Year: 1886

page_text: Date of Application, 6th Mar., 1886.
Complete Left, 6th Dec., 1886.
Complete Accepted, 7th Jan., 1887.
[Communicated from abroad by the ACTIENGESELLSCHAFT FARBENFABRIKEN Vorm
FRIEDRICH BAYER AND CO., of Elberfeld, in the Empire of Germany.]
I JAMES YATE JOHNSON, of 47 Lincolns Inn Fields in the County of Middlesex,
Gentleman, do hereby declare the nature of this Invention, to be as follows:-
By heating benzidine with fuming sulphuric acid to about one hundred and seventy
degrees centigrade, four different benzidine sulpho acids are produced, or the like.
result may be obtained with fuming sulphuric acid, pyro-sulphuric acid, sulphuric
acid anhydride or monochlorhydrine or inixtures of these agents with sulphuric acid
of about 66. density.
According to this invention a fifth sulpho acid namely benzidine monosulpho acid
is obtained by heating benzidine tolidine or a salt or salts thereof such as benzidine
sulphate with a sulphuric Acid to about One hundred and seventy degrees centigrade
as hereinafter described This benzidine monosulpho acid differs from the other
benzidine sulpho acids obtained as aforesaid inasmuch as it can be separated from its
salts by means of acetic acid. The quantity obtained depends on the strength of the
acid the elevation of the temperature and the duration of the action.
When mono hydratic sulphuric acid or sulphuric acid at 66 is employed in place
of the fuming sulphuric acid the aforesaid monosulpho acid is obtained almost
exclusively.
In carrying out this invention about one part of benzidine or preferably benzidine
sulphate is added to about two parts of monohydratic sulphuric acid and heated to
one hundred and seventy degrees centigrade for about one and a half hours. The
melted product is poured into water, the sulpho acid separating therefrom is filtered
the residue is dissolved in an alkali and the filtering repeated in order to remove any
unchanged benzidine that may still remain and the benzidine monosulpho acid is
separated from the filtrate by means of an acid. In case di- tri- or tebra-sulphoacids
have been formed in the treatment with sulphuric acid which results from too pro-
longed expossure to the action of the sulphuric acid the mono sulpho acid is separated
from the alkaline solution of the sulpho acid mixture by means of acetic acid.

page_text: The benzidine mono sulpho acid thus obtained is in the form of a white finely
crystalline deposit or precipitate which dissolves with great difficulty even in boiling
water and is practically insoluble in alcohol and ether. It dissolves in strong mineral
acids forming salts which are again decomposed when treated with water.
Its tebrazo compound differs from that of bensidine disulpho acids being readily
soluble in water and forms with Phenols, amides and the sulpho or carbo. acids and
substitution products thereof a great number of azo dyes which are very similar to but
somewhat bluer than those of tebrazo diphenyl. In like manner tolidine mono sulpho
acids resembling the benzidine mono sulpho acid as regards the dyes obtained there-
from is produced from tolidine or any of its salts.
A yellow dye is produced by causing tebrazo diphenyl or tetrazo ditoyl mono
sulpho acid to act upon aniline, tolindine, xylidine, annidine, or their mono and
disulpho acids, the action of the same on phenol-resorcin, alpha and beta naphthol or
their mono and disulpho acids or their carbo acids produces dyes varying from red to
violet, a very beautiful blue red is obtained by the action of the aforesaid tetrazo
diphenyl or tetrazo ditolyl mono sulpho acid on alpha and beta nophthylamine and
the mono and disulpho acids thereof and splendid intense yellowish red to blueish red
by the action on the mono or dialkylised compounds of the amides or phenols.
The production of these dyes is effected by the action of one molecule of tetrazo-
diphenyl or tetrazo ditolyl mono sulpho acid upon two molecules of phenol or phenol
sulpho acid, amido or amido sulpho acids.
The number of the combinations hereby rendered possible is greatly increased by
bringing together one molecule of tetrazo diphenyl or tetrazo ditolyl mono sulpho
acid and one molecule of phenol etcetera in an organic acid solution and allowing
the intermediate products thereby obtained to act upon one molecule of another phenol
amide or their sulpho carbo acids and substitution products.
