A New Manufacture of Colouring Matters.
Year: 1891

page_text: Date of Application, 31st Oct., 1891
Complete Specification Left, 30th July, 1892-Accepted, 3rd Sept.. 1892
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBWERKE VORMALS MEISTER LUCIUS
AND BRUNING, of Hoechst "/ Main, Germany, Manufacturers.]
A New Manufacture of Colouring Matters.
1, OLIVER IMRAY of No. 28 Southampton Buildings in the County of London
Chartered Patent Agent do hereby declare the nature of this invention to be as
follows:-
Though of the ten possible isomeric naphthylenediamines seven have been
produced and most of these have been tried as to their capability of producing
azo-colouring matters (see Lange. Chem. Zeit. 1888 p. 856) only one member of the
series has been considered suitable for the practical manufacture of coloring
matters.
This member is the 15 naphthylenediamine from which as described in the
German Letters Patent No. 39954 are produced substantive colouring matter's
taking on unmordanted cotton by combining one molecule of 15 tetrazo-naphthy-
lene-chloride with two molecules of some other component. The colouring matters
produced in this way have been prominent amongst the group of colouring matters
deriving from the various naphthylenediamines and dye yellow, red and violet
shades, but being very defective in quality the place which they have occupied in
practice is of no importance whatever.
My foreign correspondents have discovered, that from the 1-4 naphthylene-
diamine, which by reason of certain difficulties has not as yet been employed for
the production of colouring matters, there can under certain conditions be produced
colouring matters very valuable for dyeing wool, giving in acid bath shades varying
from red-brown, red, blue violet to pure blue. These conditions are:
(1) That only one amido group be diazotised and that the combination be made
with only one component, such for example as a phenol, a naphthol, or its sulphonic
acid, for example a naphtholsulphonic acid, an oxycarbonic acid, an amine or its
sulphonic acid for example alpha naphthylamine and naphthylamine-sulphonic acid.
(2) That there be diazotised first one amido group and afterwards the second
amido group and that the diazo groups thus obtained, be combined, in manner
hereafter described, successively with two molecules of the same or two molecules
of a different phenol, or amine or their sulphonic acids or carbonic acids etc. etc.
In this mauner can be formed two series of coloring matters of two different

page_text: naphthylene-diamine and 40 parts of R salt is mixed with 20 parts of caustic soda,
and while it is kept agitated the mixture is boiled in an open vessel or under
pressure at 120° to 125° C. until a sample on being super-saturated with acetic
acid no longer turns its violet colour to blue and can be smoothly diazotised.
According to the nature of the coloring matter, the quantity of alkali used and
the temperature of the heating, the saponification will be complete in from two to
six hours. When the saponification is complete, the mass is acidulated with acetic
acid or dilute mineral acid. A part of the coloring matter separates by itself, the
remainder is precipitated by the addition of common salt; it is treated further in
the usual manner.
The saponification can also be made by heating with sulphuric acid of 30 per cent.,
and also. but with less success. by heating with water alone under pressure.
In the production of the coloring matters of the type I. by the process B, the
reduction of the nitro group in the azo-colouring matters derived from 1-4 naphthyl-
amine into the amido group succeeds only under certain conditions. When acid
reducing agents are employed, there take place along with the action upon the
nitro group a more or less considerable and even quantitative splitting off of the
nitro-coloring matters with regard to the double binding of the nitrogens in
the azo-group, so that the product resulting when these agents are used is never
quite uniform.
When the so-called alkaline reducing agents are used, the azo group remains
intact and the nitro group alone is converted quantitatively into the amido group.
Alkaline reducing agents of favorable action is neutral or alkaline solutions are for
example: glucose, stannous oxide, zinc powder sulphides of alkalies, for example
sulphide of ammonium, or sulphide of sodium, polysulphurets of alkalies, hydrated
ferrous oxide etc. etc.
The production of the coloring matters according to the process B, is described
more fully in the following examples.
1. PRODUCTION OF THE NITRO COLORING MATTER FROM R SALT.
188 parts of 14 nitro-naphthylamine are suspended in 250 parts of water and
while well agitated mixed with 400 parts of hydrochloric acid of 30 per cent. After
the temperature by means of ice has been reduced to 15° C. a solution of 69 parts
of sodium nitrite in 200 parts of water is caused to flow slowly in while agitation is
maintained; care is taken that during the operation the temperature of the
diazotation mixture does not rise much above 150° C. The formation of the diazo-.
compound is complete in two hours at the most, whereupon it is added to a solution
of 370 parts of beta-naphthol disulphonate of sodium R, which solution is kept.
alkaline by adding soda or which is mixed with a sufficient quantity of acetate of
sodium. The formation of the coloring matter immediately, begins and is complete
in a few hours.
For obtaining the coloring matter, the liquid which has thickened is heated to
from 60 to 70° C. and the coloring matter is precipitated from it by the addition of
common salt.
The coloring matter is treated in the usual manner and will dye beautiful blueish
claret red shades.
2. REDUCTION OF THE NITRO COLORING MATTER OBTAINED AS DESCRIBED
UNDER 1, INTO THE CORRESPONDING AMIDO COLORING MATTER.
The reduction as mentioned above proceeds very smoothly in neutral or alkaline
solution. Example: The nitro coloring matter prepared as described under 1, is
dissolved in 15 to 20 times the quantity of warm water and while it is kept agitated

