Improvement in the Manufacture of Sulpho Acids of the Naphthalene Series, and of Coloring Matters Derived therefrom.
Year: 1895

page_text: Date of Application, 14th Oct., 1895
Complete Specification Left, 14:h July, 1896-Accepted, 15th Aug., 1896
[Communicated from abroad by FARBWERK MÜHLHEIM, of Mühlheim on the
Main, in the Empire of Germany.]
Improvement in the Manufacture of Sulpho Acids of the Naphthalene
Series, and of Coloring Matters Derived therefrom.
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 to be as follows:-
It has been found that the amidonaphthol monosulphoacid which is produced by
melting a naphthylamine 3.4 disulphoacid with alkalies and which has proved to be
of little technical value, can be transformed by sulphonation into a very valuable
higher sulphoacid. This latter acid, which is probably a disulphoacid, does not
seem to be identical with any of the hitherto produced sulphoacids of amido-
naphthol and proves to be an excellent raw material for the manufacture of
azodyestuffs.
1. It can be combined with mono-diazo bodies (derived from aromatic amines or
amidoazocompounds) yielding valuable dyestuffs of varying shades.
2. It can also be combined with tetrazobodies, or with the intermediate products
resulting from the combination of one molecular proportion of the tetrazocompound
with one molecular proportion of the known azodyestuff components. In the
production of such dyestuff's one or two molecular proportions of a diazotizable
component (or an amine which when combined forms a true amidoazocompound
which can be further diazotized) can be introduced as "middic component.'
"
3. It has been found to be a diazotizable middle component, so that it can be
used as such in the manufacture of azodyestuffs, and that azodyestuff's containing
the new acid as end-component, can be diazotized on the fibre and combined with
amines or phenols.
4. It reacts easily with several and especially with two diazo-groups (for
instance with two molecular proportions of diazo-nitrobenzene) rielding a new series
of polyazodyestuffs of differing and very valuable shades.
Dated this 14th day of October 1895
HASELTINE, LAKE & Co.,
45 Southampton Buildings, London, W.C., Agents for the Applicant.
Improvement in the Manufacture of Sulpho Acids of the Naphthalene
Series, and of Coloring Matters Derived therefrom.
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 an ascertained in and by the following
statement :-
The 1.8 amidonaphthol-3-monosulphoacid (which can be produced, as is well

page_text: known, by melting 1-naphthylamine 3.8 disulphoacid with caustic alkalies) has not
proved to be of technical value because the azodyestuff's deriving therefrom are of
à doll shade and not stable against alkalis or acids.
Now I have found that by sulphonating this monosulphoacid, a disulphoacid is
obtained which is of the highest value for technical purposes inasmuch as the
azodyes deriving from this disulphoncid are more stable and of a considerably more
pure and pronounced shade. Moreover, in some cases, the yields of colouring
matter are greater by employing the disulpho- instead of the monosulpho acid.
This is especially the case with azodyes formed by the action of several inolecules
of a diazocompound on one molecule of the disulphioacid.
The chemical constitution of this disulphoacid has been ascertained in the
following way: When the said disulphoncid is heated with dilute mineralic acids,
the last introduced sulpho group is eliminated and 1.8 amidonaphthol-3-mon-sulpho-
acid is regenerated when on the contrary the disulphoacid is heated with dilute
alkalies at elevated temperatures, the last introduced sulpho group remains
unaltered while the amido group is transformed into the hydroxyl group and a
dioxy naphthalenedisulpho acid is formed which is identical with that described in
the Specification of former Patent No. 17141" and having the following
constitution
When diazocompounds react on this acid they cannot enter into the paraposition
to the O-group, because this paraposition, being free in the monosulphoacid, is
now occupied by a sulpho group, from this point of view, the nature of the present
invention can be defined as "producing azodyes not directly from 1.8 amido-
naphthol-3 monosulpho-acid, but first introducing a new sulphogroup into the
paraposition to the OH-group, thus preventing the diazo group from entering into
that place in the molecule, and producing in such a manner azodyes of greater
value than those deriving from the mono-sulphoacid directly."
In order to illustrate the manner in which this invention is carried out in
practice, give the following directions.

