The Preparation of New Sulphonic Aolds Suitable for the Manufacture of Colouring Matters.
Year: 1889

page_text: Date of Application, 6th July, 1889
Complete Specification Left, 3rd Apr., 1890-Accepted, 10th May, 1890
PROVISIONAL SPECIFICATION.
The Preparation of New Sulphonic Aolds Suitable for the
Manufacture of Colouring Matters.
We THE CLAYTON ANILINE Co. Limited of Clayton near Manchester in the
County of Lancaster and CHARLES DREYFUS Managing Director to the said Company
do hereby declare the nature of this Invention to be as follows:-
This Invention relates to the production of new sulphonic acids from phenyl and
tolyl ẞ naphtylamine. By sulphonating phenyl ẞ naphtylamine at 100° Centigrade
with six times its own weight of strong sulphuric acid Streiff obtained a trisulphonic
acid of phenyl B-naphtylamine (Analine der Chemie und Pharmacie 209, 160). In his
German Patent application No. Z 1021 Zimmer describes a method of producing a
new sulphonic acid of phenyl ẞ-naphtylamine. In this specification Zimmer states
that by treating phenyl ẞ naphtylamine at 2 to 45° with 3 to 4 times its own weight
of sulphuric acid monohydrate, or fuming sulphuric acid he obtains 90-95% of a
pure monosulphonic acid. The sulphonation product is thrown upon ice and the
sulphonic acid is filtered off and transformed into salts in a manner well known to
chemists. The sodium salt is described as being soluble in 5-6 parts of boiling
water and cristallizing in silver glittering laminæ containing 2 molecules of water of
crystallization and dissolving in alcohol of 85-90 % with blue fluorescence.
We have found that when carrying the sulphonation out under the conditions as
stated in Zimmers Specification we get a mixture of two monosulphonic acids which
can easily be separated by the different solubility of their ammonium salts in cold
water. The one giving a but slightly soluble ammonium salt we call A acid (pheny
naphtylamine A monosulphonic acid) and the other giving an ammonium salt which
is easily soluble in cold water we call B acid (phenyl ẞ naphtylamine B mono-
sulphonic acid). The sodium salt of the A acid crystallizes in needles without any
water of crystallization (found 2.3% of water C, H.-NHC₁, H, SO3 Na + H, O
would require 2.8 %) and dissolves in 4 parts of boiling water and in alcohol
without fluorescense. The sodium salt of the B acid crystallizes in laminæ which
contain 3 molecules of water of crystallization (found 13.96 instead of 14.4 % of
water) and dissolves in its own weight of boiling water and in alcohol with blue
fluorescense. It is evident that these two are different and that Zimmers acid is a
mixture of the two acids.
For the preparation and separation of these monosulphonic acids we proceed as
follows.
On
100 parts of phenyl ẞ naphtylamine are dissolved in 400 parts of sulphuric acid
monohydrate taking care not to allow the temperature to rise above 50° C. After
about 2 days standing at about 15° to 20° C..the sulphuric acid solution is. thrown
into 1600 parts of cold water and the whole kept a short time at boiling point till the
mixed sulphonic acids separate out as a granulated powder, this is filtered off washed
and by boiling with 1600 parts of water and sufficient quantity of ammonia liquor,
transformed into a hot solution of the ammonium salts which is when necessary,
filtered off from the little phenyl-naphtylamine which may be unacted on.
cooling the ammonium salt of the A acid separates out and is filtered off on boiling
down the filtrate to about 400 parts a small quantity of the same salt will be obtained.
The filtrate contains a solution of the ammonium salt of the B acid from which on
adding a solution of caustic soda or sodium-chloride the sodium salt of the B acid is
precipitated, the salts of the two acids thus obtained can easily be purified by
recrystallisation from water. The quantities of the two acids vary according to the
temperature used, the lower the temperature is kept during the sulphonation, the
larger is the quantity of A acid formed. At about 15 to 20° C. we get 1 parts of

page_text: A acid and 6 parts of B acid. On the whole the salts of the B acid are more easily
soluble than those of the A acid.
The A acid forms salts with. the following substances.
Sodium Crystallizing in needles, its saturated solution contains at the boiling
point (101° C.) 19% of dry salt and the salt dissolves without fluorescense in a'cohol
of 90 %
:
Sodium Crystallizing in laminæ its saturated solution contains at the boiling
point (104° C.) 48.3 % of dry salt, is soluble in alcohol with blue fluoressence.
Ammonia-Crystallizing in long needles; its saturated solution contains at 20°
53.9% of dry salt.
