Improvements in and relating to the Manufacture of Substantive Dyestuffs and of Materials therefor.
Year: 1890

page_text: Date of Application, 21st June, 1890
Complete Specification Left, 20th Mar., 1891-Accepted, 25th Apr., 1891
PROVISIONAL SPECIFICATION.
Improvements in and relating to the Manufacture of Substantive
Dyestuffs and of Materials therefor.
I, JAMES YATE JOHNSON, of 47, Lincoln's Inn Fields, in the County of
Middlesex, Gentleman, do hereby declare the nature of this invention, which
has been communicated to ine from abroad by the Badische Anilin and Soda
Fabrik, of Ludwigshafen-on-Rhine, in the Empire of Germany
This invention is based upon the following observations:
(1) That the 11' naphthylamine-mono sulpho acid on melting with a caustic
alkali yields a new 11' amido-naphthol ;
(2) This amido-naphthol can be sulphonated with concentrated sulphuric acid to
yield a new sulpho acid;
(3) This sulpho acid combines with the tetrazo compounds from benzidine,
orthotolidine, orthodiansidine, and diamido-stilbene to yield substantive dyestuff's
which are not however considered to be of very great technical value as they give
rather dull colours:
(4) Bright dyestuffs can be obtained if previously to combination with the
tetrazo-compounds, an acid radicle of the fatty or aromatic series be introduced
into the amido group of the 1-1' amido-naphthol sulpho-acid. These dyestuff's dye.
unmordanted cotton from the caustic alkaline bath good fast colours;
(5) These colouring matters can be further improved by introducing carboxyl-
groups or additional sulpho groups into their molecule. They then fix themselves
on unmordanted cotton from a boiling neutral or ordinary alkaline or soap bath,
and so render the use of the caustic alkaline bath unnecessary.
1. The new 11' amido-naphthol is obtained by melting 11' naphthylamine
sulpho acid (see Erdmann, Annalen der Chemie 247 318 and Schultz Berichte der
deutschen Chemischen Gesellschaft 20, 3161) with three times the quantity by
weight of caustic alkali at a temperature of about 200 to 210° C.
2. The new sulpho acid of the 11' amido-naphthol can be obtained by sulpho-
nating with four times the quantity by weight of concentrated sulphuric acid at
about 15 to 20° Centigrade.
3. The introduction of an acid radicle of either the fatty or aromatic series into
the amido group of the 11' amido naphthol mono sulpho acid is effected by the
action of the corresponding acid chloride on an alkaline solution of the sodium salt
of the 11 amido naphthol mono sulpho acid, or by treating this salt with the
corresponding acid anhydride. Thus for instance benzoyl 11' amido naphthol-
sulpho-acid can be prepared by the action of benzoyl-chloride upon the above
named sodium salt in alkaline solution. It is readily soluble in pure water and is
precipitated by common salt.
4. In order to obtain the hereinbefore mentioned series of dyestuffs from the
tetrazo-derivatives of benzidine, tolidine, dianisidine and diamido-stilbene the
solutions of the tetrazo-compounds which can be obtained in the well known way
are run into an alkaline solution of an equivalent quantity of the substituted
11 amido-naphthol sulpho acid, two molecular proportions of the latter compound
being taken for one molecular proportion of the base. The mixture is well stirred
until the formation of the dyestuff is complete.
5. To obtain the dyestuffs which can be applied without the use of a caustic
alkaline bath and which have as above mentioned the sulpho- or carboxyl-groups
introduced into their molecule, instead of the diamido-bases above mentioned there
are taken their sulpho- or carboxyl derivatives, preferably ortho-diamido-di-phenic-
acid or benzidine mono-sulpho acid. Thus, for instance, about thirty five parts by

page_text: weight of the hydrochloride of ortho-diamido-diphenic acid can be diazotized at a
low temperature and then be mixed with an alkaline solution of about eighty parts
by weight of benzoyl 11' amido-naphthol mono sulpho acid (or an equivalent
quantity of some other substitution compound as hereinbefore mentioned) and
stirred for say about two days when the formation of the dyestuff's will be complete.
