Improvements in the Production of Amido-naphthol-mono-sulphonic Acids, and the Manufacture of their Diazo Compounds and Azo Coloring Matters, therefrom.
Year: 1889

page_text: Date of Application, 26th Sept., 1889
Complete Specification Left, 1st Jan., 1890-Accepted, 10th-May, 1890-
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBWERKE VORMALS MEISTER LUCIUS
AND BRUNING, of Hoechst-am-Maine, in the Empire of Germany, Chemical
Manufacturers.]
Improvements in the Production of Amido-naphthol-mono-sulphonic
Acids, and the Manufacture of their Diazo Compounds and 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 to be as follows:
When the beta-naphthylamine disulphonic acids corresponding to the beta-naphthol-
disulphonic acids and Y described in the Specification No. 1715 of, 1878 are heated
together with alkalis to 200°-280° C. the sulpho groups are replaced successively by
the hydroxyl groups and in the first stage amido-naphthol-mono-sulphonic acids are
obtained.
Example: 30 parts by weight of beta-naphthylamine-disulphonic acid R are mixed
in a vessel with an agitator, with 60 parts by weight of caustic soda and 20 parts by
weight of water and heated slowly. The temperature is raised to 230-250° 0.
kept so for 1 hour and then heated to 260°-280° C. for 10 minutes more, when
the amido naphthol mono sulphonic acid is formed.
In order to liberate the same, the melt is dissolved in water and saturated with
hydrochloric acid. The new acid is deposited, from the hot solution in form of a
crystalline precipitate and is obtained by filtration.
The caustic soda may be replaced by some other alkalis, and instead of open vessels
closed vessels may be used.
The temperatures to be observed and the duration of the action vary according to
the larger or smaller quantity of alkali employed.
The amido naphthol sulphonic acids obtained in the way described are soluble with
great difficulty in hot water and from all the non-diazotable amido naphthol sulphonic
acids which were known up to this day (Witt. Ber. d. deutsch. chem. Ges. XXI
p. 3474) they are distinguished in that when they are treated with nitrous acid,
they form diazo compounds which can be converted into azo colouring matters in
the usual manner.
The following table indicates the characteristic qualities of the bodies produced.
Amida nonhthalauluhanis äaid from hota-nanlúhylamine disuluhonic acid.

page_text: COMPLETE SPECIFICATION.
Improvements in the Production of Amido-naphthol-mono-sulphonic
Acids, and the Manufacture of their Diazo Compounds and 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:-
When the beta-naphthylamine disulphonic acids corresponding to the beta-naphthol
disulphonic acids R and Y described in the Specification No. 1715 of 1878 are heated
together with alkalies to 200°-280° C., the sulpho groups are replaced successively
by the hydroxyl-groups, and in the first stage amido-naphthol-mono-sulphonic acids
are obtained.
Example: 30 parts by weight of beta naphthylamine-disulphonic acid R are mixed
in a vessel with an agitator, with 60 parts by weight of caustic soda and 2) parts by
weight of water and beated slowly. The temperature is raised to 230°-250° C.;
kept so for 1 hour and then heated to 260°-280° C. for 10 minutes more, when the
amido-naphthol mono-sulphonic acid is formed.
In order to liberate the same, the melt is dissolve in water and saturated with
hydrochloric acid. The new acid is deposited from the hot solution in form of a
crystalline precipitate and is obtained by filtration.
The caustic soda may be replaced by some other alkalies, and instead of open
vessels closed vessel may be used.
The temperatures to be observed and the duration of the action vary according to
the larger or smaller quantity of alkali employed.
The amido naphthol sulphonic acids obtained in the way described are soluble with
great difficulty in hot water and from all the non-diazotable amido-naphthol sulphonic
acids which wore know up to this day (Witt. Bér. d. deutsch. chem. Ges. XXI
p. 3174)
they are distinguished in that when they are treated with nitrous acid, they form
diazo compounds which can be converted into azo coloring matters in the usual
manner.
For example: 244 parts of amido naphtholmono-sulphonate of sodium Rare
dissolved in 300 parts of water, and to the solution are added 25 parts of hydrochloric
acid of 33 per cent. The acid, which will separate is, while being kept agitated,
diazotised by adding by degreos 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 a red-orange colored powder.
The diazo compound is of rather difficult solnbility in cold water; in a large
quantity of warm water it dissolves without appreciable decomposition, but boiled, it
decomposes, setting free the nitrogen.
With phenoles and naphthols and their sulphonic acids it forms azo-coloring
matters.
If for example the diazo-compound obtained in the way described above, is
introduced into a solution of 144 parts 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
pressing-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 com-
pounds, or of a mono-or-disulphonic acid of a phenol, for example the alpha naphthol
sulphonic 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 matters:

page_text: If for the amido naphtholmonosulphonic acid R is substituted its isomer Y the
coloring matters resulting dye still bluer and purer shades.
In order to produce azo coloring matters from the amido-naphtholsulphonic acids,
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, dimethoxybenzidine or
diamido stilbene, is introduced into a solution of 245 parts by weight of amido-
naphtholsulphonic acid Y in 600 parts by weight of water and 35 parts by weight of
soda and while being kept agitated is left at first during 12 hours at ordinary tem-
perature and then during 12 hours 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 blue
black, according to which tetrazo compound had been used. The coloring matter is
precipitated by means of common salt, pressed off and dried.
The following table indicates the characteristic qualities of the bodies produced.
Amido naphtholsulphonic acid from beta naphthylamine disulphonic acid.
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 naphthol sulphonates by heating beta naphthylamine
disulphonic acids with caustic alkalies under or without pressure to 200°-280° ().,
substantially as described.
2. The amido naphthol sulphonates prepared substantially as described, their diazo
compounds and the coloring matters derived therefrom.
Dated this 1st day of January 1840
ABEL & IMRAY,
Agents for the Applicant.