Year: 1884

page_text: We DR LEO GANS of Frankfort on Main and DR MEINHARD HOFFMANN' of
Mainkur near Frankfort on Main in the Empire of Germany Chemists, seek leave
to amend the Specification of Letters Patent, N° 816 of 1884, as shown in red
ink in the copy of the original Specification hereunto annexed marked "A."
Our reasons for making this amendment are as follows:-
First. We desire more fully to explain the conditions in respect to temperature
under which the process given as " Example 1" may be advantageously conducted.
Second. We desire to remove from the Specification the statement of the nature
of the bye products obtained in the same process because the said statement is
superfluous to the full description of the invention and is not strictly accurate
as especially in working on a large scale mixtures of sulphonic acids are obtained
as bye products..
Third. We desire the alteration at page 4 lines 8 and 9 because we have found
that not only alpha monosulphonic acid but also another monosulphonic acid may
form part of the mass before the operation is terminated.

page_text: wrom reference to the amendment of the said Specification I hereby allow
1. The excision of the words on page 3 lines 41 and 42 commencing at " which
separates itself" down to "formed."
2. The excision of the word "alpha'
"acid " into "acids" on line 9.
I do not allow
"
on page 4 line 8 and the alteration of
1. The insertion of the words "or further un to 90° (!" on neon 2 line

page_text: Coloring matters therefrom.
We DR LEO GANS of Frankfort on Main and DR MEINHARD HOFFMANN
of Mainkur near Frankfort on Main in the Empire of Germany Chemists do
hereby declare the nature of our Invention for "THE MANUFACTURE OF NEW
COLOR-YIELDING PRODUCTS AND OF COLORING Matters THEREFROM to be as
follows:-
:-
"1
Our Invention relates to a new method or methods of producing new disulpho
acids of beta-naphtol and of beta naphtylamine and of obtaining useful coloring
matters therefrom belonging to the class of azo colors.
It is well known that by treating bata naphtol with commercial sulphuric acid
at the temperature of 100° C. or below, two mono-sulphonic acids of beta naphtol
are obtained the one described by Schaeffer (Ann. Chem. 152, 296) and the other
called by its inventor (Patent No 1225) alphamonosulphonic acid of beta naphtol
corresponding with the difficultly soluble monosulphonic acid of beta naphtylamine
and characterized by the solubility of its sodium salt in alcohol of 90°.
We have found that this alphamonosulphonic acid can be transformed into a
new disulphonic acid of beta naphtol which we call gamma disulphonic acid of
beta naphtol.
In order to get the new acid we proceed as follows:-
50 Ko of finely powdered potassium salt of the beta naphtol alpha monosulphonic
acid are mixed with
150 Ko commercial sulphonic acid (66° Bé.) and heated to 40-50° C. during
5-6 hours. After that time the new acid is formed and a sample of the mixture
gives with ammonia a solution showing a pure blue fluorescence. This point being
reached the mass is in the usual manner converted into the potassium salt of the
gamma disulphonic acid of beta naphtol.
The exact time during which the sulphonic acid is acting upon the alpha
monosulphonic acid and other details may be varied for we get the identical result
by heating the mixture 1 to 2 hours at 100° C. or leaving it standing 8-10 days
at a temperature of 25° C. and other means well known to chemists as sulphurating
agents may be made to answer the purpose.
Also we succeed in starting from the beta naphtol directly but in all cases
alphamonosulphonic acid is formed as an intermediate substance.
A third method of obtaining the new disulphonic acid of beta naphtol we found
by decomposing the corresponding diazo betanaphtylamine disulphonic acid by
acidulated boiling water. This betanaphty lamine-disulphonic acid which till now
has not been known is obtained by heating betanaphtylaminesulphate with vitriol
oil of 20-30% anhydrous acid at 110-140° C. until a sample of the mixture
easily dissolves in cold water or by heating the difficultly soluble mono-sulphonic
acid of betanaphtylamine with commercial sulphuric acid of 66° Bé. at 110° C.
until the above mentioned point has been reached. The formation of the diazo
°

