Note: Descriptions are shown in the official language in which they were submitted.
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COMPOSITION AND METHOD FOR BLEACHING A SUBSTRATE
FIELD OF INVENTION
This invention relates to compositions and methods for
catalytically bleaching substrates with atmospheric oxygen,
using a metal-ligand complex as catalyst, which compositions
are formulated as liquids. This invention also relates to a
method of treating textiles, such as laundry fabrics, using
a metal-ligand complex as catalyst whereby bleaching with
atmospheric oxygen is catalysed after the treatment, wherein
the treatment composition is formulated as a liquid.
BACKGROUND OF INVENTION
Peroxygen bleaches are well known for their ability to
remove stains from substrates. Traditionally, the substrate
is subjected to hydrogen peroxide, or to substances which
can generate hydroperoxyl radicals, such as inorganic or
organic peroxides. Generally, these systems must be
activated. One method of activation is to employ wash
temperatures of 60°C or higher. However, these high
temperatures often lead to inefficient cleaning, and can
also cause premature damage to the substrate.
A preferred approach to generating hydroperoxyl bleach
species is the use of inorganic peroxides coupled with
organic precursor compounds. These systems are employed for
many commercial laundry powders. For example, various
European systems are based on tetraacetyl ethylenediamine
(TAED) as the organic precursor coupled with sodium
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perborate or sodium percarbonate, whereas in the United
States laundry bleach products are typically based on sodium
nonanoyloxybenzenesulphonate (SNOBS) as the organic
precursor coupled with sodium perborate.
Precursor systems are generally effective but still exhibit
several disadvantages. For example, organic precursors are
moderately sophisticated molecules requiring multi-step
manufacturing processes resulting in high capital costs.
Also, precursor systems have large formulation space
requirements so that a significant proportion of a laundry
powder must be devoted to the bleach components, leaving
less room for other active ingredients and complicating the
development of concentrated powders. Moreover, precursor
systems do not bleach very efficiently in countries where
consumers have wash habits entailing low dosage, short wash
times, cold temperatures and low wash liquor to substrate
ratios.
Alternatively, or additionally, hydrogen peroxide and peroxy
systems can be activated by bleach catalysts, such as by
complexes of iron and the ligand N4Py (i.e. N, N-
bis(pyridin-2-yl-methyl)-bis(pyridin-2-yl)methylamine)
disclosed in W095/34628, or the ligand Tpen (i.e. N, N, N',
N'-tetra(pyridin-2-yl-methyl)ethylenediamine) disclosed in
W097/48787. These publications do not foresee a role in
providing storage stable liquid bleaching compositions even
if, according to these publications, molecular oxygen may be
used as the oxidant as an alternative to peroxide generating
systems.
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As discussed by N.J. Milne in J. of Surfactants and
Detergents, Vol 1, no 2, 253-261 (1998), it has long been
thought desirable to be able to use atmospheric oxygen (air)
as the source for a bleaching species. The use of
atmospheric oxygen (air) as the source for a bleaching
species would avoid the need for costly hydroperoxyl
generating systems. Unfortunately, air as such is
kinetically inert towards bleaching substrates and exhibits
no bleaching ability. Recently some progress has been made
in this area. For example, WO 97/38074 reports the use of
air for oxidising stains on fabrics by bubbling air through
an aqueous solution containing an aldehyde and a radical
initiator. A broad range of aliphatic, aromatic and
heterocyclic aldehydes is reported to be useful,
particularly para-substituted aldehydes such as 4-methyl-,
4-ethyl- and 4-isopropyl benzaldehyde, whereas the range of
initiators disclosed includes N-hydroxysuccinimide, various
peroxides and transition metal coordination complexes.
However, although this system employs molecular oxygen from
the air, the aldehyde component and radical initiators such
as peroxides are consumed during the bleaching process.
These components must therefore be included in the
composition in relatively high amounts so as not to become
depleted before completion of the bleaching process in the
wash cycle. Moreover, the spent components represent a
waste of resources as they can no longer participate in the
bleaching process.
