Note: Descriptions are shown in the official language in which they were submitted.
1~3~iP7
The present invention relates to novel basic azo compounds, pro-
cesses for their production, and their use as dyes for colouring and printing
textiles, paper and leather, as well as for the preparation of inks.
The novel basic azo compounds have the formula I
[~ ~ 5 ~ \ D ~ - N =~N ~ ~ / 1i3 ~
wherein X is one or more of the radicals (CH2.NR.CO(CH2)nA) and/or
(SO2NH(CH2)nA), R is hydrogen or an alkyl group of 1 to 4 carbon atoms, A
is a non-quaternised or quaternised basic radical, n is 1 to 4, m is 1 to 4
M is hydrogen or any cation, p is 0 to 2, with the proviso that the value
is m is as great or greater than p, and wherein the benzene radicals B
obtionally contain one or more identical or different substituents selected
from alkyl groups of 1 to 4 carbon atoms, halogen, alkoxy groups having 1 to
4 carbon atoms, N02, OH, S02NH2, S02NH-alkyl Cl-C4, S02N(alkyl Cl-C4)2,
benzthiazol, S02-heterocyclic with an N-atom linked to S02, unsubstituted
phenyl, and phenyl substituted by halogen and alkyl Cl-C4, and the benzene
radicals D optionally contain one or more identical or different substituents
namely halogen, alkyl Cl-C4~and alkoxy Cl-C4.
R as an alkyl group of 1 to 4 carbon atoms is e.g. an unbranched
or a brqched alkyl group, for example the methyl, ethyl, n-propyl, isopropyl,
n-butyl, sec-butyl and tert-butyl group. In preferred azo compounds, R is
hydrogen.
As a non-quaternised or quaternised basic group, A has e.g. the
following values:
a) as a basic group, e.g. the radical ~ T
~ T
~ - 1 -
~ *
.: .
113~317
wherein Tl is hydrogen or a low molecular alkyl radical which i5 unsub-
stituted or substituted by hydroxyl, or a cyclohexyl radical which is
Imsubstituted or substituted by 1 to 3 methyl radicals, or is a phenyl
radical, and T2 is a low molecular alkyl radical which is unsubstitu-
ted or substituted by hydroxyl, or Tl and T2 together with the nitro-
gen atom to which they are at~ached form a hydrogenated heterocyclic
ring which may contain a further heteroatom, e.g. the morpholine ring:
b~ as a quaternised group, e.g. the radical of the formula
Rl
a ) (~ R2 ~ ~)
. . . 2
wherein each of Rl and R2 independently is hydrogen, an alkyl radical
of 1 to 4 carbon atoms which is unsubstituted or substituted e.g. by
hydroxyl, such as the methyl, ethyl, n-propyl, isopropyl, n-butyl,
sec-butyl and tert-butyl radical, an unsubstituted or sub8tituted
cycloalykl group, especially the cyclohexyl group which is unsubstitu-
ted or substituted by one or more alkyl groups, in particular the C~3
group, or is an aryl radical, especially the phenyl radical; or R
and R2 together with the nitrogen atom to which they are attached
form a heterocyclic ring, such as the pyrrolidine, piperidine, morpho-
line or piperazine ring,
R3
b) - ~ - R
S
wherein each of R3 and R4 independently is hydrogen, an unsubstituted
or substituted alkyl radical of 1 to 4 carbon atoms, such as the
methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl
radical, or the hydroxyethyl or aminoethyl radical; an unsubstituted
or substituted cycloalkyl group, especially the cyclohexyl group, or
an aryl radical, such as the phenyl radical, and R5 is an alkyl group
.
1~3~817
-- 3 --
of 1 to 4 carbon atoms; or R3 and R4 together with the nitrogen atom
to which they are attached form a heterocyclic ring, in particular the
pyrrolidine, piperidine, morpholine or piperazine ring; or R3, R4 and
R5 together with the nitrogen atom to which they are attached form a
heterocyclic ring which may contain a further heteroatom, such as
~, O or S, e.g. the pyridine ring which may be substituted by OH, NH2,
COOH, CN or lower alkyl, or the ring of the formula
H2 H
C - C 2
HC~
2 H2
c) -(~ - R2 ~ X ~)
OR6
... . . . . .
wherein Rl ant R2 have the meanings assigned to them under a) and R6
is an alkyl radical of l to 4 carbon atoms, ant wherein in all quater-
nised basic radicals, X~i8 an anion.
