Note: Descriptions are shown in the official language in which they were submitted.
-
S~l
Case 150-4353
IMPP~OVEMENTS IN OR RELATING TO ORGANIC C0~P0TJ~3S
The present invention relates to anionic disazo
compounds, their preparation and use as anionic dye~
stuffs.
More particularly, the present invention provides
compounds of formula I,
A - N = N~N = N - K
N 2 10
in which A is the radical of a sulpho group containing
diazo component of the aniline series or
l- or 2-aminonaphthalene series,
K is a coupling component radical of the
phenol series, the free hydroxy group of
which may be etherified or acylated,
Rl is hydrogen, Cl_4alkoxy or Cl_4alkyl option
ally monosubstituted by halogen,
R2 is Cl 4alkyl, -CO(Cl 6)alkyl, -COO(Cl_6)-
alkyl, -CONH2, -CONH(Cl 6)alkyl, -CON(Cl_6-
alkyl)2, -CONH (C2 6)hydroxyalkyl or -CON-
(C2 6hydroxyalkyl)2 with the hydroxy group
in other than the l-position, and
Rlo is hydrogen or Cl ~alkyl
and the molecule contains one single sulphonic acid group
which is in the radical A,
,, ~
53~3~
15~-4~
and mixtures of such compounds, ~,7hich compounds are in
free acid or salt form.
Any alkyl or alkoxy groups as Rl, preferably
; contain l or 2 carbon atoms, more preferably 1 carbon
atom, any alkyl substituted by halogen is preferably
monochloro(Cl 2)alkyl.
Rl is preferably Ri, where Rl is hydrogen, methyl,
ethyl, methoxy or ethoxy. More preferably Rl is Rl,
where Rl is hydrogen, methyl or methoxy. Most preferably
Rl is Rl', where Rl' is hydrogen or methoxy,
with hydrogen being especially preferred.
Any alkyl as R2 is preferably methyl or ethyl,
especially methyl. Any Cl 6alkyl group in R2 which lS
bound to -CO-, -COO- or -CON~(H) preferably contains l
to 4 carbon atoms, more preferably 1 or 2 carbon atoms,
and is most preferably methyl. Any C2 6hydroxyalkyl
group is preferably 2-hydroxyethyl or 2- or 3-hydroxy-
propyl.
R2 is preferably R2, where R2 is -CO(Cl 4)alkyl,
-COO(Cl 4)alkyl or -CONH2. More preferably R2 is R2,
where R2 is -CO(Cl 2)alkyl, -COO(Cl 2)alkyl or -CONH2.
Most preferably R2 is R2', where R2' is -COCH3, -COOCH3
or -CONH2, especially -COCH3.
Any alkyl as Rlo is preferably methyl or ethyl,
especially methyl.
Rlo is preferably hydrogen, methyl or ethyl, more
preferabl~ hydrogen or methyl, especially hydrogen.
- 2 -
S~33~
15~-~353
A is preferably a radical of formula (a) or (b3,
R3 ~ or
4 S03H S03H
(a) (b)
in which R3 is hydrogen, halogen, Cl 4alkyl optionally
monosubstituted by halogen; Cl 4alkoxy, mono-
Cl 6alkylamino, di-Cl 6alkylamino, Cl 6alkyl-
carbonylamino,Cl l2alk~xyca~onylalmin~ or N-Cl 4-
alkyl-N-(Cl 6alkyl or Cl l~a~oxy)c ~ onyl-amino, ar,d
R4 is hydrogen, halogen, Cl 4alkyl or Cl 4alkoxy.