Accordingly, it would be desirable to be able to provide a
bleaching system based on atmospheric oxygen or air that
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does not rely primarily on hydrogen peroxide or a
hydroperoxyl generating system, and that does not require
the presence of organic components such as aldehydes that
are consumed in the process. Moreover, it would be
desirable to provide such a bleaching system that is
effective in aqueous medium.
It may also be noted that the known art teaches a bleaching
effect only as long as the substrate is being subjected to
the bleaching treatment. Thus, there is no expectation that
hydrogen peroxide or peroxy bleach systems could continue to
provide a bleaching effect on a treated substrate, such as a
laundry fabric after washing and drying, since the bleaching
species themselves or any activators necessary for the
bleaching systems would be assumed to be removed from the
substrate, or consumed or deactivated, on completing the
wash cycle and drying.
It would be therefore also be desirable to be able to treat
a textile such that, after the treatment is completed, a
bleaching effect is observed on the textile. Furthermore,
it would be desirable to be able to provide a bleach
treatment for textiles such as laundry fabrics whereby
residual bleaching occurs in the presence of air when the
treated fabric has been treated and is dry. It would be
desirable for the residual bleaching of dry textiles to be
conducted irrespective of exposure to light.
A further disadvantage associated with conventional
bleaching compositions based on hydrogen peroxide or peroxy
systems such those containing organic peroxyacids is that
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the compositions tend to be chemically or physically
unstable in the presence of liquid solvents, carriers or
other liquid components such as surfactants, particularly
when formulated as aqueous compositions. Consequently, when
formulated as liquids, these bleaching compositions on the
one hand do not exhibit satisfactory storage stability,
resulting in a rapid loss of bleaching activity or in a loss
of structural integrity, for example phase separation, or
require the incorporation of additional stabilising systems
to minimise these effects with attendant disadvantages in
terms of cost or processing. Decomposition of a hydrogen
peroxide or peroxy liquid bleaching composition in a sealed
container leads to an increase in the internal pressure of
the sealed container. The increase in the internal
pressure leads to the possibility of the sealed container
rupturing in a dangerous manner. In the presence of
surfactants, decomposition of the hydrogen peroxide or
peroxy liquid bleaching composition leads to foaming of the
composition. On the other hand, liquid bleaching
compositions are conveniently dosed into containers for
storage or for use, or otherwise handled, and are desired by
the consumer, particularly in the United States of America.
It would therefore also be desirable to be able to provide a
bleaching composition in the form of a liquid, which is
chemically and physically stable, without at least some of
the disadvantages hitherto associated with liquid bleaching
compositions. It would furthermore be desirable to be able
to provide chemically and physically storage stable
detergent bleaching compositions or rinse conditioning
bleach compositions in the form of a liquid.
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Application WO00/29537, filed 9 November 1999, was published
after the filing date of the present application disclosing
theoretical examples of compositions for bleaching with a
transition metal complex in the absence of an added
peroxygen bleach. Application WO00/29537 has no evidence of
efficacy and includes two classes of ligands: some cross-
bridged macrocyclic ligands and some macrocyclic ligands.
The macrocyclic ligands are disclosed as manganese complexes
and are not found in the priority document of WO00/29537;
namely US serial number 60/108,292 filed 13 November 1998.
The theoretical examples given are for a heavy-duty granular
laundry detergent and heavy-duty liquid laundry detergent.
In both these examples the exemplified bleach catalyst is
5,12-dimethyl-1,5,8,12-tetra-bicyclo[6.6.2.]hexadecane
manganese (II) chloride. There are no examples
demonstrating any bleaching effect. The use of manganese
complexes in laundry applications is less preferred because
of dye/textile damage under specific conditions.
