REACTIVE DYE COMPOUNDS

COMPOSES DE COLORANTS REACTIFS

English Abstract

New, highly multifunctional reactive dye compounds are provided. The number of
leaving groups in the non-chromophoric part of the molecule added to the
number of chromophore moieties is at least equal to 5, preferably in the range
of from 5 to 12, more preferably from 5 to 6. The new reactive dye compounds
preferably have at least two asymmetric bridges.

French Abstract

L'invention concerne de nouveaux composés de colorants réactifs hautement multifonctionnels. Le nombre de groupes partants dans la partie non-chromophore de la molécule ajouté au nombre de fractions chromophores est au moins égal à 5, se situant de préférence dans une gamme allant de 5 à 12, et idéalement de 5 à 6. Les nouveaux composés de colorants réactifs ont de préférence au moins deux ponts asymétriques.

Claims

CLAIMS
1. A reactive dye compound comprising at least one chromophoric moiety D and
at
least one leaving group Y wherein the sum of the number of chromophoric moiety
or moieties D and the number of leaving group or groups Y is at least equal to
5,
preferably in the range of from 5 to 12, more preferably from 5 to 6.
2. A reactive dye compound according to Claim 1 wherein the reactive dye
compounds comprises at least two asymmetric bridging moieties, preferably at
least two dissymmetric bridging moieties.
3. A reactive dye according to Claim 2 wherein the bridging moieties are
selected
from the group consisting of cysteamine, cysteine and derivatives thereof,
even
more preferably from the group consisting of cysteamine and cysteine.
4. A reactive dye compound having the formula (I) below:
<IMG>
wherein
.cndot. D is a chromophore;
.cndot. L is a linking moiety, preferably selected from the group consisting
of -NR-, -
C(O)NR-, -NRSO2-, -(CH2)k- and -SO2-(CH2)k- wherein R is H or C1-C4 alkyl
which can be substituted by halogen, preferably fluorine or chlorine,
hydroxyl,
cyano, C1-C4 alkoxy, C2-C5 alkoxycarbonyl, carboxyl, sulfamoyl, sulfo or
sulfato and wherein k is an integer with a value between 1 and 4.
.cndot. Z is any moiety forming at least three covalent bonds with other
moieties,
preferably selected from the group consisting of nitrogen (N),
<IMG> and aromatic compounds, more preferably from the

group consisting of aromatic compounds activated by election withdrawing
groups and N-heterocycles, even more preferably from the group consisting of
triazine, pyrimidine, quinoxaline, pyrimidinone, phthalazine, pyridazone,
pyrazine
and
<IMG>
still more preferably from the group consisting of triazine, pyrimidine, and
quinoxaline, still even more preferably from triazine;
.cndot. Y is any leaving group, preferably selected from the group consisting
of -Cl, -
Br, -F, -I, -SO3H, -OSO3H, -SSO3H, -O-C6H4-SO3H, -OCO-CH3, -OPO3H2, -OCO-
C6H5, -OSO2-C1-C4 alkyl, -OSO2-N(C1-C4 alkyl)2,
<IMGS>
and quaternized nitrogen derivatives, more preferably selected from the group
consisting of -Cl, -Br, -F and -OSO3H, even more preferably from the group
consisting of -F and -Cl when Y is bonded to an N-containing heterocycle and -
Br
when Y is bonded to
<IMG>
.cndot. G1 is selected from the group consisting of Y and ~ B ~ G2;
.cndot. G2 is selected from the group consisting of
46

<IMGS>
.cndot. B is a bridging moiety selected from the group consisting of
~S~,
<IMG>
~ S ~ CR'2 ~ CR'2 ~
wherein R' is selected from the group consisting of H, C1-C10 alkyl group, C1-
C10 carboxylic acid and sulphonate, preferably H; and
wherein R" is selected from the group consisting of H, C1-C4 allyl group and
~ CR'2 ~ CR'2 ~ S ~ G2;
B preferably being ~ NH ~ CH2 ~ CH2 ~ S ~ or
~ NH ~ CHCOOH~CH2 ~ S ~,
.cndot. wherein there is more than one D, R, R', R", L, Z, Y, G1, G2 or B
these are not
necessarily the same; and
.cndot. wherein the reactive dye compound comprises at least one group G2;
and salts and esters thereof.
47

5. A reactive dye compound according to Claim 4 having the formula (II):
<IMG>
wherein
.cndot. D is as defined in Claim 4;
.cndot. L is as defined in Claim 4;
.cndot. Z is as defined in Claim 4;
.cndot. Y is as defined in Claim 4;
.cndot. B is
<IMG>
wherein R' is selected from the group consisting of H, C1-C10 alkyl group, C1-
C10 carboxylic acid and sulphonate, preferably H; and
R" is selected from the group consisting of H, C1-C4 alkyl group,
B preferably being ~ NH ~ CH2 ~ CH2 ~ S ~ or
~ NH ~ CHCOOH~CH2 ~ S ~,
.cndot. wherein when there is more than one D, L, Z, I', R, R', R" or B group
these are
not necessarily the same;
and salts and esters thereof.
6. A reactive dye compound according to Claim 4 having the formula (III):
48

<IMG>
wherein
.cndot. D is as defined in Claim 4;
.cndot. L is as defined in Claim 4;
.cndot. Z is as defined in Claim 4;
.cndot. Y is as defined in Claim 4;
.cndot. G1 is as defined in Claim 4;
.cndot. G2 is as defined in Claim 4;
.cndot. B is
<IMG>
wherein R' is selected from the group consisting of H, C1-C10 alkyl group, C1-
C10 carboxylic acid and sulphonate, preferably H; and
R" is selected from the group consisting of H and C1-C4 alkyl group,
B preferably being ~ NH ~ CH2 ~ CH2 ~ S ~ or
~ NH ~ CHCOOH~CH2 ~ S ~;
.cndot. wherein when there is more than one D, R, R', R", L, Z, Y, G1, G2 or B
group
these are not necessarily the same; and
.cndot. wherein the reactive dye compound comprises at least one group G2;
and salts and esters thereof.
7. A reactive dye compound according to Claim 4 having the formula (IV):
<IMG>
wherein
49

.cndot. D is as defined in Claim 4;
.cndot. L is as defined in Claim 4;
.cndot. Z is as defined in Claim 4;
.cndot. Y is as defined in Claim 4 ;
.cndot. G1 is as defined in Claim 4;
.cndot. G2 is as defined in Claim 4;
.cndot. B is as defined in Claim4;
.cndot. wherein at least one, and preferably all, B is ~ S ~,
.cndot. wherein when there is more than one B, D, R, L, Z, Y, G1 or G2 within
the same
molecule these are not necessarily the same; and
.cndot. wherein the reactive dye compound comprises at least one group G2;
and salts and esters thereof.
8. A reactive dye compound according to Claim 4 having the formula (V):
<IMG>
wherein
.cndot. D is as defined in Claim 4;
.cndot. L is as defined in Claim 4;
.cndot. Z is as defined in Claim 4;
.cndot. Y is as defined in Claim 4;
.cndot. G1 is as defined in Claim 4;
.cndot. G2 is as defined in Claim 4;
.cndot. B is a bridging group selected from the group consisting of
<IMG>
wherein R" is selected from the group consisting of H, C1-C4 allyl group and

~ CR'2 ~ CR'2 ~ S ~ G2 ; and
wherein R' is selected from the group consisting of H, C1-C 10 alkyl group, C1-
C10 carboxylic acid and sulphonate, preferably H,
.cndot. wherein when there is more than one D, R, R', R", L, Z, Y, G1, G2, or
B group
they are not necessarily the same; and
.cndot. wherein the reactive dye compound comprises at least one bridging
group B
wherein R" is ~ CR'2 ~ CR'2 ~ S ~ G2 ;
and salts and esters thereof.
9. A reactive dye compound according to Claim 4 having the formula (VI):
<IMG>
wherein
.cndot. D is as defined in Claim 4;
.cndot. L is as defined in Claim 4;
.cndot. Z is as defined in Claim 4;
.cndot. Y is as defined in Claim 4;
.cndot. G1 is as defined in Claim 4;
.cndot. G2 is as defined in Claim 4;
.cndot. B is a bridging moiety, preferably selected from the group consisting
of
~ S ~,
<IMG>
51