K is preferably a radical of formula (c) or (d),
5a
or ~ OR5b
R6a R6b
(c) (d)
in ~7hich
10each of R5a and R5b is hydrogen, Cl_4alkyl, C2_4hYdrXY~
alkyl with the hydroxy group in other than the l-posi-
tion; -COR8, -COOR8 or -S02 ~ Rg
in which R8 is Cl_l2alkyl or phenyl-Cl 4alkyl, and
Rg is hydrogen, halogen, Cl 4alkyl or Cl 4alkoxy,
15R6a is an aliphatic, cycloa.liphatic, carbocyclic
aromatic or araliphatic radical; halogen,
Cl_4alkXy, -NRllCO(Cl_6)alkyl or -NRllCOO-
(Cl 6)alkyl,
~5~3~
; 150-43r~3
R7 is hydrogen, halogen, Cl 4alkyl, Cl 4alkG~y
or -NRllCO(Cl 6)alkyl, ~7ith the proviso that
R7 is other than -NRllCO~Cl_6)alkYl ~Ihen R6a
is -NRllCO(Cl 6)alkyl;
R6b is hydrogen, cl_4alkyl, cl_4alkoxy, halogen~
-NRllCO(Cl 6)alkyl or -NRllCOO(Cl_6) Y
Rll is hydrogen or Cl_4alkyl.
By halogen is meant fluorine, chlorine or bromine.
Any halogen on a phenyl ring is preferably chlorine or
bromine, especially chlorine; any alkyl substituted by
halogen is preferably substituted by fluorine, chlorine
or bromine, especially by chlorine.
Any unsubstituted or substituted alkyl groups as
R3 preferably contain l or 2 carbon atoms, especially
1 carbon atom; R3 iS preferably unsubstituted alkyl. Any
alkyl as R4 is preferably methyl or ethyl, especially
methyl. Any alkoxy as R3 or R4 is preferably methoxy
or ethoxy, especially methoxy.
Any mono-alkylamino group as R3 preferably contains
a methyl- or ethyl-,especially a methyl group. ~ny di-
alkylamino group as R3 preferably contains methyl- and/
or ethyl groups, especially methyl groups. Any Cl 4-alkyl
in N-a~yl~N-a~ylcarbonyl- or -N-alkoxycarbonyl-am~a as R3 is prefer-
ably methyl. Any alkylcarbonylc~uno as R3 iS most preferc~bly aoetam~do;
- 25 any alko~c~rbonylanQno is preferably Cl 4aIkoxy-, m~st preferably Cl 2-
a~.~ycar'~nylc~no, or C~ 12alkox~carhonylamino.
R3 is preferably R3, where R3 iS hydrogen, halogen,
Cl_4alkyl, Cl 4alkoxy or acetamido. More preferably R3
-- 4 --
150-4353
is R3, where R3 is hydrogen, chlorine, Cl_2alkyl, Cl 2-
alkoxy or acetamido. Most preferably R3 is R3', where
R3' is hydrogen, chlorine, methyl, methoxy or acetamiao,
especially hydrogen.
R4 is preferably R4, where R4 is hydrogen, halogen,
Cl 2alkyl or Cl 2alkoxy. More preferably R4 is R4, where
R4 is hydrogen, chlorine, methyl or methoxy. Most pre-
ferably R4 is hydrogen. Preferably R4 is hydrogen, when
R3, R3, R3 or R3' is acetamiao.
When both R3 and R4 are hydrogen the sulpho group
is preferably in the 3- or 4-position (with the azo group
in the 1- position).l~hen one of R3 and R4 is hydrogen and the
other is other than hydrogen the preferred positions are
2,4; 2,5; 2,6 or 3,4, especially 2,4 or 2,5. ~hen both
R3 and R4 are other than hydrogen the three substituents
are preferably in the 2,3,5-; 2,4,5- or 2,4,6 positions
and most preferably in the 2,4,5- or 2,4,6-positions.
Especially preferred is the radical of formula (a),
wherein (i) both R3 and R4 are hydrogen and the sulpho
group is in the 3- or 4-position; or wherein
(ii) one of R3 and R4 is hydrogen and the other
is chlorine, methyl or methoxy,the positions for R3 or
R4 and the sulpho group are 2,4 or 2,5; or wherein R4
is hydrogen and R3 is acetamido in the 4- or 5-position
~nd the sulpho group is in the 2-position; or wherein
~5~3~
15~-4353
(iii) R3 and R4, independently, are methyl, methoYsy
or chlorine and R3, R4 and the sulpho group are in the
2,4,5- or 2,4,6-positions.
