Improvements in the Manufacture of Poly-azo-dyestuffs.
Year: 1899

page_text: Date of Application, 18th Feb., 1899
Complete Specification Left, 16th Nov., 1899-Accepted, 23rd Dec., 1899
Date of Application, foth red., 1899
Complete Specification Left, 16th Nov., 1899-Accepted, 23rd Dec., 1899
Improvements in the Manufacture of Poly-azo-dyestuffs.
1, HENRY HARRIS LAKE, of the Firm of Haseltine, Lake & Co., Patent Agents,
45, Southampton Buildings, in the County of Middlesex, do hereby declare the
nature of this invention to be as follows;-
This invention relates to improvements in the manufacture of poly-azo-dye-
stuffs.
By the action of two molecular proportions of diazotized para-nitraniline or para-
amido-acet-anilide upon phenylene-diamine, toluylene-diamine, or their sulphonic
acids, disazo-dyestuffs are obtained, which, by the reduction of the nitro-group,
or by splitting off the acetyl group respectively, yield new amido-disazo colouring
matters, from which, by tetrazotising and combining with two molecules of the
same, or two molecules of different amines, phenols, amidophenols, their sulphonic-
or carboxylic acids, new valuable substantive dyes result. Some of them are
distinguished by special greenish blue shades and particular fastness, and they
may be diazotized on the fibre as well as in substance and further combined with
amines, phenoles, amidophenols, their sulphonic- and carboxylic acids, to form
other dyestuffs. Those shades are of particular value, which are produced on the
fibre and by the combination with components containing no sulpho-groups.
The following examples may illustrate the manner, in which the invention may
be carried out and brought into practical effect.
The parts are by weight.
1. Combine in a weakly alkaline solution 22.4 parts of the sodium salt of toluylene
diamine sulphonic acid, with 27.6 parts of paranitraniline, diazotized in the usual
manner with 13.8 parts of sodium nitrite. The precipitating dyestuff may be
reduced either directly or after filtering off.
By combining in a weakly acetic solution, and replacing the para-nitraniline
by the equimolecular proportion of para-amido-acetanilide, a disazodyestuff is
obtained, containing two acetylated amido-groups instead of the two nitro-groups.
Now, 52.5 parts of the dinitro-diamido disazo-dyestuff are dissolved in about
600 parts of water, and then at a temperature of 50-60° C. reduced with 96 parts"
of crystallized sodium sulphide, dissolved in a proportional quantity of water.
Maintain the temperature during one to one hour and a half, until the colour
of the solution changes no more. The quantity of the sodium sulphide may be
varied without altering essentially the result.
After reducing, precipitate the dyestuff at the ordinary temperature by exactly
naturalizing with the muriatic acid or another mineral acid. It forms a black
lustred powder, which dissolves in a solution of sodium carbonate as well as in
diluted mineral acids with a brown yellow colour.
The same product is arrived at by saponifying with diluted alkalies or mineral
acids the dyestuff obtained from para-amido-acetanilide.

page_text: II. 22 parts of the tetra-amido disazo-dyestuff above described are diazotized
in a hydrochloric acid solution with 6.9 parts of sodium nitrite, whilst cooling with
ice, then mix the resulting brown-red moderately soluble tetrazo compound with
the aqueous solution of 35 parts of 1.8-amidonaphtol- 3.6-disulpho acid H, adding
as much sodium carbonate, as to keep the final reaction weakly alkaline. The
formation of the dyestuff is soon completed; it is precipitated with common salt,
and forms a grey black to black powder, which dissolves in concentrated sulphuric
with a blue colour. Its aqueous solution is pure blue, and does not change on
adding soda, but turns into violet on addition of diluted muriatic acid. The
dyestuff dyes cotton directly a greenish blue.
Dated this 18th day of Fab 1800
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C.,
Agents for the Applicant.
Improvements in the Manufacture of Poly-azo-dyestuffs.
I, HENRY HARRIS LAKE, of the Firm of Haseltine, Lake & Co., Patent Agents,
45, Southampton Buildings, in the County of Middlesex, 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 improvements in the manufacture of poly-azo-dyestuffs.
By the action of two molecular proportions of diazotized para-nitraniline or
para-amido-acet-anilide upon phenylene diamine, toluylenediamine, or their sul-
phonic acids, disazo dyestuffs are obtained, which, by the reduction of the nitro-
group, or by splitting off the acetylgroup respectively, yield new amidodisazo
solouring matters, from which, by tetrazotizing and combining with two mole-
cules of the same, or two molecules of different amines, phenols, amidophenols,
their sulphonic or carboxylic acids, new valuable substantive dyes result. Some
of them are distinguished by special greenish blue shades and particular fastness,
and they may be diazotized upon the fibre as well as in substance and further
combined with amines, phenols, amidophenols, their sulphonic- or carboxylicacids,
to form other dyestuffs. Those shades are of particular value, which are produced
on the fibre and by the combination with components, containing no sulphogroups.
Most of the new dyestuffs possess the valuable property to yield equal shades
both on cotton and wool, and are thus particularly fitted for dyeing goods, com-
posed of a mixture of wool and cotton.
The following examples may illustrate the manner, in which my invention may
be carried out and brought into practical effect.
The parts are by weight.
I: I combine in a weakly alkaline solution 22.4 parts of the sodiumsalt of the
toluylenediaminesulphonic-acid,
(CH:NH:NH:S0 H-1:2:6:4:)
3
with 27.6 parts of para-nitraniline, diazotized in the usual manner with 13.8 parts
of sodium nitrite. The precipitating dye-stuff may be reduced either directly
or after filtering off.
By combining in a weakly acetic acid solution, and replacing the nara-nitronilina