Potassium Crystallizing in laminæ, soluble in water.
Calcium Crystallizing in needles or prisms soluble in water.
The barium and copper salts are nearly insoluble precipitates.
By sulphonating ortho tolyl ẞ naphtylamine in the same way as described for the
treatment of phenyl 3 naphtylamine we get a mixture of two monosulpho-acids, the
one giving a nearly insoluble calcium salt we call ortho tolyl ẞ naphtylamine
A monosulphonic acid, and the other, giving a soluble calcium salt we call ortho tolyl
naphtylamine B monosulphonic acid.
For the preparation and separation of the said acids we dissolve 100 parts of ortho-
tolyl naphtylamine in 500 parts of sulphuric acid monohydrate at a temperature
of 10° to 50° C.; this solution is allowed to stand at this temperature till the
sulphonation is finished that is till a sample will dissolve perfectly in diluted caustic
.soda. At 10 to 20° this takes from 2 to 4 days and at 40° only about 12 hours. On
throwing the product into 1600 parts of cold water the mixed sulphonic acids separate
out and these are after filtration from the mother liquor transformed into a solution
of the sodium salt by boiling with 2000 parts of water and sufficient quantity of
caustic soda; by double decomposition with calcium chloride the calcium salts of the
two acids are formed.
The liquid is separated by filtration from the crystals which are then extracted with
hot water till the filtrate gives no precipitate with carbonate of soda. The residue
represents the calcium salt of the A acid and the filtrates contain a solution of the
calcium salt of the B acid both these salts can easily be converted into alkali
salts by double decomposition with a carbonate of an alkali.
:
These sulphonic acids either mixed or separated can be used for combining with
diazo compounds for the production of colouring matters.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents. 4
COMPLETE SPECIFICATION.
The Preparation of New Sulphonic Acids Suitable for the
Manufacture of Colouring Matters.
03
We THE CLAYTON ANILINE COMPANY Limited of Clayton near Manchester in the
County of Lancaster and CHARLES DREYFUS Managing Director to the said Company!
do hereby declare the nature of the said invention and in what manner the same is
to be performed to be particularly described and ascertained in and by the following
statement:
.
. I
This Invention relates to the production of new sulphonic acids from phenyl- and
tolvl: beta nan
amine

page_text: By sulphonating phenyl beta naphthylamine at 100° Centigrade with six times
its own weight of strong sulphuric acid, Streiff obtained a trisulphonic acid of
phenyl-beta naphthylamine (Annalen der Chemie und Pharmacie 209-160). In the
Specification of his German patent No. 45940 Zimmer describes a method of
producing a new sulphonic acid of phenyl beta naphthylamine. In this specification
Zimmer states that by treating phenyl beta naphthylamine at 25 to 45° Centigrade
with 3 to 4 times its own weight of sulphuric acid monohydrate or fuming sulphuric
acid, he obtains 90 to 95 per cent. of a pure monosulphonic acid. The sulphonation
product is thrown upon ice and the sulphonic acid is filtered off and transformed into
salts in a manner well known to chemists; the sodium salt is described as being
soluble in 5 to 6 parts of boiling water and crystallizing in silver glittering lamina
containing two molecules of water of crystallization and dissolving in alcohol of 85
to 90 per cent. with blue fluorescence.
We have found that when carrying the sulfonation out, under the conditions as
stated in Zimmer's specification, we get a mixture of two monosulphonic acids which
can easily be separated by the different solubility of their ammonium salts in cold
water the one giving a but slightly soluble ammonium salt we call A acid (phenyl
beta naphthylamine A monosulphonic acid) and the other, giving an ammonium salt
which is easily soluble in cold water, we call B acid (phenyl beta naphthylamine
B monosulphonic acid). The sodium salt of the A acid crystallizes in needles without
any water of crystallisation (found 2.3 per cent. of water: C H.–NHC. Hy SO,
Na +H, Owould require 2.8 per cent.) and dissolves in 4 parts of boiling water
and in alcohol without fluorescence. The sodium salt of the B acid crystallizes in
lamine which contain three molecules of water of crystallisation (found 13.96 per cent.
instead of 144 per cent. of water which is the theoretical) and dissolves in its own
weight of boiling water and in alcohol with blue fluorescence. It is evident that
these two are different and that Zimmer's acid is a mixture of the two acids.
