AN IMPROVED METHOD OF OBTAINING ANTHRACEN OUT OF ASPHALTOS, THAT IS TO BAY, PITCH PRODUCED FROM COAL TAR, AND OF PREPARING TWO COLORING MATTERS FROM THE ANTHRACEN
Year: 1869

page_text: LETTERS PATENT to Julius Brönner and Hermann Gutzkow, both of
Frankfort-on-the-Maine, in the Kingdom of Prussia, for the In-
vention of "AN IMPROVED METHOD OF OBTAINING ANTHRACEN OUT OF
ASPHALTOS, THAT IS TO BAY, PITCH PRODUCED FROM COAL TAR, AND OF
PREPARING TWO COLORING MATTERS FROM THE ANTHRACEN."
Sealed the 30th July 1869, and dated the 28th May 1869.
PROVISIONAL SPECIFICATION left by the said Julius Brönner and
Hermann Gutzkow at the Office of the Commissioners of Patents,
with their Petition, on the 28th May 1869.
We, JULIUS BRÖNNER and HERMANN GUTZкOW, both of Frankfort-
on-the-Maine, in the Kingdom of Prussia, do hereby declare the nature
of the said Invention for "AN IMPROVED METHOD OF OBTAINING ANTHRACEN
OUT OF ASPHALTOS, THAT IS TO SAY, PITCH PRODUCED FROM COAL TAR, AND OF
PREPARING TWO COLORING MATTERS FROM THE ANTHRACEN," to be as
follows:-
In order to obtain anthracen and similar substances out of asphaltos
we distil it by the aid of superheated steam in a gas retort and lead the
vapours by the shortest way through a large pipe into an intermediary.

page_text: barrel out of which the raw condensed masses of anthracen can be
drained off. We lead the gases which are not yet condensed out of this
intermediate room through a large refrigerator, and from thence either
into a gas holder or into the open air, or make use of them directly for
heating. Out of the anthracen (sufficiently purified) obtained in this
way, and out of the anthracen (sufficiently purified) prepared from the
heavy oil of coal tar, we produce the two coloring matters in the
following way-By means of oxydation or substitution we transform
the anthracen into a new product. For this purpose we employ any
known means of oxydation or substitution capable of causing this
alteration, for example the bichromate of potassa and sulphuric acid
or crystallized acetic acid, but particularly nitric acid diluted or con-
centrated. We purify this new product either by crystallization, sub-
limation, or in any other way, and by oxydation of the said product, and
if necessary for the complete developement of the two coloring matters
by further treatment with alcalics we prepare the two coloring matters.
We also prepare them directly from the unpurified product. For this
purpose we dissolve it best in sulphuric acid, and for the oxydation we
take any substance giving oxygen, such for example as nitric acid and
the nitrates, sulphates, oxyds, and protoxyds of metals, and their com-
binations with acids, combinations that are capable of being reduced,
arsenic acid, chronic acid, or other acids giving oxygen, or the chlorides
of metals.
We operate usually in the following way:-We mix anthracen at
an ordinary or at an clevated temperature with double its weight of
nitric acid of 1-5-1-3 specific gravity, wash the new product with water
and dissolve it purified or not purified in the necessary quantity of
sulphuric acid. For better dissolving we heat it, and then add the
necessary quantity of a salt of mercury, for instance, of protonitrate of
mercury or deutonitrate of mercury, and execute the process by heating
or otherwise. When the coloring matters are formed we treat them, if
necessary, to the complete developement of the two coloring matters
by alcalies. We then dissolve the coloring matters in a suitable manner
either by cold or boiling water, by alcohol, ether, sulphuret of carbon, by
dissolved alums, by dissolved alcalics, or by other means. We then
evaporate the liquids or precipitate by acids, and finally purify the two
coloring matters by crystallization, or by sublimation, or by any other
means. According to the oxydizing substances which we have chosen
to use, to the quantity we have used, or according to the degree of

