Improvements in the Manufacture or Production of Naphthylamine Sulpho Acids.
Year: 1893

page_text: Date of Application, 9th Aug., 1893
Complete Specification Left, 9th May, 1894-Accepted, 9th June, 1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
Improvements in the Manufacture or Production of Naphthylamine
Sulpho Acids.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
After Armstrong and Wynne (see Proceedings of the Chemical Society 1890:16)
had proved the composition of the naphthol yellow S, it became evident that the
alpha naphthylamine trisulpho acid described in the lapsed German Patent
No 22545, possessed the composition represented by the following scheme :
This follows from the fact, that the said naphthylamine trisulpho acid, wher
treated with a mixture of nitrous and nitric acid, yields naphthol yellow S.
The naphthylamine trisulpho acid obtainable, as described in the Specification
of the above German Patent (by sulphonating alpha naphthionic acid), is not a
pure product, for in the Specification of the German Patent No. 41957, it is stated
that on sulphonating alpha naphthionic acid, three different alpha naphthylamine
disulpho acids are first formed. The naphthylamine trisulpho acid produced as
described in the above Patent No. 22545, therefore, must be a mixture of at
least two isomeric acids, of which the one is the aforesaid ai-naphthylamine
Bia, B, trisulpho acid, whilst the other must be the isomeric a, naphthylamine-
Ba, trisulpho acid.
Friedländer (see Fortschritte der Theer farbenfabrikation I, page 331) mentions,
that the production of alpha naphthylamine trisulpho acid by means of the process
described in the above Patent No. 22545, can be scarcely carried out on a large
scale, as the said process yields but a small amount of acid, and that not pure.
My foreign correspondents have now found that pure alpha naphthylamine
trisulpho acids are obtained in comparatively large quantities, when the two
naphthylamine disulpho acids described in the German Patent No. 41957, and
marked with the numbers II" and "III" (viz., a, naphthylamine a, B-disulpho
acid, and a naphthylamine a, ẞ, disulpho acid) are subjected to a treatment with
fuming sulphuric acid at temperatures from about 50 to 100 degrees centigrade.
The researches of my foreign correspondents have shown, that the sulpho groups
introduced replace the hydrogen atom in the position ortho to the amido group, and
וגםD

page_text: the above acid "II" yields the a, naphthylamine a, ẞ, B, trisulpho acid, whilst the
isomeric a naphthylamine-a, B. B-trisulpho acid is obtained from the so-called
acid "III" My foreign correspondents have further ascertained, that in place of
employing the said acids " II" and "III," the alpha naphthylamine-beta-mono
sulpho acids beta and delta of Clève can be used, and that the alpha naphthylamine
beta monosulpho acid beta of Clève, yields a,-naphthylamine a, B₁ ẞ, trisulpho
acid, whilst the alpha naphthylamine beta mono sulpho acid delta of Clève, yields
a, naphthylamine ẞ, a, ß, trisulpho acid.
The completion of the reaction in all cases is ascertainable by the fact that a
sample taken out from the sulphonation mixture, and treated in a suitable manner,
does not act on diazo compounds, for instance, diazotised sulphanilic acid, to form
colouring matter.
When the reaction has been found to be complete, the formed trisulpho acids
are isolated in the usual manner, viz., by pouring the sulphonation mixture into
cold water, adding slacked lime, filtering off the precipitated calcium sulphate,
and evaporating the filtrate thus obtained.
The following example will serve to illustrate the nature of this invention
and the manner in which it can be carried into practical effect. The parts are by
weight
PRODUCTION OF αν NAPHTHYLAMINE B₁ α ß TRISULPHO ACID.
