The Preparation of Amidonaphtolsulphonic Acid and of Coloring Matters therefrom.
Year: 1889

page_text: Date of Application, 22nd Oct., 1889
Complete Specification Left, 16th July, 1890-Accepted, 16th Aug., 1890
The Preparation of Amidonaphtolsulphonic Acid and of Coloring
Matters therefrom.
I, SYDNEY PITT, of Sutton, in the County of Surrey, Gentleman, (a communication
to me from abroad by Leopold Cassella & Co. of Frankfort-on-Main, in the Empire
of Germany, Manufacturing Chemists,) do hereby declare the nature of this invention
to be as follows:-
We have found that by treating certain disulphonic acids of the naphtylamines with
caustic alkalies in a suitable manner, one of their sulpho groups can be replaced by
the hydroxyle group; these naphtylamine disulphonic acids are thus transformed into
amidonaphtolmonosulphonic acids.
As an example we describe the derivative from the ẞ naphtylamine y disulphonic
acid of the British patent No. 8164, which is also obtained by heating the naphtol
y disulphonic acid with ammonia.
In an autoclave are heated 36 kilogrammes ẞ naphtylamine disulphonic acid with
50 kilogr. caustic soda of 40° Be. during 16 hours at about 200° C.; the melt is
diluted with water, and acidulated, sulphurous acid escapes and the amidonaphtol-
monosulphonic acid is precipitated in the form of small colorless crystals.
The salts of this acid are easily soluble in water, the sodium salt crystallizes in
needles, the acid itself is difficultly soluble in water. When nitrite of soda is added
to the acid solution a yellow body separates which is scarcely soluble and which by the
action of an alkali, especially under the influence of heat is transformed into a violet
coloring matter. It has the properties of a diazo compound and combines with amines
and phenols forming azoic colors.
The amidonaphtolmonosulphonic acid reacts very easily on diazo bodies. Two
different classes of dyestuffs are obtained when the operation takes place in acid or in
an alkaline solution; the products resulting from the operation in acid solution have
the general character of colors derived from naphtylamines substituted by hydroxyle,
whilst the products resulting from the operation in alkaline solution have the character
of azotized colors derived from naphtoles substituted by NH. The colours of both
these classes have a remarkably great resistance against the action of alkalies (milling,
scouring) and dye wool very evenly. The dyestuffs deriving from tetrazo bodies dye
unmordanted cotton deep shades varying from violet and blue to black.
In order to describe how we operate we give the following examples:
Example I. 14 kilogr. p. nitraniline are diazotised and the diazo compound is
caused to run into the solution of 27 kilogr. amidonaphtolsulphonate of sodium
containing an excess of acetate of sodium. The resulting dyestuff is easily soluble;
it dyes wool a reddish violet. If the operation is made in alkaline solution, for
instance in presence of soda, a blue solution is obtained from which acids precipitate a
dyestuff which dyes wool a brownish red.
Example II. 30 kilogr. ẞ naphtylaminedisulphonic acid are diazotized and combined
with 27 kilogr. amidonaphtolsulphonate of sodium in solution containing acetic acid.
A blueish red results, which dyes wool very evenly.
Example III. 35 kilogr. amidoazobenzoldisulphoacid are diazotised and combined
in slightly acidulated solution with 27 kilogr. amidonaphtolsulphonate of sodium. The
resulting dyestuff is easily soluble, it dyes wool a blueish violet, the analogous dyestuff
resulting from the formation in alkaline solution dyes wool a brown shade.
Example IV. 50 kilogr. of the dyestuff resulting from naphtylaminedisulphonic
acid and a-naphtylamine are diazotized and the diazo-azo-compound is introduced into
the weakly acidulated solution of 27 kilogr. amidonaphtolsulphonate of sodium. A
greenish black dyestuff results which on wool produces a black fast to washing.

page_text: Example V. 184 kilogr. benzidine are diazolized and in alkaline solution combined
with 54 kilogr. amidonaphtolsulphonate of sodium. A difficultly soluble precipitate
of a dyestuff is formed immediately which dyes unmordanted cotton in alkaline or in
neutral both containing some common salt, a blueish black of great intensity. The
same combination in acid solution produces a violet dyestuff.
Example VI. The amidonaphtolesulphonic acid may also be used for the production
of mixed coloring matters. For this purpose we may first combine tetrazodiphenyle
or similar tetrazo-compounds with one equivalent of the amidonaphtolsulphonic acid
and then react with this intermediate product on phenols, amines or their sulphoacids or
employ the inverse method, combining the intermediate products oftetrazodiphenyle etc.,
and amines or phenols with amidonaphtol-sulphonic acid. For instance 21 kilogr.
tolidine are diazotised and first combined in well cooled alkaline solution with 27 kilogr.
of amidonaphtolsulphonic acid, the intermediate product which is nearly insoluble in
water is introduced into an alkaline solution of 35 kilogr. ẞ naphtole & disulphonic
acid. The dyestuff dyes cotton a deep blue.
The diazo compounds enumerated in the above examples can be replaced by equivalent
quantities of the diazo derivatives of aniline, the toluidines, the naphtylamines,
amidoazotoluole, tolidine, diamido stilbene, or their sulpho acids, diamidodiphenolethers,
diamidoaethoxydiphenyle, the diazoazo compounds of British Patent No. 921485.