~ S ~ CR'2 ~ CR'2 ~
wherein R" is selected from the group consisting of H, C1-C4 alkyl group and
~ CR'2 ~ CR'2 ~ S ~ G2
wherein R' is selected from the group consisting of H, C1-C10 alkyl group, C1-
C 10 carboxylic acid and sulphonate, preferably H,
B preferably being ~ NH ~ CH2 ~ CH2 ~ S ~ or
~ NH~CHCOOH~CH2 ~ S ~,
.cndot. wherein when there is more than one D, R, R', R", L, Z, Y, G1, G2 or B
group
they are not necessarily the same;
and salts and esters thereof.
10. A reactive dye compound according to Claim 1 having the formula (VII):
<IMG>
wherein
.cndot. D is as defined in Claim 4;
.cndot. L is as defined in Claim 4;
.cndot. Z is as defined in Claim 4;
.cndot. Y is as defined in Claim 4;
.cndot. B is selected from the group consisting of
<IMG>
~ S ~ CR'2 ~ CR'2 ~
wherein R" is selected from the group consisting of H and C1-C4 alkyl group;
and
52

wherein R' is selected from the group consisting of H, C1-C10 alkyl group, C1-
C10 carboxylic acid and sulphonate, preferably H;
B preferably being ~ NH ~ CH2 ~ CH2 ~ S ~ or
~ NH~CHCOOH~CH2 ~ S ~,
.cndot. wherein each of R, R', R", L, Z, Y and B are not necessarily the same;
and salts and esters thereof.
11. A reactive dye compound according to Claim 1 having the formula (VIII):
<IMG>
wherein
.cndot. D is as defined in Claim 4;
.cndot. L is as defined in Claim 4;
.cndot. Z is as defined in Claim 4;
.cndot. Y is as defined in Claim 4;
.cndot. R is selected from the group consisting of H, C1-C10 alkyl group, C1-
C10
carboxylic acid and sulphonate, preferably H and COOH, more preferably H;
.cndot. wherein each of D, R, Z and Y within are not necessarily the same;
and salts and esters thereof.
12. A reactive dye compound according to Claim 1 having the formula (IX):
53

<IMG>
wherein
.cndot. D is as defined in claim 4;
.cndot. Z is as defined in claim 4;
.cndot. Y is as defined in claim 4;
.cndot. R is selected from the group consisting of H, C1-C10 alkyl group, C1-
C10
carboxylic acid and sulphonate, preferably H and COON, more preferably H;
.cndot. wherein each of Z or Y are not necessarily the same;
and salts and esters thereof.
13. A method for synthesizing a reactive dye compound according to Claim 1
using a
starting reactive dye compound and bridging moiety B as defined in Claim 4,
wherein said method comprises the steps of:
a) reacting said starting dye compound with said bridging group B and forming
one bond, and
b) reacting the second moiety of said bridging group B with a moiety 2 as
defined
in Claim 4.
14. A method according to Claim 13, wherein said bridging moiety B is
dissymmetric.
15. A method according to Claim 14, wherein said bridging moiety B has the
following formula:
<IMG>
wherein R' is selected from the group consisting of H, C1-C10 alkyl group, C1-
C10
54

carboxylic acid and sulphonate, preferably H; and R" is selected from the
group
consisting of H and C1-C4 alkyl group.
16. A method according to Claim 15, wherein at least one R' is COOH.
17. A method according to Claims 13 to 16 wherein step a) and/or step b) is
repeated
at least two times.
18. A method for dyeing a substrate wherein said method comprises the step of
applying a composition comprising a reactive dye compound according to any of
Claims 1 to 12.