The following are given as examples of the formation of the dye according to this
invention without limiting myself to the precise quantities or proportions specified.
First. Ten parts by weight of the benzidine monosulpho acid obtained and purified
as above described are placed in suspension in twenty parts by weight of water mixed
with twelve parts of muriatic or hydrochlaric acid at twenty one degrees Beaune and
then diazotised with a solution of 53 parts of sodium nitrite in twice the quantity
of water. The yellowish red solution thus obtained is poured slowly into twenty
parts by weight of beta naphthylamine beta monosulpho acid (obtained by treating
heta naphthylamine with sulphuric acid according to the Neville Winter process)
in suspension in water and acetate of soda (about forty parts by weight) is added
until the resulting brown precipitate ceases to colour the test paper.
===
After standing for about twenty four hours the precipitate which is now of a red
colour is filtered off, converted to its soda salt by means of soda and dried. A
beautiful red powder is thus obtained which dissolves very readily in water forming
a splendid blueish red dye capable of dyeing raw cotton a beautiful red like alizarine
in a boiling alkaline bath and is but slightly affected by acids.
Second. A red dye bluer than the foregoing is obtained by the action of one
molecule of the tetrazo compound produced as hereinbefore described upon one
molecule of beta naphthylamine and afterwards upon one molecule of beta naphthy-
lamine sulpho neid. The tetrazo compound of about ten parts by weight of benzidine
mono sulpho acid is allowed to run slowly into a watery solution of about six and a
half parts by weight of beta naphthylamine hydrochlorate and about fifteen parts of
acetate of soda and after standing for a short time a watery solution of about ten parts
by weight of beta naphthylamine monosulpho acid soda (monosulphate of soda) is
added. The precipitate which is black in the first instance gradually turning to a
brownish red and becoming a splendid blueish red in a soda lye is filtered and dried.

page_text: Improvements in the Manufacture of Azo Dyes and Benzidine ana
Tolidine Monosulpho Acids.
I, JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex,
Gentleman do hereby declare the nature of this Invention which Invention has been
communicated to me from abroad by the Actiengesellschaft Farbenfabriken vorm
Friedrich Bayer & Co., of Elberfield in the Empire of Germany and in what
manner the same is to be performed, to be particularly described and ascertained in
and by the following statement:-
By heating Benzidine with fuming Sulphuric acid to about 170 degrees Centigrade
four different benzidene sulpho acids are produced or the like result may be obtained
with pyrosulphuric acid, Sulphuric acid anhydride or monochlorhydrine or mixtures
of these agents with sulphuric acid of about 66 density.
According to this Invention a fifth sulpho acid namely benzidine monosulpho acid
is obtained by heating benzidine tolidine or a salt or salts thereof such as benzidine
sulphate or one of its salts with sulphuric acid to about 170 degrees centigrade as
hereinafter described. The benzidine mono sulpho acid differs from the other
benzidine sulpho acids obtained as aforesaid inasmuch as it can be separated from
its salts by means of Acetic acid. The quantity obtained depends on the strength of
the acid the elevation of the temperature and the duration of the action.
When mono hydratic sulphuric acid or sulphuric acid at 66" is employed in placo
of the fuming sulphuric acid the aforesaid mono sulpho acid is obtained almost
exclusively.
In carrying out this invention about one part of benzidine or preferably benzidine
sulphate is added to about two parts of mono hydratic sulphuric acid and heated to
170° centigrade for about one and a half hours. The melted product is poured into
water, the sulpho or sulphonic acid separating therefrom is filtered, the residue
dissolved in an alkali and the filtering repeated in order to remove any unchanged
benzidine that may still remain and the benzidine mono sulpho or sulphonic acid is
separated from the filtrate by means of an acid. In case di, tri or tetra-sulpho acids
have been formed in the treatment with sulphuric acid which results from too pro-
longed exposure to the action of the suphuric acid, the mono sulpho acid is separated
from the alkaline solution of the sulpho acid mixture by means of acetic acid.
The benzidine mono sulpho acid thus obtained is in the form of a white finely
crystalline deposit or precipitate which dissolves with great difficulty even in boiling
water and is practically insoluble in alcohol and ether. It dissolves in strong mineral
acids forming salts which are again decomposed when treated with water.