In preferred azo compounds, A is a pyridine ring and X ~ is
any anion.
Where A is a quaternised basic group, suitable anions are both
inorganic and organic anions, e.g.: halogen, such as chloride, bromide
or iodide, sulfate, methyl sulfate, aminosulfate, perchlorate, carbo-
..
nate, bicarbonate, phosphate, phosphomolybdate, phosphotungstate,phosphotungstomolybdate, benzenesulfonate, naphthalenesulfonate,
4-chlorobenzenesulfonate, oxalate, maleate, acetate, propionate,
lactate, succinate, chloroacetate, tartrate, methanesulfonate or
benzoate ions, or complex anions, such as those of zinc chloride
double salts. Preferred anions are the chloride, acetate, zinc chloride
.
or methyl sulfate ions.
1~3g~1~
-- 4 --
M as a cation is e.g. the Li, Na, K or NH4 ion; preferably it
is the Na ion.
If the benzene radicals B are further substituted, they can
contain one or more identical or different substituents, e.g. an alkyl
group of 1 to 4 carbon atoms, halogen, such as fluorine, chlorine
or bromine, a phenyl group which is unsubstituted or substituted e.g.
by halogen or alkyl; an alkoxy group, N02, OH, a S02NH2 group which
is mono- or disubstituted (e.g. by alkyl) at the nitrogen atom, an
S2 ~ ~ group in which the nitrogen atom, optionally together with a
further heteroatom, e.g. an oxygen atom, forms part of a heterocyclic
ring; or a heterocyclic group, especially the benzthiazole group.
In preferred azo compounds, the benzene radicals B are further
substituted by an alkyl group of 1 to 2 carbon atoms, especially by
the CH3 group, in particular in the para-position to the nitrogen
atom.
If the benzene raticals D are further substitutet, these can
also contain one or more itentical or different substituents, e.g.
halogen, such as fluorine, chlorine or bromine; alkyl or alkoxy groups,
each containing 1 to 4 carbon atoms, e.g. methyl, ethyl, n-propyl,
isopropyl, n-butyl, sec-butyl and tert-butyl, or methoxy, ethoxy,
propoxy or butoxy. In preferred azo compounds, the benzene radicals D
are not further substituted.
Particularly interesting azo compounds are those of the formula
I, ~herein R is hydrogen, A is a quaternised basic radical, especially
one of the formula
. .. ..
- R
R5
wherein R3, R4 and R5 together with the nitrogen atom to which they
:, .
.
113~817
-- 5 --
are attached are linked to a pyridine ring, and X ~ is any anion, n is
1 and m is 2, p is O, and wherein the benzene radical B is further
substituted by an alkyl group of 1 to 2 carbon atoms, especially by
l:he CH3 group, and the benzene radical D is not further substituted.
The azo compounds of the formula I are obtained in known
manner. One possibility consists e.g. in
a) introducing the group
-CH27-CO-(CH2)n-halogen and/or -S02NH(CH2) -halogen
wherein R and n are as defined for formula I, 1 to 4 times into an
azo compound of ~he formula II
~ 3 ~ -\ D / \ , / ~ \.~ (II)
~,
wherein B and D are as defined for formula I, then replacing the
halogen atom by a basic group A or by a quaternised basic group
A ~ X ~ wherein X ~ is any anion, and, if desired, converting the
basic group A by quaternisation into a quaternised basic group, and
if desired, subsequently introducing a SO3M group; or
b) introducing the group
-CH2-~-CO-(CH2)n-A and/or -S02NH(CH2)nA
R
wherein A is a basic group and R and n are as defined for formula I,
1 to 4 times into an azo compound of the formula II, and, if desired,
subsequently quaternising the basic group A and then, if desired,
introducing a SO3-M group.
The starting compounds of the formula II are ~nown (Helv. Chem.
Acta 1944, p. l ff) and can be obtained by known methods.
.. .
: : . :
: ~ .
.. : .
-
': ' '
.
