Year: 1889

page_text: Date of Application, 26th Sept., 1889
Complete Specification Left, 1st Jan., 1890-Accepted, 10th May, 1890

page_text: Qazo com
or night yellow colour and rather difficult solubility in water, which
treated in well known manner furnishes azo colouring inatters.
.II
When the salts of amido-oxy-naphthalin disulphonic acid described above are
heated with caustic alkalis to 240° 280° Ca further sulpho group is replaced by the
hydroxyl group and there is formed an amido-dioxy-naphthalin mono sulphonic acid.
Example. If the heating is continued after the stage-mentioned above siihe
thickening of the melt, further reaction will set in, and after two hours the inter-
mediary amido-oxy-naphthalin disulphonic acid will be found transformed into
amido-dioxy-naphthalin-mono-sulphonic acid.
In order to set free this body, the melt is dissolved in water and largely super-
saturated with hydrochloric acid. The amido dioxy naphthalin monosulphonic acid is
deposited directly from the hot solution in the form of a 'crystalline precipitate and
may be obtained-by.filtration.
By redissolving and precipitating from the hot solution of the sodium salt, :the
free acid is obtained in the form of very brilliant -needles about a centimeter in
length. The free acid is soluble in water with great difficulty. The alkali salts.on
the contrary are easily soluble, with blue violet fluorescence.
Their neutral solutions are coloured dark brown by ferric chloride and chloride<of
lime. By an excess of the laiter agent the colouring is gradually, while becoming
dull, turned into light.brownish.
By nitrous acid, the amido-dioxy-naphthalin monosulphonic acid is converted into.a
red colored diazc-compound which when treated in well known manner produces
azo colouring matters.
Not only by the analytic numbers is the amido-dioxy-naphthalinmonosulphonic
acid to be recognized from the amido-oxy-naphthalin-disulphonic acid but also by the
difficult solubility of the free acid, which is deposited from hot anil (tolerably diluted
solutions of the salts on the addition of mineral acids, and moreover by the scarlet red
colour:of its diazo compound.
In the processes described above under I and II, for the sodium salt may be
substituted some other sult, for the caustic soda some other alkali, and instead of open
vessels closed wessels may betused.
The temperature employed and the duration of the action vary accorlling to the
larger or smaller quantity of alkali used.
'Dated'this 26th day of September 1889.
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Improvements in the Production.of Amido-oxy-naphthalindisulphonic
Acid, and of Amido-dioxy-naphthalin-monosulphonic Acid, and
the Manufacture of their Diazo-compounds, and of. Azo Coloring
Matters therefrom.
I, OLIVER IMRAY, of, No. 28. Southampton Buildings, Chancery Lane, in the County
of London, Fellow of the Institute of Patent Agents, 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.:-
In the beta-naphthylaminetrisulphonates corresponding to the betanaphtholtri-
sulphonic acid described in the Specification No. 2511 of 1882 may be replaced
successively two eulpho groups by hydroxyl groups, by-melting them together with
caustic alkalis. In this manner are:formed, in the first stage,amido-oxy-naphthalin-
disulphonates and secondly, amido-dioxy-naphthalin-monosulphonates..

page_text: In order to produce amido-oxy-naphthalin-disulphonic acid my correspondents
proceed for examplo as follows:-
100 parts hy weight of beta-naphthylamine-trisulphonate of sodium are well
mixed with 50 parts by weight of water and 200 parts by weight of caustic. soda,
and heated to 220°-260° C The transposition begins at 200°-210°. but at tem-
peratures below 230° it requires a rather long time, 12 to 18 hours, for its completion.
When the temperature is raised beyond this point, the transposition takes place
rapidly. When the temperature is raised to 240°-260° C. the melt takes a red
colour and begins to foam violently. A short time after, from a quarter to half an
hour, the foaming ceases and the melt thickens. At this stage the conversion of the
beta-naphthylaminetrisulphonic acid into amido-oxy-naphthalindisulphonic acid is
complete.
In order to liberate this body, the melt is dissolved in water, strongly acidulated
with hydrochloric acid, and left to crystallise.
The acid sodium salt of the new compound is deposited in the form of a white
micro-crystalline precipitate. The solution of the amido-oxy-naphthalinsulphonate
may however be used directly for other purposes after being freed from the sulphurous
acid.
The free amido-oxy-naphthalin-disulphonic acid, as well as its salts, are very readily
soluble in water.
The acid salts in solution show a violet-blue fluorescence, which turns blue-green
on the addition of an alkali.
By ferric chloride is produced, in a neutral solution of the salts, a dark brown
coloration which is rendered more intense by an excess.
A solution of chlorido of lime produces a similar coloration, but on the addition
of an excess it disappears after a short time completely.
Although the amido-oxy-naphthalin-disulphonic acids at present known are not
diazotable (Witt B. d. d. ch. Ges. XXI p. 3474) the amido-oxy-naphthalin disulphonic
acid, according to this invention, is converted easily by means of nitrous acid into a
diazo compound of light yellow colour and rather difficult solubility in water, which,
treated in manner described later on furnishes azo coloring matters.
When the salts of amido-oxy-naphthalin-disulphonic acid described above are
heated with caustic alkalis to 210° 280° C. a further sulpho group is replaced by
the hydroxyl group and there is formed an amido-dioxy-naphthalin-mono-sulphonic
acid.
Example: If the heating is continued after the stage mentioned above, ciz.: the
thickening of the melt, further reaction will set in, and after two hours the inter-
mediary amido-oxy-naphthalindisulphonic acid will he found transformed into amido-
dioxy-naphthalin-monosulphonic acid.
In order to set free this body, the melt is dissolved in water and largely
supersaturated with hydrochloric acid. The amido-dioxy-naphthalin-monosulphonic
acid is deposited directly from the hot solution in the form of a crystallino precipitate,
and may be obtained by filtration. By redissolving and precipitating from the hot
solution of the sodium salt, the free acid is obtained in the form of very brilliant
needles about a centimeter in length.
The free acid is soluble in water with great difficulty. The alkali salts on the
contrary are easily soluble with blue-violet fluorescence.
t
Their neutral solutions are coloured dark brown by ferric chloride and chloride of
lime. By an excess of the latter agent the colouring is gradually turned, while
hecoming dull, into light brownish.