I~hen the naphthalene radical of formula (b) is
bound in the l-position,the sulpho group is preferably
in the 4-, 5-, 6-, 7- or 8-position, especially in the
4- or 5-position. ~hen the naphthalene radical is bound
in the 2-position,the sulpho group is preferably in the
1-, 5-, 6-, 7- or 8-position, especially in the 1-, 5-
or 6-position.
The radical (b) is preferably (bl), where (bl) is
4- or 5-sulphonaphthyl-1 or 1-, 5- or 6-sulphonaphthyl-2.
Any unsubstituted or substituted alkyl as R5a or
R5b is preferably straight chain; any unsubstituted
alkyl is preferably methyl or ethyl; any substituted
alkyl is preferably 2-hydroxyethyl or 2- or 3-hydroxy-
propyl. Any -COR8 group as R5a or R5b preferably contains
R8a,where R8a is straight chain or branched Cl 4alkyl
or phenyl-(Cl 3)alkyl; more preferably it contains R8a,
where R8a is methyl, ethyl or benzyl. Any -COOR8 group
as R5a or R5b preferably contains R8b, where R~3b is
straight chain or branched Cl 12alkyl or phenyl-(Cl_3)-
alkyl; more preferably it contains R8b, where R8b is
straight chain or branched C8 12alkyl or benzyl; most
preferably it contains R8b, where R8b is C8_12alkyl.
In the -S0 ~ 9 group any halogen as Rg is most pre-
,
, . . .
15~ J~
ferably chlorine; any alkyl is preferably rnethyl or
ethyl, especially methyl, and any alkoY.y is prefPrably
methoxy or ethoxy.
R5a is preferably R5a, where R5a is hydrogen,
methyl, ethyl, 2-hydroxyethyl, -COR8a, -COOR8b, phenyl-
sulphonyl or tosyl. More preferably R5a is R5a, T,7here
R5a is hydrogen, methyl, ethyl or -COOR8b (especially
-COOR8b). Even more preferably R5~ is R5a, where R5a
is hydrogen, methyl or ethyl. Most preferably R5a is
R5Va , where R5Va is hydrogen or methyl, especially
hydrogen.
R5b is preferably R5b, where R5b is hydrogen,
straight chain Cl ~alkyl, 2-hydroxyethyl, 2- or 3-
hydroxypropyl, -COR8a, -COOR8b, phenylsulphonyl or tosyl.
More preferably R5b is R5b, where R5b is hydrogen,
straight chain Cl 4alkyl, -COR8a, -COOR8b (especially
-COOR8b); phenylsulphonyl or tosyl. Even more prefer-
ably R5b is R5b, where R5b is hydrogen or straight chain
Cl 4alkyl. Most preferably R5b is R5ibV~ where R5ibV is me-
- 20 thyl or ethyl, especially methyl.
Any alkyl as Rll in the groups R6a, R6b or R7 is
preferably methyl or ethyl, especially methyl.
Rll is preferably hydrog~n or me~yl, especially hydro~n-
Any aliphatic, cycloaliphatic, carbocyclic aro-
25 mal:ic or araliphatic groups as R6a may contain con-
ventional substituents, for example substituents selected
from the group consisting of halogen (fluorine, chlorine
or bromine~, Cl 4alkyl and Cl 4alkoxy; additionally,
particularly any aliphatlc group may contain hydroxy-
-- 7 ~
. .
~ S~3~ 15~-~353
or cyano-groups.
Any aliphatic group as R6a i8 preferably an un-
substituted straight chain or branched alkyl group con-
taining 1-lO carbon atoms, more preferably 1-6 and
especially 1-4 carbon atoms. Any cycloaliphatic group
preferably contains 5-7 carbon atoms, especially 6
carbon atoms. Any carbocyclic aromatic or araliphatic
group as R6a is preferably an unsubstituted or substi-
tuted phenyl- or phenyl-(Cl 4)alkyl-group in which the sub-
stituents are selected from the group consisting ofhalogen, Cl 4alkyl and Cl_4alkoxy.
Any halogen as R6a is preferably chlorine; any
alkoxy is preferably methoxy or ethoxy.
Any -NCOalkyl or NCOOalkyl groups as R6a pre-
ferably contain Cl 4alkyl groups, especially Cl 2alkylgroups.