page_text: at a temperature of from 50 to 60° C. is mixed in successive portions with a solution
of sulphide of sodium of 20 per cent. until a sample on the addition of a further
quantity of sulphide of sodium and on being heated no longer turns more blueish
and on being acidulated develops copious quantities of sulphide of hydrogen,
Experience soon enables the operator to recognise exactly the point of com-
pleteness. It has been found that a correct proportion of the nitro coloring matter
prepared from 188 parts of 14 nitro naphthylamine and 370 parts of R salt
constitute 2500 parts of a sulphide of sodium solution, containing 500 parts of
crystallised sulphide of sodium.
The reduction immediately begins with considerable self heating and is complete
at a temperature of from 60 to 70° C. after an hour at the most or at ordinary
temperature after hours at the most.
The solution of the novel coloring matter thus formed is acidulated with acetic
acid or with dilute mineral acid, in which operation according to the quantity or
strength of the acid, the sodium salt (for example when acetic acid is used and the
acetate or the salt for example when hydrochloric acid is used the hydrochlorate) of
the coloring matter precipitates.
The precipitation is rendered complete by the addition of common salt. The
coloring matter may be purified by repeated dissolving and precipitating in the
usual manner.
For the reduction may also be directly used the coloring matter paste obtained
as described under 1 after being neutralized.
The other reducing agents such as glucose etc. etc. have an action like that of the
sulphide of sodium, with all these agents the completeness of the re-action is to be
recognized in manner set forth and a quantitative production of the desired coloring
matter will be obtained.
A splitting off of the double binding of the nitro atoms in the azo group will take
place only when a large excess of the reducing agent is used and when the heating
is kept on for too long a time. When the operation under the conditions mentioned
is interrupted at the right moment, the yield of coloring matter will be quantitative.
The coloring matters prepared by the processes A and B have the generic
formula.
standing for the radical of a phenol or a base or a sulphonic or a carbonic acid
of these two bodies, in consequence the coloring matters are members of a type not
known before.
They differ from the acetylised non-saponified products, by giving partly
beautiful red shades but mostly shades ranging from violet blue to pure blue,
whereas the former ones only produce blueish red shades.
The amido group contained in the radical of the naphthylenediamine gives to the
novel coloring matters a strong basic character; with mineral acid they form in the
wet state fast salts colored mostly brick red to brownish brick red, and when
submitted in the usual manner to the action of nitrous acid they are easily trans-
formed into diazo compounds, which combine with a further molecule of a phenol,
a base or the sulphonic or carbonic acid of the same, to form the novel coloring
matters of the type II.; thus constituting the raw material or intermediate product
for the production of a great many valuable coloring matters.
For the components mentioned in the above example may be substituted a large
number of others, phenols, bases, their sulphonic or carbonic acids etc. etc. Such
components are for example:
T 1