~13~817
Finally, a further variant for obtaining the compounds of theformula I consists in introducing the group -(CH2NR.CO.(CH2) A) and/or
-S02NH(CH2) A 1 to 2 times into an amine of the formula
I~ 5 ~ D ~--NH2
subsequently, if desired, sulfonating and diazotising and proceeding
analogously in accordance with Helv. Chem. Acta 1944, p. 1 ff.
In this variant of the process, the introduction of a quaterni-
sable basic group -CH2-N(R)-C0-(CH2)nA and~or -S02NH(CH2)nA, wherein
R, A and n are as defined for formula I, is accomplished in known
manner, e.g. by reacting the compound of the formula II with e.g.
N-methylolchloroacetamide in concentrated sulfuric acid or phosphoric
acid, optionally in the presence of P205, at 0 to 50C, preferably
at room temperature, and then, by amination, replacing the chlorine
atom of N~methylolchloroacetamite by a basic or especially a cationic
group A, or by replacing the chlorine atom of N-methylolchloroacetamite
by a basic group A and then converting this basic group by quaterni-
sation into a quaterniset group A.
The quaternisation is also carried out in known manner, e.g. in
an inert solvent such as chlorobenzene, or, if tesired, in an aqueous
suspension or without a solvent in an excess of the quaternising agent,
at a temperature of about 20 to 120C, with a quaternising agent.
~ xamples of suitable quaternising agents are alkyl halides,
such as methyl or ethyl chloride, methyl, ethyl or butyl bromide, or
methyl or ethyl iodide, and especially alkyl sulfates, such as di-
methyl, diethyl or dibutyl sulfate, or benzyl chloride, chloroacet- :
amide, acrylates, epoxide~, such as ethylene oxide, epichlorohydrin
and alkyl esters of aromatic sulfonic acids, such as methyl-p-toluene-
sulfonate, methylbenzene sulfonate, ant the propyl and butyl esters of
. , .
-
~3~817
benzenesulfonic acid.
Should it be desired that the azo compounds of the formula I containa -S03-M group, then this group can be introduced before or after the
quaternisation reaction, e.g. by sulfonation with sulfuric acid.
The novel basic non-quaternised or quaternised azo compounds of the
formula I are employed as dyes for dyeing and printing textiles, leather and
paper and also for the preparation of inks.
Thus, this invention also provides for a process for colouring and
printing textiles, paper and leather and for the preparation of inks, as well
as for the mass colouration of synthetic linear polyamides and for the pro-
duction of lacquers by using an azo compound of the invention or the azo
compound obtained by the process of the invention as a dye.
Suitable textiles for dyeing and printing with these dyes are:
natural and regenerated cellulosic fabrics, especially cotton and viscose,
on which fabrics brilliant yellow dyeings are obtained; natural polyamide
material, such as wool and silk, and acid-modified polyamide material, as
well as acrylic fibres, especially wet tow and modified polyester material
which can be dyed with basic dyes. The azo compounds of the formula I have
good affinity for these textiles, especially on cellulosic fabrics, a good
degree of exhaustion, and the dyeings obtained have very good fastness proper-
ties, in particular wetfastness properties, such as fastness to water, water/
alcohol, and especially light.
It is furthermore advantageous that the azo compounds of the formula
I exhaust onto the cellulose material without subjecting the material to a
pretreatment and without the further addition of salt to the dyebath.
The azo compounds of the formula I are yellow compounds. For
their application it is further not necessary to add fixing agents to the bath.
`~3
. - 7 -
113~81~
A further utility of the azo compounds of the formula I is for
colouring paper of all kinds, especially of bleached, unsized and
- 7a -
`~
, ~ , .
. ~
~13~817
sized lignin-free paper. In particular, the lightfastness on paper is
unexpectedly high to a degree which is not usually obtained with con-
ventional yellow dyes for paper, thereby affording the possibility
of using the dyes of the invention in the document sector. These
compounds are most suitable for colouring unsized paper (tissues) on
account of their very high standard affinity for this substrate.
The azo compounds of the invention exhaust very well onto these
substrates, while the wastewaters remain virtually colourless even
in the production of deep shades (up to 1~1 reference type strength).
This is a prime ecological advantage, especially in view of present
wastewater legislation, and also whenever the process is carried out
with wastewater recycling.