Description

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Reactive Dire Compounds
~ Technical Field
The present invention relates to reactive dye compounds. In particular the
present
invention relates to reactive dye compounds comprising at least one
chromophoric moiety
D and at least one leaving group Y. The sum of the number of chromophoric
moiety or
moieties D and the number of leaving group or groups Y is at least equal to 5.
Background of the Invention
Reactive dye compounds are known in the art for dyeing various substrates.
Such
substrates include for example proteinaceous materials such as keratin, e.g.
found in hair,
skin and nails and various animal body parts such as horns, hooves and
feathers, and
other naturally occurring protein containing materials, e.g. silk and
saccharide-derived
materials such as those derived from cellulose or cellulose derivatives, e.g.
natural
products such as cotton, and synthetic fibres such as polyamides.
Examples of classes of such reactive dyes which are well known in the art
include dyes
containing a mono- or dichloro- or fluoro- 1,3,5-triazinyl group, trichloro-
pyrimidyl or
mono-chloro-difluoro pyrimidyl group, alpha,beta-dihalogen-propionyl group,
beta-
halogenoethyl-sulphonyl group, beta-halogenoethylsulphamyl group, chloroacetyl
amino,
beta-(chloro-methyl)-beta-sulphatoethylsulphamyl group, or a vinyl sulphonyl,
2,4-
dinitro-3,5-difluoroaryl group.
In the case of the dyes containing a triazinyl group or a pyrimidyl group, in
place of the
reactive halogen atoms one can use other groups which dissociate on reaction
with a
nucleophile (leaving groups). Canadian Patent 771632, for example, discloses
examples
of such other groups including sulphonic acid, thiocyanate, sulphophenoxy,
sulphophenyl
thio, nitrosulphophenoxy groups, and quaternary ammonium groups.
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Dyes and Pigments 14, 1990, pages 239-263, "Synthesis and Application of
Reactive
Dyes with Heterocyclic Reactive Systems" discloses fibre reactive dyes
containing
monochloro- or dichloro- pyrimidine heterocycle with quaternary anunonium
substituents.
There are many different types of reactive dyes for dyeing cellulosic and
polyamide-type
substrates described in the art. W09951684, Lewis et al., incorporated herein
by
reference, discloses reactive dyes comprising a) at least one chromophore
moiety, b) at
least one nitrogen-containing heterocycle, c) a linking group to link each
chromophore
moiety to each nitrogen-containing heterocycle characterised in that at least
one nitrogen-
containing heterocycle is substituted with at least one thio-derivative and at
least one
quaternized nitrogen derivative. These reactive dyes exhibit increased values
of
Exhaustion (E) and Fixation (F) compared to previous reactive dyes. A high
Exhaustion
value for a particular dye compound means that a low level of spent dye
remains in the
effluent after the dyeing process is complete. The Fixation Value (F) of a
reactive dye
compound is a measure of the extent of covalent bonding with the substrate
based on the
dye originally absorbed during the dyeing process.
In addition to these properties, it is also important that the reactive dyes
perforni well
once they have been applied to the textile. The industrial tests commonly used
to assess
the performance of dyed textiles measure their light fastness, wet and dry
crock
resistance, dye-transfer staining behavior and wash fastness. In the light
fastness test,
dyed samples are placed in a sunlight-mimicking unit and irradiated for set
amounts of
time. The stain test is carried out by attaching to a sample a multifiber test
strip. The
swatches are run in consumer-mimicking conditions in a washing machine. The
test is
designed to evaluate any cross staining propensity of dye that might be
removed in
washing to stain other fibers. The wash fastness test measures the color
change on the
fabric from the original shade. The sample is washed under consumer-mimicking
conditions in a washing machine and the assessment is done visually by a
trained
(experienced) technician.
Summary of the Invention
According to the present invention there is provided reactive dye compounds
comprising
at least one chromophoric moiety D and at least one leaving group Y, wherein
the sum of
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the number of chramophoric moiety or moieties D and the number of leaving
group or
groups Y is at least equal to 5, preferably in the range of from 5 to 12, more
preferably
from 5 to 6.
According to the present inventions there is also provided new reactive dye
compounds
having at least two asymmetric bridging moieties. The asymmetric bridging
moieties are
preferably dissymmetric, and are more preferably selected from the group
consisting of
cysteamine, cysteine and derivatives thereof, even more preferably from the
group
consisting of cysteamine and cysteine.
The preferred class of compounds according to the present invention has the
general
formula (I):
D L Z B Z G1
G1 G1 (I)
The precise meaning of D, L, B, Z and G1 is disclosed in the detailed
description section
below.
The compounds of the present invention exhibit excellent Exhaustion (E) and
Fixation (F)
values and also provide good results in terms of light fastness, wet and diy
crock
resistance, perspiration, dye-transfer staining and wash fastness. In
addition, the
compounds of the present invention provide significantly more intense dyeing,
i.e. greater
colour intensity in the dyed substrate than comparative dyeings with
commercially
available reactive dyes applied at equivalent depth of shades.
Detailed Description of the Invention
As used herein the term "reactive dye" means a dye containing one or more
reactive
groups capable of forming covalent bonds with the substrate to be dyed, or a
dye that
forms such a reactive group in situ.
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Preferred compounds according to the present invention have the following
formula (I)
D L Z B Z G1
G1 G1 (I)
The precise meaning of D, L, B, Z and G1 is disclosed below.
Chromophore Moie ,tar (D)
The reactive dye compounds herein can comprise one or more chromophore
moieties D.
In reactive dye compounds comprising two or more chromophore moieties these
can be
the same or different. Preferably the reactive dye compounds herein comprise
from one to
six chromophore moieties, more preferably from one to three chromophore
moieties.
Any chromophore moieties suitable for use for dyeing substrates can be used in
the
present invention. The teen cluomophore as used herein means any photoactive
compound and includes any coloured or non-coloured light absorbing species,
e.g.
fluorescent brighteners, UV absorbers, IR absorbing dyes. The term chromophore
as used
herein also includes organic radical such as (3-sulphatoethylsulphonyl
benzene, vinyl
sulphonyl benzene, chloroethylsulphonyl benzene, (3-S-thiosulphatoethyl
sulphonyl
benzene, di(aminoethylsulphonyl) benzene provided that the reactive dye
compound
contains at least one other chromophore group.
Suitable chromophore moieties for use in the dye compounds herein include the
radicals
of monoazo, diazo or polyazo dyes, or heavy metal complex azo dyes derived
therefrom,
anthraquinone, phthalocyanine, formazan, azomethine, dioxazine, phenazine,
stilbene,
triphenylmethane, xanthene, thioxanthene, nitroaryl, naphthoquinone,
pyrenequinone or
perylenetetracarbimide dyes.
Other suitable chromophore moieties for use in the dye compounds herein
include those
disclosed in EP-A-0,735,107 (Ciba-Geigy), incorporated herein by reference,
including
the radicals described therein which contain substituents customary for
organic dyes,
such as sulphonate substituents which enhance the water-soluble properties of
the dye
compound.
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Examples of chromophore D moieties for use herein are polysulphonated azo
chromophores such as those present in ProcionTM dyes commercially available
from
BASF. Typical chromophores D are exempliEed by those in ProcionTM Red MX-8B,
ProcionTM Yellow MX-8G, ProcionTM Yellow MX-3R and ProcionTM Blue MX-2G.
C1
S03H OH
N=N / \ N
C1
\
H03S S03H
1 o ProcionT"' Red MX-8B
,ct
N--~~
N=N ~ ~ NH~ N
\N
C1
S03H 1~
C=O
NHS
ProcionT"" Yellow MX-3R
S03H S03H Cl
NH2 OH N
N / \ N N ~'~ ~~ \\N
N
HO S \ / ~ Cl
H03S ~ ~S03H
ProcionT"~ Blue MX-2G
Conveniently the chromophoric part may be represented as D, thus these dyes
can be
represented by:
~~N~GI
--~N~ ~\~N
C1
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Other suitable chromophores are present in DrimalanTM and DrimareneTM dyes
commercially available from Clariant and LevafixTM dyes commercially available
from
DyStar.
Linking Moiety (L)
The prefeiTed compounds herein further comprise a linking moiety L that links
each
multi-bonding moiety Z (such as nitrogen-containing heterocycles) to each
chromophore
moiety D. Any linking moiety suitable for use in dyeing substrates can be used
in the
presentinvention.
Preferably the linking moiety is selected from the group consisting of -NR-, -
C(O)NR-,
NRSO~~ -(CH~)k- and -SOZ (CHZ)k- wherein R is H or Cl-Cq. alkyl which can be
substituted by halogen, preferably fluorine or chlorine, hydroxyl, cyano, C1-
C4 alkoxy,
G2-CS alkoxycarbonyl, carboxyl, sulfamoyl, sulfo or sulfato and wherein k is
an integer
with a value between 1 and 4. When the linking moiety is dissymmetric (such as
C(O)NR-, -NRSOz-), the D and Z moieties can be linked to any side of the
linking
moiety. When Z is a triazine or pyrimidine, a preferred linking moiety is NR,
preferably
where R is H or Cl-C4 alkyl, more preferably where R is H or CH3, especially
H. When
Z is quinoxaline or phthalazine, a preferred linking moiety is -NR(C=O)-,
where R is H
or G1-C4 al)'-yl, more preferably where R is H or CH3, especially H.
Mufti-bondin _ moiety
The mufti-bonding moieties Z are functionally defined as moieties forming
covalent
bonds with at least,3 other moieties. In fornmla (I) to (IX) described below,
these other
moieties are selected from the group consisting of the linking moiety L
defined above,
bridging moiety B and moiety G1, which are defined hereafter. The exact nature
of the
moieties to which the Z moiety bonds depends on the position of the moiety Z
inside the
reactive-dye molecule as described in the general formula (I) or in the other
preferred
formula (II) to (IX). The number of mufti-bonding moieties Z in the reactive
dyes of
formula (II) to (IX) of the present invention is at least 2, and for the
reactive dyes of
fornmla (I) it is at least three (the reactive dye compounds of formula (I)
comprise at least
one group G2, defined below).
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In one reactive dye molecule, if there is two or more mufti-bonding moieties Z
these can
be the same or different.
Preferred Z moieties are selected from the group consisting of nitrogen (N),
- CH - CH2 - and aromatic compounds. Especially preferred are aromatic N-
heterocycles and aromatic compounds activated by elech~on withdrawing groups.
When Z is - CH - CH2 - ~ there is no preference to which carbon atom
(primary or secondary) the other moieties (e.g. L, B and G1) are connected.
Preferably, the Z moieties herein comprise at least one aromatic compound.
More
preferably all Z moieties are selected from aromatic compounds, especially
nitrogen
containing heterocycles. Suitable nitrogen containing heterocycles for use
herein include
monocyclic, bicyclic or polycyclic, unsaturated heterocycles containing at
least one
nitrogen heteroatom. When monocyclic rings are used, they are preferably
selected from
unsaturated rings having from about 3 to about 7 ring atoms, especially 5 or 6
ring atoms,
comprising from about 1 to about 3 nitrogen heteroatoms, preferably 2 or 3
nitrogen
heteroatoms. When bicyclic heterocycles are used, they preferably comprise an
unsaturated nitrogen containing heterocycle having 3 to 7 ring atoms,
preferably an
unsaturated nitrogen containing heterocycle having 5 or 6 ring atoms
comprising 1 or 2
nitrogen atoms, fused to a 5 to 7 membered carbocycle preferably. a 6-membered
unsaturated carbocycle. When bicyclic heterocycles are used, the other
moieties (e.g. L, B
and G 1 ) are preferably attached to the nitrogen containing heterocyclic
ring.
Preferred for use herein are 5 or 6 membered unsaturated nitrogen containing
monocyclic
heterocyclic rings comprising 2 or 3 nitrogen heteroatoms or bicyclic rings
containing a 5
or 6 membered unsaturated heterocyclic ring containing 2 nitrogen heteroatom
fused to a
6 membered unsaturated carbocycle.
Examples of suitable heterocycles for use herein include, but are not
necessarily limited
to triazine, pyrimidine, quinoxaline, pyrimidinone, phthalazine, pyridazone
and pyrazine.
Preferred for use in the compounds herein are triazine, pyrimidine and
quinoxaline.
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Aromatic compounds activated by electron withdrawing groups such as NO, NOz,
CN,
CHO, SOZMe, NMe3+, CF3, COOH, COO-C1-C4 allyl, S03 , preferably NO or NOZ, are
also suitable. An example of a suitable activated benzene ring is
NOZ
NO~
In addition to the bonding to L, B and G1, a Z moiety can be optionally bonded
to other
moieties such as one or more leaving group Y defined below.
Leavin~arou~Y
The reactive dyes of the present invention comprise at least one leaving group
Y. The
function of the leaving group Y is to be substituted during the dyeing process
by a
substituting nucleophilic group on the surface of the substrate. The covalent
bond fornled
after the substitution accounts for the stability of the color on the
substrate after the
dyeing process is completed. Therefore reactive dyes preferably contain more
than one
leaving group. In the case of cellulosic fibers, the substitution process is
usually carried
out in alkaline condition (pH > 8) in order to generate a sufficient
concentration of
nucleophilie cellulosate anions.
All groups capable of being substituted in the condition of the dyeing process
are
suitable. Examples of leaving groups are -Cl, -Br, -F, -I, -S03H, -OS03H, -
SS03H, -O-
C6H4-S03H, -OCO-CH3, -OP03H2, -OCO-C6H5, -OSOZ C,-C4 alkyl, -OSOZ-N(C,-C4
alkyl)Z,
O
COOH
O ~ ~ COOH
,
and quaternized nitrogen derivatives.
Preferred leaving groups Y are selected from the group consisting of -Cl, -Br,
-F and -
OS03H, more preferably from the group consisting of -Cl and -F when Y is
bonded to an
N-containing heterocycle and -Br when Y is bonded to
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- CH - CH2 -
Examples of suitable quaternized nitrogen derivatives are described in
W099/51684,
Brock et al. Particularly preferred quaternized nitrogen derivatives for use
herein are
nicotinate, diazabicyclooctane (DABCO), dimethylaminobetaine and
isonicotinate,
especially nicotinate.
In one reactive dye compound comprising more than one leaving group Y, these
can be
the same or different.
Group G 1
G 1 is selected from Y (leaving group as described above) and -B-G2. The
function of
G1 is to increase the mufti-functionality of the reactive dye molecule by
either providing
a leaving group Y or a group G2 that comprises a mufti-bonding group Z. G2 is
defined
hereafter. In reactive dye compounds comprising two or more groups G1, these
can be the
same or different.
Gro ~ G2
G~ is selected from
Z L D,
L
D
Z L D, and
Y
Z I'
~r
9

