Improvements in the Manufacture of Alpha-naphthol and of Alpha Naphthol sulphonic Acids from the corresponding Amido Compounds.
Year: 1892

page_text: Date of Application, 8th Aug., 1892
Complete Specification Left, 8th May, 1893-4ccepted. 10th June, 1893
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBWERKE VORMALS MEISTER LUCIUS
AND BRUNING, of Hoechst a Main, Germany, Chemical Manufacturers.]
Improvements in the Manufacture of Alpha-naphthol and of Alpha
Naphthol sulphonic Acids from the corresponding Amido
Compounds.
I, CHARLES DENTON ABEL, of No. 28 Southampton Buildings, Chancery Lane
in the County of London, Consulting Engineer and Patent Agent, do hereby declare
the nature of this invention to be as follows:-
The alpha naphthol of commerce contains from 10 to 15 per cent. of beta naphthol,
and up to the present time no process existed by which the simultaneous formation
of this admixture could be avoided, nor has any process been discovered by which
the said admixture could be removed from the alpha naphthol produced. Neither
does there exist a precise process for the separation of the alpha and beta
naphthalin sulphonic acids which are formed simultaneously in the sulphonisation of
naphthalin; in consequence hereof the alpha naphthalin sulphonic acid, which is
used for the production of alpha naphthol contains a large proportion of beta
naphthalin sulphonic acid, which in being melted with caustic soda, produces beta-
naphthol; the only means for removing the said admixture from the alpha-naphthol
is by often repeated recrystallisation from benzene.
Various attempts have been made to find a way for the production of pure alpha
naphthol, but up to the present time none had met with a real success.
My foreign correspondents have discovered however that a good yield of pure
alpha naphthol can be obtained from alpha naphthylamine when the salts of this
body are heated together with water under pressure. In the same manner are
readily obtained from the various alpha naphthylamine sulphonic acids the corre-
sponding alpha naphthol sulphonic acids.
40 parts by weight of sulphate of alpha-naphthylamine are well mixed with 200
parts by weight of water and in an autoclave heated at 200° C. for from 1 to 4
hours.
After cooling down, the alpha naphthol will have become deposited at the bottom.
of the vessel in the form of a solid cake. In order to remove the small quantity of
by-products boiling at a higher temperature, the alpha naphthol is submitted to.
distillation.
b. For the sulphate of alpha naphthylamine may be substituted hydrochlorate of
alpha naphthylamine.
40 parts by weight of hydrochlorate of alpha-naphthylamine are heated together.
with 200 parts by weight of water in an autoclave at from 170° to 220° C. for from.
1 to 4 hours. The alpha naphthol is obtained in the manner above described.
In the same manner can be heated to elevated degrees of temperature the various.
peri-naphthylamine mono-, di- and trisulphonic acids together with water, without
any splitting off of sulpho-groups while on the other hand the amido group is
replaced by hydroxyl. This reaction constitutes a great progress in the manufacture
of the naphthol sulphonic acids concerned, as the production of these sulphonic acids
which are of such importance for the manufacture of azo coloring matters, could
only be effected by the complicated and expensive process of converting them into
diazo-compounds, and by subsequent boiling with water according to Griess's,
reaction.