R6a is preferably R6a, where R6a is straight chain
or branched Cl 6alkyl, cyclohexyl, phenyl, benzyl,
chlorine, methoxy, ethoxy or acetamido. More preferably
R6a is R6a, where R6a is straight chain or branched
Cl 4alkyl, benzyl, chlorine, methoxy or ethoxy. Most
preferably R6a i5 R6a, where R6a is straight chain or
branched Cl 4alkyl or chlorine.
Any halogen as R7 is preferably chlorine; any
2S alkyl or alkoxy groups preferably contain l or 2 carbon
atoms, especially l carhon atom. Any -NCOalkyl as R7
preferably contains Cl 4alkyl groups, more preferably
Cl 2alkyl groups, and is most preferably acetamido.
/
. '~ .
~ .
~53~1
15~-4~53
R7 is preferably R7, where R7 is hydrogen, chlorlne,
; methyl, ethyl, methoxy, ethoxy or acetamido. More prefer-
ably R7 is R7, where R7 is hydrogen, chlorine, methyl,
methoxy or acetamido, especially hydrogen.
Any halogen as R6b is preferably chlorine or bromine;
any alkyl or alkoxy groups as R6b preferably contain l or
2 carbon atoms, especially 1 carbon atom. Any -NCOalkyl or
~NCOOalkyl groups as R6b preferably contain Cl 4alkyl,
especially methyl.
R6b is preferably R6b, where R6b is hydrogen, chlor-
ine, bromine, methyl, ethyl, methoxy, ethoxy or acetamido.
More preferably R6b is R6b~ where R6b is hydrogen, chlor-
ine, methyl, methoxy or acetamido, especially hydrogen.
A is preferably a group (al), where (al) is a group
f formula (a), wherein R3 is R3 and R4 is R4, or of for-
mula (bl). More preferably A is a group (a2), where (a2)
is a group of formula (a), wherein R3 is R3 and R4 is R4,
or of formula (b1). Most preferably A is a group (a3), where
(a3) is a group of formula (a), wherein R3 is R3', espe-
cially hydrogen, and R4 is R4, especially hydrogen. In thegroups (al) to (a3) the substituents are in the above-
given preferred positions.
K is preferably a group (cl), where (cl) is a group
of formula (c), wherein R5a is R5a, R6a 6a 7
R7; or a group (dl), where (dl) is a group of formula (d),
wherein R5b is R5b (especially RSb) and R6b is R6b- More
preferably K is a group (c2), where (c2) is a group of
. g _
50-~353
formula (c), wherein R5a is R5a, R6a is R6a 7 7
- or a group (d2), where (d2) is a group of formula (dj,
5b is R5b and R6b is R6b- Even more prefer~bly
K is a group (c3), where (C3) is a group of formula (c),
wherein R5a is R5aV (especially hydrogen), R6a is R6' and
R7 is hydrogen; or a group (d2). Still further more pre-
ferably K is a group (d3), where (d3) is a group of for-
mula (d), wherein R5b is R5b and R6b 6b
preferably K is a group (d4), where (d4) is a group of for-
mula (d), wherein R5b is ~5ibv (especially methyl) and R6b
is hydrogen.
Preferred compounds of formula I are
. (1) those wherei.n A is a group (al) or (b~
(2) those wherein A is a group (a2) or (bl);
(3) those wherein Rl is Ri, R2 is R2 and Rlo is hydrogen;
(4) those wherein K is a group (cl) or (dl);
(5) those wherein K is a group (C3) or (d2);
(6) those wherein K is a group (d2);
(7) those of formula Ia,
~1
: 2 ~ N K Ia
,
NHR2
in which A2 is a group of formula (a2)
R3 ~ (a2) and
R4 SO~H
K2 is a group of formula (d3)
- 10 -
-. :
~; ' '
' ' '
~ ~5~3~
1~0-43~3
OR5b (d~) t
R6b
(8) those of (7), where.in A2 is a group (a3);
(9) those of (7), wherein K2 is a group (d4),
and especially the group ~ OCH3;
(lO) those of (7), (8) or (9), wherein Rl is P~l',
especially hydrogen, and R2 is R2', especially
-COCH3.