CA 02449050 2003-11-28
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The function of G2 is to increase the mufti-functionality of the reactive dye
compound by
increasing the number of leaving groups Y or chromophore moieties D. In
reactive dye
compounds comprising two or more groups G2, these can be the same or
different.
Brid_i~n ng ioiety B
The function of the bridging moieties B is to provide a junction between two 2
groups.
The bridging moieties are preferably selected from the group consisting of
S ,
- S - CR'2 - CR'2 - N - , and
R"
- S - CR'2 - CR'2
wherein R' is selected from the group consisting of H, C1-C10 alkyl group, C1-
C10
carboxylic acid and sulphonate, preferably H, and
wherein R" is selected from the group consisting of H, C1-C4 alkyl group and
- CR'~ - CR'~ S - G? .
R' and R" can be the same or different inside a given bridging moiety.
Preferred bridging moieties are asymmetric, more preferably dissymmetric.
Asymmetric
as used herein means that the bridging moiety comprises at least t<vo
different functional
groups that have reacted to form covalent bonds with other functional group.
Dissymrnetric as used herein means that the bridging moiety comprises two
different
functional groups with different affinity for the Z moieties. Preferred
dissymmetric
bridging moieties are based on cysteamine or cysteine and have the fornmla:
- S - CR'~ - CR'2 - N -
R"
wherein R' and R" are as defined above. Even more preferred bridging moieties
are
cysteamine or cysteine:
- S - CH2 -' CH2 - NH-
cysteamine

CA 02449050 2003-11-28
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- S - CHZ - CH(COOH) - NH-
cysteine
It has now been found that asymmetric, preferably dissymmetric, bridging
moieties allow
a better control of the synthesis of reactive dye molecules. By choosing
parameters such
as the reaction temperature and pH, it is possible to control the number and
the vvay
bridging moieties attach to other moieties such as a mufti-bonding moiety Z.
It can also
be controlled by what end (the sulphur or the nihogen end in the case of
cysteamine or
cysteine) they will bond to a pauticular Z moiety.
In reactive dye compounds comprising two or more bridging moieties B, these
can be the
same or different.
Following fornmla (II) to (VI) below represent various embodiments of
preferred reactive
dyes according to formula (I) defined above.
Formula (VII), (VIII) and (IX) represent other preferred reactive dye
compounds
according to the present invention.
Preferred reactive dyes having the fornmla (II) below:
D L Z B Z Y
B Y
Z Zr
(a)
wherein
~ D is as defined in formula (I) above;
~ L is as defined in formula (I) above;
~ Z is as defined in fornmla (I) above;
~ Y is as defined in formula (I) above;
~ B is
11

CA 02449050 2003-11-28
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- S - CR'Z - CR'2 - N -
R..
a
wherein R' is selected from the group consisting of H, C1-C10 alkyl group, C1-
C 10 carboxylic acid and sulphonate, preferably H; and
R" is selected from the group consisting of H and C1-C4 alkyl group,
B preferably being NH CHz - CH2 - S - or
- ~ CHCOOH-CH2 - S ,
~ wherein when there is more than one D, L, Z, Y, R, R', R" or B group these
are
not necessarily the same;
and salts and esters thereof.
Preferred reactive dyes having the formula (III) below:
z B z G1
(III)
Y G1
wherein
~ D is as defined in formula (I) above;
~ L is as defined in formula (I) above;
~ Z is as defined in formula (I) above;
~ Y is as defined in formula (I) above;
~ G1 is as defined in formula (I) above;
~ G2 is as defined in formula (I) above;
~ B is
S - CR'' - CR'., - N -
R"
wherein R' is selected from the group consisting of H, C1-C10 alkyl group, C1-
C 10 carboxylic acid and sulphonate, preferably H; and
R" is selected from the group consisting of H and C1-C4 alkyl group,
12

CA 02449050 2003-11-28
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B preferably being - NH - CHz - CHZ - S - or
NH CHCOOH-CH2 - S ,
~ wherein when there is more than one D, R, R', R", L, Z, Y, G1, G2 or B group
these are not necessarily the same; and
~ wherein the reactive dye compound comprises at least one group G2;
and salts and esters thereof.
Preferred reactive dyes having the formula (IV) below:
D L Z B Z G1
G1 G1 (N)
wherein
~ D is as defined in formula (I) above;
~ L is as defined in formula (I) above;
~ Z is as defined in formula (I) above;
~ Y is as defined in formula (I) above;
~ G 1 is as defined in Formula (I) above;
~ G2 is as defined in Formula (I) above;
~ B is as defined in Formula (I) above;
~ wherein at least one, and preferably all, B is - S -,
~ wherein when there is more than one B, D, R, L, Z, Y, G 1 or G2 within the
same
molecule these are not necessarily the same; and
~ wherein the reactive dye compound comprises at least one group G2;
and salts and esters thereof.
PrefeiTed reactive dues having the formula (V) below:
D L Z B Z Gl
Y G1 (V)
13

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wherein
~ D is as defined in formula (I) above;
~ L is as defined in fornula (I) above;
~ 2 is as defined in fornula (I) above;
~ Y is as defined in fornmla (I) above;
~ G1 is as defined in Formula (I) above;
~ G2 is as defined in Formula (I) above;
~ B is a bridging group selected from the group consisting of
- S - CR'2 - CR'2 - N -
R~~ and
- S - CR'2 - CR'.,
wherein R" is selected from the group consisting of H, C1-C4 alkyl group and
- CR'., - CR'., - S G2 ; and
wherein R' is selected from the group consisting of H, C 1-C 10 alkyl group, C
1-
C10 carboxylic acid and sulphonate, preferably H,
~ wherein when there is more than one D, R, R', R", L, Z, Y, G1, G?, or B
group
these are not necessarily the same; and
~ wherein the reactive dye compound comprises at least one bridging group B
wherein R" is CR~2 - CR'2 S G2 ;
and salts and esters thereof.
14