page_text: 600 parts of water, and then, at a temperature of 50-60 degrees Centigrade,
reduced with 96 parts of sodium sulphide, dissolved in a proportional quantity
of water. I maintain the temperature for from one hour to one and a half hours,
until the colour of the solution shows no further change. The quantity of the
sodium sulphide may be varied without altering essentially the result.
After reducing, I precipitate the dyestuff at the ordinary temperature by exactly
neutralizing with muriatic acid. It forms a black-lustred powder, which dissolves
in a solution of sodium carbonate as well as in diluted mineral acids with a brown
yellow colour.
The same product is obtained by saponifying the dyestuff from para-amido-
acet-anilide with diluted alkalies or mineral acids.
The dyestuff, obtained according to the preceding example, will, hereinafter
be designated as base A."
"
Similar products result by replacing the above mentioned toluylenediamine
sulphonic acid, by other isomeric sulphonic or carboxylic acids of phenylenedia-
mine or toluylenediamine, being capable of combining with two molecules of a
diazocompound.
If in the above given example instead of meta-diamine-sulphonic acids the
meta-diamines (meta-phenylene-diamine, or meta-toluylene-diamine) themselves
be employed, products are obtained, which are insoluble in diluted alkalies, but
besides this, show properties similar to those of the sulphonated products and can
be used in an analogous manner for the production of dyestuffs.
In the following, the term "base N" represents the analogues of the colour
base A, that is to say those amidoazo colouring matters which contain in their
molecule, in place of the toluylenediaminesulphonic acid,
(C H;N H,;N H,SO, H−1;2;4;0)
used in "the base A" its above mentioned substitutes.
II. 22 parts of the base A or the equivalent quantity of one of the bases N are
diazotized in a hydrochloric acid solution with 6.9 parts of sodium nitrite, whilst
cooling with ice. The resulting brown red moderately soluble tetrazo-compound
is mixed with the aqueous solution of 35 parts of 1.8-amidonaphtol-3.6-disulphonic
acid H, and as much sodium carbonate added, as will keep the final
reaction slightly alkaline. The formation of the dyestuff is soon completed, it is
precipitated with common salt, and forms a grey to black powder, which dissolved
in concentrated sulphuric acid with a blue colour. Its aqueous solution is pure
blue, and does not change on adding soda, but turns into violet on addition of
diluted muriatic acid. The dyestuff dyes cotton directly a greenish blue.
By employing 2.8-amidonaphtol-6-mono-sulphonic acid instead of the above
named amidonaphtoldisulphonic acid H, a black colouring matter results.
The shades of the dyestuff's produced vary from greenish blue to violet and
black according to the amidonaphtolsulphonic acids used in the combination.
The following amidonaphtolsulphonic acids have been found to give valuable
results, i.e. amidonaphtoldisulphonic acids 1.8.4.6, 1.8.3.5, 1.8.2.4, 2.8.3.6,
1.5.3.7, and the amidonaphtolmonosulphonic acids 1.8.4, 1.8.5, 1.5.7, 2.5.7.
If one of the bases N be used in the place of the base A, there are produced
colouring matters, differing more in their solubility, than in other properties.
III. The tetrazo compound formed from 22 parts of the base A or from the
equivalent quantity of one of the sulphonated bases N is introduced into a mixture
of 11 parts of phenylenediamine in an aqueous solution and 250 parts of sodium
acetate. After six hours stirring, the formation of the dyestuff is completed;
it is then rendered slightly alkaline by means of sodium carbonate or diluted
soda lye, slowly heated and precipitated with common salt. The dyestuff thus
obtained, dyes cotton a black violet.
In this example, phenylenediamine may be replaced by toluylenediamine, of the
sulphonic or carboxylic acids of both, thus yielding dyestuffs of very similar
properties.