page_text: otized colors derived from naphthols substituted by NH, which is proved by the
ct, that the latter derivatives can be diazotised again and that the resulting diazo
ompounds combine again with amines and phenoles. The colors of both classes of
midonaphtolsulphonic acid compounds formed in acid or in alkaline solution have a
emarkably great resistance against the action of alkalis (milling, scouring) and dye
ool very evenly. The dyestuffs deriving from tetrazo bodies, dye unmordanted
otton deep shudes varying from violet and blue to black.
In order to describe how we operate we give the following examples:
Example I. 14 kilogrammes p. nitraniline are diazotised and the diazo compound is
easily
aused to run into the solution of 27 kilogramines amidonaphtol y sulphonate of
odium containing an excess of acetate of sodium. The resulting dyestuff
oluble; it dyes wool a re.ldish violet. If the operation is made in alkaline solution,
or instance in presence of soda, a blue solution is obtained from which acids precipitate
a dyestuff which dyes wool a brownish red.
Example II. 30 kilogrammes ẞ naphtylamine disulphonic acid are diazotized and
combined with 27 kilogrammes amidonaphthol y sulphonate of sodium in solution
containing acetic acid. A blueish red results, which dyes wool very evenly.
Example III. 35 kilogrammes amidoazobenzoldisulpho acid are diazotised and
combined in slightly acidulated solution with 27 kilogrammes amidonaphtol
y sulphonate of sodium. The resulting dyestuff is easily soluble, it dyes wool a blueish
violet, the analogeous dyestuff resulting from the formation in alkaline solution dyes
wool a brown shade.
Example IV. 50 kilogrammes of the dyestuff resulting from naphtylamine-
naphtylamine are diazotized and the diazo-azo-compound is
disulphonic acid and a
introduced into the weakly acidulated solution of 27 kilogrammes ainido naphthol
A greenish black dyestuff results which on wool produces a
y sulphonate of sodium.
black fast to washing.
Example V. 184 kilogramines benzidine are diazotised and in alkaline solution
combined with 54 kilogrammes amidonaphtol y sulphonate of sodium. A difficultly
soluble precipitate of a dyestuff is formed immediately which dyes unmordanted
cotton in alkaline or in neutral bath containing some common salt, a blueish black of
great intensity. The same combination in acid solution produces a violet dyestuff.
Example VI. The amidonaphtol y sulphonic acid may as well be used for the pro-
duction of mixed coloring matters. For this purpose we may first combine tetrazo-
diphenyle or similar tetrazo compounds with one equivalent of the amidonaphtol
y sulphonic acid and then react with this intermediate product on phenols, amines or
their sulpho acids or employ the inverse method, combining the intermediate products
of tetrazo diphenyl etc. and amines or phenols with amidonaphtol y sulphonic acid.
For instance 21 kilogrammes tolidine are diazotized and first combined in well
O cooled alkaline solution with 27 kilogrammes of amidonaphtol y sulphonic acid, the
intermediate product which is nearly insoluble in water is introduced into an alkaline
solution of 35 kilogrammes ẞ naphtol & disulphonic acid. The dyestuff dyes cotton
a deep blue.
The diazo compounds enumerated in the above examples can be replaced by
5 equivalent quantities of the diazo derivatives of aniline, the toluidines, the naphtyl
ainines, amidoazetoluol, tolidine, diamidostilbene, or their sulphoacids, diamido
diphenolethers, diamidoaethoxydyphenyle, the diazoazocompounds of British paten
No. 921455
The combination with salicylic acid yields red to violet dyestuffs of remarkably
50 great fastness, with phenols and metadiamines brown to violet dyestuffs, with naphty
amines and their sulpho-acids red to violet dyestuffs and with naphtol, dioxynaphtalin
and their sulpho-acids violet blue to black dyestuffs.
Having now particularly described and ascertained the nature of my said inver
tion and in what manner the same is to be performed I declare that what
55 claim is:-
14
:-
The process or processes substantially as described for the production of colorin

page_text: matters from amidonaphtol y sulphonic acid by combining the same in alkaline solution
with the diazocompounds of mon-amines such as: aniline, toluidine, xylidine, a or ẞ
naphtylamine, amidoazobenzol, amidoazot oluol, or their sulpho acids, or of paradiamines
such as benzidine, methylebenzidine, tolidine, diamidoethoxydiphenyl, diamido-
diphenolet her, diamidostilben, or of those amidoazosulphoacids which are obtained by
the reaction of diazosulphonic acids upon a naphtylamine.
2nd. The process or processes substantially as described for the production of
coloring inatters from the amidonaphtol y sulphonic acid by combining the same in
neutral or weakly acidulated solution with the diazo compounds mentioned in the
1st claim.
3rd. The process or processes substantially as described for the production of mixed
azo colors by combining one of the two azo groups of the tetrazoderivatives of the
above named paradiamines with the amidonaphtol y sulphonic acid in alkaline or in
acid solution and combining the other one with a phenol compound such as salicylic
acid, a
or naphtol, dioxynaphtaline or their sulpho acids or with an amine, as
an. phenylenediamine, in. toluylenediamine, a or ẞ naphtylamine or their sulpho acids.
4th. As new articles of manufacture the coloring matters produced substantially
as herein described and claimed in the foregoing claiming clauses.
Dated this 1st day of July 1890.
CARPMAEL & Co.,
Agents for the Applicant.