SUMMARY OF INVENTION
We have now found that it is possible to achieve a
chemically and physically stable bleaching composition in
the form of a liquid, by using an organic substance that
forms a complex which catalyses the bleaching of substrates
using atmospheric oxygen or air, and formulating the organic
substance in a liquid that is substantially devoid of
peroxygen bleach or a peroxy-based or -generating bleach
system. Moreover, we have found that these organic
substances can be formulated together with detergent or
rinse conditioning agents, in a liquid that is substantially
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devoid of peroxygen bleach or a peroxy-based or -generating
bleach system, to provide chemically and physically stable
detergent bleaching compositions or rinse conditioning
bleach compositions, in the form of a liquid.
Accordingly, in a first aspect, the present invention a
liquid bleaching composition comprising an organic substance
which forms a complex with a transition metal, the complex
catalysing bleaching of a substrate by atmospheric oxygen,
and a liquid carrier or solvent, wherein the composition is
substantially devoid of peroxygen bleach or a peroxy-based
or -generating bleach system. The composition is therefore
preferably insensitive or stable to catalase, which acts on
peroxy species.
In a second aspect, the present invention provides a method
of bleaching a substrate comprising applying to the
substrate a liquid bleaching composition that comprises an
organic substance which forms a complex with a transition
metal, the complex catalysing bleaching of the substrate by
atmospheric oxygen, and a liquid carrier or solvent, wherein
the composition is substantially devoid of peroxygen bleach
or a peroxy-based or -generating bleach system.
Furthermore, in a third aspect, the present invention
provides the use of an organic substance which forms a
complex with a transition metal, the complex catalysing
bleaching of a substrate by the atmospheric oxygen, as a
catalytic bleaching agent in a liquid bleaching composition
substantially devoid of peroxygen bleach or a peroxy-based
or -generating bleach system.
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We have also found that the liquid bleaching compositions in
accordance with the present invention are surprisingly
effective in catalysing bleaching of substrates by
atmospheric oxygen after treatment of the substrate.
Accordingly, in a fourth aspect, the present invention
provides a method of treating a textile by contacting the
textile with a liquid bleaching composition that comprises
an organic substance which forms a complex with a transition
metal, the complex catalysing bleaching by atmospheric
oxygen, and a liquid carrier or solvent, wherein the
composition is substantially devoid of peroxygen bleach or a
peroxy-based or -generating bleach system, whereby the
complex catalyses bleaching of the textile by atmospheric
oxygen after the treatment.
The present invention requires all or the majority of the
bleaching species in the liquid bleaching composition (on an
equivalent weight basis) to be derived from atmospheric
oxygen. Thus, the liquid composition will be made wholly or
substantially devoid of peroxygen bleach or a peroxy-based
or -generating bleach system. The organic substance is a
catalyst for the bleaching process and, as such, is not
consumed but can continue to participate in the bleaching
process. Since the bleaching system of the type used in the
liquid bleaching composition is catalytically activated and
the bleaching species is derived from atmospheric oxygen,
the present invention is advantageous in that it provides a
bleaching composition which is not only convenient to handle
by virtue of being in the form of a liquid, but which also
is both cost-effective and environmentally friendly.
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The liquid bleaching composition may be formulated as a
concentrated bleaching liquid for direct application to a
substrate, or for application to a substrate following
dilution, such as dilution before or during use of the
S liquid composition by the consumer or in washing apparatus.
The liquid bleaching composition can for example be
formulated as an aqueous medium, or so as to be dispersable
into an aqueous medium, and is therefore particularly
applicable to bleaching of laundry fabrics. Therefore,
whilst the composition and method according to the present
invention may be used for bleaching any suitable substrate,
the preferred substrate is a laundry fabric. Bleaching may
be carried out by simply leaving the substrate in contact
for a sufficient period of time with a bleach medium
constituted by or prepared from the liquid bleaching
composition. Preferably, however, the bleach medium on or
containing the substrate is agitated.
An advantage of the method according to the fourth aspect of
the invention is that, by enabling a bleaching effect even
after the textile has been treated, the benefits of
bleaching can be prolonged on the textile. Furthermore,
since a bleaching effect is conferred to the. textile after
the treatment, the treatment itself, such as a laundry wash
cycle, may for example be shortened.