page_text: compound and its transformation into the corresponding naphtol disulphonic acid
is effected in the usual way.
The salts of the gamma disulphonic acid in general crystallize easily, the
potassium salt is soluble in 2, 5 parts of boiling water and is obtained from this
solution in large shining crystals. By combination with aromatic diazo compounds
new and valuable coloring matters are formed the production of which is a
principal object of our Invention. A great number of shades are obtained by
altering the nature of the combined diazo compounds, thus we obtain colors from
yellow to red, violet and brown by the use of aniline, toluidine, xylidine, cumidine,
a and naphtylamine, amidoazobenzol, amidoazotoluol, amidoazoxylol, the mixed
amido-azo compounds, the amido phenols, the methyl and ethyl ethers thereof and
of the sulphonic acids of the named bases as well as from the diazo compounds of
the nitranilines, nitrotoluidines and the nitroamidophenols.
Also the diazo compound of the betanaphtylamine disulphonic acid described
above is very fit to form new colors if in place of being transformed into the
corresponding naphtol combination it is combined with the equivalent quantities of
certain aromatic amines or naphtol sulphonic acids. We particularly mention the
violet color formed by combination with alphanaphtylamine in acidulated solution
and the scarlet red produced by combination with betanaphtol alpha disulphonic
acid in alkaline solution.
In the following we give furthermore some examples of the production of
coloring matters in accordance with our Invention.
In order to obtain a yellow color we transform 87 parts of metanitraniline in a
manner well known to chemists into its diazo compound and add the alkaline
solution of 24 parts potassium salt of gamma disulphonic acid.
We produce an orange color by making in the usual way diazo benzol chloride
out of 58 parts aniline and add an alkaline solution of 24 parts potassium salt
of gamma disulphonic acid, the coloring matter crystallizes in large golden yellow
lainelles.
In order to produce a very fine scarlet shade of (Ponceau 3 R) we transform
22.3 parts of the difficultly soluble alphanaphtylamine sulphonic acid into its diazo
compound and mix it with the alkaline aqueous solution of 38 parts potassium
salt of gamma disulphonic acid the greatest part of the coloring matter separates
after some time by addition of common salt in green shining crystals. In place of
the a naphtylamin-sulphonic acid we may employ 179 parts a naphtylamine
chlorhydrate.
A scarlet very fit for dyeing mordanced cotton is obtained as follows:-
12.4 parts of amidoazobenzole are converted into its diazo-compound which is
introduced into a solution of 24 parts of the potassium salt of our gamma
disulphonic acid to which a sufficient quantity of alkali is added. By addition
of some common salt the new coloring matter is obtained in form of green crystals.
All these coloring matters may be purified in the usual way by recrystallization
from water.

page_text: We, DR LEO GANS of Frankfort on Main and DR MEINHARD HOFFMANN of
Mainkur near Frankfort on Main in the Empire of Germany Chemists do hereby
declare the nature of our Invention for "THE MANUFACTURE OF NEW COLOR-
YIELDING PRODUCTS AND OF COLORING MATTERS THEREFROM and in what
manner the same is to be performed to be particularly described and ascertained in
and by the following statement:-
"
Our Invention relates to a new method or methods of producing new disulpho
acids of beta naphtol and of beta naphtylamine and of obtaining useful coloring
matters therefrom belonging to the class of azo colors.
It is well known that by treating beta naphtol with commercial sulphuric acid
at the temperature of 100° C. or below, two monosulphonic acids of beta naphtol
are obtained the one described by Schaeffer (Ann. Chem. 152. 296) and the other
called by its inventor (Patent N° 1225) alphamonosulphonic acid of beta naphtol
corresponding with the difficultly soluble monosulphonic acid of beta naphtylamine
and characterized by the solubility of its sodium salt in alcohol of 90°.
We have found that this alphamonosulphonic acid can be transformed into a
new disulphonic acid of beta naphtol which we call gamma disulphonic acid of beta
naphtol.
In order to get the new acid from alphamonosulphonic acids or their salts we
proceed as follows:
50 Kº of finely powdered potassium salt of the beta naphtol alphamonosulphonic
acid are mixed with.
150 K° commercial sulphuric acid (66° Bé.) and heated to 40-50° C. during
5-6 hours. After that time the new acid is formed and a sample of the mixture
gives with ammonia a solution showing a pure blue fluorescence. This point being
reached the mass is in the usual manner converted into the potassium salt of the
gamma disulphonic acid of beta naptol.
The exact time during which the sulphuric acid is acting upon the alpha-
monosulphonic acid and other details may be varied, for we get the identical result
by heating for example the mixture 1 to 2 hours at 100° C. or leaving it standing
8-10 days at a temperature of 25° C. and other means well known to chemists as
sulphurating agents may be made to answer the purpose.
We also succeed in starting direct from the beta naphtol. In order to
characterize the conditions under which favorable yields of gamma disulphonic acid
are obtained from beta naphtol we give the following examples :-
·
Ex. 1. Naphtol is first converted into naphtylsulphonic acid, which is then
cautiously treated with sulphurating agents.
1 part of finely powdered beta naphtol is mixed with 5 parts of sulphuric acid
(66 Bé.) and cooled down to 0° C.; the temperature of the mixture is then gradually

