Production of Oxysulphonic Acids of Naphthalin.
Year: 1889

page_text: Date of Application, 11th June, 1889
Complete Specification Left, 6th Mar., 1890-Accepted, 12th Apr., 1890
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBWERKE VORMALS MEISTER LUCIUS AND
BRUNING, of Hoechst-am-Maine, in the Empire of Germany, a Company
carrying on business as Chemical Manufacturers.]
Production of Oxysulphonic Acids of Naphthalin.
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:―
This invention relates to the production of oxynaphthalin sulphonic acids from
the betanaphtholdisulphonic acids R and Y described in the patent Specification
No. 1715 of 1878 and from the betanaphtholtrisulphonic acid described in the patent
Specification No. 2544 of 1882 by heating the same with caustic alkalies.
A. PRODUCTION OF DIOXYNAPHTHALINMONO-SULPHONIC ACIDS.
When the salts of the betanaphtholdisulphonic acids R and Y referred to in the
Specification No. 1715 of 1878 are heated with caustic alkalies to 200°-280° C. until
a sample dissolved in water shows no longer the characteristic fluorescence of these
salts, there will have been produced a dioxynaphthalinmono sulphonic acid.
Example: 35 parts by weight of naphtholdisulphonate of sodium are dissolved
in a small quantity of water and 15 to 20 parts by weight of caustic soda are added
to the solution. It is heated then in a closed vessel furnished with an agitator
to 220°-230° C. for about 3 to 7 hours until the fluorescence disappears.
Afterwards the melt is poured into water strongly acidulated and left to cool. The
dioxynaphthalinsulphonate of sodium separates in form of crystals and is obtained in
the usual way.
From the betanaphtholdisulphonic acid R is obtained a dioxynaphthalinmono
sulphonate of sodium which is with great difficulty soluble in common salt solution
and is precipitated from its aqueous solution in the form of brilliant leaflets by the
addition of common salt solution.
A drop of ferric chloride solution produces in its neutral aqueous solution an
intense violet colour, which on the addition of soda turns to brown red. The
violet solution is discolored by a few drops of sulphuric acid, the addition of an
equivalent quantity of alkali restores the colour.
The dioxynaphthalinmonosulphonate of sodium produced from the betanaphtoldi-
sulphonic acid Y is much more readily soluble in common salt solution than its
isomere previously described. It dissolves readily in that solution at high temperature
and crystallises from it in the form of compact noedles about one centimetre in
length.
With ferric chloride this new body produces a green-yellow solution fading
rapidly and by this reaction it may be readily distinguished from the sulphonate
produced in the manner set forth from the salt R.

page_text: 3
· B.-PRODUCTION OF THE DIOXYNAPHTHALINDISULPHONIC ACID.
When the betanaphtholtrisulphonates described in the patent Specification
No. 2544 of 1882 are heated with caustic alkalies to 200°-280° C. until a sample
dissolved in water just loses the characteristic green fluorescence, there will have
been formed a dioxynaphthalin-disulphonic acid.
Example:-45 parts by weight of betanaphtholtrisulphonate of sodium are
dissolved in a small quantity of water and to the solution are added 15 to 20 parts
by weight of caustic soda. The mixture is then heated in a closed vessei furnished
with an agitator to 220°-230° C. for about 3 to 4 hours until the disappearance of
the green fluorescence.
Afterwards the melt is poured into water strongly acidulated and left to cool.
The dioxynaphthalindisulphonate of sodium separates in micro-crystalline form and
is obtained in the usual manner.
The dioxynaphthalindisulphonate of sodium produced in this way dissolves in
water very readily. In a common salt solution it dissolves at high temperature
and crystallises from it on cooling. Treated with ferric chloride in neutral solution
it furnishes a pure blue solution which gradually turns to grey blue. On the
addition of a few drops of sulphuric acid the solution takes a pale greenish yellow
.shade.
This dioxynaphthalindisulphonic acid produces with diazo compounds, as for
example diazo-xylol and diazo-cumol, pure, red and clear coloring matters, whereas
the dioxynaphthalindisulphonic acid obtained in the way described in the German
patent No. 40893 produces with diazo compounds brown coloring matters.
