The Manufacture of Chemical Compounds suitable for the Production of Colouring Matters, in Bulk or on Fibre, and other purposes FROM TEZODIMETHIPHENYL CHLOR AND B
Year: 1895

page_text: PROVIDIONAL DIE
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co, of Elberfeld, Germany ]
The Manufacture of Chemical Compounds suitable for the
Production of Colouring Matters, in Bulk or on Fibre, and
other purposes
I PHILIP ARTHUR NEWTON of The Office for Patents 6 Breams Buildings,
Chancery Lane in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows
-
tetrazo salts
"
My foreign correspondents have found that beta-naphthol-trisulphonic acids, or
salts thereof, when added to solutions of a tetrazo salt of a paradiamine, yield salts
of the tetrazo compounds used, which dissolve with difficulty in water, and there-
My foreign correspondents
fore are precipitated from the resulting solution
hereinafter briefly term these new salts of tetrazo compounds as
The researches of my foreign correspondents have further shewn, that these
"tetrazo salts resulting from the interaction of tetrazo compounds and ẞ-naphthol
trisulphonic acids, or salts thereof, can be profitably used for the production of azo
dye-stuffs in bulk and on fibre, for my foreign correspondents have ascertained that
the said "tetrazo salts," when allowed to act on dye-stuff components yield real
dye-stuffs, the beta naphthol trisulphonic acids being displaced during the formation
of the dye-stuffs
"
According to the re earches of my foreign corespondents, the aforementioned
new "tetrazo salts are distinguished by enon of their stability, and can be used
in place of the usual tetrazo compounds of paia-diamines, which are more or less
readily decomposed
In order to illustrate one method of practically producing the "tetrazo salts
herembefore defined, the following example is given, the parts being by weight
PRODUCTION OF A
te
"
TETRAZO SALT
FROM TETRAZODIMETHOXYDIPHENYL
CHLORIDE AND B₁-\\PHTHOL-ẞ, ẞ3 a4 TRISULI HONATE OF SODIUM
'
A solution of 45 parts of ẞ₁ naphthol-ß2 ß¸ α trisulphonate of sodium is allowed
to flow into a concentrated solution of tetrazo-methoxydiphenylchloride, prepared
in the usual manner from 123 parts of dianısıaine and 7 parts of sodium nitrite in
immediately
The so-formed "tetrazo salt
the presence of hydrochlone acid
begins to separate, and the precipitation is profitably hastened by the addition of
common salt If the sepuation is completed, the precipitate is filtered off and
pressed The "tetrazo alt" thus obtained from dimethoxydiphenylchloride

page_text: and ẞ naphthol ẞ₂ ẞ₁ a trisulphonate of sodium, has probably the following
composition
It can be kept for a long time, as it is comparatively stable, and may be used in
the production of dye-stuffs in bulk or on fibie in place of the tetrazo dimethoxy-
diphenyhl cloride, which, however, must be freshly prepared, when it is to be used
for the production of dye-stuffs either in bulk or on fibie
The process proceeds in an analogous manner, if either corresponding quantities
of other para diamido compounds, or substituted para diamido compounds capable
of yielding tetrazo derivatives, are employed in place of dianisidine used in the
preceding example, or if equivalent quantities of other beta naphtholtrisulphonic
acids, or salts thereot, are allowed to act on the tetrazo derivatives of paradiamido
compounds
86
According to the researches of my foreign correspondents, mixtures of alpha
and beta naphthol trisulphonic acids, or salts thereof for instance, the mixture
resulting from the fusion, with alkalies, of naphthalene tetra-sulphonic acid, and
containing an alpha & beta naphtholti sulphonic acid, may be used in place of the
betanaphthol trisulphonic acids previously isolated In this case, the tetrazo
derivatives of the para diamines combine with the beta naphthol tisulphonic acids
or salts thereof, to form almost insoluble tetrazo salts,' whilst the said tetrazo
derivatives yield with the alpha naphtholtrisulphonic acids, or salts thereof,
tetrazo salts" soluble with readiness Owing to this different degree of solubility,