page_text: 4
By nitrous acid the amido-dioxy-naphthalin-mono-sulphonic acid is converted into
a red colored diazo compound, which when treated in manner described later on,
produces azo coloring matters. As mentioned before, the bodies thus obtained
form with nitrous acid diazo compounds which can be converted into azo coloring
matters.
For example:-
The
36 parts of amido naphtholdisulphonate of sodium or the equivalent quantity of
amido dioxynaphthalin-disulphonate of sodium are dissolved in 300 parts of water,
and to the solution are added 25 parts of hydrochloric acid of 33 per cent.
acid which will separate, is, while being kept agitated, diazotised by adding by
degrees a solution of 7 parts of nitrite of soda in 70 parts of water. Shortly after
the last portions of the nitrite solution have been added, the nitrous acid will have
been used up and the diazo, compound will have formed. After some time it separates
in form of an orange yellow or a red colored powder. The diazo coupound is of
rather difficult solubility in cold water in a large quantity of warm water it
dissolves without appreciable decomposition, but boiled, it decomposes setting free the
nitrogen.
Not only by the analytic numbers is the amido-dioxy-naphthalin-monosulphonic
acid to be recognized from the amido-oxy-naphthalin-disulphonic acid but also by
the difficult solubility of the free acid, which is deposited from hot and tolerably
diluted solutions of the salts on the addition of mineral acids, and moreover by the
scarlet-red colour of its diazo compound.
In the processes described above under I and II, for the sodium salt may be
substituted some other salt; for the caustic soda some other alkali and instead of
open vessels closed vessels may be used.
The temperature employed and the duration of the action vary according to the
larger or smaller quantity of alkali used.
If now for example the diazo compound. obtained in the way described above, is
introduced into a solution of 144 paris by weight of beta-naphthol in 20 parts by
weight of ammonia and 600 parts by weight of water, there forms an azo coloring
matter which can be separated completely by means of common salt. and subsequent
.prossing-off.
In this way, and when for the mentioned quantity of beta naphthol is substituted
an equivalent quantity of some other phenol, for example, resorcine and similar
compounds, or of a mono- or disulphonic acid of a phenol, for example, the alpha-
naphtholsulphonic acid of Neville and Winter, or the beta-naphthol-disulphonic
acid R, there are obtained, red coloring matters with blueish tint; when phenol or
alpha-naphthol are used, there are obtained yellow-red to yellow-brown coloring
inatters.
If for the amidonaphtholdisulphonic acid is substituted the amidodioxynaphthalin-
⚫monosulpbonic acid, the coloring matters obtained dye more brownish hued shades.
In order to produce azo-colouring matters from the amidonaphtholdisulphonic
acid or the amido-dioxy-naphilalin-monosulphonic acid I may also proceed in the
following way, that is to say, by causing diazo- or tetrazo compounds to act upon
the said bodies.
For example: The tetrazo compound produced in the usual manner from 9:2
parts by weight of benzidine or an equivalent quantity of tolidine, dimethoxy-
benzidine or diamidostilben is introduced into a solution of 33 parts by weight of
amidonaphtholdisulphonic acid or an equivalent quantity of amido dioxynaphthalin-
mono-sulphonic acid in 600 parts by weight of water and 60 parts by weight of soda,
and while being kept agitated, left at first during 12 hours at ordinary temperature
and then during 12 bours at from 35 to 40° C. At the end of this time there will
have formed coloring matters varying in shade from black-violet to the blue black
according to which tetrazo compound had been used: This coloring matter is
precipitated by means of common salt, pressed off and dried.

page_text: 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.
1. The production of amido-oxy-naphthalin-disulphonates by heating beta-naphthyl-
amine-trisulphonates with caustic alkalis, under or without pressure, to 200-260° C.,
substantially as described.
2. The production of amido dioxy-naphthalin-monosulphonates by heating :
a) bela-naphthylamine-trisulphonates.
b) amido-oxy-naphthalin-disulphonates with caustic alkalies, under or without
pressure, to 240°-280° C., substantially as described.
3. The amido-naphthalin-sulphonates produced in manner described, their diazo-
compounds and the azo coloring matters derived therefrom.
Dated this 1st day of January 1890.
ABEL & IMRAY,
Agents for the Applicant.