It can be separated by precipitation with common salt solution, and purified if
necessary by repeatedly redissolving and reprecipitating.
Dated this 21st day of June 1890.
J H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
Improvements in and relating to the Manufacture of Substantive
Dyestuffs and of Materials therefor.
I JAMES YATE JOHNSON, of 47, Lincoln's Inn Fields, in the County of
Middlesex, Gentleman, do hereby declare the nature of this invention (which has
been communicated to me from abroad by the Badische Anilin and Soda Fabrick,
of Ludwigshafen-on-Rhine, in the Empire of Germany,) and in what manner
the same is to be performed, to be particularly described and ascertained in and
by the following statement:-
This invention is based upon the following observations:
(1) That 11 naphthylamine-mono-sulpho-acid on melting with a caustic alkali
yields a new 11' amido-naphthol.
(2) This amido-naphthol can be sulphonated with concentrated sulphuric acid to
yield a new sulpho-acid.
(3) This sulpho-acid combines with the tetrazo-compounds from benzidine,
orthotolidine, ortho-di-anisidine, and diamido stilbene to yield substantive dyestuff's
which are not however considered to be of very great technical value as they give
rather dull colours.
(4) Bright dyestuff's can be obtained if previously to combination with the
tetrazo-compounds an acid radicle of the fatty or aromatic series be introduced into
the amido-group of the 11' amido-naphthol-sulpho-acid. These dyestuff's dye
unmordanted cotton from the caustic alkaline bath good fast colours.
(5) Improved colouring matters can be obtained by using such materials that the
finished dyes contain carboxyl-groups or additional sulpho-groups in their molecule.
They are then more soluble and fix themselves on unmordanted cotton from a
boiling neutral or ordinary alkaline or soap bath, and so render the use of the
caustic alkaline bath unnecessary.
The following examples illustrate the manner in which the invention may be
carried into practical effect (the parts being by weight).
EXAMPLE 1.
PRODUCTION OF A NEW 11' AMIDO-NAPHTHOL, A NEW MATERIAL FOR USE IN
THE MANUFACTURE OF DYESTUFFS.
Take about one part of 11' naphthylamine-mono-sulpho-acid (also called
18 naphthylamine sulpho acid; see Erdmann Annalen der Chemie 247 318 and
Schultz Berichte der Deutschen Chemischen Gesellschaft 20, 3161) and add it
gradually to about three parts of a melted mixture of caustic potash and caustic
soda in equal proportions (with a little water added) at a temperature of about two
hundred to two hundred and ten degrees Centigrade. Then raise the temperature
to and maintaining it at about two hundred and thirty to two hundred and forty
degrees Centigrade until the following test indicates the end of the operation,
dissolve test portions from time to time in about ten times the quantity of boiling
dilute hydrochloric acid of such strength that an acid solution is obtained, filter .if

page_text: necessary then if on cooling 11' naphthylamine-mono-sulpho-acid separates the
heating is continued, if no such separation takes place the operation is interrupted.
The new 11' amido-naphthol can best be isolated by dissolving the melt in about
twenty parts of hydrochloric acid (containing about fifteen per cent, real hydro-
5 chloric acid HCl) and adding one part of Glauber's salt stirring well. The new
amido naphthol separates out in the form of its difficultly soluble sulphate. Filter
press and dry.
The new amido-naphthol thus obtained can be used in the manufacture of dye-
stuffs as herein described as part of this invention and it is capable of combination
with diazo compounds.
TREPARATION OF A NEW AMIDO-NAPHTHOL-MONO-SULPHO-ACID
A NEW
MATERIAL SUITED FOR USE IN THE MANUFACTURE OF DYESTUFFS.
Stir together about one part of 1.1' amido-naphthol sulphate with about four
parts of ordinary concentrated sulphuric acid at the ordinary temperature of the
atmosphere for say about six to eight hours. At a temperature of about fifteen to
twenty degrees Centigrade the desired mono-sulpho-acid forms. It is but slightly
soluble in water and the progress of the operation can at any time be ascertained by
precipitating a test portion of the acid mixture with water and adding soda solution.