the almost insoluble "tetrazo salts" derived from beta naphtholtrisulphonic acids,
or salts thereof, can be easily separated from the soluble tetrazo salts derived fiom
alpha naphthol trisulphonic acids, or salts thereof Inversely, this different
behaviour of alpha and beta naphthol trisulphonic acids, or salts thereof, may be
profitably used for separating these isomeric acids, vz, by converting them in the
manner hereinbefore defined into "tetrazo salts," filtering off the insoluble "tetrazo
salt" derived from betanaphtholtrisulphonic acid, and treating this 'tetrazo salt'
in a suitable manner, that the betanaphthol trisulphonic acid is set free, whilst the
alpha naphtholtrisulphonic acid is obtained by a suitable treatment of the filtrate
containing the "tetrazo salt" derived from alpha naphthol tuisulphonic acid
method of separating alpha and beta naphtholtrisulphonic acid is of a great
practical value, as the separation of these acids has hitherto been attended with
great difficulty
This
The "tetrazo salts" hereinbefore defined, and derived from beta naphthol
trisulphonic acids, can be used for the production of dye-stuffs, either in bulk or
on fibre, in place of the usual tetrazo compounds of pira-diamines, and all processes
which are known and in use for producing colouring matters in bulk, or on fibre,
from the usual tetrazo derivatives of paradiamines, may be used on preparing

page_text: dye-stuffs in bulk, or on fibre, by means of the "tetrazo salts" hereinbefore
defined
My foreign correspondents have described in the foregoing example a distinct
method for practically producing one of the "tetrazo salts herein before defined
Of course, they do not limit themselves to the particulars given in the above
example, as these directions can be varied, without altering thereby the nature of
this invention, which relates to the production of "tetrazo salts," suitable for the
manufacture of colouring-matters, either in bulk or on fibre, from beta naphthol
trisulphonic acids, or salts thereof, and the tetrazo derivatives of paradiamines or
substituted paradiamines
NEWTON & SON,
Agents for the Applicant
The Manufacture of Chemical Compounds suitable for the
Production of Colouring Matters, in Bulk or on Fibre, and
other purposes
I PHILIP ARTHUR 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 and in what manner the same is to be performed, to be
particularly described and ascertained in and by the following statement
My foreign correspondents have found that on adding certain salts of beta
naphtholtrisulphonic acid to acid or neutial solutions of tetrazo deivatives of
paradiamines (such as teti azodiphenylchloride tetiazo ditolylchloride, tetrazo
dialky ldioxydiphenylchloude, or the like), betanaphtholtrisulphonates of the
tetiazo compounds are produced, and that as these salts are not easily soluble in
water, they are precipitated from the solutions, no azo dye-stuffs being formed
under such conditions They are deposited in the form of crystalline orange-
colomed precipitates, which, if dissolved in pure water, afford from yellow to
orange or brown coloured liquids
My foreign corespondents hereinafter briefly term these new beta-naphthol-
tulphonates of tetrazo compounds, " tetrazo salts
"
The researches of my foreign correspondents have further shown, that these
⚫ tetrazo salts resemble the tetrazo compounds from which they are formed,
inasmuch as they can be used with advantage in producing azo dye-stuffs, as such,
and on fibres, as, when allowed to act on the usual dye-stuff components, the new
tetrazo salts" yield true azo colouring matters, the beta naphthol tri-sulphonic
acid being liberated during the process
As aforementioned, the new " tetrazo salts are distinguished by then stability,
and my foreign correspondents therefore propose to make use of them in place of
the ordinary tetiazo derivatives of para diamines, which are more or less readily
decomposed
The chemical behaviour of these tetrazo salts 1s as follows-On adding
solution of sodium carbonate to a solution of the "tetrazo salt obtained from
any tetrazo compound, and an alkaline salt of beta, naphthol-beta, beta, alpha.