C. PRODUCTION OF TRIOXYNAPHTHALINMONO-SULPHONIC ACID.
When the betanaphtholtrisulphonates referred to in the patent Specification
No. 2544 of 1882 are heated beyond the limit prescribed in B that is to say
beyond the disappearance of the green fluorescence, preferably up to 2500-320° C.
and in presence of a larger quantity of caustic alkali, the dioxynaphthalindisulphonic
acid formed intermittently is convorted into the trioxynaphthalinmonosulphonic
acid.
Example 45 parts by weight of betanaphtholtrisulphonate of sodium are
dissolved in a small quantity of water, 30 to 40 parts by weight of caustic soda are
added and the whole is heated in a closed vessel furnished with an agitator at first to
230° C. for 5 hours and then to 260°-270° C. for about 12 hours until the solution
rendered neutral after expelling tho sulphurous acid, takes on the addition of ferric
chloride a blue violet colour, which, on the addition of soda solution, does not
disappear but turns to intense red.
For the betanaphtholtrisulphonic acid in this process may be substituted the
dioxynaphtalindisulphonic acid produced as described in B with like result.
The melt is afterwards poured into water made strongly acid and left to cool.
The trioxynaphthalinmonosulphonate of sodium separates in the form of brilliant
tablets, and is obtained by recrystallisation in the form of large compact crystals.
In the three processes described, for the caustic soda may be substitute.l another
alkali, and open vessels may be used instead of closed vessels.
The temperature and duration of the action vary according to the quantity of
alkali employed.
The oxynaphthalinsulphonates may be used for ulterior purposes directly in their
solution after previous expulsion of the sulphurous acid.
Dated this 11th day of June 1889.
ABEL & IMRAY,
Agents for the Applicant,

page_text: COMPLETE SPECIFICATION.
Production of Oxysulphonic Acids of Naphthalin.
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 :-
This invention relates to the production of oxynaphthalinsulphonic acids from the
betanaphtholdisulphonic acids R and Y described in the patent Specification No. 1715
of 1878 and from the hetanaphtboltrisulphonic acid described in the patent
Specification No. 2544 of 1882 by heating the same with caustic alkalies.
A. PRODUCTION OF DIOXYNAPHTHALINMONOSULPHONIC ACIDS.
When the salts of the betanaphtholdisulphonic acids R and Y referred to in the
Specification No. 1715 of 1878 are heated with caustic alkalies to 200°-260° C. until
a sample dissolved in water shows no longer the characteristic fluorescence of these
salts, there will have been produced a dioxynaphthalin monosulphonic acid.
Example 3 parts by weight of naphtholdisulphonate of sodium are dissolved
in a small quantity of water and 15 to 20 parts by weight of caustic soda are added
to the solution. It is then heated in a closed vessel furnished with an agitator to 226°—
230° C. for about 3 to 7 hours until the fluorescence disappears.
Afterwards the selt is poured into water, strongly acidulated and left to cool. The
dioxynaphthalinsulphonate of sodium separates in form of crystals and is obtained
in the usual way.
From the betanaphtholdisulphonic acid R is obtained a dioxynaphthalinmono-
sulphonate of sodium which is with great difficulty soluble in common salt solution
and is precipitated from its aqueous solution in the form of brilliant leaflets by the
addition of common salt solution.
A drop of ferric chloride solution produces in its neutral aqueous solution an intense
violet colour, which on the addition of soda turns to brown red. The violet solution
is discoloured by a few drops of sulphuric acid; the addition of an equivalent
quantity of alkali restores the colour.
.
The dioxynaphthalinmonosulphonate of sodium produced from the betanaphtho!-
disulphonic acid Y is much more readily soluble in common salt solution than its
isomere previously described. It dissolves readily in that solution at high temperature
and crystallises from it in the form of compact needles about one centimetre in
length.
With ferric chloride this new body produces a green yellow solution fading rapidly
and by this reaction it may be readily distinguished from the sulphonate produced in
the manner set forth from the salt R.
B. PRODUCTION OF THE DIOXYNAPHTHALINDISULPHONIC ACID.
When the betanaphtholtrisulphonates described in the patent Specification No. 2 44
of 1882 are heated with caustic alkalies to 200°-280° C. until a sample dissolved in
water just loses the characteristic green fluorescence, there will have been formed a
dioxynaphthalindisulphonic acid.