page_text: without cooling into 5 parts by weight of concentrated sulphuric acid, the mono-
sulphoncid first becomes dissolved, but after some time the disulphoacid separates
from the solution in a crystalline state. The mass is then poured into ice water,
the whole is dissolved in hot water and the disulphoacid is precipitated from the
hot watery solution by salting out.
The disulphoacid (or probably its acid sodium salt) produced in such a way is
hardly soluble in cold water more easily in hot water. The alkaline solution
shows a strong violet fluorescence. The diazocompound is of a yellow colour and
soluble with difficulty in water. By heating the disulphoacid with dilute sulphuric
acid (about 20%) up to 200° C., or better by boiling it with dilute sulphuric acid
at 140° C., 1.8 amidonaphthol-3-sulpho-acid is regenerated.
1. DYESTUFFS FORMED BY THE ACTION OF ONE MOLECULAR QUANTITY
OF A DIAZO- OR DIAZOAZOCOMPOUND ON ONE MOLECULAR QUANTITY OF
THE ACID B.
When diazobenzene is combined with 1.8 amidonaphthol-3-monosulphoneid in
an alkaline solution, an azodye is obtained being fixable on wool in dull red tints,
whilst by employing the acid B a new dyestuff results which dyes wool in bright
claret tints. In the like manner a-diazonaphthalene when combined with the
disulphoacid yields a violet, and diazoazobenzene a blueish black dyestuff, both
advantageously differing from those obtained with the monosulphoacid.
When diazoazonaphthalenesulphoacid (which can be produced by diazotizing
B-naphthylamine-S-sulphoacid, combining with a-naphthylamine and diazotizing
again) is combined with the acid B in an alkaline solution, a dyestuff is obtained
which can be easily salted out and which dyes wool in greenish black shades.
The corresponding dye from amidonaphthol monosulphoacid dyes wool in reddish
grey shades.
When diazotized naphthionic acid is coupled with the acid B in a solution
rendered weakly acid by acetic acid, an azodye is obtained yielding beautiful
violet tints on wool. In the like manner diazotized,
Paranitraniline
->
-
-
reddish violet shade

page_text: 2. DYESTUFFS
FORMED BY THE ACTION OF ONE MOLECULAR PROPORTION
OF A TETRAZOCOMPOUND ON TWO MOLECULAR PROPORTIONS OF THE
ACID B, OR ON ONE MOLECULAR PROPORTION OF THE ACID BAND ONE
MOLECULAR PROPORTION OF ANOTHER AZODY ESTUFF COMPONENT.
When tetrazoditolyl is combined with two molecular proportions of the neid B
in a concentrated alkaline solution, a so called intermediate product is first formed
which after some time is transformed into the tetrazodye. This latter one dyes
unmordauted cotton in beautiful blue shindes, whilst the corresponting dye derived
from the monosulphoacid yields a greyish violet. A like advantage is obtained
by employing other teniazocompounds, for instance tetrazo diphenolether, or by
employing the neid B instead of the inonosulphoacid for the production of the
so called mixed tetrazodyes.
3. DYESTUFFS
FORMED BY THE ACTION OF MORE THAN ONE MOLECULAR
PROPORTIONS OF A DIAZO, (TETRAZO) COMPOUND ON ONE MOLECULAR
PROPORTION OF THE ACID B.
Diazotized parauitraniline is combined with one molecular quantity of the
acid B in a weakly acidulated watery colution, the obtained monoazalye is
dissolved in an excess of carbonate of soda and a molecular quantity of diazotized
sulphauilic acid is again added. A blueish green dyestuff is thus obtained whilst
amidonaphtholmonosulphoacid produces a dirty greenish grey dye. Instead of the
just mentioned diazocompounds, others may be used, for instance dinzotized
a-naphthylamine or naphthionic acid or 3-naphthylaminedisulphoacid G.
Diazolized sulphanilic acid is combined with one molecular proportion of the
ned B in a weakly acidulated watery solution, the obtained monoazolye is
dissolved in an excess of carbonate of soda and a molecular quantity of the inter-
mediate product obtained from tetrazodiphenyl and salicylic acid is addet. After
standing some time a dyestuff is obtained which dyes un rdantel cotton in green
shades, whilst the corresp: uding dyestuff derived from amidonaphthol monosulpho-
neid is practically useless. Instead of the diazocompound of sulphanilic acid,
other diazocompounds may be used, such as those derived from ortho- or
parateluidine, paranitranitine, ß-naphthylaminedisulphoneid G.
Tetrazdiphenylchloride is combined with one molecular proportion of the
acid B in an alkaline solution, one molecular proportion of metaphenylenediamine
is added, and the obtained tetrazodye is then combined in an alkaline solution with
about 22 molecular proportions of diazotized sulphanilic acid. A dyestuff is
finally obtained dyeing unmordanted cotton in greyish shades. Instead of
dinzotized sulphanitic acid, diazotized paranitraniline or dinzonaphthalene may
be used.
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 1 declare that what I claim is :-
1. The process of producing amidonaphtholdisulphoacid B, which process
consists in sulphonating 1.8 amidonaphthol-3-monosulphoacid.
2. The employment of amidonaphtholdisulphoacid B for the preparation of
azo-colouring matters.
3. The process of producing azo-colouring matters from 1.8 amidonaphthol-
3-monosulphoneid which process consists in first introducing into this sulphoacid
one sulphogroup in the para osition to the hydroxyl-group and then reacting with
diazo- or tetrazocompounds on the so formed disulphoacid.

page_text: 4. The amidonaphtholdisulpho acid B produced as claimed under the 1st claiming
clause.
5. The azocolouring matters produced as claimed under the 2nd and 3rd claiming
clauses.
1 1
1
1000
HASELTINE, LAKE & Co.,
45 Southampton Buildings, London, W.C., Agents for the Applicant.