page_text: Alpha naphthol, tri sulphonic acid the anhydride of which is the naphtho
sulton disulphonic acid of German Letters Patent 56058.
Beta naphthol mono-sulphonic acid of Schäffer
Cruman Dot 19097
"
"
tri
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22038
Dioxy naphthalin-mono-sulphonic acid G} obtained by melting with caustic
""
"
"
alkalies the naphthol disulphonic acids R & G of the German Pat.
3229
Dioxy naphtalin mono sulphonic acid obtained by melting with caustic alkalies
the alpha naphthol disulphonic acid E of the German Patent 45776.
Dioxy naphthalin mono sulphonic acids obtained by melting with caustic
alkalies the alpha naphthol disulphonic acid S of the German Patent 40571
Dioxy-naphthalin-mono-sulphonic acid of the German Pat. 42261
"
"
"
di
"
"
23
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isomere A
"
obtained by melting with
caustic alkali the beta-naphtholtrisulphonic acid of the German Patent
22038.
"
Dioxy naphthalin disulphonic acid obtained by melting with caustic alkali the
alpha-naphtholtrisulphonic acid produced by further sulphonisation of the
alpha-naphtholdisulphonic acid S of the German Patent 40571.
Dioxy-naphthalin-disulphonic acid obtained by melting with caustic alkali
the alpha naphtholtrisulphonic acid of the German Patent 10785.
Dioxy-naphthalin-disulphonic acid obtained by melting with caustic alkali the
naptho sulton-disulphonic acid of the German Patent 56058 and known as
*
chromotropacid.".
Trioxy-naphthalin-mono-sulphonic acid obtained by melting with caustic alkali
the naphtol tri-sulphonic acid of the German Patent 22038.

page_text: As mentioned herein before, the coloring matters, which are obtained according to
the processes A and B and which are identical, can be easily diazotised and these
diazo compounds very casily combine with phenols and bases and the sulphonic
and carbonic acids of the same, to form novel valuable coloring matters.
Example: 517 parts of the coloring matter having the composition of the
type I. produced from beta-naphtoldisulphonic acid R and having the formula
SOH
are dissolved in the 8 to 10 fold quantity of water
HNH
-
N, CH, (SO,Na),
In this operation
and admixed with.365 parts of hydrochloric acid of 30 per cent.
the blue solution of the commencement changes into a red paste, consisting of the
hydrochlorate of the raw material which dissolves with difficulty.
The solution is then cooled by means of ice and at a temperature of about
0 to 5° C. is admixed by degrees and while being kept agitated, with a solution
of 70 parts of nitrite in 300 parts of water and is left to repose for several hours.
The diazotation is complete when a sample on being diluted with water furnishes a
perfectly clear solution.
:
The diazo-compound thus produced is caused to flow, while being kept well
agitated, into a solution, cooled down to about 0° C., of 385 parts of beta-naphthol-
disulphonate of sodium R and 275 parts of soda in about 7000 parts of water; the
formation of the coloring matter immediately sets in and is complete after a few
hours.
The greatest part of the coloring matter separates of itself; the remainder is
precipitated by the addition of common salt; it is obtained in the usual manner.
These coloring matters dye in light shades a pure greenish-blue, in dark shades a
black-blue.
For the soda may be substituted as condensation agent another alkali, for
example caustic soda or acetate of soda.
The coloring matter produced as described in the example has the formula
TT OH