For the preparation and separation of these monosulphonic acids we proceed as
follows:
100 parts by weight of phenyl beta naphthylamine are dissolved in 400 parts by
weight of sulphuric acid monohydrate taking care not to let the temperature rise
above 50° Centigrade after about 2 days standing at about 15° to 20° Centigrade the
sulphuric acid solution is thrown into 1600 parts by weight of cold water and the
whole kept a short time at boiling point till the mixed sulphonic acids separate out
as a granulated powder. This is filtered off washed and by boiling with 1600 parts
by weight of water and sufficient quantity of ammonia liquor, is transformed into a
hot solution of the ammonium salts, which is, when necessary, filtered off from the
little phenylnaphthylamine which may be unacted upon. On cooling the ammonia
salt of the A acid separates out and is filtered off. On boiling down the filtrate to
about 400 parts, a small quantity of the same salt will be obtained. The filtrate
contains a solution of the ammonium salt of the B acid, from which on adding a
solution of caustic soda or sodium-chloride the sodium salt of the B acid is
precipitated. The salts of the two acids thus obtained can easily be purified by
recrystallisation from water.
The quantities of the two acids vary according to the temperature used; the lower
the temperature is kept during the sulphonation the larger is the quantity of A acid
formed. At about 15 to 20° Centigrade we get 2 parts of A acid and 3 parts
of B acid.
On the whole the salts of the B acid are more easily soluble than are those of
the A acid.
The. A acid forms salts with the following substances viz. :—
:
Sodium Crystallizing in needles; its saturated solution contains at the boiling
point (101° Centigrade) 19 per cent. of dry salt and the salt dissolves without
fluorescence in alcohol of 90 per cent.
Ammonia Crystallizing in laminæ ; its saturated solution contains at 20° Centi
grade 042 per cent. of dry salt. ·
Potassium Crystallizing in needles; soluble in water.

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:
Barium Nearly insoluble, amorphous precipitate.
Copper Soluble crystals.
The B acid forms salts with
Sodium Crystallizing in laminæ ; its saturated solution contains at the boiling
point (104° Centigrade) 48.3 per cent. of dry salt; is soluble in alcohol with blue
fluorescence.
Ammonia Crystallizing in long needles; its saturated solution, contains
at 20° Centigrade 53-9 per cent. of dry salt.
Potassium Crystallizing in laminæ, soluble in water.
Calcium Crystallizing in needles or prisms, soluble in water.
The barium and copper salts are nearly insoluble precipitates.
By sulphonating ortho-tolyl beta naphthylamine in the way described for the treat-
ment of phenyl beta naphthylamine we obtain a mixture of two monosulphonic-acids,
the one giving a nearly insoluble calcium salt we call ortho tolyl beta naphthylamine
A mono sulphonic acid, and the other, giving a soluble calcium salt, we call ortho-tolyl
beta naphthylamine B monosulphonic acid.
For the preparation and separation of the said acids we dissolve 100 parts by
weight of ortho tolyl beta naphthylamine in 500 parts by weight of sulphuric acid
monohydrate at a temperature of 10 to 50° Centigrade. The solution is allowed to
stand at this temperature till the sulphonation is finished, that is till a sample will
dissolve perfectly in diluted caustic soda. At 10 to 20° Centigrade this takes from 2
to 4 days and at 40° Centigrade only about 12 hours. On throwing the product
into 1600 parts by weight of water the mixed sulphonic acids separate out and these
are, after filtration from the mother liquor, transformed into a solution of the sodium.
salt by boiling with 2000 parts by weight of water and sufficient quantity of caustic
soda, by double decomposition with calcium chloride the calcium salts of the two
acids are formed.
The liquid is separated by filtration from the crystals which are then extracted with
hot water till the filtrate gives no precipitate with carbonate of soda. The residue
represents the calcium salt of the A acid and the filtrates contain a solution of the
calcium salt of the B acid, both these salts can easily be converted into alkali salts by
double decomposition with a carbonate of an alkali.
A saturated solution at about 15° Centigrade of the sodium salt of ortho-tolyl-beta
naphthylamine A sulphonic acid contains roughly 1.8 per cent. of dry salt; a similar.
solution of the isomere B acid contains 2-3 per cent. of dry salt.
Having now particularly described and ascertained the nature of our said inven-
tion and in what manner the same is to be performed we declare that what we
claim is :-
1. The separation of the herein before mentioned so called phenyl beta naphthyl-
amine monosulphonic acid of Zimmer into two distinct sulphonic acids as herein
before described.
2. The preparation of ortho tolyl beta naphthylamine monosulphonic acids as herein
before described.
3. The separation of the ortho tolyl beta naphthylamine monosulphonic acids as
herein before described.