The present invention further provides a process
for the production of compounds of formula I comprising
coupling the diazonium derivative of the compound of
formula II, Rl
A - N = N ~ N~I2 II
2Rlo
or a mixture thereof,
with a coupling component of the phenol series, and
optionally etherifying or acylating the hydroxy group.
Thus, compounds of formula Ib,
~1
Al - N = N~ N - N - Kl Ib
NR2R10
in which Al is a group of formula (a) or (b),
Kl is a group of formula (c) or (d) and
Rl, R2 and Rlo are as de~ined above,
and mixtures thereof are obtained comprising
-- 11 --
~S3~
150-~3~3
a) coupling the diazonium derivative of the compound o'
formula IIa,
~R l
A - N = N ~ NH2 IIa
NR2 Rlo
or a mixture thereof,
with a phenol of formula IIIa or IIIb
H
H ~ R7 IIIa or -~ H~ OH IIIb
R6 R6b
~ S or a mixture thereof,
: to obtain a compound of formula Ix,
~1
;~ Al - N - N ~ N = N - KlX Ix
2 lO
: in which KlX i5 a group of formula tax~ or (bx),
H
7 ~ax) or ~ OH (bx)
R6a 6b
or a mixture thereof,
or
b) etherifying or acylating a compound of formula Ix
or a mixture thereof,
to obtain a compound of formula Ib wherein R5a or
R5b is other than hydrogen.
- 12 -
., .
'',~' :
" ~' , ~ ,
~ 3~ 150~4-~,53
The coupling reaction may be effected in a~cord-
ance with known methods; suitably, coupling i5 effec.ed in
alkaline medium at the pH range of 9 to 13, the preferred
pH being from 10 to 12. Diazotization of a compound of
formula II or IIa to produce the starting materials thereof
may also be carried out in conventional manner.
The etherification or acylation may be effected in
known manner. Suitably, the etherification is carried out
employing the corresponding dialkylsulphate or alkylene-
oxide. The reaction is suitably carried out in aqueousalkaline medium, the preferred pH being from 9 to 11. The
reaction temperature is suitably from 30 to 90C, more
preferably from 40 to 70C.
Acylation is suitably effected employing the
corresponding acid chloride. The reaction mixture is pre-
~erably aqueous which is made alkaline with soda, the
preferred pH being vom 8 to 10. The reaction temperature
is suitably between 30 an~ 90C`C, preferably between 60 and
70C.
The compounds of formula I may be isolated in accord-
ance with known methods. In general owing to the process/
isolation conditions, the compounds of formula I may be ob-
tained in salt form.
~Ihen the compounds of formula I are in the salt form,
the catiGn of the sulpho group is not critical and may be any
of those non chromophoric cations conventional in anionic dye-
stu~f~. Examples of such cations are alkali metal cations and
~ 13 -
~ 33~ 150-~35~
cations of the ammonium type including unsubstituted and
substituted ammonium cations e.g., lithium, sodium,
potassium, a~nonium, mono-, di-, tri- and tetra-methyl-
ammonium, triethylammonium and mono-, di- and tri-ethanol-
ammonium. The preferred cations are the alkali metal cations
including ammonium, with sodium being the most preferred.
The compounds of formula I which are in the salt form
may he converted into the free acid form or into other salt
forms in accordance with known methods.
The starting materia]s of formula II are either known
or may be prepared in accordance with known methods from
available starting materials. Thus, the compounds of formula
II are obtained by coupling the diazonium deriva~ive of an
amine A-NH2 in a weakly acid to neutral medium with the
corresponding aniline of formula IV,
,~ .:
~H ~ NH2 IV
N 2Rlo
or a derivative thereof reacted with w-methanesulphonic
acid. Compounds of ~ormula IV and phenols of formula IIIa
or IIIb are either known or may be prepared in accordance
with known methods from available starting materials.
The compounds of formula I and mixtures thereof are
useful for dyeing or printing anionic dyeable substrates.
Suitable substrates include leather, natural or synthetic
polyamides, polyurethanes and basic-modified polyolefins.