page_text: When there are employed as components equivalent quantities of an amido-
sulphonic acid or of an amine for example naphthionic acid, alpha-naphthyl-amine,
coloring matters are obtained having the formulae.
Very interesting is the regularity with which the shades of the coloring matters
obtained turn from brown-red through claret-red, violet, to blue, according as
there are employed as components, lower molecular compounds such as benzene-
derivatives or higher molecular compounds of the naphthalin-series.
A further regularity consists in, that the shade of the coloring matters produced
according to the process C, such as for example the coloring matters mentioned in
the last examples, which all contain one same component (the betanaphtholdi-
sulphonic acid R), turns to greenish blue when the second component contains a
hydroxyl group or an amido group in the beta-position, whereas it turns to from
red violet to violet red when the groups mentioned occupy the alpha position.
From what is said it follows that the most valuable coloring matters of these
series are those which contain naphthalin derivatives as components; the shades of
the same lie between violet-claret red and blue or black bluc.
They are rendered prominent above the diazo coloring matters known before and
produced in other ways by their extraordinary fastness and strength and the
clearness of their shades the reason of this is that they possess more auxochromes
in the molecule than the others referred to.
For the second components mentioned in the example may be substituted all
those components that have been mentioned for the processes A and B; but with
several phenols, for example phenol and with several carbonic acids for example
salicylic acid, the combination proceeds with great difficulty whereas with others,
for example the beta-naphthol-oxy-naphthoic acid of the melting point 216° C., it
proceeds very easily and smoothly.
There may also be substituted for the raw materials mentioned in the example
all the coloring matters, that can be produced according to the processes A and B.
Dated this 30th day of October 1891.
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
A New Manufacture of Colouring Matters.
I, OLIVER IMRAY, of No. 28 Southampton Buildings, in the County of London,
Chartered Patent Agent, do hereby declare the nature of this invention and in
what manner the same is to be performed to be particularly described and
ascertained in and by the following statement :-
Though of the ten possible isomeric naphthylenediamines seven have been
produced and most of these have been tried as to their capability of producing azo-
colouring matters (see Lange. Chem. Zeit. 1888 p. 856) only one member of the
series has been considered suitable for the practical manufacture of coloring
matters.
This member is the 15 naphthylenediamine from which as described in the
German Letters Patent No. 39954 are produced substantive colouring matters
taking on unmordanted cotton by combining one molecule of 15 tetrazo-naphthy-
lene-chloride with two molecules of some other component. The colouring matters
produced in this way have been prominent amongst the group of colouring matters

page_text: deriving from the various naphthylenediamines and dye yellow, red and violet
shades, but being very defective in quality the place which they have occupied in
practice is of no importance whatever.
My foreign correspondents have discovered, that from the 14 naphthylene-
diamine, which by reason of certain difficulties has not as yet been employed for
the production of colouring matters; there can under certain conditions be produced
colouring matters very valuable for dyeing wool giving in acid bath shades varying
from red-brown, red, blue violet to pure blue. These conditions are:
(1) That only one amido group be diazotised and that the combination be made
with only one component such for example as a phenol, a naphthol, or its sulphonic
acid, for example a naptholsulphonic acid, an oxycarbonic acid an amine or its
sulphonic acid for example alpha naphthylamine and naphthylamine sulphonic
acid.
(2) That there be diazotised first one amido group and afterwards the second
amido group and that the diazo groups thus obtained, be combined, in manner
hereinafter described, successively with two molecules of the same or two mole-
cules of a different phenol, or amine or their sulphonic acids or carbonic acids
etc. etc.
In this manner can be formed two series of coloring matters of two different

page_text: TROCESS A.
The production of the novel coloring matters of the type I according to A is
effected in the following manner.
1. PRODUCTION OF THE ACETYLISED COLORING MATTER FROM R SALT
20 parts by weight of monacet 1-4 naphthylenediamine in fine powder are well
mixed with 10 times to 20 times the quantity of water and to this mixture while it
is kept agitated and cooled are added 27 parts of hydrochloric acid of 30 per cent.
HCI, by which means the aceto naphthylenediamine is dissolved. Great care is to
be taken to avoid self heating as otherwise a considerable quantity of the acetyl-
derivative would be saponified...
When all the naphthylenediamine is dissolved, the solution is cooled down to 0° C.
and then mixed with an equally cooled solution of 7 parts of nitrite in 3 times or
4 times the weight of water, during which operation a rise of temperature is
checked by adding ice.
When the nitrite is used up, the diazo compound is mixed, as speedily as possible
with a cooled solution of 40 parts of beta-naphthol disulphonate of sodium R and
100 parts of acetate of sodium in about 400 to 600 parts of water and kept
agitated for 6 to 10 hours. Most of the blueish magenta, red azo-coloring matter
formed separates. The remainder is precipitated by the addition of common salt,
filtered off and freed from the mother lye by pressing off, repeated dissolving,
precipitating by means of common salt solution and pressing off.
The coloring matters produced in this way from one molecule of aceto naphthy-
lene diamine and one molecule of a component for example oxynaphthalene sulphonic
acids; naphthylamine sulphonic acid etc. etc., dye beautiful shades ranging from
blueish magenta red to claret red.
2. SAPONIFICATION OF THE COLORING MATTER FORMED FROM DIAZOȚISED
ACETYL-NAPHTHYLENEDIAMINE.
The coloring matter obtained in the manner above described is dissolved in
water to form a solution of about 15 to 20 per cent, and mixed with a suitable
quantity of caustic soda, for example the coloring matter formed from 20 parts of
acet-naphthylene diamine and 40 parts of R salt is mixed with 20 parts of caustic
soda, and while it is kept agitated the mixture is boiled in an open vessel or
under pressure at 120° to 125° C. until a sample on being super-saturated with
acetic acid no longer turns its violet colour to blue and can be smoothly diazotised.
According to the nature of the coloring matter, the quantity of alkali used and
the temperature of the heating the saponification will be complete in from two
to six hours. When the saponification is complete, the mass is acidulated with
acetic acid or dilute mineral acid. A part of the coloring matter separates by
itself the remainder is precipitated by the addition of common salt; it is treated
further in the usual manner.
The saponification can also be made by heating with sulphuric acid of 30 per cent.,
and also, but with less success by heating with water alone under pressure.