1 part of a naphthylamine-3, mono sulpho acid (Clève's delta acid) is gradually
stirred into 3-5 parts of fuming sulphuric acid (containing 25 per cent. of anhydride),
whilst the mixture is carefully cooled. The resulting liquid is kept at from 50 to
60 degrees centigrade, until a test portion taken out readily dissolves in water, which
is the case after from about 3 to 4 hours. After cooling again, 1 part of fuming
sulphuric acid (containing 70 per cent. of anhydride) is added, and the resulting liquid
is heated at from 80 to 90 degrees centigrade, until a sample taken out will not act
on diazotised sulphanilic acid to form a dye-stuff. It is noticeable that if the
a naphthylamine a, B. disulphe acid (so-called acid III), which was first formed
from the a, naphthylamine 3, monosulpho acid, has remained unaltered, this acid, in
a solution rendered alkaline by means of sodium carbonate, would yield an orange
coloured dye, which would be turned into bluish violet by an addition of muriatic
acid. The sulphonation mixture is then neutralised by means of slacked lime, and
after filtering off the precipitate calcium sulphate, a solution in water of the
calcium salt of the a, naphthylamine ẞ, a, ß, trisulpho acid is obtained. In order
to obtain a perfectly pure acid, the calcium salt is converted by means of sodium.
carbonate into the neutral sodium salt. The resulting solution of the latter is
concentrated by evaporation. On adding muriatic acid to this concentrated
solution, the acid sodium salt of the above trisulpho acid separates in little white
brilliant needles.
The isomeric a1 naphthylamine B, as ß, trisulpho acid is obtained in a. manner
analogous to that described in the above example, if the isomeric a, naphthyl-
amine 3 mono sulpho acid (Clève's beta acid) is employed in place of a naphthyl-
amine, mono sulpho acid (Clève's delta acid). In this case, a, naphthylamine
a, B, disulpho acid is first formed, which, by further sulphonation, is converted into
a, naphthylamine ẞ, a, ẞ, trisulpho acid.
The above two naphthylamine trisulpho acids can also be obtained, if in place
of a a naphthylamine B, mono sulpho acid, or a, naphthylamine a mono sulpho
acid, the corresponding disulpho acids, viz., a naphthylamine a, ẞ, disulpho acid, or
a naphthylamine as ẞ, disulpho acid, are used, and treated with sulphonating
agents in a suitable manner.
The resulting naphthylamine trisulpho acids, and salts thereof, are very similar
one to another respectively. The salts (especially the tertiary salts) show...in

page_text: watery solution a beautiful pure blue fluorescence, and materially vary as to their
solubility in water, the salts of the ai naphthylamine B, a, ß, trisulpho acid, for
example, being much more soluble than those of the isomeric acid.
My foreign correspondents have described in the above. example a distinct
method of producing one of the above trisulpho acids, and it is mentioned that
the other trisulpho acid results in an analogous way. Of course, my foreign
correspondents do not limit themselves to the directions above given, as the latter
can be varied. For instance, the free alpha naphthylamine mono- or disulpho
acids can be replaced by the corresponding quantities of salts thereof. The
strength of the fuming sulphuric acid employed can vary within certain limits,
and, accordingly, the temperature and duration of reaction may be varied. Such or
similar modifications do not alter the nature of this invention, which generally
relates to the production of pure a, naphthylamine B. a, B, trisulpho acid, or salts
'thereof, from a naphthylamine B. mono sulpho acid, or a naphthylamine
a, 4 disulpho acid, or salts thereof, and to the production of pure a, naphthyl-
amine ẞ as ẞ, trisulpho acid, or salts thereof, from a₁ naphthylamine ẞa mono sulpho
acid, or a naphthylamine as ẞ, disulpho acid, or salts thereof.
1000
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Improvements in the Manufacture or Production of Naphthylamine
Sulpho Acids.
I, HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Laue in the County of London, Patent Agent, 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 :—
After Armstrong and Wynne (see Proceedings of the Chemical Society 1890; 16)
had ascertained the composition of naphthol yellow S, it became evident that
the alpha-naphthylaminetrisulphonic acid described in the lapsed German Patent
No. 22545 possessed the composition represented by the following scheme :-
:-
This follows from the fact that the said naphthylaminetrisulphonic acid is
converted by a mixture of nitrous and nitric acids, into naphthol yellow S.