CA 02449050 2003-11-28
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Preferred reactive dyes having the formula (VI) below:
D L CH CH2 B Z G'1
B
G1
Z G1
G1 (VI)
wherein
~ D is as defined in formula (I) above;
~ L is as defined in formula (I) above;
~ Z is as defined in fornmla (I) above
~ Y as defined in fornmla (I) above
~ G 1 is as defined in Formula (I) above;
~ G2 is as defined in Formula (I) above;
~ B is a bridging moiety, preferably selected from the group consisting of
- S-
- S - CR'2 - CR'2 - N - , and
R"
S - CR'., - CR'
wherein R" is selected from the group consisting of H, C1-C4 alkyl group and
CR'., - CR'2 - S G2
wherein R' is selected from the group consisting of H, C 1-C 10 alkyl group, C
1-
C 10 carboxylic acid and sulphonate, preferably H,
B preferably being NH r- CHz - CH2 - S or
~ CHCOOH-CH2 - S - ;

CA 02449050 2003-11-28
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~ wherein when there is more than one D, R, R', R", L, Z, Y, G1, G2 or B group
these are not necessarily the same;
and salts and esters thereof.
Other preferred reactive dies accordin tg o the present invention have the
fornmla (VII)
1 ..1 ... __ ..
~r
L B Z
Y
D\ ~r
\ L B Z
wherein
~ D is as defined in fornnila (I) above;
~ L is as defined in formula (I) above;
~ Z is as defined in formula (I) above;
~ Y is as defined in formula (I) above
~ B is selected from the group consisting of
- S - CR'~ - CR'Z - N - , and
R"
S - CR'., - CR'
wherein R" is selected from the group consisting of H and C1-C4 alkyl group;
and
wherein R' is selected from the group consisting of H, C1-C10 alkyl group, C1-
C10 carboxyylic acid and sulphonate, preferably H;
B preferably being NH CH2 - CH2 - S - or
NH CHCOOH-CH2 S ,
~ wherein each of R, R', R", L, Z, Y, or B are not necessarily the same;
and salts and esters thereof.
16

CA 02449050 2003-11-28
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Other preferred reactive dyes accordin tg o the present invention have the
formula (VIII):
n
D-NH Z S NH Z HN-D
S S
R NH R NH
Z Z
~' Y 1' Y (VIII)
wherein
~ D is as defined in forniula (I) above;
~ Z is as defined in formula (I) above;
~ Y is as defined in fornlula (I) above
~ R is selected from the group consisting of H, C,-C,o alkyl group, C,-G,~
carbo~.ylic acid and sulphonate, preferably H and COOH, more preferably H;
~ wherein each of D, R, Z and Y are not necessarily the same;
and salts and esters thereof.
Other prefeiTed reactive dues accordin tg o the present invention have the
formula (I~):
~T
NH Z
I Y
D-S02 S CR
Y
Z
1' (IX)
wlierein
~ D is as defined in fornmla (I) above;
~ Z is as defined in formula (I) above;
17

CA 02449050 2003-11-28
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~ I' is as defined in fornmla (I) above;
~ R is selected from the group consisting of H, C,-C,o alkyl group, C,-C,o
carboxylic acid and sulphonate, preferably H and COOH, more preferably H;
~ wherein each of Z or Y are not necessarily the same;
and salts and esters thereof.
1o Method of preparation
The present invention furthermore relates to processes for the preparation of
the dyes
herein. In general, reactive dye compounds according to the present invention
such as
those having the general fornmla (I) to (IX) can be prepared by reacting
suitable
precursors with one another, at least one of which contains a group D-L-Z,
wherein D, L
and Z are as defined above. Various methods of preparations as well as
different reactive
dye molecules will be exemplified hereafter. The person skilled in the art can
easily apply
the following general reactions and the specific reactions exemplified to
synthesize the
different dyes covered by the present invention and in particular according to
formula (I)
to (IX) but not specifically exemplified.
One method for synthesizing reactive dyes according to the present invention
using a
starting reactive dye compound and bridging moiety B comprises the steps of:
a) reacting said starting dye compound with said bridging group B and forming
one bond, and
b) reacting the second moiety of said bridging group B with a moiety Z.
B is preferably dissymmetric and more preferably has the following formula:
S - CR'2 - CR'., - N -
R"
wherein R' is selected from the group consisting of H, C 1-C 10 alkyl group, C
1-C 10
carboxylic acid and sulphonate, preferably H; and R" is selected from the
group
consisting of H and C1-C4 alkyl group.
More preferably at least one R' is COOH.
Steps a) and/or step b) are preferably repeated at least twice.
18

CA 02449050 2003-11-28
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Synthesis of reactive dyes according to formula (II)
A general 2-steps synthesis route for these compounds is illustrated in
Diagram 1 below.
The starting material is a chromophore dye linked to a multi-bonding moiety Z
comprising at least 2 leaving groups such as chlorine. These starting
materials are
commercially available or can be easily synthesized by the person skilled in
the art. The
first step of the reaction consists of the substitution of the two leaving
groups by two
bridging groups such as cysteamine. The second step of the reaction consists
of the
substitution of a Z multi-bonding moiety on the unreacted side of the two
bridging
moieties.
19

CA 02449050 2003-11-28
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Y
D L Z
2 HSCR'ZCR'2NH2
Y
SCR'~CR'ZNHZ
D L Z
( 1 ) SCR'~GR'2NH~
Y
2 Y Z
Y
I'
SCR''CR'.,NH Z
Y
D L Z I,
SCR'2CR'2NH Z
(2) Y
Diagram 1
Alternatively, it would be obvious for the person skilled in the art that the
dissymmetric
bridging moiety can be first reacted with the multi-bonding Z moiety. The
mercapto (-
SH) moiety is more reactive than the amino (-NHZ) moiety, therefore this will
lead to a
final reactive dye wherein the starting reactive dye is linked to the amino
moiety of the
bridging group instead of its mercapto moiety.
Synthesis of reactive dues according to formula (III)
A general 2-step synthesis route for these compounds is illustrated in Diagram
2 below.
The starting material is a chromophore dye linked to a multi-bonding moiety Z

CA 02449050 2003-11-28
WO 02/096995 PCT/US02/16420
comprising at least 2 leaving groups such as chlorine. These starting
materials are
commercially available or can be easily synthesized by the person skilled in
the art.
The first step of the reaction consists of the substitution of one of the
leaving group by an
asymmetric or dissymmetric bridging moiety B such as cysteamine. To avoid
multi-
substitution, the starting reactive dye and the bridging moiety B should be
introduced in
equimolar quantity and the temperature of the reaction sufficiently low. In
the second
step, two moles of the inteumediates obtained after the first step are reacted
with one mole
of a Z multi-bonding moiety to give the final reactive dye. The reactive dyes
according to
formula (III) have at least ? chromophore dye moieties and this synthesis can
be easily
adapted to obtain reactive dyes with two different chromophores by reacting
the multi-
bonding Z moiety to interniediates with different dye chromophores as is
exposed in the
following diagram.
Alternatively, the asymmetric bridging moiety B can be first reacted with the
multi-
bonding Z moiety. In the case of cysteamine, the mercapto (-SH) moiety is more
reactive
than the amino (-NHz) moiety. In the anal reactive dye, the starting reactive
dye is
therefore linked to the amino moiety of the bridging moiety instead of its
mercapto
moiety.
21

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When all starting reactive dues are the same:
Dia,Tram 2
y SCR'~CR'2NH2
HSCR'2CR'2NH~
D L Z ~ ~ D L Z .
Y Y (3)
SCR'~CR'2NH2 y
2 D L Z + Y Z'
Y y
SCR'., CR'2NH HNCR.,'C R.,'S
D L Z Z~ Z L D
Y Y
~' (4)
A third group (3) can be substituted on the Z' group to give a molecule
comprising 3 dye
moieties.
When the starting reactive dies are different:
The first step is repeated once for each different starting reactive dye. They
are
subsequently substituted on the Z' moiety. With two different starting
reactive dyes, the
anal compound is:
SCR'ZCR'.,NH HNCR~'CR.,'S
D1 L Z z' Z L DZ
Y Y
Y l5)
As usual, inside one reactive dye compound each of L, Z, R' and Y groups can
be the
same or different.
22

