Improvements in and relating to the Manufacture of Colouring Matters.
Year: 1895

page_text: Date of Application, 29th May, 1895
Complete Specification Left, 24 h Mar., 1896-Accepted, 25th Apr., 1893
[Communicated from abroad by FARBWERK MÜHLHEIM, of Mühlheim-on-the-
Main, in the Empire of Germany.]
Improvements in and relating to 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 to be as follows :-
-
This invention relates to improvements in the manufacture of azocolouring
matters and to new raw materials necessary for the production of such colouring
matters.
Monoalkyl betanaphthylamines have been found to be excellent raw materials
for the production of monoalkylamidonaphthol monosulpho acids containing the
alkylamido groups in the beta position. For this purpose they are transformed by
sulphonation into disulphoacids either directly or by first producing monosulpho-
acids and further sulphonating the latter, and these disulphoacids are then heated
with causti alkalies at an elevated temperature. The obtained alkylamido-
naphtholsulphoacids are hardly soluble in cold water and can be combined with
diazo or tetrazo bodies yielding new azodyestuffs of very pure shades, the shades
differing in a manner according to the combination being effected in an alkaline or
can likewise be
an acid solution. The new alkylamidonaphtholsulpho acids
employed as developers being combined on the fibre with diazo or tetrazo
compounds.
Dated this 20th day of Mo 1805
HASELTINE, LAKE & Co.,
45 Southampton Buildings, London, W.C., Agents for the Applicant.
Improvements in and relating to the Manufacture of Colouring
Matters.
1, 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 :-
The invention consists in producing a series of colouring matters derived from a
new ethylamidonaphtholsulphoacid, which latter and a method of producing it
I will first proceed to describe.
When the chlorhydrate of ethylbetanaphthylamine is dissolved in three parts by
weight of monohydrate of sulphuric acid and fuming sulphuric of 20% SO, is
added at a temperature of 40° C. until a sample diluted with water and treated
with alkali shows that sulphonation is finished, isomeric monosulphoacids are
produced which are soluble with difficulty in cold water, one of them forming
a sodium salt which is easily soluble in cold spirit. This latter monosulphoacid
I call A.
When however the chlorhydrate of ethylbetanaphthylamine is sulphurized with

page_text: monohydrate of sulphuric acid during several hours at 140° C., another mono-
sulphonic acid is formed being likewise soluble with difficulty in water. This
sulphoacid I will call B.
-
By further sulphonating the acids A or B with five parts of fuming sulphuric
acid of 20% SO, at 100-120° C. a disulphonic acid is formed, the alkaline
solution of which shows a blueish green fluorescence. This acid is easily soluble
in water. By heating this disulphonic acid with caustic potash together with some
water at about 200° C (a process which is generally well known for the purpose of
substituting the OH
for the SOH group), the new ethylamidonaphtholmono-
sulphoacid is produced and can be isolated by acidifying the rather concentrated
alkaline solution. It is soluble with difficulty in cold water. The alkaline
solution shows a violet fluorescence. When combined with tetrazostilbene-
disulphoacid in an alkaline solution, a blueish violet colouring matter is obtained.
The formula of this ethylamidonaphtholsulphoacid is considered to be the
following.
Now I have found that the azodyes derived from this ethylamidonaphtholsulpho-
acid excel by a great purity of shade and by a remarkable affinity for the cotton
fibre. This is not only the case as regards tetrazodyes (derived from benzidine
and the like) but also as regards the so called disazodyes derived from diazo-
azocompounds. Thus for instance colouring matters produced from diazo-azo-
naphthalenedisulphoacid and naphtholsulphoacids (which are known in the trade as
naphthol black") are not regarded as direct cotton dyeing materials, whilst by
substituting the new ethylamidonaphtholsulphoacid for the before mentioned
naphtholsulphoacids, beautiful violet colouring matters are obtained which can be
easily fixed on cotton. Thus the introduction of my new acid makes this class of
disazodyes hitherto only useful for the animal fibre also valuable for direct cotton
dyeing.
<
The disazodyes produced in such a way have proved to be the most valuable
derivatives of my new ethylamidonaphtholsulphoacid. They can be represented
by the following formula :
✗ signifying the rest of the new ethylamidonaphtholsulphoacid.
R, signifying the rest of an amine (or a substituted amine) which when combined
with diazocompounds can be further diazotized, such as aniline (in the form of
amidoazobenzene or its sulphoacids) orthotoluidine (in the form of amidoazotoluene
or its sulphoacids), paraxylidine (for instance in the form of sulphanilic acid-azo-
paraxylidine), acidylmetadiamines (see former Letters Patent No. 10668"),
alphanaphthylamine or its 6 or 7 monosulphoacid.
R signifying the rest of an amine (or a substituted amine) the diazocompound
of which is generally not capable of yielding direct azo-cotton dyes, such as for
instance