Its tetrazo compound differs from that of benzidine, disulpho acids, being readily
soluble in water and forms with phenols amides and the sulpho or carbonic acids and
substitution products thereof a great number of azo dyes which are very similar to but
somewhat bluer than those of tetrazo diphenyl. In like manner tolidino mono sulpho
acid resembling the benzidine mono sulpho acid as regards the dyes obtained there-
from is produced from tolidine or any of its salts.
A yellow dye is produced by causing tetrazo diphenyl or tetrazo ditolyl mono
sulpho or sulphonic acid to act upon aniline, tolindine, xylidine anisdine or their mono

page_text: and disulpho acids the action of the same on phenol, resorein alpha and beta naphthol
or their mono and disulpho acids or their carbonic acids produces dyes varying from
red to violet. A very beautiful blue red is obtained by the action of the aforesaid
tetrazo diphenyl or tetrazo ditolyl mono sulpho (sulphonie) acid an alpha and beta
naphthylamine and the mono and disulpho acids thereof and splendid intense yellowish
red to blueish red by the action on the mono or dialkylised compounds of the amides
or phenols.
The production of these dyes is effected by the action of one molecule of tetrazo
liphenyl or tetrazo ditolyl mono sulpho or sulphonic acid upon two molecules of phenol
or phenol sulpho acid are of amides or amido sulpho acids.
The number of the combinations hereby rendered possible is greatly increased by.
bringing together one molecule of tetrazo diphenyl or tetrazo ditolyl mono sulpho or
sulphonic acid and one molecule of phenol etcetera in an organic acid solution and
allowing the intermediate products thereby obtained to act upon one molecule of
another phenol, amide or their sulpho, carbonic acids and substitution products.
The following are given as examples of the formation of the dye according to this
invention without limiting myself to the precise quantities or proportions specified.
First Ten parts by weight of the benzidine monosulpho acid obtained and purified
as above described are placed in suspension in 20 parts by weight of water mixed
with 12 parts of muriatic or hydrochloric acid at 21 degrees Beaume and then
diazolised with a solution of 53 parts of sodium nitrite in twice the quantity of water.
The yellowish red solution thus obtained is poured slowly into 20 parts by weight of
beta naphthylamine beta monosulpho acid (obtained by treating heta naphthylamine
with sulphuric acid according to the Neville Winter process) in suspension in water
and acetate of soda (about forty parts by weight) is added until the resulting brown
precipitate ceases to colour the test paper.
H
After standing for about 24 hours the precipitate which is now of a red colour is
filtered off converted to its soda salt by means of soda and dried. A beautiful red
powder is thus obtained which dissolves very readily in water forming a splendid
blueish red dye capable of dyeing raw cotton a beautiful red like alizarine in a boiling
alkaline bath and is but slightly affected by acids.
Second. A red dye bluer than the foregoing is obtained by the action of one
molecule of the tetrazo compound produced as hereinbefore described upon one
molecule of beta naphthylamine and afterwards upon one molecule of beta naptlyla-
mine sulpho acid. The tetrazo compound of about ten parts by weight of benzidine
mono sulpho acid is allowed to run slowly into a watery solution of about six and a
half parts by weight of beta naphthylamine hydrochlorate and about fifteen parts of
acetate of soda and after standing for a short time a watery solution of about 10 parts
by weight of beta naphthylamine mono sulpho acid soda (monosulphate of soda) is
added. The precipate which is black in the first instance gradually turning to a
brownish red and becoming a splendid blueish red in a soda lye is filtered and dried.
Having now particularly described and ascertained the nature of the said Invention
and in what manner the sune is to be performed I declare that what I claim is.
First. The processes for producing colouring matters by the action of Tetrazo-
diphenyl monosulpho or sulphonic acid or Tetrazo ditolyl monosulpho or sulphonic
acid on the above mentioned bodies substantially as hereinbefore described.
Second. As a new product of manufacture the colouring matters obtained by the
action of Tetrazodiphenyl monosulpho or sulphonic acid or Tetrazoditolyl monosulpho
or sulphonic acid on the above mentioned bodies substantially as hereinbefore
described.
J. HENRY JOHNSON.