page_text: EXAMPLES.
1. NAPTHOLSULPHONIC ACID 1.8 (S) GERMAN PATENT 40571.
10 parts by weight of naphthylamine sulphonic acid S (1.8) German Patent
40571, together with 40 parts by weight of water, are heated in an autoclave at
from 180° to 220° C. for from 5 to 8 hours. After cooling down the mass is
filtered and from the filtrate the naphthol sulphonic acid is obtained by precipitation
by means of common salt or by evaporation.
2. NAPTHOLDISULPHONIC ACID & GERMAN PATENT 45776.
10 parts by weight of naphthylamine disulphonic acids (acid sodium salt) and
40 parts by weight of water are heated in an autoclave at 180° C. for from 5 to 8
hours. The naphthol-disulphonic acid is obtained as before described.
3. ALPHA NAPHTHOLTRISULPHONIC ACID GERMAN PATENT 56058.
10 parts by weight of naphthylamine trisulphonic acid, obtained by nitration and
subsequent reduction of the naphthalin trisulphonic acid of the German Patent
38281, are heated together with 40 parts by weight of water in an autoclave at
from 180° to 250° C. for from 5 to 10 hours. The naphtholtrisulphonic acid thus
formed is obtained in manner described in the first example.
L
Dated this 8th day of August 1892.
AREL & IMRAY
10 parts by weight of naphthylamine disulphonic acid (acid sodium salt) and
40 parts by weight of water are heated in an autoclave at 180° C. for from 5 to 8
hours. The naphthol-disulphonic acid is obtained as before described.
3. ALPHA NAPHTHOLTRISULPHONIC ACID GERMAN PATENT 56058.
10 parts by weight of naphthylamine trisulphonic acid, obtained by nitration and
subsequent reduction of the naphthalin trisulphonic acid of the German Patent
38281, are heated together with 40 parts by weight of water in an autoclave at
from 180° to 250° C. for from 5 to 10 hours. The naphtholtrisulphonic acid thus
formed is obtained in manner described in the first example.
Dated this 8th day of August 1892.
AREL & IMRA
Agents for the Applicant.
COMPLETE SPECIFICATION.
Improvements in the Manufacture of Alpha-naphthol and of Alpha
Naphthol sulphonic Acids from the corresponding Amido
Compounds.
1, CHARLES DENTON ABEL of No. 28 Southampton Buildings Chancery Lane
in the County of London, Consulting Engineer and 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 :-
The alpha naphthol of commerce contains from 10 to 15 per cent. of beta
naphthol, and up to the present time no process existed by which the simultaneous
formation of this admixture could be avoided, nor has any process been discovered
by which the said admixture could be removed from the alpha naphthol produced.
Neither does there exist a precise process for the separation of the alpha and beta
naphthalin sulphonic acids which are formed simultaneously in the sulphonisation
of naphthalin; in consequence hereof the alpha naphthalin sulphonic acid, which
is used for the production of alpha naphthol contains a large proportion of beta
naphthalin sulphonic acid, which in being melted with caustic soda, produces beta
naphthol; the only means for removing the said admixture from the alpha naphthol
is by often repeated recrystallisation from benzene.
Various attempts have been made to find a way for the production of pure
alpha naphthol, but up to the present time none had met with a real success.
My foreign correspondents have discovered however that a good yield of pure
alpha naphthol can be obtained from alpha naphthylamine when the salts of this
body are heated together with water under pressure. In the same manner are
readily obtained from the various alpha naphthylamine sulphonic acids the
corresponding alpha naphthol-sulphonic acids.

page_text: a. Alpha naphthol.
40 parts by weight of sulphate of alpha-naphthylamine are well mixed with
200 parts by weight of water and in an autoclave heated at 200° C. for from 1 to
4 hours.
After cooling down, the alpha naphthol will have become deposited at the
bottom of the vessel in the form of a solid cake. In order to remove the small
quantity of by-products boiling at a higher temperature, the alpha naphthol is
submitted to distillation.
b. For the sulphate of alpha naphthylamine may be substituted hydrochlorate of
alpha naphthylamine.
40 parts by weight of hydrochlorate of alpha-naphthylamine are heated together
with 200 parts by weight of water in an autoclave at from 170° to 220° C. for
from 1 to 4 hours. The alpha naphthol is obtained in the manner above
described.
In the same manner can be heated to elevated degrees of temperature the
various peri-naphthylamine mono- di- and trisulphonic acids together with water,
without any splitting off of sulpho-groups while on the other hand the amido group
is replaced by hydroxyl. This reaction constitutes a great progress in the manu-
facture of the naphthol sulphonic acids concerned, as the production of these
sulphonic acids which are of such importance for the manufacture of azo coloring
matters, could only be effected by the complicated and expensive process of
converting them into diazo-compounds, and by subsequent boiling with water
according to Griess's reaction.
2. NAPHTHOLDISULPHONIC ACID & GERMAN PATENT 45776.
E
10 parts by weight of naphthylamine disulphonic acid (acid sodium salt) and
40 parts by weight of water are heated in an autoclave at 180° C. for from 5 to
58 hours. The naphtholdisulphonic acid is obtained as before described.
3. ALPHA NAPHTHOLTRISULPHONIC ACID GERMAN PATENT 56058.
10 parts by weight of naphthylamine trisulphonic acid, obtained by nitration
and subsequent reduction of the naphthalin trisulphonic acid of the German
Patent 38281, are heated together with 40 parts by weight of water in an autoclave
at from 180° to 250° C. for from 5 to 10 hours. The naphthol-trisulphonic acid
thus formed is obtained in manner described in the first example.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The herein described process for the manufacture of alphanaphthol from
a naphthylamine by heating salts of a naphthylamine with water at high
temperature under pressure.
2. The herein described process for the manufacture of naphtholsulphonic

page_text: E
acid S 1:8 of the German Patent 40571, naphtholdisulphonic acid of the German
Patent 45776 and naphtholtrisulphonic acid of the German Patent 56058 by
heating with water at high temperature under pressure respectively :-the naphthyl-
amine sulphonic acid 1:8 of the German Patent 40571 the naphthylamine disul-
phonic acid of the German Patent 45776 and the naphthylamine trisulphonic acid
obtained by nitration and reduction of the naphthaline trisulphonic acid described
in the German Patent 38281.
ليم
ה וימ
1
1000
ABEL & IMRAY,
Agents for the Applicant.