The present invention also extends to a commercial package
comprising a liquid bleaching composition comprising a
ligand or complex as defined below together with
instructions for its use.
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The present invention also extends to use of a ligand or
complex as defined below in the manufacture of a liquid
bleaching composition, the bleaching composition
substantially devoid of peroxygen bleach or a peroxy-based
or peroxy-generating bleach system.
DETAILED DESCRIPTION OF THE INVENTION
The catalyst may comprise a preformed complex of a ligand
and a transition metal. Alternatively, the catalyst may
comprise a free ligand that complexes with a transition
metal already present in the water or that complexes with a
transition metal present in the substrate. The catalyst may
also be included in the form of a composition of a free
ligand or a transition metal-substitutable metal-ligand
complex, and a source of transition metal, whereby the
complex is formed in situ in the medium. It is preferred
that the catalyst is a pentadentate ligand or complex
thereof.
The ligand forms a complex with one or more transition
metals, in the latter case for example as a dinuclear
complex. Suitable transition metals include for example:
manganese in oxidation states II-V, iron II-V, copper I-III,
cobalt I-III, titanium II-IV, tungsten IV-VI, vanadium II-V
and molybdenum II-VI.
The transition metal complex preferably is of the general
formula:
~MaLxXn~ ~'m
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in which:
M represents a metal selected from Mn(II)-(III)-(IV)-
(V) , Cu(I) - (II) - (III) , Fe (II) - (III) - (IV) - (V) , Co (I) - (II) -
(III), Ti(II)-(III)-(IV), V(II)-(III)-(IV)-(V), Mo(II)-
(III) - (IV) - (V) - (VI) and W (IV) - (V) - (VI) , preferably from
Fe(II)-(III)-(IV)-(V);
L represents the ligand, preferably N,N-bis(pyridin-2-
yl-methyl)-1,1-bis(pyridin-2-yl)-1-aminoethane, or its
protonated or deprotonated analogue;
X represents a coordinating species selected from any
mono, bi or tri charged anions and any neutral molecules
able to coordinate the metal in a mono, bi or tridentate
manner;
Y represents any non-coordinated counter ion;
a represents an integer from 1 to 10;
k represents an integer from 1 to 10;
n represents zero or an integer from 1 to 10;
m represents zero or an integer from 1 to 20.
Preferably, the complex is an iron complex comprising the
ligand N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-1-
aminoethane. However, it will be appreciated that the
pretreatment method of the present invention may instead, or
additionally, use other ligands and transition metal
complexes, provided that the complex formed is capable of
catalysing stain bleaching by atmospheric oxygen. Suitable
classes of ligands are described below:
(A) Ligands of the general formula (IA):
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Z1-(Ql)\
T C-(Q3)-U
Z1-(Ql)/
( IA)
wherein
Z1 groups independently represent a coordinating group
selected from hydroxy, amino, -NHR or -N(R)2 (wherein R=C1_s-
alkyl), carboxylate, amido, -NH-C(NH)NH2, hydroxyphenyl, a
heterocyclic ring optionally substituted by one or more
functional groups E or a heteroaromatic ring optionally
substituted by one or more functional groups E, the
heteroaromatic ring being selected from pyridine,
pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole,
quinoline, quinoxaline, triazole, isoquinoline, carbazole,
indole, isoindole, oxazole and thiazole;
Q1 and Q3 independently represent a group of the
formula
5 7
c
a n
R6 R8
wherein
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> a+b+c > 1; a=0-5; b=0-5; c=0-5; n=0 or 1
(preferably n=0);
Y independently represents a group selected from -O-, -