page_text: .
increased to 60° C. within 36 hours. Principally gamma disulphonic acid of beta
naphtol is formed which--separates--itself-in--the smelt, as by product--almost
exclusively the beta-naphtel-monosulphonio-acid-of-Schaeffer-is-formed.
Ex. 2. Beta naphtol is first converted by known processes into the mixture of
the monosulphonic acids which is then treated with sulphurating agents, under
conditions which avoid the formation of the known disulphonic acids of beta
naphtol.
1 part of beta naphtol is treated with 2 parts of sulphuric acid of 66° Bé. at
40-60° C. until solution sets in, then further 2 parts of sulphuric acid of 66° Bé.
are added and the whole is kept at this temperature until the smelt becomes thick,
or it is left standing from 8 to 10 days at 20° C.
These examples may show that this reaction requires a certain correspondence
between the quantity or strength of sulphuric acid, the temperature and the
duration of the operation; the same result may be obtained by increase of strength
or quantity of the sulphuric acid and by diminution of temperature, or by a higher
temperature and a shorter time of reaction. A suitable variation of these
conditions allows sulphuric acid of 66° to be replaced by other known sulphurating
agents.
The sulphuration can be regarded as finished as soon as alpha monosulphonic
acids can not any longer be traced.
The separation of the sulphonic acids of beta naphtol formed in the réaction
above described can be effected by crystallization of their salts; the salts of barium,
sodium and potassium are very well fit for this purpose, experience having taught
that these salts of the sulphonic acids formed besides the gamma disulphonic acid
crystallize first.
In many cases especially when the gamma disulphonic acid is to be employed for
the production of azo colors, it is advantageous to effect the separation by fractional
precipitation with diazo compounds.
In order to carry out this method of purification we proceed as follows:
With a solution of diazo alpha naphtaline of known strength we determine by
titration the quantity of the sulphonic acids, which accompany the gamma
disulphonic acid, contained in the alkaline solution of the sodium salts of the acids,
which are obtained in the usual way out of the crude sulphurated mixture. The
gamma disulphonic acid does not immediately form a coloring matter with the
diazo alpha naphtaline, whilst all other sulphonic acids which accompany the same
do immediately form azo colors. This circumstance renders possible..the above,
method of determination. In conformity with its result, the accompanying
naphtolsulphonic acids are then precipitated by an equivalent quantity of diazo
compounds of benzol, toluol, xylol, of their sulphonic acids or of other diazo
compounds. Thus azo colors are obtained which are separated by filtration, if
necessary the solution is previously saturated with common salt. The filtered
liquor contains the sodium salt of the gamma disulphonic acid.
A third method of obtaining the new disulphonic acid of beta naphtol we found
by decomposing the corresponding diazo beta naphtylamine disulphonic acid by
acidulated boiling water. This beta-naphtylamine disulphonic acid which until
now has not been known is obtained by heating betanaphtylamine sulphate with
oil of vitriol of 20-30° anhydrous acid at 110-140° C. until a sample of the
mixture easily dissolves in cold water, or by heating the difficultly soluble
monosulphonic acid of beta naphtylamine with commercial sulphuric acid of
66° Bé. at 110° C. until the above mentioned point has been reached. The
formation of the diazo compound and its transformation into the corresponding.
naphtol disulphonic acid is effected in the usual way, that is to say the diazo
compound is formed by the addition of an equivalent quantity of nitrite of sodium
and is transformed. by pouring it into hot water containing sulphuric acid and
boiling in the saine,
J