trisulphonic acid, at first almost no change is noticed, but after some time the
"tetrazo salt" begins to alter, a red colouration appearing, as the tetrazo compound
and the separated betanaphtholtrisulphonic acid interact to form an intermediate
product, which then gradually changes into the diazo dye-stuff the liquid assuming
a blue colour, owing to the fact that this disazo dye-stuff readily dissolves in water,
affording a bluish-red or violet coloured liquid On the other hand, if solutions of
the "tetrazo salts" hereinbefore defined are mixed with an alkaline solution of

page_text: beta naphthol, the formation of the insoluble disazo compound from the original
tetrazo compound, and betanaphthol, at once begins The beta naphtholtrisulphonic
acid does not combine with the tetrazo compound, but remains dissolved in the
form of its alkaline salt, which causes the intense green fluorescence of the
solution
" are used
The process proceeds in an analogous manner, if these "tetrazo salts
for producing azo colours on fibres In this case, the original tetrazo compound
always combines with the betanaphthol or other dye-stuff component, the beta-
naphtholtrisulphonic acid contained in the "tetrazo salts" used, being displaced
without combining with the tetrazo compound to form a disazo dye-stuff
Owing to their possessing these properties, my foreign correspondents assume
that the tetrazo salts above referred to (in contradistinction to the products
described in the German Patent No 22038, and in the Berichte der Deutschen
Chemishen Gesellschaft, volume 27, page 1209) are not hydroxy azo compounds,
but betanaphthol trisulphonic salts of the tetrizo compounds used, as above
stated
In order to illustrate a method of practically producing the tetrazo salts
herein before defined, the following example is given, the parts being by weight
66
PRODUCTION OF A TETRAZO SALT
ROM TETRAZO DIMETHOXYDIPHENYL
CHLORIDE AND SODIUM BETA1 NAPHTHOL BET 2 BETA AI PHA TRI-
SULPHONATE
A solution of 45 parts of sodium beta, naphthol-beta, beta, alpha, trisulphonate
is allowed to flow into as concentiated solution as possible of tetiazo-dimethoxy-
diphenylchloride, prepared in a suitable manner from 12 3 parts of dianisidine and
7 parts of sodium nitrite in the presence of muntic acid The "tetrazo salt "
immediately begins to separate, but the precipitation is with advantage hastened
by adding common salt When the separation is complete, the precipitate is
filtered off and piessed The "tetrizo salt" thus obtained from tetrazo dimethoxy-
diphenylchloride and sodium beta, naphthol beta, beta, alpha trisulphonate, is
probably of the composition represented by the following formula

page_text: The process proceeds in an analogous manner if corresponding quantities of
othe para diamido compounds or substituted para-diamido compounds, such as
benzidine, tolidine, nitrobenzidine, nitro tolidine, or the like, capable of yielding
tetrazo derivatives, are substituted for the dianısıdıne used in the preceding
example
Instead of the betanaphtholtrisulphonic acid prescribed in the above example,
the isomeric betanaphthol trisulphonic acid may be used which is formed together
with an alphanaphtholti sulphonic acid (as described in the Specification of Letters
Patent No 2074 dated 30th December 1893), on sulphonating naphthalene beta
beta, disulphonic acid, and fusing the naphthalene tetrasulphonic acid so produced
with alkalies According to the researches of my foreign correspondents, eithei
the last named betanaphthol tisulphonic and may be used after it has bren
Isolated in
suitable manner, or the mixture of the two acids may be directly
used It is unnecessary to separate the two aids, as the said alph inaphtholtri-
sulphonic acid and tetizo salts of paridiamido compounds, form "tetrizo salts,
which are readily soluble, and therefore iemain dissolved, whereas the isomeric
beta acid forms teti 170 salts" which dissolve with comparative difficulty and
therefore are either at once deposited, or can easily be precipitated and isolated
Inversely, this different behaviour of the alpha and beta naphtholttisulphonic acids
herembefore defined may be advantageously made use of as a means of separating
'filten off the
these isomeric acids, uz, by converting them into " tetrazo salt