5 S-, -SO-, -S02-, -C(O)-, arylene, alkylene, heteroarylene,
heterocycloalkylene, - (G) P-, -P (O) - and - (G) N- , wherein G
is selected from hydrogen, alkyl, aryl, arylalkyl,
cycloalkyl, each except hydrogen being optionally
substituted by one or more functional groups E;
R5, R6, R7, R8 independently represent a group selected
from hydrogen, hydroxyl, halogen, -R and -OR, wherein R
represents alkyl, alkenyl, cycloalkyl, heterocycloalkyl,
aryl, heteroaryl or a carbonyl derivative group, R being
optionally substituted by one or more functional groups E,
or R5 together with R6, or R7 together with R8, or
both, represent oxygen,
or R5 together with R7 and/or independently R6 together
with R8, or R5 together with R8 and/or independently R6
together with R7, represent C1_6-alkylene optionally
substituted by C1_4-alkyl, -F, -C1, -Br or -I;
T represents a non-coordinated group selected from
hydrogen, hydroxyl, halogen, -R and -OR, wherein R
represents alkyl, alkenyl, cycloalkyl, heterocycloalkyl,
aryl, arylalkyl, heteroaryl or a carbonyl derivative group,
R being optionally substituted by one or more functional
groups E (preferably T= -H, -OH, methyl, methoxy or benzyl);
U represents either a non-coordinated group T
independently defined as above or a coordinating group of
the general formula (IIA), (IIIA) or (IVA):
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-N~
(Q
(IIA)
(IIIA)
~,Ql)-Z1
-Q -(~)yT
(Ql)-Zl
(IVA)
wherein
Q2 and Q4 are independently defined as for Q1 and Q3;
Q represents -N(T)- (wherein T is independently defined
as above), or an optionally substituted heterocyclic ring or
an optionally substituted heteroaromatic ring selected from
pyridine, pyrimidine, pyrazine, pyrazole, imidazole,
benzimidazole, quinoline, quinoxaline, triazole,
isoquinoline, carbazole, indole, isoindole, oxazole and
thiazole;
Z2 is independently defined as for Z1;
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Z3 groups independently represent -N(T)- (wherein T is
independently defined as above);
Z4 represents a coordinating or non-coordinating group
selected from hydrogen, hydroxyl, halogen, -NH-C(NH)NH2, -R
and -OR, wherein R= alkyl, alkenyl, cycloalkyl,
heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative
group, R being optionally substituted by one or more
functional groups E, or Z4 represents a group of the general
formula (IIAa)
Z2--(~) ~(Ql)-Zl
/N -(~)- .C~-T
(QlrZ1
(IIAa)
and
1 < j < 4.
Preferably, Z1, Z2 and Z4 independently represent an
optionally substituted heterocyclic ring or an optionally
substituted heteroaromatic ring selected from pyridine,
pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole,
quinoline, quinoxaline, triazole, isoquinoline, carbazole,
indole, isoindole, oxazole and thiazole. More preferably,
Z1, Z2 and Z4 independently represent groups selected from
optionally substituted pyridin-2-yl, optionally substituted
imidazol-2-yl, optionally substituted imidazol-4-yl,
optionally substituted pyrazol-1-yl, and optionally
substituted quinolin-2-yl. Most preferred is that Z1, Z2
and Z4 each represent optionally substituted pyridin-2-yl.
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The groups Z1, Z2 and Z4 if substituted, are preferably
substituted by a group selected from C1_4-alkyl, aryl,
arylalkyl, heteroaryl, methoxy, hydroxy, nitro, amino,
carboxyl, halo, and carbonyl. Preferred is that Z1, Z2 and
Z4 are each substituted by a methyl group. Also, we prefer
that the Z1 groups represent identical groups.
Each Q1 preferably represents a covalent bond or C1-C4-
alkylene, more preferably a covalent bond, methylene or
ethylene, most preferably a covalent bond.
Group Q preferably represents a covalent bond or C1-C4-
alkylene, more preferably a covalent bond.