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Examples
The following examples serve to illustrate the compounds and compositions of
the
present invention.
The starting compounds and components given in the examples above are usually
used in
form of their sodium salts. The starting reactive dye compounds can be
purified by
conventional means from the cormnercially available reactive dyes mentioned in
the
examples below.
Examples 1, 2, 3, 4 and 5 exemplify reactive dye compounds according to
Formula (II).
Examples 6, 7 and S exemplify reactive dye compounds according to Formula
(III).
Example 9 exemplifies reactive dye compounds according to Formula (IV).
Examples 10, 11 and 12 exemplify reactive dye compounds according to Formula
(V).
Examples 13 and 14 exemplify reactive dye compounds according to Fornmla (VI).
Examples 15, 16, 17 and 1 S exemplify reactive dye compounds according to
Formula
(VII).
Example 1
Cysteamine hydrochloride (0.2 mol) was dissolved in water ( 150 ml) and the pH
of the
solution adjusted to 7.5 with the addition of solid sodium carbonate at
20°C. To this
solution was added slowly a solution of 0.1 mol of a dichloro-5-triazine dye,
ProcionTM
Yellow MX-3R dissolved in 300 ml water.
The nucleophilic substitution with the thiol started immediately resulting in
the fornlation
of compound 1 (a). The liberated HCl was continuously neutralized by additions
of
sodium carbonate. After 5-S hours this first-stage reaction was complete as
indicated by
stabilisation of the pH. At this stage the bis-cysteamine dye 1(a) was
isolated by reducing
the pH to 4; the solid dye was filtered off and washed with a sodium sulphate
solution
(20% w/w) to remove unreacted cysteamine.
The above reaction is summarized in the diagram below:
N C1
D-HN r20°C, pH-7.5 N SCHZCH.,NHZ
D-HN
N N
2 HSCHZCHZNHZ N N (la)
C1
SCHZCHZNHZ
23

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Cyanuric chloride (0.2 mol) was dissolved in acetone (400 ml) and to this
solution was
added slowly, with good stirring, an aqueous solution of 1(a) prepared above
(0.1 mol of
dye dissolved in 200 ml water at pH 7.5 - set with sodium carbonate). The
temperature
was maintained at 20°C. The reaction liberated hydrochloric acid and
the pH was
therefore maintained at 7.5 by portion wise additions of solid sodium
carbonate as
required. After 6 hours the pH stabilized indicating that the reaction was
complete.
Sodium sulphate was added to the solution to "salt out" the dye (1b) which was
filtered
and dried in a dessicator.
N SGH2CH~NH2 CI N Cl
D-HN
N N + N N
SCH2CH~NH., C1
°C
pH = 7.5
N
N SCH2CH2NH Cl
D HN
N N
N N
Cl
N
SCH2CH2NH C1
N N
Cl (1b)
Example 2:
15 The same procedure as in example 1 was followed except that cysteine
hydrochloride was
used instead of cysteamine hydrochloride to produce the dye (2b) below:
24

CA 02449050 2003-11-28
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COOH
N
N S HN Cl
D-HN
N N
N N
N C1
HN C1
N N
COOH
C1
The additional carboxylate groups present in the cysteine linkage means that
the aqueous
solubility of this dye is higher at pH values greater than 4. The use of such
dyes in pad-
batch, pad-steam or pad-bake processes requires high aqueous solubility (>80g
dW 3) and
thus the cysteine crosslinl: would provide excellent dyes for this purpose.
Example 3:
In this example a trichloropyrimidine dye, DrimareneTM Yellow X-4RNA
(Clariantl was
used instead of the ProcionTM MX dye as for example 1. The same synthesis
route was
used only for the difference that the temperature of the first stage of the
reaction was
30°C instead of ?0°C. The following diagram summarizes the
synthesis.

CA 02449050 2003-11-28
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N Cl
D HN
2 HSCH2CH.,NH2
,N
30° C
Gl pH = 7
N SCH.,CH2NH2
D-HN
,N (3a)
Cl
SCH2CH2NH.,
~0°C
N N pH 7.5
C1
C1 N Cl
N C1
N SCH2CH2NH
D-HN
N N
N
G1 C1
I N C1
SCH.,CH2NH
N N
C1 (3b)
26

CA 02449050 2003-11-28
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Exam 1p a 4:
In this example a ?,4-difluoro-5-chloro pyrimidine dye, DrimareneTM Golden
Yellow h-
2R (Clariant) was used as starting reactive dye.
N F
D-HN
2 HSCH2CHZNH2
N
Cl ~ 20°C
F pH 7
N SCH2CH2NH2
D-HN
N (4a)
SCH2CH~NHz
F N F
20°C
pH 7 2
N
C1
F
N
N SCHZCHzNH F
D-HN
N
i N Cl
I N F
SCHZCHZNH F
,N
C1
F (4b)
27

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Example 5:
In this example, the starting reactive dye was an amido quinoxaline dye. The
starting
material can be prepared by reacting a corresponding quinoxaline carbonyl
halide with a
dye comprising an amino group.
O
N Cl
D-HN C
+ 2 HSCH.,CHZNH.,
N C1
30°C
pH 7
O
II N SCH2CHZNH.,
D-HN C \
/ (5a)
N
SCH2CH2NH~
C1 N C1
20°C
N N pH 7
C1 ~ N C1
O NH
II N S N N
D-HN C \
C1
N S
N C1
NH
N~N
(5b)
C1
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Example 6:
Cyanuric chloride (2,4,6-trichloro-1,3,5-triazine) (0.1 mol) was dissolved in
acetone (200
ml). A solution of cysteamine hydrochloride (0.3 mol in 100 ml water) was
slowly added
to this solution. The pH of the solution was maintained at 7-8 by the addition
of solid
sodium carbonate. After 7 hours at 20°C the pH stabilized and compound
(6a)
precipitated.
Compound (6a) (0.1 mol) was dissolved in water (100 ml) by warming to
30°C at pH 6.
0.3 mol of Procion Yellow MX-3R dissolved in 300 ml water was slowly added.
The pH
was maintained at 6-7 by the addition of solid sodium carbonate. After 6
hours, the pH
stabilized indicating the formation of dye (6b).
The dye was "salted out" by the addition of sodium sulphate, filtered and
washed with an
almost saturated sodium sulphate aqueous solution. The dye was dried in a
dessicator.
C1 N Cl NH2CH2CH~S N SCHZCH.,NHz
+ 3HSCHZCH2NH2 ~
NON ~ o N~N
~0 C
pH 7-8
Cl SCH2CHZNHz
(6a)
29

CA 02449050 2003-11-28
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Cl N NH D
NON
C1
20°C - 30°C
pH 7
D NH ~ S
~N~~ S ~N~ ~ N NH D
IYNO NN IYNON
NON
C1 ~ S C1
NH
NON
N~ NH D (6b)
C1
Example 7:
This example illushates the synthesis of a reactive dye comprising 3 dye
chromophores.
The starting material was a dichlorotriazine reactive dye such as ProcionTM
Red MX-8B.
In the first stage of the reaction, an aqueous solution comprising 3 moles of
cysteamine
was slowly added to an aqueous solution of the starting dye (3 moles). In the
second stage
of the reaction 1 mole of cyanuric chloride dissolved in acetone was added.
One third of
the cyanuric chloride reacted at 0°C. When the pH stabilized, the
temperature was raised
at 40°C where the second third reacted. Finally the temperature was
raised to about 80°C
and the last third reacted. The pH was constantly maintained at 7.5 by the
addition of
Na2C03 to neutralize the production of HCl during the reaction.