The dyeings are wetfast, i.e. they show no tentency to bleeding
when coloured paper in the wet state is brought into contact with
moist white paper. This is an especially tesirable property for
tissues, with which it is to be expected that the colouret paper in
the wet state (e.g. soaked with water, alcohol, surfactant solution
etc.) will come into contact with other surfaces, such as textiles,
paper and the like, which have to be protected against soiling.
The high affinity for paper and the high rate of exhaustion of
the azo dyes of the formula I is most advantageous for the continous
colouration of paper and thus makes possible a much broader use of
this economic procesr, which has the following advantages:
a) a simpler and more rapid correction of the shade and therefore less
loss of non-standard paper (broke) in comparison with the batchwise
colouring of pulp;
b) a better constancy of shade; and
c) when the dye is added shortly before the stock preparation in the
dilute paper pulp, a thorough cleansing of the hollander, mixing
chest etc.,after each batch is no longer necessary, while at the same
time the operation is shortened and the process optimised.
~.. ~... ._ _.. ..... _. _ .. .. ~.. ... _ .. _ _. .. : .. . ______ ., _ _.. _~__.__. .. __ _. _.. _._. _._.. _ ...
,
,. ~
' : ., ~ '` - :~''
~3~7
Further, the novel azo compounds are used for dyeing leather
material by a very wide variety of application methods, such as spray-
ing, brushing and immersing, and for the preparation of inks, especi-
ally for ball-point pens.
Finally, the novel a7O compounds of the formula I are used for
the mass colouration of synthetic linear polyamides, such as poly-
hexamethylene-adipamide. The colouration of the polyamide chips is
effected in particular from an aqueous bath in the presence of wetting
or dispersing agents and optionally salts, and by subsequent melting
and forming.
In view of the reducible properties of the fused polyamide
melts and the high melt temperature (about 270-300C), the use of
these dyes of the formula I consistutes a surprising enlargement of
the stock of technical knowledge,
The following Examples illu~trate the invention without
implying any restriction to what is described therein. Parts and
percentages are by weight.
Example 1: 48 pares of 4,4'-bis(6-methyl-2-benzthiazole)azobenzene
I (obtained according to the particulars of Helv. Chem. Acta 1944, 27,1) and 28 parts of N-methylolchloroacetamide are added at 0-50C to
500 parts of 98~ sulfuric acid. The reaction mixture is then stirred
for 15 hours at room temperature. The solution is poured on ice,
whereupon the reac1ion product precipitates. The precipitate is
collected by filtration, washed neutral with water and dried, affor-
ding 55 parts of the compound of the formula
`:
., .., . ..: .. .. .
r T 11 ~ . .-N~N~ S il t
S/ ~ 2N~COC82Cl.
113~B17
-- 10 --
30 parts of this compound are heated for 1 hour to 100C in 250 parts
of pyridine. The precipitated dye of the formula
r .~ s~ ~ ca31
C1~3
is isolated by filtration and dried. It colours paper and cotton in
bright yellow shades of very good fastness properties and has excellent
build-up.
Similar dycs with equally good properties are obtained by using
-picoline or y-picoline, or a mixture of both, instead of pyridine.
Example 2: A mixture of 48 parts of 4,4'-bis(6-methyl-2-benzthiazole)-
azobenzene and 40 parts of N-methylolchloroacetamide are added at
0-5C to 500 parts of monohydrate. The reaction mixture iB stirred
for 15 hours at 50C ant then pouret on ice. The precipitatet reaction
product is then filtered with suction, washéd neutral with water and
dried, afforting 68 parts of the compounds of the formula
~ t i~ --N-N-- ~-- f ~
~ 2N~COC~2C~ 2
30 parts of this compound are reacted with 250 parts of pyridine as
described in Example 1. The resultant dye of the formula
N N ~
. .
.
li3~L131 7
exhausts very well on paper and cotton and the bright yellow dyeings
obtained have excellent wetfastness properties and very good light-
fastness.
The above procedure is repeated, substituting 200parts of o-di-
chlorobenzene and 15 parts of triethylenediamine for the 250 parts of
pyridine. The product is the cationic compound of the formula
- t il ~ N-N--; ~- - ~ 2Cl~
L /1~ 2~C~2
which colours paper and cotton in bright yellow shades and exhausts
well.
I Example 3: 25.4 parts of the compound of the formula
~03H
C~ ~ / \6/ \ ~ \ fi
S03H_
are stirred in 80 parts of chlorosulfonic acid for 6 hours at 90C.