The naphthylaminetrisulphonic acid obtainable as described in the Specification
not a pure
of the above German Patent (by sulphonating alphaṇaphthionic acid)
product, for in the German Patent No. 41957, it is stated that, on sulphonating
alphanaphthionic acid, three different alphanaphthylaminedisulphonic acids are
first formed. The naphthylaminetrisulphonic acid produced as described in the
above Patent No. 22545, therefore, must be a mixture of at least two isomeric

page_text: acids, of which the one is the aforesaid alpha, naphthylamine beta, alpha, beta,
trisulphonic acid, whilst the other must be the isomeric alpha, naphthylamine betai
alpha, beta, trisulphonic acid.
Friedländer (see Fortschritte der Theer-farbenfabrikation, volume I, page 331)
mentions, that the production of alphanaphthylaminetrisulphonic acid by means of
the process described in the above Patent No. 22545, can scarcely be carried out
on a large scale, as the said process yields but a small amount of acid, and that
impure.
group;
My foreign correspondents have now found, that pure alphanaphthylamine
trisulphonic acids are obtained in comparatively large quantities, when the two
naphthylaminedisulphonic acids described in the German Patent No. 41957, and
numbered "II" and "III" (viz., alpha,-naphthylamine-alpha, beta,-disulphonic
acid and alpha, naphthylamine-alpha, beta, disulphonic acid,) are acted on by
fuming sulphuric acid at temperatures from about 50 to 100 degrees centigrade.
The researches of my foreign correspondents have shewn, that the new sulpho group
displaces the hydrogen atom in the ortho position relatively to the amido
the No. II acid yielding alpha, naphthylamine alpha, beta, betas trisulphonic acid,
whilst the isomeric alpha, naphthylamine-alpha, beta, beta-trisulphonic acid is
obtained from the No. III acid. My foreign correspondents have further ascer-
tained, that in place of the said acids "II" and "III," Clève's naphthylamine-
beta-monosulphonic acids beta and delta, can be respectively used, Clève's alphai
naphthylamine beta-monosulphonic acid yielding alpha, naphthylamine-alpha, beta,
beta, trisulpho acid, whilst Clève's alpha, naphthylamine beta-monosulphonic acid
yields alpha, naphthylamine beta, alpha, beta-trisulphonic acid.
The completion of the action is in all cases ascertainable from the fact that the
trisulphonic acids do not act on diazo compounds, for instance, diazotised
sulphanilic acid, to form colouring-matters.
When the action is at an end, the trisulphonic acids are isolated in a suitable
manner, for instance, by pouring the sulphonation mixture into cold water, adding
slaked lime, filtering off the precipitated calcium sulphate, evaporating the filtrates
thus obtained, converting the resulting calcium salts into the neutral sodium salts,
and transforming the latter neutral sodium salts into the acid sodium salts.
The following example will serve to illustrate the nature of this invention, and
the manner in which it can be carried into practice. The parts are by weight.
PRODUCTION OF ALPHA NAPHTHYLAMINE-BETA1
TRISULPHONIC ACID.
ALPHA, BETAL
1 part of alpha naphthylamine beta-monosulphonic acid (Clève's delta acid) is
gradually stirred into 3-5 parts of fuming sulphuric acid (containing 25 per cent. of
anhydride), the mixture being carefully cooled. The resulting liquid is then kept
at from 50 to 60 degrees centigrade, until a test portion readily disolves in water,
which is the case after from about 3 to 4 hours. After again cooling, 1 part of
fuming sulphuric acid (containing 70 per cent. of anhydride) is added, and the
mixture is heated at from 80 to 90 degrees centigrade, until a sample is found not
to act on diazotised sulphanilic acid to form a dye-stuff. It is to be noted that if
any of the alpha, naphthylamine-alpha, beta disulphonic acid (acid No. III)
which is first formed from the alpha, naphthylamine-beta, monosulpho acid, remain
unaltered, its presence is indicated by the formation of an orange coloured azo dye,
which will turn bluish-violet by the addition of muriatic acid. The sulphonation
mixture having been neutralised by slaked lime, and the precipitated calcium
sulphate filtered off, a solution of the calcium salt of alpha, naphthylamine beta,
alpha, beta, trisulphonic acid is obtained, from which the acid may be separated in
a pure state, as acid sodium salt, by converting it by means of sodium carbonate
into the neutral sodium salt, concentrating the solution of the latter by evaporation,

page_text: and subsequently adding muriatic acid. The acid sodium salt of the trisulphonio.