Especially suitable are textile substrates consisting of
3~
4353
or comprising natural and synthetic polyamides, such as
wool and silk, and particularly nylon. The dyestuffs may
advantageously be used for carpet printing.
The compounds of formula I and mixtures thereof, may
be employed as such or may be used in the form of liquid
or solid preparations. The preparation of stable liquid,
for example concentrated aqueous preparations, or solid
preparations may be carried out in accordance with con-
ventional methods, for example by dissolving in suitable
solvents e.g. water, optionally with the addition of con-
ventional additives such as solubiliziny agents, for
example urea, or by grinding or granulating. Such prepara-
tions may be obtained in accordance with the procedure
described in French Patents 1,572,030 or 1,581,900.
Further, the compounds of formula I and mixtures
thereof, may be made up into preparations which are dis-
persible in cold water. Such dispersions may be prepared,
for example, by grinding the dye dry or wet in aqueous
dispexsing medium in the presence of one or more con-
2~ ventional anionic dispersing agents and optionally in the
presence of other conventional additives, optionally with
subsequent spray drying. The preparations so obtained are
finely dispersed in cold water.
Dyeing and printing may be carried out in accordance
with known methods, for example pad dyeing or exhaust
dyeing, especially the latter since the compounds of
- 15 -
533~
15~-435~
formula I and mixtures thereof exhaust from a neutral
dyebath. Furthermore, the compounds o~ formula I
and mixtures thereof are also useful for use in the
"space-dyeing" process.
The compounds of formula I and mixtures thereof are
well soluble in water, build-up well, migrate well and give
even dyeings, especially on stripy nylon. The dyeinys
obtained possess notable light-fastness. Furthermore, the
compounds of formula I and their mixtures give dyeings
which have notable general fastnesses, such as wet-fast-
nesses, especially wash-, water-, milling- and sweat-fast-
ness.
The compounds of formula I are suitab~e for com~ining
with other anionic dyes which exhaust from a neutral dyebath,
whereby tone-in-tone dyeinys having the above-mentioned
advantageous properties are obtained. Further, such dyeings
do not exhiblt cataly~ic fading.
The following Examples further serve to illustrate the
invention. In the Examples, all parts are by weight and all
2~ degrees are in degrees Centigrade.
- 16 -
33~
150~43~3
Exam~le
.. ,
17.3 Parts sodium salt of l-aminobenzene-3-sulphonic
acid are dissolved in 80 parts water and are then mixed
with 6.9 parts sodium nitrite. This solution is slowly
added with stirring to a mixture of 50 parts ice and 28
parts 30% hydrochloric acid. After 1 hour at 5-10, the
excess of nitrous acid is destroyed by adding a small
~uantity of amidosulphonic acid. The diazonium suspension
obtained is added to a solution of 18.7 parts 3-amino-
acetanilide in the hydrochloric acid salt form and 5 partscalcinated sodium carbonate in 150 parts water and 100
parts ice, at 0-5 while stirring, the pH being maintained
at 6-7 by the addition of calcinated sodium carbonate.
After stirring for 1 hour, the monoazo compound is salted
out by the addition of sodium chloride. The precipitated
dyestuff is isolated by filtering and washed with 5~ sodium
chloride solution.
The paste obtained is dissolved in 170 parts water of
60 and is then mixed with 6.9 parts sodium nitrite. This
solution is slowly added dropwise to a mixture of 60 parts
ice and 28 parts hydrochloric acid, the temperature being
kept at 5-10 by the addition of ice. After 2 hours the
excess of nitrous acid is destroyed by the addition of
amidosulphonic acid. The diazonium suspension is slowly
added to a solution of g.5 parts phenol and 13 par~s 30%
caustic soda in 1~0 parts wa-~er at room temperature. After
- 17 -
~ 15~~4353
15 minutes the coupliny reaction is complete. The dyestuf
is pecipitated by the addition of sodium chloride at p~ 9,
and is isolated by filtering, washed with 5% sodium chloride
solution and dried. The dyestuff which, ln the free acid
form, corresponds to the formula
N = ~ ~ = ~ OH
SO3H NHCOCH3
; is obtained in the sodium salt form and gives dyeings on
natural or synthetic polyamides of reddish-yellow shades
which have good light- and wet~fastnesses.