in.oluble "tetrazo salt derived from beta naphtholti sulphonic acid and treiting
this "tetiaz) salt in suitable manner, so that the beta naphtholti sulphonie acul
1s set fice whil t the alpha naphtholti sulphonic is obtained by a suitable further
treatment of the filtiate containing the "teti 10 salt "derived from alph in aphthol
ti sulphonic cid This method of separatin, alpha and betinaphtholti ulphomo
acid is of considerable pi tctical value, is the separation of these acids has hithcito
been attended with gient difficulty
›
The tetrazo salts neieinbefore defined can be used in producing dye-stuffs,
either as such, or on fibres, instead of the ordinary tetrazo derivatives of pari-
diamines For this purpose, two molecular proportions of the known dye- tuff
components are allowed to act on a molecular proportion of these "tetrizo salts,'
in which case the "tetrazo salts are decomposed, betanaphthol trisulphonic acid
being liberated, the simple tetrazo derivative thus produced combining with the
dye stuff components used to form the desired disazo colouring matter
My foreign correspondents have described in the foregoing example a distinct
method for practically producing one of the "tetizo salts hercinbefore defined
Of course they do not limit themselves to the particulars given in the above
example as these duections can be varied without altering thereby the nature of
this invention which relates to the production of "tetrazo salts' suitable for the
manufacture of colouring matters, either as such, or on fibres, by the intui action of
salts of certain betanaphtholtrisulphonic acids, and the usual tetrazo derivatives of
paradanines, or substituted para diamines
Having now particularly described and ascertained the nature of the sind inven-
tion and in what manner the same is to be performed, as communicated to me
from abroad, I declare that what I claim 19
1 The production of betanaphtholtrisulphonic "tetrazo salts' from certain
betanaphtholti sulphonates and tetrazo salts of paradiamido compounds prepired
with the aid of mineral acids
2 Ihe process for producing stable betinaphtholtrisulphonic "tetrazo salts,'
which process consists in allowing two molecular proportions of an all line salt
of beta, naphthol beta beta, alpha, tu sulphonic acid, or of the beta naphthol
trisulphonic acid which is formed together with an alphanaphtholtri ulphonic acid,
on sulphonating naphthalene beta, bet, disulphonic acid, and subsequently fusing
the naphthalene tetrasulphonic acid so formed with alkalies to act in presence of
a mineral neid, or in neutral solution, on one molecular proportion of a tetrazo salt

page_text: of a paradiamido compound, and subsequently isolating in a suitable manner the
so-formed betanaphtholti isulphonic " tetrazo salts "
3 The use of tetrazo salts of benzidine, tolidine, dianısıdine, mononitrobenzidine,
mononitrotolidine, or the like paradiamines, or substituted paradiamines, in the
process illustrated by the foregoing Claim Two
4 The production of "tetrazo salts" from the mixture of alpha and beta-
naphtholtrisulphonic acid obtainable by sulphonating naphthalene beta₁ beta,
disulphonic acid, and fusing the naphthalene tett asulphonic acid so produced with
alkalies, which process consists in allowing two molecular proportions of a mixture
of the alkaline salts of these two acids to act in an acid oi neutral solution on one
molecular proportion of a tetrazo salt of a paradiamido compound, and subsequently
separating the difficultly soluble betanaphthol trisulphonic "tetrazo salts
produced, from the comparatively soluble alphanaphthol ti sulphonic "tetrazo
salts
80
5 The use of the betanaphthol trisulphonic tetrazo salts hereinbefore defined,
for producing disazo dye-stuffs, as such, or on fibres
6 Ihe production of disazo dye stuffs, as such, or on fibres, from the beta
naphtholti isulphonic "tetrazo salts 'herein before defined, which process consists
in allowing one molecular proportion of these "tetrazo salts" to act on two
molecular proportions of the usual dye-stuff components
"
7 As new products of manufacture the new betanaphtholtrisulphonic "tetrazo
salts produced by the process hereinbefore defined, or in any other manner
affording the same result
Dated this 4th day of February 1896
NEWTON & SON,
Agents for the Applicant