Example: 45 parts by weight of betanaphtholtrisulphonate of sodium are
dissolved in a small quantity of water and to the solution are added 15 to 20 parts
by weight of caustic soda. The mixture is then heated in a closed vessel furnished
with an agitator to 220°-230° C. for about 3 to 4 hours until the disappearance of the
green fluorescence.
Afterwards the melt is poured into water strongly acidulated and left to cool. The
dioxynaphthalindisulphonate of sodium separates in micro crystalline form and is
obtained in the usual-manner.
The dioxynaphthalindisulphonate of sodium produced in this way dissolves in water

page_text: very readily. In a common salt solution it dissolves at high temperature and
crystallises from it on cooling. Treated with ferric chloride in neutral solution it
furnishes a pure blue solution which gradually turns to grey blue. On the addition
of a few drops of sulphuric acid the solution takes a pale greenish yellow shade.
This dioxynaphthalindisulphonic acid produces with diazo compounds, as for
example diazoxylol and diazo cumol, pure red and clear colouring matters, whereas
the dioxynaphthalindisulphonic acid obtained in the way described in the German
Patent No. 40893 produces with diazo compounds brown colouring matters.
( PRODUCTION OF TRIOXYNAPHTH ALINMONOSULPHONIC ACID.
When the betanaphtholtrisulphonates referred to in the patent Specification No. 2544
of 1882 are heated beyond the limit prescribed in B, that is to say, beyond the
disappearance of the green fluorescence, preferably up to 250°-320° C. and in
presence of a larger quantity of caustic alkali, the dioxynaphthalindisulphonic acid
formed intermittently is converted into the trioxynaphthalinmonosulphonic acid.
Example 45 parts by weight of betanaphtholtrisulphonate of sodium are
dissolved in a small quantity of water, 30 to 40 parts by weight of caustic soda are
added and the whole is heated in a closed vessel furnished with an agitator at first
to 230° C): for 5 hours, and then to 260°-27° C. for about 12 hours, until the solution
rendered neutral, after expelling the sulphurous acid, takes on the addition of ferric
chloride a blue violet colour, which, on the addition of soda solution, does not disappear
but turns to intense red.
For the betanaphtholtrisulphonic acid in this process may be substituted the
dioxynaphthalindisulphonic acid produced as described in B, with like result.
The melt is afterwards poured into water made strongly acid and left to cool.
The trioxynaphthalinmonosulphonate of sodium separates in the form of brilliant
tablets and is obtained by recrystallisation in the form of large compact crystals.
In the three processes described for the caustic soda may be substituted another
alkali and open vessels may be used instead of closed vessels.
The temperature and duration of the action vary according to the quantity of alkali
employed.
The oxy naphthalinsulphonates after expulsion of the sulphurous acid may be used
directly in their solutions for ulterior purposes, such as for example the production of
azo colouring matters as in the following example.
26-2 parts by weight of dioxynaphthalinmonosulphonate of sodium, or an equivalent
quantity of dioxynaphthalindisulphonate of sodium or of trioxynaphthalinmonosul-
phonate of sodium or an equivalent quantity of one of the solutions of these obtained
as above set forth, are mixed with 150 parts by weight of soda cooled down
to 0-8° C. and then combined with some diazo compound, for example the diazo
compound obtained in manner well known, from 14.3 parts by weight of alpha-
naphthylamine. In this way deep violet red colouring matters are obtained.
If for the alphanaphthylamine is substituted another base, such as aniline, toluidine,
xylidine, cumidine, betanaphthylamine or the sulphonic acid of any of these, the
colouring matters obtained have tints of more yellow character.
If a tetrazo compound of benzidine, tolidine, dimethoxy-benzidine is used there
result colouring matters that dye unmordanted cotton blue violet tints.
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 :-
The production of oxynaphthalinsulphonic acids by heating the naphthol di- and tri-
sulphonic acids with caustic alkalies and the use of the said acids as described.
Dated this Sixth day of March 1890
ABEL & IMRAY,
Agents for the Applicant.