CA 02449050 2003-11-28
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D ~ N Cl D NH N SCHZCH.,NHZ
20°C, pH 7
NO N + HSCHZCHzNH~ NO N
O (7a)
CI C1
D NH N SCH.,CHZNH~ C1 N CI
3 NO N + N ON
pH 7
Cl 1 ) 0 - 5°C CI
2) 40°C
3) SO°C
D NH
\ 'N"S NH"N' / S N NH D
IYNO~N INYO~N
NON
CI CNH CI
cab)
s
O
NON
ONONH D
CI
Example 8:
In this example, the starting material was a dichlorotriazine reactive dye
(ProcionT"'
Yellow MX-3R). In the first stage of the reaction, an aqueous solution
comprising 2
moles of cysteamine was slowly added to an aqueous solution of the starting
dye (2
moles). In the second stage of the reaction 1 mole of cyanuric chloride
dissolved in
acetone was added and the temperature kept at 0°C until the pH
stabilized. The
temperature was then raised at 40°C until the pH stabilized. The pH was
constantly
maintained at 7.5 by the addition of Na2C03 to neutralize the production of
HCl during
the reaction.
31

CA 02449050 2003-11-28
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D NH N Cl D NH
N~ SCHzCHzNH2
20°C, pH 7
N N HSCH.,CH2NH.,
NO N
Cl . CI (8a)
D-NH N SCHzCH.,NH., Cl N Cl
2 NON + NON
C1 C1
pH 7
1)0-5°C
2) 40°C
n NH~
D NH N S HN~N~ S N NH-D
YIN
N~ N N NON
(8b)
C1 C1 G1
32

CA 02449050 2003-11-28
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Exam 1p a 9:
This example illustrates the synthesis of a reactive dye according to formula
(IV). The
starting material for this example was a commercially available 1,3,5-triazine-
2,4,6-
trithiol trisodium salt (available from Degussa). 3 moles of starting reactive
dye (for
example ProcionT"' Yellow M~-3R) were slowly added to an alkaline solution of
1 mol
trimercapto-5-triazine (pH 9, 40°C). The pH was maintained at 9 by
addition of sodium
carbonate. The stabilization of the pH indicated the end of the reaction.
Na+ S- N S- Na+ D NH N CI
+ 3
NON NO N
S- Na CI
pH 9
40°C
C1 CI
N~N N~N
/ \N S S N/ \
D NH ~N~ NH D
NON
S
NON
~N~NH D 9
Cl ( )
33

CA 02449050 2003-11-28
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Exam 1p a 10:
This example illustrates the synthesis of a reactive dye according to formula
(IV). The
starting material was a commercially available N-(2-mercaptoethyl)cysteamine.
In the
first stage of the reaction, 2 mol of ProcionTM Red MX-8B were added to an
aqueous
solution of the dithiol at 20°C. The pH was maintained at 7.5 during
the reaction by
addition of NazC03. In the second stage of the reaction, one mole of cyanuric
chloride
(dissolved in acetone) was slowly added to the above aqueous solution. The pH
was
maintained at 7.5 (by addition of Na~C03) and the temperature at 15°C.
D ~ N C1
NH
+ 2
NO N
HS HS Cl
pH 7.5
20°C
H
N ~ N NH D
S
NON
S
~ C1
NI 'N
( 10a)
N ~Cl
D NH
C1 N G1 C1 N ~ C1
N~ N N N
Cl N~ N NH D
( l 0a)
pH 7.5 NON
15°C S
N ~ N C1
lOb
N~GI ( )
D
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CA 02449050 2003-11-28
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Example 11
This example illustrates the synthesis of a reactive dye according to formula
(V) having 3
chromophore moieties. The starting material is tri-2-mercapto-ethylamine
(TMEA).
TMEA is dissolved in water. 3 moles of ProcionTM Yellow MY3R for each mol of
TMEA
were added (pH 7.5). During all the reaction the pH and temperature were kept
at
respectively 7.5 (by addition of Na2C03) and 20°C. The dye was "salted
out" as described
previously after the pH stabilized.
HS D NH N Cl
+ 3
NO N
N Cl
pH 7; 20°C
HS HS
D NH N C1
N u" N
S
D N N N ~ D
N s1
NO N ~ ~ NON
Cl Cl ( 11 a)
Example 12:
This example illustrates the synthesis of a reactive dye according to formula
(V). The
starting material was 1-amino-diethyl-2,2'-bis-isothiouronium chloride. 3
moles of the 1
amino-diethyl-2,2'-bis-isothiouronium chloride were dissolved in water and the
pH
adjusted to 7.5. Cyanuric chloride (1 mol) dissolved in acetone was added
slowly at 5°C,
then when no more HCl was produced, the temperature was increased at
40°C. When the
pH stabilized again, the temperature was raised to 90°C. The pH is kept
at 7.5 during all
reaction by addition of Na2C03. In the second stage of the reaction, the
isothiouronium

CA 02449050 2003-11-28
WO 02/096995 PCT/US02/16420
moiety was hydrolyzed with dilute NaOH (added to the solution until pH 10.S is
reached). In the last stage, 6 moles of dye or mixtures of dyes dissolved in
acetone were
added at ?0°C (the pH is kept at 7.5°C by addition of Na2C03).
3 NH Cl N ~Cl
NO N
S=C(~2)2+,C1_ S C(NHZ)z+,CI
CI
pH 7.S
1 ) S°C
2) 40°C
3) 90°C
s=c(NHZ)2+,cr s=c(NH~>~+,cr
N \ 'N\ /N
_ ~IN'~~N
S=C(NH~)2+,Cl ~ S=C(NH~)~+,Cl-
N
s=c(~z>Z+,cl- s=c(NH~)Z+,cl- (
36

CA 02449050 2003-11-28
WO 02/096995 PCT/US02/16420
S SH
N \ 'N\ /N
NaOH INO NN ~ + 6 H2NCONH2
( 12a)
S
SH
N
SH SH (12b)
D NH N
C1 pH 7
~OO 20°C
N~N
TIC1
C1
N"N
N N
OO~S S N NH D
D ~ N
N \ 'N\ /N
D NH N ~ ~IN'O~N ~O N NH-D
~O~S S~ O
N N NON
N
CI C1
D ~ N S S ~N~ NOD
O~ N O
NYN \ /N
C1 ~IC'1
( 12c)
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Exam 1p a 13
This example illustrates the synthesis of a reactive dye according to formula
(VI) from a-
(3-dibromo-propionamido or a-bromoacrylamide starting dyes. Examples of such
starting
dyes can be bought from Ciba under the trademark LamasolTM. In this example, 1
mol of
LamasolTM Blue 3R (Ciba) was reacted with 2 moles of cysteamine at 30°C
and at pH 7.5.
When the reaction was complete, 2 moles of cyanuric chloride were added while
the pH
and temperature were kept at respectively 7.5 by addition of Na2C03 at
10°C.
D-HN-CO- ~ H-CH2 Br + 2 HSCHZCHZNH~
Br
pH 7.5
30°C
D-HN-CO-CH-CHI S NH2
S NH.,
- (13a)
C~~N~CI
pH 7.5 ~N'~~N
10°C
C1
~C1
D-HN-CO-CH-CHI ~NH --C~ N
- Cl N
C1
NH
N-
C1 (13b)
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Example 14:
This example is similar to example 13. 2,4,6-trifluoro-5-chloro-pyrimidine was
used
instead of cyanuric chloride. The other conditions are identical.
D-HN-CO-CH-CHz Br + 2 HSCHzCHZNH2
Br
pH 7.5
30°C
D-HN-CO-CH-GH~-S NHZ
S NHz
( 14a)
F N\ / F
pH 7.5 2 0O
10°C N
C1
F
F
N--C
D-HN-CO-CH-CH -~NH ON
2
F C1 F
S NH
14b
c1 F c >
Examples 15, 16, 17 and 18:
The following examples illustrate some reactive dye compounds according to
fornmla
(VII). The first step of the synthesis consists of the substitution or
addition on a starting
reactive dye of 2 leaving groups by two cysteamine derivatives. In the second
step of the
39