page_text: The salts of the gamma disulphonic acid in general crystallize easily; the
potassium salt is soluble in 2.5 parts of boiling water and is obtained from this
solution in large shining crystals. By combination with aromatic diazo compounds
new and valuable coloring matters are formed, the production of which is a principal
object of our Invention. A great number of shades are obtained by altering the
nature of the combined diazo compounds, thus we obtain colors from yellow to
red, claret and brown by the use of aniline, toluidine, xylidine, cumidine, alpha and
beta naphtylamine, methylnaphtylamine, benzidine, amidoazobenzol, amidoazotoluol,
amidoazoxylol, the mixed amidoazo compounds, the amidophenols, the methyl and
ethyl ethers thereof and of the sulphonic acids of the named bases as well as from
the diazo compounds of the nitranilines, nitrotoluidines, and the nitroamidophenols.
Also the diazo compound of the beta naphtylamine disulphonic acid described
above is very fit to form new colors if in place of being transformed into the
corresponding naphtol combination, it is combined with the equivalent quantities
of certain aromatic amines or naphtol sulphonic acids. We particularly mention
the violet color, formed by combination with alphanaphtylamine in acidulated
solution and the scarlet red produced by combination with betanaphtol alpha-
disulphonic acid in alkaline solution.
In the following we give furthermore some examples of the production of
coloring matters in accordance with our Invention.
In order to obtain a yellow color we transform 8.7 parts of metanitraniliue in a
manner well known to chemists into its diazo compound and add the alkaline
solution of 24 parts potassium salt of betanaphtol gamma-disulphonic acid.
We produce an orange color by making in the usual way diazobenzol chloride
out of 5-8 parts aniline and add an alkaline solution of 24 parts potassium salt of
betanaphtol gamma-disulphonic acid, the coloring matter crystallizes in. large
golden yellow lamellæ.
In order to produce a very fine scarlet (shade of Ponceau 3 R) we transform
22.3 parts of the difficultly soluble alphanaphtylamine sulphonic acid into its diazo
compound and mix it with the alkaline aqueous solution of 38 parts potassium salt
of betanaphtol gamma-disulphonic acid; the coloring matter separates by addition
of common salt.
A scarlet very fit for dyeing mordanted cotton is obtained as follows: 124 parts
of amidoazobenzole are converted into its diazo compound which is introduced into
a solution of 24 parts of the potassium salt of our betanaphtol gamma-disulphonic
acid to which a sufficient quantity of alkali is added. By addition of some
common salt the new coloring matter is obtained in form of green crystals forming
a red powder after being dried.
All these coloring matters may be purified in the usual way by recrystallization
from water.
Having now particularly described and ascertained the nature of our said
Invention and in what manner the same is to be performed we declare that what
we claim is
First. The new color yielding product which we call betanaphtol gamma
disulphonic acid and the method or methods of producing and separating the same
substantially as herein-before described.
Second. The new color yielding product betanaphtylamine disulphonic acid
corresponding with the betanaphtol gamma-disulphonic acid and the method or
methods of producing the same substantially as herein before described.
Third. The yellow brown and red azo colors as herein described and the
preparation of the same by the reaction of the said betanaphtol gamma-disulphonic
acid or its salts upon diazo or diazoazo derivatives or compounds of the benzo!
series or of naphtaline or the sulpho acids thereof hereinbefore mentioned
substantially as described.

page_text: Fourth. The violet, brown, yellow, and red coloring matters herein described
and the preparation of the same by the reaction of the diazo compounds of the new
beta naphtylamine disulphonic acid with the napthylamines, dimethylaniline
and its homologues, diphenylamine, methyldiphenylamine, metaphenylenediamine,
metatoluylenediamine or with naphtols or their sulphonic acids substantially as
described.