page_text: coloring matter may be purified by repeated dissolving and precipitating in the
usual manner.
For the reduction may also be directly used the coloring matter paste obtained
as described under 1 after being neutralized.
The other reducing agents such as glucose etc. etc. have an action like that of the
sulphide of sodium, with all these agents the completeness of the reaction is to be
recognized in manner set forth and a quantitative production of the desired
coloring matter will be obtained.
A splitting off of the double binding of the nitrogen atoms in the azo group will
take place only when a large excess of the reducing agent is used and when
the heating is kept on for too long a time. When the operation under the
conditions mentioned is interrupted at the right moment the yield of coloring
matter will be quantitative.
The coloring matters prepared by the processes A and B have the generic
a standing for the radical of a phenol or a base or a sulphonic or a carbonic acid or
these two bodies, in consequence the coloring matters are members of a type not
known before.
They differ from the acetylised non saponified products, by giving partly
beautiful red shades but mostly shades ranging from violet blue to pure blue,
whereas the former ones only produce blueish red shades.
The amido group contained in the radical of the naphthylenediamine gives to the
novel coloring matters a strong basic character with mineral acid they form in the
wet state fast salts colored mostly brick red to brownish brick red, and when
submitted in the usual manner to the action of nitrous acid they are easily trans-
formed into diazo compounds, which combine with a further molecule of a phenol,
a base or the sulphonic or carbonic acid of the same, to form the novel coloring
matters of the type II; thus constituting the raw material or intermediate product
for the production of a great many valuable coloring matters.
Such
For the components mentioned in the above example may be substituted a large
number of others, phenols, bases, their sulphonic or carbonic acids etc. etc.
components are for example:
3229
alkalies the naphthol disulphonic acids R and G of the German Patent
Dioxy naphthalin mono sulphonic acid obtained by melting with caustic alkalies
the alpha naphthol disulphonic acid E of the German Patent 45776.
Dioxy naphthalin mono sulphonic acid S obtained by melting with caustic
alkalies the alpha naphthol disulphonic acid S of the German Patent 40571

page_text: Dioxy naphthalin mono sulphonic acid of the German Patent 42261
"
22
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di
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دو
isomere A
"
997
22
B)} obtained by.melting with
caustic alkali the beta-naphtholtrisulphonic acid of the German Patent
22038.
Dioxy naphthalin disulphonic acid obtained by melting with caustic alkali the
alpha-naphthol trisulphonic acid produced by further sulphonisation of the
alpha-naphtholdisulphonic acid S of the German Patent 40571.
Dioxy naphthalin disulphonic acid obtained by melting with caustic alkali the
alpha naphtholtrisulphonic acid of the German Patent 10785.
Dioxy naphthalin disulphonic acid obtained by melting with caustic alkali the
naphtho sulton disulphonic acid of the German Patent 56058 and known as
chromotropacid."
66
Trioxy naphthalin mono sulphonic acid obtained by melting with caustic alkali
the naphthol trisulphonic acid of the German Patent 22038.
Phenol,
Cresol,
Resorcine,
Mono and dioxy benzoic acids, oxysulphobenzoic acids
Oxytoluylic acids, oxyphthalic acids.
Resorcylic acid.
Mono and dioxyphthalic acids.
Alpha naphthol.
Beta-naphthol-dioxy naphthalines.
Beta-oxynapthoic acid of the melting point 216° C.
Alpha-oxynaphthoic acid, m-oxydiphenylamine
Amido-naphtholes.
Primary bases, such as aniline, isomeres, homologues and analogues, such as
alpha naphthylamine etc. etc. further
Secondary bases, such as mono-methyl mono ethyl aniline, isomeres, homo-
logues and analogues for example, methyl, alpha, naphthylamine, phenyl
alpha-naphthylamine, diphenylamine etc. etc. and also
Tertiary bases, such as dimethylaniline, isomeres, homologues, and analogues,
such as dimethyl naphthylamine, phenyl naphthylamine etc. etc. :
be used as components, but the coloring matters produced from these bodies
1 be found of insufficient quality, their sulphonic acids on the contrary furnish
lies of good quality, such sulphonic acids for example are, the:
Naphthionic acid,
Naphthalidin sulphonic acid,
Aluha naphthylamine disuluhonic acid Dahl HIL