Example 2 --
The etherification of the hydroxy group of the disazo
dyestuff obtained by the method of Example 1 is carried
out as follo~Js: The filtered and washed dyestuff of Exa~ple
1 in paste form is dissolved in water of 45-50 by adding
of 10 parts 30% sodium hydroxide solution. To this solution
25 parts dime-thylsulphate are added while stirring vigorously,
the pH being kept at 10.5-11.0 by the addition of 30% sodium
hydroxide solution. After 4 hours the etherification is
complete. Precipitation of the dyestuff is completed by
20 adding sodiu~ chloride. The dyestuff is isolated by filter- -
ing, washed with 5% sodium chloride solution and dried. The
disazo compound which~ in the free acid form, corresponds
to the formula
- 18 -
.,
' '
, ' '
3~
150 4~5:~
~N = N~ N = N~oCH3
S03H NHCOCH3
is obtained in the sodium salt form and gives dyeings on
natura], or synthetic polyar,~ides of reddish yellow-shades.
The dyeings have yood light- and wet-fastnesses.
In analogy with the procedure described in Example 1
using a mixture of l-aminobenzene-3- and -4-sulphonic acid
o (in the ratio of approximately 1:1) instead of l-amino-
benzene-3-sulphonic acid, the mixture of corresponding
dyestuffs is obtained which can be etherified according to
the method described in Example 2. This mixture of dyes
(containing hydroxy groups or methoxy groups) is parti-
cularly well soluble in water and therefore especially use-
ful for dyeing of natural or synthetlc polyamides, giving
dyeings of reddish-yellow shades which have good light-and
wet-fastnesses.
In the following tables further dyestuffs are given
which are prepared in analogy with the procedure described
in Example 1 or 2. These dyestuffs, owing to the reaction-
ana isolation-steps, are obtained in the sodium salt form.
The dyestuffs correspond to the general formula A,
R3 ~1
N = N ~ N = N ~ OR5 A
S03H NHR2
for Table l;
-- 19 --
/
~S331 1~0-4353
to the general formula B,
Rl OR5
N = N~N = N ~ B
SO3H NHCOCH3 R7
for Table 2;
and to the general formula C,
A - N = N~N = N~oR5 C
R
NHR2 6
for Table 3 .
; 5 The symbol I in the last column of the tables denotes
the dye shade on natural or synthetic polyamides, especially
on nylon, where
a is reddish-yellow; b is orange; c is scarlet-red;
d is red; e is yellowish-red; f is brownish-yellowr
g is brownish-red; and h is brown.
The polyamide dyeings obtained have good light- and
: wet-fastnesses.
- 20 -
3~
15~ 5
Table 1 / fonnula
- Example positio
. S03H R3 Rl R2 ¦ R5 ¦ I
3 4 H ~rCOCH~ a
4 4 H H do. CH3 a
3 H OCH3do. H c
6 3 E do.do. CH3 c
7 4 H do.do. do.
