Improvements in the Manufacture and Production of Substantive Colouring Matters.
Year: 1890

page_text: Date of Application, 3rd May, 1890
Complete Specification Left, 30th Dec., 1890-Accepted, 31st Jan., 1891
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture and Production of Substantive
Colouring Matters.
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 com-
inunicated to me from abroad by the Badische Anilin & Soda Fabrik of
Ludwigshafen-on-the-Rhine in the Empire of Germany) to be as follows:-
-
This invention is based on the discovery that useful substantive dyestuffs can be
obtained from the dihydro-oxynaphthaline having the constitution represented by
the formula
and which is known to chemists as [111] dihydroxynaphthaline (or 1-8 dioxy-
naphthaline) (Journal of the Chemical Society 56, 157 Annalen der Chemie
247, 356).
The said dyestuffs are the disazocompounds resulting from the combination of
the above mentioned [11] dihydroxynaphthaline with the tetrazo compounds
derived from benzidine, tolidine, diamidostilbene and dianisidine respectively and
they dye cotton (from a boiling and strongly alkaline bath) various shades of blue,
without the aid of a mordant. They are characterized by great affinity for the
fibre and the colours obtained are practically unaffected by treatment with acetic
acid, so that the new dyestuffs differ essentially from the previously known
corresponding compounds derived from other dihydroxynaphthialines which are
either easily changed by acids or else have but little affinity for vegetable fibre.
The new dyestuffs fix themselves on cotton from the boiling caustic alkaline bath
and after rinsing with water, the colour remains fast on the fibre even in boiling
water.
The following examples will serve to further illustrate the production of the new
dyestuffs in accordance with this invention; the parts heing by weight.
1. To produce a dyestuff from the tetrazo-compound of benzidine and the 1·11
hydroxynaphthaline, take about nine and one fifth parts of benzidine base and
dissolve them by mixing with about one hundred and eighty parts of water and
about forty four parts of hydrochloric acid containing about twenty five per cent. of
real hydrochloric acid [HC1] and heat the mixture. Cool the solution and when
cold add about fifty parts of ice and then run in gradually about seven parts of
sodium nitrite (containing about ninety-six per cent. real nitrite Na NO,) dissolved
in about twenty-five parts of water. Next run the solution of tetrazodiphenyl thus
obtained into a solution containing about sixteen and a half parts of [111]
dihydroxynaphthaline about four parts of caustic soda, about five thousand parts
of water and about forty one parts of crystallized sodium acetate and just acidified
with acetic acid. Stir for say two hours, filter off the precipitated colouring matter
press and preserve for use in the form of paste.
2. To obtain the corresponding dyestuff from tolidine substitute in the above.
example ten and three fifths parts of ortho-tolidine base for the nine and one
fifth parts of benzidine base and in other respects proceed in exactly the
same wav.

page_text: 3. To obtain the diamostilbene dyestuff substitute for the benzidine base in
example, ten and a half parts of diamidostilbene base and in other respects
proceed in the same way.
4. To obtain the corresponding dyestuil" from dianisidine substitute for the
benzidine base in example 1, twelve parts of dianisidine and in other respect<
proceed in the same way.
If the combination of the dihydroxyphthaline with the tetrazo compounds be
performed in a solution rendered alkaline with soda it often happens that diazo
bodies insoluble in alkaline solution are formed as bye-products, and as these are
(on account of their insolubility) useless as dyes it is preferred to perform the
combinations as described in acetic acid solution.
Daid this 2nd day at Vow tum
J. 11. JOHNSON & Co.,
Agents.
COMPLETE SPECIFICATION.
Improvements in the Manufacture and Production of Substantive
Colouring Matters.
1. JAMES YATE Jonssox of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of this invention (which has been com-
municated to me from abroad by the Badische Anilin and Soda Fabrik of
Ludwigshaf-on-th-Rhin 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 on the discovery that useful substantive dyestuff's can be
obtained from the dihydroxy naphthalene having the constitution represented by the
farmula
and which is known to chemists as [11] dihydroxynaphthalene, (or 1-8 dioxy-
naphthalene, see the Journal of the Chemical Society, 56, 157 and Annalen der
Chemie 247, 350). The said dyestuffs are the disazocompounds resulting from the
combination of the above mentioned [11] dihydroxy naphthalene with the tetrazo
compounds derived from benzidine, tolidine, diamidostilbene or dianisidine respec-
tively and they dye cotton (from a boiling and strongly alkaline bath) various
shades of blue without the aid of a mordant. They are characterised by a great
affinity for the fibre and the colours obtained, are practically unaffected by treat-a
ment with nectic acid, so that the new dyestuff's differ essentially from the
previously known corresponding compounds derived from othur dihydroxy-
naphthalenes which either are easily changed by acids or have but little affinity for
vegetable fibre.
The new dyestuffs fix themselves on cotton from a boiling caustic alkaline bath
and after rinsing with water, the colour remains fast on the fibre, even in boiling
water. Prolonged boiling, however gradually renders the shade less clear.
The following examples will serve to illustrate the production of the new dye-
stuffs in accordance with this invention: the parts being by weight.
1. To produce a dyestuff from the tetrazo compound of benzidine and the [1·11] 4
hydroxynaphthalene, take about nine and one fifth parts of benzidine base and
dissolve them by mixing with about one hundred and eighty parts of water and
about forty four parts of hydrochloric acid containing about twenty five per cent.
of real hydrochloric acid (H CI) and heat the mixture. Cool the solution and

page_text: when cold add about fifty parts of ice and then run in gradually about seven parts
of sodium nitrite (containing about ninety six per cent. real nitrite Na NO.)
dissolved in about twenty five parts of water. Next run the solution of tetrazo-
diphenyl thus obtained in the well known way into a solution containing about
sixteen parts of [111] dihydroxynaphthalene, about four parts of caustic soda,
about five thousand parts of water and about forty one parts of crystallized
sodium acetate and which is finally just acidified with acetic acid. Stir for say
two hours, filter off the precipitated colouring matter, press and preserve for use
in the form of paste.
2. To obtain the corresponding dyestuff from tolidine, substitute ten and three
fifths parts of orthotolidine base for the nine and one fifth parts of benzidine base
(in example 1) and in other respects proceed in exactly the same way as described
under example 1.
3. To obtain the diamidostilbene dyestuff substitute for the benzidine base (in
example 1) ten and a half parts of diamidostilbene base and in other respects
proceed in the same way as described under example 1.
4. To obtain the corresponding dyestuff from dianisidine, substitute for the
benzidine base (in example 1) twelve parts of dianisidine and in other respects
proceed in the same way as described under example 1.
If the combination of the dihydroxynaphthalene with the tetrazocompounds be
performed in a solution rendered alkaline with soda it often happens, that disazo
bodies insoluble in alkaline solution are formed as bye-products, and as these on
account of their insolubility are useless as dyes it is preferred to perform the
combinations as described in acetic acid solution.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed 1 declare that what I
claim is :-
The new substantive colouring matters hereinbefore described being the dis-azo-
compounds of [111] dihydroxynaphthalene with benzidine, tolidine, diamido-stilbene
or dianisidine.
Dated this 30th day of December 1890
J. H. JOHNSON & Co.,
Agents.