Year: 1896

page_text: Date of Application, 16th Mar., 1896
Complete Specification Left, 14th
ec., 1896-Accepted, 13th Feb., 1847
R₁ signifying the "rest" of an amine which when combined with diazocompounds
can be further diazotized and R signifying the "rest" of an amine the diazo
compound of which is generally not capable of yielding direct azo-cotton-dyes.
I have now found that the same process can be applied to amidonaphtholsulphoacids
of the following formula.
where X signifies hydrogen or another radical instead of ethyl, such as for instance
phenyl, or to the corresponding disulphoacids.
Dated this 16th day of Munah 1
1904
HASELTINE, LAKE & Co.,
45 Southampton Buildings, W.C., Agents for the Applicant.

page_text: Improvements in the Manufacture of Colouring Matters.
I, HENRY HARRIS LAKE, of the Firm of Haseltine, Lake & Co., Patent Agents,
45 Southampton Buildings, in the County of Middlesex, 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 :-
This invention relates to the manufacture of colouring matters.
As described in my Complete Specification No. 1066993 red to violet disazocolouring
matters which dye unmordanted cotton can be produced by combining ethyl-amido-
naphtholsulphoacid the formula of which is considered to be
OH
SO₂H.
NHCH,
with diazo azo compounds of the following formula
R N N R₁-N-N-
-
R signifying the "rest" of an amine, which, when combined with diazocompounds
can be further diazotized, and R, signifying the "rest" of an amine, the diazo-
compound of which is generally not capable of yielding direct azo cotton dyes.
I have now found that, more generally speaking, amidonaphtholsulphoacids the
formula of which can be reduced to the following scheme
yield results very similar to those obtained with the ethylated acid described in the
Specification of iny aforesaid Patent No. 1066985.
This rule I have ascertained by examining the following acids:
(1) 2. amido-5-naphthol-7-sulphoacid see Letters Patent 26143.
(2) 2. amido-5-naphthol-1.7-disulpho acid see Letters Patent 20580°³.
(3) 2. phenylamido-5-naphthol-7-sulphoacid.
This acid may be prepared by heating 2-naphthylamine 5-7 disulphoacid (see
Letters Patent 26143) with one part by weight of aniline and 0-6 parts by weight
of aniline salt during about 6 hours up to the boiling point, rendering the melt
alkaline by adding carbonate of soda solution removing the aniline with steam,
evaporating the solution containing the phenylated acid to dryness and melting
the residue with about 15 parts of caustic potash lye of about 50% during 14 hours
up to about 210-20° C. By acidification the phenylamidonaphtholsulphoacid which
is hardly soluble, separates from the solution. Its alkaline solution shows a violet
fluorescence.

page_text: The process for combining the diazocompounds of the amines of the series R
with the amines of the series R₁, and the process of further diazotizing the thus
obtained amidoazocompounds is well known and I make no claim so far as such
process is concerned.
My claim is only for the combination of such diazo-azocompound with the amido-
naphtholsulphoacids, such as above mentioned, and in this regard the following
general observations may be made first.
Of course, the affinity of the new dyestuffs for the cotton fibre depends in some
degree upon their solubility or upon the number of sulphogroups contained in the
molecule of these dyestuffs. I have found however, that even the combinations of
amidoazobenzenedisulphoacid with amidonaphtholsulphoacid, or of alphanaphthyl-
amine 3.6 disulphoacid-azo-alphanaphthylamine with amidonaphtholdisulphoacid show
a considerable affinity to the cotton fibre.
By employing, as middle components or as amines of the series R₁, amines of the
benzene series, the shade of the disazo-dye will be red to violet red, whilst alpha-
naphthylamine (or its 6- or 7- sulphoacid) yields a reddish to blueish violet shade.
Unsubstituted amidonaphtholsulphoacid yields a shade which is somewhat more
reddish than that obtained with the ethyl- or phenylderivative. The amidonaphthol-
disulphoacid yields a product of greater solubility in water.
In some cases, when only one sulphogroup is contained in the molecule of the
resulting dye, the latter especially when dried is not easily soluble in water. In
such cases it is advisable not to dry the same but to keep it in the form of a
paste.
The amines of the series R and R, are the same as indicated in my former
Letters Patent 1066995.
In order to further illustrate my process I will give the following examples which
of course may be varied according to the nature of the invention.
(1) Prepare the amidoazocompound from diazotized paratoluidinemetasulphonic
acid (obtained by reducing paranitrotoluolsulphoacid) and alphanaphthylamine,
dissolve the same in carbonate of soda solution, add a molecular quantity of nitrite of
sodium, and pour the solution into cold dilute hydrochloric acid. When after a
prolonged stirring the second diazotation is finished, pour the diazo-azocompound into
a solution of a molecular quantity of amidonaphtholsulphoacid kept alkaline by
carbonate of soda. Isolate the violet colouring matter by salting out in the heat.
(2) Diazotize the amidoazocompound formed by combining diazonaphthionic acid
with Cleve's acid, and combine the diazoazocompound with a molecular quantity of
phenylamidonaphtholsulphoacid in a solution kept alkaline by carbonate of soda.
Isolate the blueish violet colouring matter by salting out in the heat.
(3) Diazotize amidoazobenzene in the usual way and pour the obtained solution
into an alkaline solution of an equivalent quantity of amidonaphtholsulphoacid.
The obtained red colouring matter separates in small crystals by adding common salt
to the hot watery solution. An analogous result is obtained, when in this example
amidonaphtholsulphoacid is replaced by the disulphoacid.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed, as communicated to me by my
foreign correspondents, I declare that what I claim is :-
1. The process of producing red to violet disazocolouring matters dyeing
unmordanted cotton, which process consists in combining the 2. amido-5-naphthol-
7 sulpboacid or 2-phenylamido-5-naphthol-7 sulphoacid or 2-amido-5-naphthol
1.7 disulphoacid with diazo-azocompounds of the following formula
RN NR₁ - N = N-
R signifying the rest of an amine (or a substituted amine) the diazocompound of
which is generally not capable of yielding direct azocotton dyes, and R₁ signifying
the "rest
of an amine (or a substituted amine), which, when combined with diazo-
compounds can be further diazotized.

page_text: 2. The process of producing red to violet red disazo colouring matters dyeing
unmordanted cotton, which process consists in combining the 2-amido-5-naphthol-
7-sulphoacid or 2 phenylamido 5-naphthol-7 sulphoacid or 2 amido-5-naphthol 1.7 di-
sulphoacid with the diazocompounds of amidoazobenzene or its monosulphoacid or
disulphoacid amidoazotoluene or its monosulphoacid or disulphoacid sulphanilic acid-
azo-paraxylidine sulphanilic acid-azo-acetylmetatoluylenediamine.
3. The process of producing reddish to blueish violet disazocolouring matters
dyeing unmordanted cotton, which process consists in combining 2-amido-5-naphthol-
7 sulphoacid or 2-phenylamido 5-naphthol-7-sulphoacid or 2-amido-5-naphthol 1.7 di-
sulphoacid with the diazocompounds
HASELTINE, LAKE & Co.,
45 Southampton Buildings, London, W.C., Agents for the Applicant.