page_text: IV. The tetrazo compound, formed from 22 parts of the base A or from the
equivalent proportion of one of the bases N, is poured into a solution of 224 parts
of naphtolsulphonic acid 1.4, and as much soda as will keep the same slightly
alkaline until the final reaction. After about six hours, the mass is warmed, and
then precipitated with common salt. The resulting colouring matter dye cotton
a greenish blue.
In the same manner, alpha- or beta-naphtol, alpha- or beta-naphtylamine,
dioxynaphtalene, as well as their sulphonic and carboxylic acids may be employed
instead of the 1.4-naphtol, sulphonic acid, yielding colouring matters; which dye
unmordanted cotton violet blue to black shades.
V. The tetrazo compounds of the above named "bases" are also capablé¹of form-
ing so called "intermediate products" and mixed tetrazodyestuffs."..
That is to say, one molecule of the tetrazocompound' may be combined with one
molecule of any of the well known colour producing agents (amine, phenol or the
like) to form an intermediate product, and the intermediate product thus formed
then further combined with one molecule of another colouring producing agent
differing from that used in the first combination.
The tetrazocompound formed from 22 parts of the base A or from the equivalent
quantity of one of the bases N is, whilst kept alkaline with soda, combined with
17 parts of the amidonaphtoldisulphonic acid H. To the reddish blue solution
of this intermediate product add 9 parts of the hydrochlorate of alpha-naphtyla
mine dissolved in water, and as much sodium carbonate, as will keep the same
alkaline until the final reaction. When the formation of the dyestuff is com-
pleted, precipitate with common salt. The colouring matter thus obtained, dyeš
unmordanted cotton bluish violet.
In the above example the amidonaphtoldisulphonic acid H may be replaced by
the equimolecular proportions of another amidonaphtolsulphonic acid as well as of
the sulphoconjugated or carboxylated derivatives of alpha- or beta-naphtylamine,
alpha- or beta-naphtol, dioxynaphtalene and of the meta-diamines of the benzenes
series or of naphtylenediamines.
On the other hand, instead of the alpha-naphtylamine one of the bodies, before
mentioned, may be used as well as also beta-naphtylamine, alpha- or beta-naphtol;
dioxynaphtalene, naphtylenediamine, and the meta-diamido- and dioxyderivatives
of the benzene series.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed, as communicated to me
by my foreign correspondent, I declare that what I claim is:
-
1. The manufacture and production of new primary disazo dyestuffs which con-
sists in the combination of two molecular proportions of diazotized para-nitraniline
or diazotized para-amido-acet-anilide respectively with one molecular proportion
of meta-phenylenediamine or meta toluylenediamine or those sulphonic acids of
these amines, which are capable of combining with two molecules of a suitable
diazobody substantially as described.
2. The manufacture and production of new amidodisazo dyestuffs, hereinbefore
named "bases," consisting in reducing with suitable reducing agents preferably
alkali-sulphides the nitrodisazocolouring matters produced according to Claim 1,
substantially as described.
3. The manufacture and production of new amido disazo dyestuffs herein before
named bases, consisting in saponifying in the usual manner the acetylamidodisazo-
dyestuffs of Claim 1, substantially as described:
4. The manufacture and production of tetrazocompounds of the above named
bases by tetrazotizing in the well known manner the new amidodisazodyestuffs
of Claim 2 and 3 substantially as described.
5. The manufacture of new tetrazodyestuffs consisting in the combination of the
tetrazo compounds obtained as described and claimed in Claim 4 with two mole-
T

page_text: cular proportions of a suitable colour producing agent, as amines, phenols,
amidophenols, diamines, dioxybodies both of the benzene and naphtalene series
as well as their sulphonic and carboxylic acids, substantially as described.
6. The manufacture and production of so called intermediate products by com-
bining one molecule of the tetrazo compounds described and claimed in Claim 4
with one molecule of any of the colour producing agents mentioned in the pre-
ceding claim, substantially as described."
7. The manufacture and production of so called mixed tetrazo dyestuffs which
consists in combining the intermediate products obtained as described in Claim 6
with one molecule of any colour producing agent differing from that used in
the formation of the intermediate product according to the preceding claim,
substantially as described.
8. As new products of manufacture, the dyestuffs, such as result from the pro-
cesses herein before described and claimed.
Dated this 16th day of November 1899
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C.,
Agents for the Applicant.