page_text: temperature we have produced, we obtain a colouring matter which can
be dissolved in alcohol, ether, or analogous substance with a yellow color
and another one which is to be dissolved in like manner with a red colour.
Being able to dissolve also in alcalies the product of the anthracen
obtained by nitric acid, or by bichromate of potassa and sulphuric acid
or by crystallized acetic acid, or by substances acting in a similar
manner, and being able to obtain the two coloring matters also in a
corresponding way by oxyds and protoxyds, by metallic salts, such as for
example deutosulphate of copper or another copper combination, or
by chlorides of metals, or by any oxydizing matter acting on the alkaline
solution of our first product; we attach no particular value to the dis-
solving in sulphuric acid, or to the oxydation by protonitrate of mercury
or deutonitrate of mercury.
Our process differs from that of Messrs. Gracbe and Liebermann,
firstly, inasmuch that we oxydize the first product we obtain from the
anthracen, whereas Messrs. Graebe and Liebermann substitute hydrogen
by brom, and then in order to remove the brom introduce twice HO
by alcalies, and, secondly, inasmuch that we not only obtain alizarinc
but also another coloring matter which is to be dissolved in alcohol and
analogous matters similar to purpurine with red color and not like
alizarine with a yellow one.
Our Invention consists, therefore, in preparing anthracen and similar
substances out of asphaltos, that is to say:-Pitch obtained from coal
tar in the above-mentioned manner, and the oxydizing of the product
which we obtain out of the anthracen, by means of nitric acid, or by the
substances we have mentioned before using in the said oxydation the
substances above mentioned, or other substances acting in a similar
manner, and in the further treatment with alkalies if necessary to the
complete developement of the two coloring matters.
Our Invention also consists in accomplishing the changing of the
anthracen into both coloring matters in one operation by uniting
(combining) the two described processes.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent,
filed by the said Julius Brönner and Hermann Gutzkow in the
Great Seal Patent Office on the 24th November 1869.
TO ALL TO WHOM THESE PRESENTS SHALL COME, we, JULIUS
BRÖNNER and HERMANN GUTZKOW, both of Frankfort-on-the-Maine,' in
the Kingdom of Prussia, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her
Letters Patent, bearing date the Twenty-eighth day of May, in the year
of our Lord One thousand eight hundred and sixty-nine, in tho thirty-
second year of Her reign, did, for Herself, Ier heirs and successors,
give and grant unto us, the said Julius Brönner and Hermann Gutzkow,
Her special licence that we, the said Julius Brönner and Hermann
Gutzkow, our executors, administrators, and assigns, or such others as wc,
the said Julius Brönner and Hermann Gutzkow, our exccutors, adminis-
trators, and assigns, should at any time agree with, and no others, from
time to time and at all times thereafter during the term therein ex-
pressed, should and lawfully might make, use, exercise, and vend, within
the United Kingdom of Great Britain and Ireland, the Ohannel Islands,
and Isle of Man, an Invention for "AN IMPROVED METHOD OF OBTAINING
ANTHRACEN OUT OF ASPHALTOS, THAT IS TO SAY, PITCH PRODUCED FROM COAL TAB,
AND OF PREPARING TWO COLORING MATTERS FROM THE ANTHRACEN," upon thic
condition (amongst others) that we, the said Julius Brönner and Hermann
Gutzkow, our executors or administrators, by an instrument in writing
under our, or one of our, their, or one of their hands and seals, should
particularly describe and ascertain the nature of tho said Invention, and
in what manner the same was to be performed, and cause the same to
be filed in the Great Seal Patent Office within six calendar months
next and immediately after the date of the said Letters Patent.
NOW KNOW YE, that we, the said Julius Brönner and Hermann
Gutzkow, do hereby declare the nature of our said Invention, and in
what manner the same is to be performed, to be particularly described
and ascertained in and by the following statement :—
In order to obtain anthracen and similar substances out of asphaltos
we distil it in a fitting apparatus, or we licat it in an apparatus for
sublimation if required by the aid of steam. We convert the anthracen
obtained by the above described method or anthracen otherwise obtained
and those carbureted hydrogens which in their properties are similar to

page_text: anthracen into an oxydized product by means of nitric acid or of
bichromate of potassa and acids, for instance bichromate of potassa and
sulphuric acid, or bichromate of potassa and acetic acid, or of acetic acid
and nitric acid, or by chlorates, for instance chlorate of potassa in com-
bination with acids, muriatic acid for example, or by other substances
acting in a similar manner. We purify this product either by crystal-
lization or by sublimation, or in any other suitable manner, or we take it
unpurified and prepare from it two coloring matters, namely, one which
by its solution in alcohol colors the alcohol yellow, and another coloring
matter or a mixture of coloring matters giving to alcohol a red or violet
color.
The first coloring matter which dyes the alcohol yellow we prepare in
the following way-We heat the above-mentioned oxydized product
together with alkalis, or we dissolve the oxydized product first in sulphuric
acid or in any other acid, or in a mixture of any acids, at an elevated or
at an ordinary temperature in order to obtain the oxydized product
instead crystallized in a flocky precipitate whereon the alkalis may
act better; after the dissolution in sulphuric or in another acid we
precipitate the product by water, and then we heat the residuum
resulting from the filtration together with alkalis as aforesaid. By.
adopting nitric acid in order to dissolve the oxydized product, or by
adopting a mixture of sulphuric acid and nitric acid or sulphuric acid
and nitrates we obtain a nitro-product which we may convert into
coloring matter by heating it likewise with alkalis or by converting it,
firstly, into a new product by reduction, that is to say, by treatment with
any substances which yield hydrogen, for instance muriatic acid and
'metals. We may also heat the thus obtained red colored substance with
alkalis to obtain a coloring matter which by its solution in alcohol dyes
the alcohol yellow. The product obtained by any of these methods we
dilute with water, neutralize with an acid, and then again wash with
water. The residuum thus obtained can either be at once employed for
dyeing and printing (under application of mordants) by distributing it
in water and heating it, or we first purify it by dissolving it in alcohol, or
by adopting other means of dissolution.
In order to obtain with
aluminic mordants a red of a yellow shade we add to the coloring
matter after having dissolved it in acids (for instance sulphuric acid)
nitric acid or nitrates (for example proto-nitrate of mercury) or hypo-
nitrous acid, or nitrites, or. hyponitric acid at an ordinary or at an
elevated temperature. In order to obtain the coloring matter or mixture