page_text: Example 517 parts of the coloring matter having the composition of the
type I. produced from beta naphtholdisulphonic acid R and having the formula
NH,
C₁₁H, {N, C₁H, {(SO₂Na), are dissolved in the 8 to 10 fold quantity of water
-
and admixed with 365 parts of hydrochloric acid of 30 per cent. In this operation
the blue solution of the commencement changes into a red paste, consisting of the
hydrochlorate of the raw material which dissolves with difficulty.
The solution is then cooled by means of ice and at a temperature of about
0 to 5° C. is admixed by degrees and while being kept agitated, with a solution of
70 parts of nitrite in 300 parts of water and is left to repose for several hours. The
diazotation is complete when a sample on being diluted with water furnishes a
perfectly clear solution.
The diazo-compound thus produced is caused to flow, while being kept well
agitated, into a solution, cooled down to about 0° C. of 385 parts of beta naphthol-
disulphonate of sodium R and 275 parts of soda in about 7000 parts of water; the
formation of the coloring matter immediately sets in and is complete after a few
hours.
The greatest part of the coloring matter separates of itself; the remainder is
precipitated by the addition of common salt; it is obtained in the usual manner.
These coloring matters dye in light shades a pure greenish-blue, in dark shades a
black-blue.
י.
"
For the soda may be substituted as condensation agent another alkali, for
example caustic soda or acetate of soda.
The coloring matter produced as described in the example has the formula
CH {N−CH (SO,Na)
C10H6 N₂-
N-C₁H OH
2 —
C₁H
JOH
(SO₂Na)₂
"
1
}
When for the beta naphtholdisulphonate of sodium R is substituted the
equivalent quantity of another component for example 250 parts of beta naphthol
miono sulphonic acid F. of German Letters Patent 42112 or 150 parts of beta'
naphthol there will result coloring matters of the formulæ :
COB
OH
10-
C10H6
N
CH
-
{N₂ = {(SO,Na),
10
(SO,Na); CH.N-CH, OH
JOH
-
{(SO₂Na),
(SO, Na); C₁HN - CH, OH
CH
N
CH
JOH
19
(SO,Na
When there are emploved as components equivalent auantities of an amic
Un
N₂- C₁₂H
C10 Ha
IN
CH
NH
6
{(SONa); C.H. N, CHÀNH
N-CH
4
он
(SO,Na)
-
-
Very interesting is the regularity with which the shades of the coloring matters
5 obtained turn from brown red through claret red, violet to blue, according as there
are employed as components, lower molecular compounds such as benzene-
derivatives or higher molecular compounds of the naphthalin-series.
1 ¦
A further regularity consists in, that the shade of the coloring matters produced
according to the process C, such as for example the coloring matters mentioned in
the last examples, which all contain one same component (the betanaphtholdi-
sulphonic acid R), turns to greenish blue when the second component contains a,
hydroxyl group or an amido group in the beta position, whereas it turns to