If a practically clear solution be obtained the mono-sulpho-acid may at once be
isolated, but if an undissolved precipitate be present in the soda solution, the
amount thereof affords an indication of the proportion of unsulphonated amido-
naphthol in the mixture and the sulphonation is continued until the test shews a
practically clear solution.
To isolate the amido-naphthol-mono-sulpho-acid pour the acid mixture into about
ten parts of ice water and filter wash press and purify by conversion into the
calcium salt by means of milk of lime, filtering the solution thereof from all
insoluble matter and reprecipitating the amido-naphthol-mono-sulpho-acid with
hydrochloric acid. Filter wash press and dry.
The new
amido-naphthol-mono-sulpho-acid can be used in the manufacture
of substantive dyestuffs as herein described as part of this invention or it can be
diazotized and the diazo-compound used in the well known way for the manufacture
of dyestuffs. It combines with diazo compounds and with the tetrazo-compounds
derived from benzidine and the other diamido-bases in use by manufacturers for the
preparation of substantive dyes.
The introduction of an acid radicle of either the fatty or aromatic series into the
amido group of the 1'1' amido-naphthol-mono-sulpho-acid is effected either by the
action of the corresponding acid chloride on an alkaline solution of the sodium salt
of the 11' amido-naphthol-sulpho-acid or by treating this salt with the corre-
sponding acid anhydride. Thus the benzoyl-derivative is best prepared by
treatment of a solution of the above mentioned salt with benzoyl-chloride while the
acetyl-compound can be obtained by the action of acetic anhydride on this salt.
PREPARATION OF 11' BENZOYL AMIDO-NAPHTHOL-MONO-SULPHO-ACID, A NEW
MATERIAL FOR THE MANUFACTURE OF DYESTUFFS.
Dissolve about ten parts of 11' amido-naphthol-mono-sulpho-acid in a solution of
about six and a quarter parts of calcined soda in about seventy five parts of water.
Cool the solution to below five degrees Centigrade, and then add carefully (during
about one hour) about six parts of benzoyl-chloride. Agitate the mixture the
whole time and keep the temperature below five degrees Centigrade. The benzoyl
amido-naphthol-mono-sulpho-acid begins to separate out in bright pale yellowish
crystals. Continue stirring until the quantity of separated benzoyl-compound no

page_text: THE PREPARATION OF 11' ACETYL-AMIDO-NAPHTHOL-MONO-SULPHO-ACID.
Make a mixture of about ten parts of glacial acetic acid and five parts of acetic
anhydride and stir into this mixture about ten parts of 11' amido-naphthol-mono-
sulpho-acid at a temperature of about ten to fifteen degrees Centigrade. Continue
stirring and raise the temperature to, and maintain for about two hours at, about
one hundred degrees Centigrade. The end of the operation can in any case be
ascertained by treating test portions of the mixture dissolved in water with
nitrous acid, the production of the diazo-compound of amido-naphthol-mono-sulpho-
acid which combines with the naphthols or their sulpho-acids (such as R salt) to
vield a colouration proves the existence of unaltered amido-naphthol-mono-sulpho-
acid in the mixture. If no such colouration can be obtained the formation of the
acetyl-derivative may be regarded as complete. This point being reached, raise the
temperature to about one hundred and twenty degrees Centigrade and evaporate to
dryness.
The greyish powder thus obtained, consisting of the sodium salt of the new
acetyl-compound, can be used without further purification.
The substituted amido-naphthol-sulpho-acid compounds thus obtained can be
used for the manufacture of substantive dyestuffs by combination with tetrazo-
compounds, in the well known way, to yield bright dyestuff's.
The combinations with the tetrazo compounds from benzidine, tolidine and the
ordinary diamido-bases in use by manufacturers for the preparation of substantive
dyes are rather insoluble in the ordinary alkaline bath and can therefore with
advantage be dyed from a caustic alkaline bath; the combinations with such
diamido-bodies as contain substituted groups which give to the finished dyestuffs
greater solubility can be dyed without the aid of a caustic alkali.