page_text: of coloring matters giving to alcohol a red or violet color we operate in
the following way :-
We treat the oxydized product above mentioned, firstly, with sulphuric
acid and then with nitric acid or nitrates, or we heat it at once with a
mixture of sulphuric acid and nitric acid, or a mixture of sulphuric acid
and nitrates until water precipitates a red or violet colored substance.
After having heated it we dilute with water, filter and wash the product
with water, or having produced the above-mentioned nitro product by a
shorter treatment with sulphuric acid and nitric acid, or sulphuric acid and
nitrates we precipitate with water, dissolve the residuum of the filtration in
sulphuric acid, and heat it after having added a metal, for instance zine.
We dilute with water and wash the red or violet colored precipitate with
water. We can at once employ the residuum obtained by any of these
methods for dyeing and printing (with or without mordants) by
distributing it in water and heating it, or we may first purify it by
dissolving it in alcohol, or by adopting other means of dissolution.
The relative proportions of the substances we use and the temperatures
at which we operate in order to obtain the first coloring matter are as
nearly as may be as follows:-We take one part of anthracen, two parts
of sulphuric acid diluted with twice to four times its weight of water, and
one part of bichromate of potassa and heat to nearly 212 degrees
Farenheit. When the conversion is complete we filter and wash the
thus obtained residuum with water until the water is colorless. We
purify this residuum by sublimation, and then we add to it double its
weight of a concentrated solution of caustic soda and heat at a
temperature of above 392 degrees Farenheit. We then dilute with water,
filter, and wash.
To obtain the second coloring matter we operateas follows:-We dissolve
the oxydized product which we obtain from anthracen in eight to ten
times its weight of sulphuric acid, and add two parts of nitric acid of a
specific gravity of 145, we heat it to about (but not above) 392
degrees Farenheit, dilute with water and wash.
Having now described the nature of our said Invention, and in what
manner the same is to be performed, we would have it distinctly
understood that we do not confine ourselves to any preciso relative
proportions of substances, nor restrict ourselves to operating at any
particular temperature, the proportions and degrees of licat above given
being only such as we have in practice found very suitable, but they

page_text: necessarily vary with the quality of the ingredients and other circum-
stances.
What wo claim as secured to us by the herein-before in part recited
Letters Patent is,-
Firstly. The use of the method hercin described of obtaining anthracen
out of asphaltos.
Secondly. The preparation out of the oxydized product obtained
from anthracen and carbureted hydrogens, which in their properties
are similar to anthracen, of two coloring matters, namely, a coloring
matter which gives to alcohol a yellow color, and which we prepare
by at once heating the oxydized product obtained from anthracen
(in the above-mentioned manner) with alkalis, or after having dissolved
the oxydized product in sulphuric acid or any other acid, or after
having produced the nitro product or the reduced nitro product we
then heat the precipitates obtained by any of the methods in a similar
manner with alkalis.
We also claim the method herein-before described of treating this
coloring matter after it is dissolved in an acid with nitric acid or
nitrates, or hyponitrous acid or nitrites, or hyponitric acid in order to
obtain from it with aluminic mordants a red of a yellow shade.
Also a coloring matter or a mixture of coloring matters dyeing alcohol
red or violet by treating the oxydized product obtained from anthracen
(in the above-mentioned manner) with sulphuric acid and nitric acid, or
sulphuric acid and nitrates, or by heating the nitro product with sulphuric
acid and a metal, zinc for instance.
In witness whereof, we, the said Julius Brönner and Hermann
Gutzkow, have hereunto set our hands and seals, this Twenty-
second day of November, in the year of our Lord One thousand
eight hundred and sixty-nine.