8 4 H do.do. C2H5 c
9 4 H H do. Tosyl a
3 H H CONIH2 H
11 3 H H do. CH3 a
12 2-NHCOCH3(4) H COCH3 H a
13 2 do. H do. CH3 a
14 2-~1HCOCil3(5) H do. do. a
3 X CH3do . do. a
16 3 H OCH3 do. C2H5 c
17 4 C~13(2) do. do. CH3 c
18 4 do. CH3 do. do. a
19 4 do. do. do. C2H5 a
do. H do. CH3 b
21 2 3( ) OCH3 do. do. c
22 5 OCH3(2) H do. C2H5 b
23 2 Cl(4) H do. CH3 a
24 2 do. H do. Tosyl a
Cl(2) H - do. CH3 a
26 3 H OCH3 do. COOCH3b
7 3 H do. do. CoocH2cH(cH3)2 b
28 3 X do. do. COOClOH21(n) b
29 4 CH3(2) do. do. C2H5 c
3o 4 Cl(2) do. do. CH3 c
31 2-~ICOCH3(4) do. do. do. c
32 3 H H 2-5 do. a
33 4 }1 H do. do. a
- 21 -
3~
~ 35
Table 1 continued
Noxa~pIe 3__ R3 R~ R2
34 4 H OCH3 COC2H5C2~5 - c
3 H H do.do. a
36 3 TT H do.Tosyl a
37 5 Cl(2) H COOCH3CH3 a
38 5 do. CH3 do.do. a
39 2 3( ) OCH3 do.do. c
2 do. H do,do. a
: 41 2 do. H do,C2H5 a
42 5 OCH3(Z) H do.CH3 b
43 4 H H do.CzH5 a
44 4 H H COOC2H5 CH3 a
3 H OC~3 CO~T2do. c
46 4 H do. do.do. c
47 4 H H do.Tosyl
,
533~
1~~43~3
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-- 24 --
S33~
-
150-43~3
Takle 3 / formula C
Exa~.ple A 1 R2 OR5 P~6 ¦ I
92 4-Sulfon~?hthyl-1 H COCH30~4) H c
93 do. H do.3( ) ~ c
94 5-Sulfonaphth~ l H do. do. H . c
do. H COC2~35 do. H c
96 do. H CO~H2 do. ~ c
97 do. H COCH OH(2~ Cl(5) c
98 6-Sulfonaphthyl-2 H do. oH(4) H b
99 do. H do. OCH3(4) H b
100 do. CH3 do. do. H c
101 do. OCH3 do. do. H d
102 do. H do.3( ) Cl(5) b
103 5-Sulfonaphthyl-2 H do.OH(4~ H b
104 do. H do.OCH3(4) H b
105 1-Sulfonaphthyl-2 CH3 do.do. H c
-Example 106
In analogy with the procedure described in ~.xam~les
l and 2 using appropriate starting materials a dyestuff
may be prepared which, in the free acid form, corresponds
to the formula OCH3
~ N = N ~ N = 21 ~OCH3
S03E~ OCH3
CH3
and is obtained in the sodium salt form. The dyestuff
gives dyeings on natural or synthetic polyamides of scarlet-
red c.hades.
The dyestuffs of Example l to 106 which are in the
lo sodium salt form may, depending on the xeaction/
isolation conditions, be obtained in accordance with known
- 25 -
3~
15~~4353
methods in free aci~ form or in other salt forms, for
example those salt forms indicated in the description
hereinbefore.
Application Example A
100 Parts of pre-wetted synthetic polyamide, for
example nylon 66, are entered at 40 into a dyebath con-
sisting of 4000 parts water, lO parts of anhydrous sodium
sulphate and 2 parts of the dyestuff of Example 2.
The dye li~uor is heated over the course of 30
minutes to boiling tempera-ture and kept at this temperature
for l hour. 4 Parts of glacial acetic acid are then added
thereto and dyeing is completed with heating for a further
30 minutes at boiling temperature. During dyeing, the water
that evaporates is continuously replaced. The reddish~
yellow dyed nylon cloth is then removed from the li~uor,
rinsed with water and dried. Wool may also be dyed by the
same process.
Similarly, the dyes of Examples 1 and 3 to 106 , or
mixtures of two or more of the dyestuffs of EY~a~ples l to 106
may be employed to dye nylon or wool in accordance with the
method described above.
- 26 -
33~
150-~3~3
A~lication ~xa,ll~le B
,,
Polyamide is printed with a printing paste con-
taining:
30 parts dyestuff of Example 2
50 parts urea
50 parts solubilizing agent te.g~ thiodiethylene
glycol)
290 parts water
500 parts suitable thickening agent (e.g. based on
carob bean gum)
20 parts acid donating agent (e.g. ammonium tartrate)
60 parts thiourea.
The printed textile goods are steamed for 40 minutes
at 102 (saturated steam), rinsed cold, subsequently washed
at 60 for 5 minutes with a dilute solution of a con-
ventional detergent and rinsed again with cold water. A
reddish-yellow print having notable light- and wet-fast-
nesses is obtained.
In analogous manner printing pastes may be made
- 20 employing the dyestuffs of Examples 1 and 3 to 106 or
mixtures o two or more of the dyestuffs of Examples 1
to 106. Such pastes may be employed for printing in
accordance with the above given procedure.
- 27 -