The reaction mixture is then poured on ice and the precipitate is
filtered with suction and washed weakly acid with 2% NaCl solution.
The moist sulfochloride is added at 0-5C to a mixture of 16.4 parts
of 3-dimethylamino-l-propylamine, 120 parts of ice and 16 parts of
sodium acetate. The reaction mixture is stirred for 10 hours at
20-25C and the compound of the formula
S02NHCH2cH2cH2~(cH3)2
il 5~ N~ - f l;
02NHCH2CH2cH2N(cH3)2
~134817
is isolated by filtration.
Quaternisation is carried out by boiling this compound with
100 parts of ethylene chlorohydrin at 120C, affording the dye of the
formula
S02~HCH2CH2CH2~ 2C~20H]Cl
~ 2 ;z ~ ~ ; 2 3
.. .. . . . .. . . . ...
which produces on paper a bright yellow colouration of good fastness
to light and water.
Example 4: 50 psrts of chemically bleached beach sulfite are mixed
with 50parts of bleached sulfite RKN 15 (degree of freeness 22 SR)
aDd 2 p-rts of the dye of the formula
C~3~ . / S~ C~3- 2C1~3
i i~ N=N~ ~ 2N~COC~2~ ~
, ,. . .. . _ , .. .
in water (pH 6, water hardness 10 dH,Ite~perature 20C, liquor ratio
1:40). After stirring for 15 minutes, paper sheets are prepared on a
Frank sheet former. The paper is coloured in a very intense yellow
shade. The wastewater is completely colourless. The de8ree of exhaus-
tion is 100%.
The light- and wetfastness properties are excellent. The fast-
ness to water determined in accordance with DIN 53 991/SNV 195 806
has e.g. the rating 4. The lightfastness determined in accordance with
SNV 196 809 has the rating 6.
:
' ' :
113~817
- 13 -
_.~ample 5: The procedure of Example 4 is repeated, but using 2 parts
oE the known dye of the formula
3\ ~-\ /S \ .,. .,. / S\ ~ ca~ ~ C~
i li ~ N-N~ i 11 \ t~
- _ _ c~2-~-Na~ 2Cl''
- 3 2
The paper is coloured in the same intense yellow shade as in Example 4.
! The degree of exhaustion, however, is only about 95%. The waterfast-
ness rating is only 2.
Example 6: The procedure of Example 4 is repeated, but using 2 parts
of the known dye of the formula
,
C~3~ S \ ~ /C~3-
t il N~ --N~N--~ I ~ 3~)2
.
The paper is coloured in a similar, somewhat brighter yellow shade
than in Example 4. The degree of exhaustion is only just 90%. The
wastewater is intensely coloured. The waterfastness rating is below 2
Example 7: A paper web of bleached beach sulfite (22 SR) is pre-
pared on a continously operating laboratory paper machine. Ten seconds
before the stock preparation, an aqueous solution of the dye of the
formula
.. .. . .
~ C~3- 2Cl~
t 11 _-~ ~--N=N--~ ~-- 11 t f G~D-~
~ , , , ~ ,
is added continously to the dilute pulp with vigorous turbulence (0.5
colouration, liquor ratio 1:400, water hardness 10 dH, pH 6, tempe-
~' ~
~13~8i7
rature 20C).
The paper web is coloured a level yellow shade of averageintensity and of very good wet- and lightfastness. The wastewater i9
completely colourless.
Example 8: 10 parts of cotton fabric (bleached mercerised cotton)
are dyed in a labora~ory beam dyeing machine in 200 part of a liquor
(water hardness 10 dH, pH 4, 3 circulations of the liquor per min-
ute) which contains 0.05 part of the dye of the formula
r~3~ . f~ B31 -- 2Cl~
~ --N5N--~ ! ! ~ ~3 3-~;
_ ~ ... ~ _ _ :a2NE~COCa2N~; ~
The temperature is raised in the course of 60 minutes to 20-100C,
then kept constant for 15 minutes.
The tyebath i8 completely exhaustet ant the cotton fabric is
tyet in an intense yellow shate. The tyeing i9 distinguished by very
good lightfastness and very goot wetfastness which compares with that
of a vat tyeing.