page_text: The production of the diazoazocompounds which are to be combined with
my new acid is well known and I make no claim so far as this production is
concerned.
Of course, the affinity of the new dyestuffs for the cotton fibre depends in some
degree on their solubility or on the number of sulphogroups contained in the
molecule of these dyestuffs. I have found however that even the combinations
of amidoazobenzenedisulphoacid or of betanaphthylamine 3.6.8 trisulphoacid-azo-
alphanaphthylamine, with my new acid show a considerable affinity for cotton
fibre.
By employing, as middle components, the above mentioned amines of the benzene
series, red to reddish violet colouring matters are obtained, whilst alpha-naphthyl-
amine yields reddish to blueish violet shades.
In order to further illustrate my process I will give the following examples.
1. Betanaphthylamine 6.8 disulphoacid (G) is diazotized in the usual way and
the diazocompound is combined with the chlorhydrate of alphanaphthylamine in a
watery solution. When after some standing the combination is finished the product
is further diazotized in an acid solution with one molecular quantity of nitrite of
sodium. The obtained diazo-azocompound is then poured into a solution of one
molecular quantity of ethylamido-naphthol monosulphoacid kept alkaline by
carbonate of soda. From the obtained violet solution the violet colouring matter
is salted out in the heat with common salt.
2. Amidoazobenzenemonosulphoacid is diazotized in the usual way and the
diazocompound is combined with one molecular quantity of ethylamidonaphthol-
sulphoacid in a watery solution which is kept alkaline by carbonate of soda. The
red colouring matter produced in such a way is salted out in the heat, then filtered
and pressed.
If, instead of amidoazobenzenemonosulphoacid, sulphanilic acid-azo-paraxyli-
dine
or sulphanilic acid azoacetylmetatoluylenediamine (according to former
Letters Patent No. 10668%) is used, colouring matters of a more violet tint are
produced.
3. Aniline is diazotized and combined with the chlorhydrate of alphanaphthyl-
amine in the usual way. When after standing for about twelve hours the
combination is complete the obtained suspension of benzene-azoalphanaphthyl-
amine chlorhydrate is further diazotized by means of sodium nitrite in an acid
solution, and the diazotized liquid is filtered and combined with one molecular
quantity of ethylamidonaphthol monosulphoacid kept alkaline by carbonate of soda.
The violet colouring matter separates at once and is best kept in the form of a
paste.
4. Amidosalicylic sulphoacid (obtained by sulphonating salicylic acid and then
nitrating and reducing) is diazotized and combined with the chlorhydrate of
alphanaphthylamine in the presence of acetate of sodium. The amidoazocompound
is thus formed after standing and stirring for some time. It is then collected in a
filter and washed with water and afterwards dissolved in carbonate of soda solution.
To this solution a molecular quantity of sodium nitrite is added and the solution
is poured into dilute cold hydrochloric acid. When after stirring for some time
the second diazotation is terminated, the diazoazocompound is poured into a
solution of one molecular quantity of ethylamidonaphtholsulphoacid kept alkaline
by carbonate of soda. The thus obtained violet dyestuff is salted out, filtered and
pressed.
5. Naphthionic acid is diazotized and combined with the sodium salt of alpha-
naphthylamine-7-sulphonic acid in the presence of acetate of sodium. The
obtained amidoazocompound is further diazotized with nitrite of sodium in an acid
solution and the obtained diazo-azosulphoacid is poured into an alkaline solution
of one molecular quantity of ethylamidonaphtholmonosulphoacid.
From the
obtained violet solution the new dyestuff is salted out in the heat with common
salt.

page_text: 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 disazo-colouring matters dyeing
unmordauted cotton, which process consists in combining the new ethylamido-
naphtholmonosulphoacid hereinbefore defined with diazo-azocompounds of the
following formula

page_text: 5. As new articles of manufacture, the red to violet disazocolouring matters
dyeing unmordanted cotton and produced substantially as hereinbefore described.
Dated this 23rd day of March 1896.
HASELTINE, LAKE & Co.,
45 Southampton Buildings, London, W.C., Agents for the Applicant.