=
Such diamido-bodies are for instance diamido-diphenic-acid (di-amido-di-phenyl-
di-carboxylic acid, NH, COOH 1:2) and benzidine mono-sulpho-acid (described
in the Specification of Letters Patent No. 3198 of the year 1886) in which cases the
presence of the carboxyl-groups and the additional sulpho-group respectively cause
PREPARATION OF
SUBSTANTIVE
NAPHTHOL-MONO-SULPHO-ACID
ALKALINE BATH.
BENZOYL-AMIDO-
CAUSTIC
DISAZO-DYES FROM 11
WHICH DYE BEST FROM A
In order to obtain this series of dyes from the tetrazo-compounds of benzidine,
tolidine, dianisidine and diamidostilbene run a solution of tetrazo compound (which
can be obtained in the well known way) into an alkaline solution of an equivalent
quantity of the substituted 11' amido-naphthol-sulpho-acid taking two molecular
proportions of the latter compound for one molecular proportion of the base. Stir
the mixture well until the formation of the dyestuff attains the maximum and then
isolate it in the usual way.
PREPARATION OF A SUBSTANTIVE DYE FROM 11' BENZOYL-AMIDO-NAPHTHOL-
MONO-SULPHO-ACID WHICH DYES COTTON FROM THE ORDINARY ALKALINE
BATII.
Take about thirty five parts of hydrochloride of diamido-di-phenic acid (di-
amido-di-phenyl-di-carboxylic acid, NH, COOH 1:2) and heat with about one
hundred parts of water until a uniform mixture is obtained; cool the mixture: add
:

page_text: about fifty eight parts of hydrochloric acid (containing above twenty five per cent...
of real acid IICI) and diazotise after addition of about fifty parts of ice with a
solution of about fourteen parts of sodium nitrite in forty parts of water. Stir
well for several hours and then run the tetrazo-compound into a solution of eighty
parts of 11' benzoyl-ainido-naphthol-sulpho-acid and eighty parts of calcined soda
in two thousand five hundred parts of water, stir for about two days precipitate
the dyestuff formed with about one thousand five hundred parts of a saturated
solution of common salt; boil and filter hot, press and dry. If it be desired to
purify the dyestuff, dissolve it again in hot water and reprecipitate -with common
salt solution. In the same way dyes can be obtained using benzidine-mono-sulpho-
acid instead of the diamido-diphenic acid, and the acetyl-derivative can be used
instead of the benzoyl-amido-naphthol-sulpho-acid.
Having now particularly described and ascertained the nature of this inven-
tion, and in what manner the same is to be performed, I declare that what I
claim is :-
First. The manufacture of substantive dyestuffs by the combination of processes
hereinbefore described, namely by melting 11' naphthylamine mono-sulpho-acid
with a caustic alkali to obtain a new 11 amido-naphthol, then sulphonating this
amido-naphthol to obtain a new mono-sulpho-acid thereof, next preparing from this
a substitution compound with an organic acid radicle and finally combining this
substituted amido-naphthol-mono-sulpho-acid with tetrazo-compounds, all substan-
tially as herein before described.
Second. The manufacture of a new 11 amido-naphthol substantially as herein-
before described.
Third. The manufacture of a new 11' amido-naphthol-mono-sulpho-acid sub-
stantially as herein before described.
Fourth. The manufacture of substituted derivatives of 1.1' amido-naphthol-mono-
sulpho-acids substantially as herein before described.
Fifth. The application of the new 1-1' amido-naphthol-mono-sulpho-acid or of its
substituted derivatives as hereinbefore explained in the manufacture of substantive,
dyestuff's by combining them with tetrazo-compounds for the production of sub-
stantive dyes, all substantially as hereinbefore described.
Sixth. The new products hereinbefore described such as are obtained as the
results of the processes hereinbefore claimed.
Dated this 10th day of M 1901