known. dium and calcium salts are crystalline bodies colorless in pure state and readily soluble in water and alcohol.

B. The sulphonic acid of the methoxidized and ethoxidized leuco bases can also be produced by treatment of the calcium or sodium salts of the metaoxytetralkyldiamidotriphenyl-methane sulphonic acids with methyl or ethyl halogenides.

EmampZa-Thirty parts, by weight, of the calcium salt of metaoxytetraethyldiamidotriphenyl methane, twenty parts, by weight, of bromoethyl, and one hundred parts, by weight, of alcohol in a vessel in a water bath are heated to boiling-point for twenty to twenty-f0 or hours. The excess of bromo-ethyl and the alcohol are distilled off. To the remaining (aqueous) solution is added a small quantity of diluted sulphuric acid, and the whole is left at rest for several days,when the greatest part of the leuco sulphonic acid of the ethoxidized base will have crystallized out. This is pressed off and converted into the calcium salt.


The calcium salts of the leuco sulphonic acids hereinbefore mentioned are converted into coloring-matter by oxidation with superoxides in presence of the calculated quantity of a mineral acid. For example, ten parts, by weight, of the calcium salt of the sulphonic acid prepared from metamethoxytetraethyldiamidotriphenyl methane are dissolved in The so-- IIO about three hundred parts, by Weight, of water. Then there are added the calculated quantities of diluted sulphuric acid and peroxide of lead filtered off from the precipitated sulphate of lead, and the blue solution of the coloring-matter is evaporated to dryness. The new coloring-matter is a copper-red powder of metallic luster, dissolving quite easily in water, giving blue color. The aqueous so1ut-ion turns green on the addition of an excess of mineral acid. The blue color of the aque-v ous solution does not disappear on the addition of soda-lye when cold, not even when it is boiled with a solution of ammonia or soda, and it turns violet only when it is boiled with soda-lye. This characteristic quality of the new coloring-mat-ter-namely, the great resistance to'the action of alkaliesis of great advantage for technical purposes and consti tutes a great merit of the invention. These compounds dye wool and silk in an acid bath green-blue, and excel in dyeing a level tint, in which respect the sulphonic acids of indigo are equaled. In consequence of the resistance to alkalies the tints produced are (compared to those produced with indigo-carmiue) very fast in washing.


Metamethoxy and metaethoxy tetralkyldiamidotriphenyl carbinol may be converted in green-blue coloring-matter identical with the coloring-matter described in sub. III by treatment with sulphuric acid or fuming sulphuric acid.

EmampZa-Ten parts, by weight, of metamethoxytetraethyldiamidotriphenyl carbinol are dissolved in one hundred parts, by weight,

' of monohydrate and the solution heated to 50 In quite the same manner analogous coloring-matter is obtained from the methyl and ethyl ethers of metaoxytetramethyldiamidotriphenyl carbinol, metaoxytetraethyldiamidotriphenyl carbin 01, metaoxydimethyldiethyldiamidotriphenyl carbinol symmetric, metaoxydimethyldiethyldiamidotriphenyl carbinol unsymmetric, metaoxytetramethyldiamidodiorthotolylphenyl carbinol, metaoxytetraethyldiamidodiorthotolylphenyl carbinol, metaoxydimethyldibenzyldiamidotrip h e nyl carbinol, metaoxydiethyldibenzyldiamidotriphenyl carbinol, metaoxydimethyldiphenyldiamidotriphenyl carbinol, and metaoxydiethyldiphenyldiamidotriphenyl carbinol.

What I claim as new, and wish to secure by Letters Patent, is-

The new fast green-blue coloring-matter obtained, as described, from the etherized compounds of metaoxytetralkyldiamidotriphenyl methane or metamethoxy or metaethoxy tetralkyldiamidotriphenyl carbinol in the form of a copper-red powder of metallic luster, easily soluble in water, and giving,when so dissolved, a blue color which remains when soda-lye is added or when boiled with a solution of ammonia or soda, changes to violet only when boiled with soda-lye, and turns green on the addition of mineral acids, as set forth.

In testimony whereof I affix my signature in presence of two witnesses.




Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US5194390 *Jul 5, 1988Mar 16, 1993Miles Inc.Composition for the assay of albumin
US20020179131 *May 31, 2002Dec 5, 2002The Regents Of The University Of MinnesotaTray apparatus and methods regarding same
Cooperative ClassificationC09B11/14