CA 02449050 2003-11-28
WO 02/096995 PCT/US02/16420
reaction, two activated N-heterocycles are reacted on the amino side of the
cysteamine
derivatives.
Ex. 15
GHZCI CH -5~~2
D/~ HS~NHa
D
~ 0
'CHZCI pH 7; 50 C ~HZ-SH NHz
(15a)
CI
N~ C1
Cl--C~ N ~NH
N cHz S -
CHZ SH ~2 ~ 1
/,. N
~1
D ~ D
'C:HZ SH ~2 pH 7; 20°C Cl
CHZ S
NH
N--
(15b) CI
Ex. 16
~ nn
~, 502 2 HS~NH~ ~ SOz S NH2
D
D
pH 7; 50°C
\SO2 SO2
( 16a)
U
Cl
N"~ Cl
2 Cl \O N N--
N NH N
S02 S
C1 ~ N
(16a) \ N Cl
pH 7~ SO.,
20°C '~ ~ N
N (16b)
Cl
Ex. 17

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WO 02/096995 PCT/US02/16420
NH- CO- CH=CH2 n
NH-CO -CH2
CH2
S
NH2
H
D S ~2 D
H 7' S0C
p
HN-CO -CH=CH2 NH-CO -CHI
CHZ
S
NH2
(
17a)
C1
C1
N
Cl--~ N
NH- CO-CH 2-CH2
S
HN
N
N
N
C1
C1 D ~
17 ~ C1
)
(
a
HN-CO-CH2-CH2 S NH--~
pH 7 N
20C
N
(I7b)
Cl
Ex. 18
HN CO-GH2-Cl HN GO-CH2-S
NH
~ 2 ', 2
~
/ /
HS
NH
, _Z
D D
pH 7; 50C
HN-CO CHI-Cl HN- CO
CHI-S
NH2
(18a)
C1
N Cl
2 Cl--CO N
N NH- CO-CH2 S
Cl /~ HN-C
N
N
(18a) , Cl
D Cl
pH 7,
20 ~- CO-CH2 S
C NH
N
N--C
C1
(18b)
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CA 02449050 2003-11-28
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Method of use
The dye compounds herein are suitable for dyeing and printing a wide variety
of
substrates, such as silk, leather, wool, polyamide, polyester fibers and
polyurethanes,
keratin fibres such as hair, and in particular cellulosic materials, such as
the natural
cellulose fibres, cotton, linen, hemp and the like, paper, and also cellulose
itself and
regenerated cellulose, and hydroxyl-containing fibres contained in blend
fabrics, for
example blends of cotton with polyester or polyamide fibres.
The reactive dye compounds of the present invention can be formulated in
various ways,
in particular in the form of a solid mixture, aqueous solutions and printing
pastes. Thus
according to the present invention there is provided a dye composition
comprising one or
more of the dye compounds described herein together with any carrier material
suitable
for use in a dye composition.
Preferred dye compositions herein comprise an acidic buffer material. Any
acidic buffer
suitable for use in dye compositions can be used herein. An example of a
suitable buffer
is a mixed phosphate buffer giving a potential aqueous solution pH of 5-
7,,preferably 6.5.
When the dye composition herein is in the forni of a paste a preferred
ingredient is a
thickening agent. Any suitable thickening agents suitable for use in dye
compositions can
be used herein.
In particular the dye compositions can be applied to cellulosic fibers
(usually 0.1 % to
10% dye on mass of fiber). It is necessary to use alkali in a axing step to
bring about
covalent bonding to the cellulosate anion. If applied to polyamides the dye is
preferably
applied at pH 3 - 6 at the boil.
When the dye composition is in the fornl of an aqueous solution or aqueous
gel/paste, the
dye composition preferably has a pH of about 5 or 6.
When the dye composition is being used for dyeing hair, the composition can
comprise
one or more of the compounds described herein either alone or in admixture
with other
well known hair dye compounds such as oxidative dyes, direct dyes, and the
like.
The dyeing and printing processes that can be used with the dyes herein are
conventional
processes which are well known and which have been widely described in the
technical
and patent literature. The dye compounds herein are suitable for dyeing both
by the
exhaust method (long liquor) and also by the pad-dyeing method, whereby the
goods are
impregnated with aqueous, salt-containing or salt-free dye solutions. In the
case of
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CA 02449050 2003-11-28
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cellulosic substrates the dye is fixed after an alkali treatment or in the
presence of alkali,
if appropriate with the application of heat. The dye compounds herein are also
suitable
for the cold pad-batch cellulosic ftber-dyeing method, after which the dye
together with
the alkali is applied to cellulosic fabric using the pad-mangle, batched on a
roller and then
fixed by storage at room temperature (usually at 4 - 24 hour s). After fixing,
the dyeings
or prints are thoroughly rinsed with cold and hot water, if appropriate with
the addition of
an agent acting as a dispersant and promoting the diffusion of the non-ftxed
portions.
Thus in accordance with another aspect of the present invention there is
provided a use of
the reactive dyes of the present invention for dyeing and printing substrates
such as
cotton, wool, nylon, silk, keratin, leather, paper and the like. The compounds
herein can
be used in methods of dyeing all of the substrates listed above by applying an
aqueous
solution of one or more of the reactive dyes of the present invention to the
substrate to be
dyed under suitable conditions of pH and temperature.
The following examples serve to illustrate the dyeing of fabric with the
reactive dyes
according to the present invention.
Example A:
The dye produced in example 1 was applied to cotton fabric by the standard
long-liquor
dyeing process. The dye bath was set with 2% (on weight of fibre or o.w.f.)
dye, 40g/1
sodium sulphate and the scoured cotton fabric; the temperature was raised to
50°C and
the fabric agitated in liquor at this temperature for 30 minutes. At this
stage sodium
carbonate 15g/1 was added and the fabric further agitated for another 30
minutes. The
bath was found to be almost water white i.e. the dyebath exhaustion was > 95
%.
The dyed sample was removed from the bath, rinsed in cold water and soaped off
at the
boil in an aqueous solution of the nonionic detergent SandozinTM NIE (? parts
per 1000);
soaping for 15 minutes at the boil removed hardly any colour. By measuring the
concentration of dye removed by the rinsing and soaping processes the degree
of dye
fixation could be measured; the Total Covalent Fixative Efficiency (%F)
related to the
dye originally applied was found to be 93%.
By way of comparison, an equivalent amount of ProcionTM fellow MX-3R was
applied
to cotton fabric in the presence of 80g/1 sodium sulphate (this dye showed
very poor
uptake on cotton or exhaustion if 40g/1 salt were to be used).
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The dyeings produced, following fixation with sodium carbonate, rinsing and
soaping off,
was very.weak compared to the dyeing produced with the dye of example 1 above;
when
Total Fixation Efficiency (%F) was calculated it was found to be only 38%. The
new
classes of dye according to the present invention are very efficient in giving
very high
levels of fixation even when dyeing cellulosic fibers from baths containing
low salt
concentrations (40g/1 sodium sulphate).
Example B:
The reactive dye (3b) obtained in example 3 was applied to cotton by the
method
described above. Deep yellow dyeings of Total Fixation Efficiency (%F) greater
than
90% were produced.
Example C:
The tri-monochloro-s-triazine dye prepared in example 7 was applied to cotton
fabric by
the following long-liquor dyeing process.
The dyebath was set with cotton fabric, 80g dm 3 sodium sulphate, 2% (owf)
dye. The
bath was raised to 80°C and dyeing continued at this temperature for 30
minutes; sodium
carbonate (20g/1) was added and dyeing continued for a further 30 minutes at
80°C. The
dyed fabric was removed from the exhausted bath, rinsed and 'soaped-off as
described in
Example A. A Total Fixation Efficiency of 91% was obtained.
Example D
The reactive dye compound (8b) prepared in example 8 was applied to cotton
fabric by
the method described above, but in this case only 2% dye (o.w.~) and 40g/1
sodium
sulphate were used. Total Fixation Efficiency was measured at 92%.
Example E
The reactive dye compound prepared in example 11 was applied by long liquor
dyeing to
cotton fabric: 3% dye (o.w.f.), 60g/1 Na,S04. The bath was raised to
80°C and dyeing
continued at this temperature for 30 minutes; sodium carbonate (20g/1) was
added and the
dyeing continued a further 30 minutes at 80°C. Cold water rinsing and
"soaping" at the
boil with non-ionic detergent (Sandozine NIE 2g/1) completes the process.
Excellent color
with deep shade was obtained. The Total Fixation Efficiency was 90%.
44