acid then separates in small white, brilliant needles.
The isomeric alpha, uaphthylamine-beta, alpha, beta, trisulphonic acid is obtained
in a manner analogous to that described in the above example, if the isomeric
alpha, naphthylamine beta, monosulphonic acid (Cleve's beta a id) is used in place.
of alpha, naphthylamine beta monosulphonic acid (Clève's delta acid). In this
case, alpha, naphthylamine-alpha, beta,-disulphonic acid is first formed, which, by
further sulphonation, is converted into alpha, naphthylamine-beta₁ alpha2 beta-
trisulphonic acid.
The said two naphthylaminetrisulphonic acids can also be obtained, if, in place of
alpha, naphthylamine beta-monosulphonic acid, or alpha, naphthylamine beta,
monosulphonic acid, the corresponding disulphonic acids, viz.: alpha, naphthylamine
alpha, beta, disulphonic acid, or alpha, naphthylamine alpha, beta, disulphonic
acid, are acted on by sulphonating agents in a suitable manner.
The resulting naphthylamine trisulphonic acids and corresponding salts are very
similar to one another. The salts (especially the tertiary salts) exhibit a beautiful
pure blue fluorescence in aqueous solution, and materially vary as to their solubility
in water, the salts of the alpha, naphthylamine-beta, alpha, betas trisulphonio
acid, for example, being much more soluble than those of the isomeric acid.
My foreign correspondents have described in the above example, a distinct.
method of producing one of the above two trisulphonic acids, and it is mentioned
that the other trisulphonic acid is formed in an analogous way. But my foreign
correspondents do not limit themselves to the directions above given, as the latter
can be varied. For instance, instead of the alphanaphthylamine mono or disulphonic
acids, corresponding quantities of salts thereof can be used. The strength of the
fuming sulphuric acid may vary within certain limits, and the temperature and
duration of action may be varied in a corresponding manner. Such or similar
modifications do not alter the nature of this invention, which generally relates to the
production of pure alpha, naphthylamine-beta,-alpha2-beta-trisulphonic acid, or
salts thereof, from alpha, naphthylamine-beta-monosulphonic acid, or alpha-
naphthylamine-alpha, beta-disulphonic acid, or salts thereof, and to the production
of pure alpha, naphthylamine-beta, alpha, beta-trisulphonic acid, or salts thereof,.
from alpha, naphthylamine-betas-monosulphonic acid, or alpha, naphthylamine.
alpha, betas disulphonic acid, or salts thereof.
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-
from abroad), I declare that what I claim is :-
1. The production of alpha naphthylamine-beta1 alpha, betas-trisulphonic acid.
from alpha, naphthylamine betas monosulphonic acid, or alpha, naphthylamine
alpha, betas disulphonic acid, or salts thereof, and fuming sulphuric acid, subse-.
quently isolating the alpha, naphthylamine-beta, alpha, beta; trisulpho acid so
formed in a suitable manner.
2. The process for producing alpha-naphthylamine beta, alpha, beta4-trisulphonic
acid, which process consists in sulphonating alpha, naphthylamine beta mono-.
sulphonic acid, or alpha, naphthylamine alpha, beta, disulphonic acid, or salts
thereof, by means of fuming sulphuric acid, and subsequently isolating the
alpha, naphthylamine beta, alpha, beta, trisulphonic acid so formed, in a suitable.
manner.