page_text: from red violet to violet red when the groups mentioned occupy the alpha
position.
From what is said it follows that the most valuable coloring matters of these
series are those which contain naphthalin derivatives as components, the shades of
the same lie between violet claret red and blue or black blue.
They are rendered prominent above the diazo coloring matters known before and
produced in other ways by their extraordinary fastness and strength and the
clearness of their shades the reason of this is that they possess more auxochromes
in the molecule than the others referred to.
For the second components mentioned in the example may be substituted all those
components that have been mentioned for the processes A and B ; but with several
phenols, for example phenol and with several carbonic acids for example salicylic
acid, the combination proceeds with great difficulty whereas with others, for
example the beta-naphthol-oxy-naphthoic acid of the melting point 216° C., it
proceeds very easily and smoothly.
There may also be substituted for the raw materials mentioned in the example
all the coloring matters, than can be produced according to the processes A
and B.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The manufacture of coloring matters deriving from the 14 naphthylene-
diamine, by the combination of the processes hereinbefore described, that is to say,
firstly by combining diazotised 1.4 monacet-naphthylenediamine with one molecule
of phenols, amines or the sulphonic- or carbonic acids of the same to form new
coloring matters to be used by themselves or as raw material for the manufacture
of other novel coloring matters, secondly by saponification of these new compounds
to form anew a novel coloring matter having the generic formula C10 H
and finally by diazotising and combining this latter product with a second similar or
different molecule of phenols, amines or the sulphonic- or carbonic acids of the same,
NH₂
N
-
to form a new coloring matter of the generic formula C₁H.{N all substan-
tially as described:
-
2 y
Excepted from the claim are those combinations that might be produced from
two phenols or their carbonic acids, from two bases or their carbonic acids and also
from two couples of the said bodies, being different one from the other.
2. The manufacture of coloring matters deriving from the 1-4 naphthylene-
diamine, by combination of the processes herein before described, that is to say
firstly by combining diazotised 14 nitronaphthylamine with one molecule of
phenols, amines or the sulphonic- or carbonic acids of the same, to form new
coloring matters to be used by themselves or as raw materials for the manufacture
of other novel coloring matters, secondly by reducing these new compounds to form
anew a novel coloring matter having the generic formula CH, {NH
finally by diazotising and combining the latter new compound with a second similar
or different molecule of phenols, amines or the sulphonic or carbonic acids of the
same, to form a new azo coloring matter of the generic formula C₁H. {N,
10
6
- I
- 2
-
y
and
all
substantially as described.
Excepted from the claim are those combinations that might be produced from
two phenols and their carbonic acids, two bases and their carbonic acids and
also from two couples of the bodies mentioned, being different one from the
other.
3. The manufacture of new azo coloring matters to be used by themselves or as

page_text: raw material for the manufacture of other coloring matters, by combining the
diazotised 14 monacet-naphthylene diamine with phenols, amines or the sulphonic
or carbonic acids of the same, substantially as described.
4. The manufacture of new azo coloring matters deriving from the 14 naph-
10 ४
1♫
thylenediamine and having the generic formula C₁H. {NH, by saponifi-
cation of the acetyl compounds, referred to in the preceding claim, substantially
as described.
5. The manufacture of new azo-coloring matters to be used by themselves or as
raw-materials for the manufacture of other coloring matters, by combining the
diazotised 14 nitro-naphthylamine with phenols, amines or the sulphonic or
carbonic acids of the same, substantially as described.
6. The manufacture of new azo coloring matters deriving from the 14 naph-
thylenediamine and having the generic formula C, H, {NH,
6
2
by reducing the
nitro-azo-colors, referred to in the preceding claim, substantially as described.
7. The manufacture of new azo coloring matters deriving from the 1-4 naph-.
thylenediamine and having the generic formula CH by diazotising the
CH{\
new compounds referred to in Claims 4 and 6, and combining the products of the
diazotation with one molecule of phenols, amines, or the sulphonic or carbonic acids
of the same, all substantially as described.
y
Excepted from the claim are those combinations that might be produced from
two phenols and their carbonic acids, two bases and their carbonic acids and
also from two couples, of the said bodies mentioned, being different one from the
other.
8. The application of the new products referred to in Claims 3, 4, 5, 6, 7 for the.
production of azo coloring matters, all substantially as described.
9. As new articles of manufacture the products resulting from the processes.
referred to in the preceding claims and their application to industrial purposes.
Dated this 30th day of July 1892.
ABEL & IMRAY,
Agents for the Applicant.