The groups R5, R6, R7, R8 preferably independently represent
a group selected from -H, hydroxy-Co-C2o-alkyl, halo-Co-CZO-
alkyl, nitroso, formyl-Co-CZO-alkyl, carboxyl-Co-C2o-alkyl and
esters and salts thereof, carbamoyl-Co-Czo-alkyl, sulfo-Co-
Czo-alkyl and esters and salts thereof , sulfamoyl-Co-CZO-
alkyl, amino-Co-C2o-alkyl, aryl-Co-CZO-alkyl, Co-Czo-alkyl,
alkoxy-Co-C8-alkyl, carbonyl-Co-C6-alkoxy, and Co-CZO-
alkylamide. Preferably, none of R5-R8 is linked together.
Non-coordinated group T preferably represents hydrogen,
hydroxy, methyl, ethyl, benzyl, or methoxy.
In one aspect, the group U in formula (IA) represents a
coordinating group of the general formula (IIA):
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-N~
(IIA)
According to this aspect, it is preferred that Z2 represents
an optionally substituted heterocyclic ring or an optionally
substituted heteroaromatic ring selected from pyridine,
pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole,
quinoline, quinoxaline, triazole, isoquinoline, carbazole,
indole, isoindole, oxazole and thiazole, more preferably
optionally substituted pyridin-2-yl or optionally
substituted benzimidazol-2-yl.
It is also preferred, in this aspect, that Z4 represents an
optionally substituted heterocyclic ring or an optionally
substituted heteroaromatic ring selected from pyridine,
pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole,
quinoline, quinoxaline, triazole, isoquinoline, carbazole,
indole, isoindole, oxazole and thiazole, more preferably
optionally substituted pyridin-2-yl, or an non-coordinating
group selected from hydrogen, hydroxy, alkoxy, alkyl,
alkenyl, cycloalkyl, aryl, or benzyl.
In preferred embodiments of this aspect, the ligand is
selected from:
1,1-bis(pyridin-2-yl)-N-methyl-N-(pyridin-2-
ylmethyl)methylamine;
1,1-bis(pyridin-2-yl)-N,N-bis(6-methyl-pyridin-2-
ylmethyl)methylamine;
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1,1-bis(pyridin-2-yl)-N,N-bis(5-carboxymethyl-pyridin-2-
ylmethyl)methylamine;
l,l-bis(pyridin-2-yl)-1-benzyl-N,N-bis(pyridin-2-
ylmethyl)methylamine; and
1,1-bis(pyridin-2y1)-N,N-bis(benzimidazol-2-
ylmethyl)methylamine.
In a variant of this aspect, the group Z4 in formula (IIA)
represents a group of the general formula (IIAa):
Z2-(~) / (Q1)-Z1
/N -(~)-~T
(Ql)-Zl
( I IAa )
In this variant, Q4 preferably represents optionally
substituted alkylene, preferably -CH2-CHOH-CHZ- or -CHz-CH2-
CH2-. In a preferred embodiment of this variant, the ligand
is:
/~
~/C-N~~N- ~-~H
wherein -Py represents pyridin-2-yl.
In another aspect, the group U in formula (IA) represents a
coordinating group of the general formula (IIIA):
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(IIIA)
wherein j is 1 or 2, preferably 1.
According to this aspect, each Q2 preferably represents -
(CHz)n- (n=2-4), and each Z3 preferably represents -N(R)-
wherein R = -H or C1_4-alkyl, preferably methyl.
In preferred embodiments of this aspect, the ligand is
selected from:
Py~ ~ ~Me Py~ ~ ,Me
H-C-N N Me-C-N N
PY PY
N N
Me Me
wherein -Py represents pyridin-2-yl.
In yet another aspect, the group U in formula (IA)
represents a coordinating group of the general formula
(IVA)
(~Ql)-Zl
-Q-(~)-~T
a o (Ql)-zl
(IVA)
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In this aspect, Q preferably represents -N(T)- (wherein T= -
H, methyl, or benzyl) or pyridin-diyl.
In preferred embodiments of this aspect, the ligand is
selected from:
PY\ I /PY PY\ /PY
Me-C-N- ~ Me Me0 /C-Q - ~ OMe
PY PY PY PY
PY\ /PY
HO-C-Q - ~ OH
PY PY
wherein -Py represents pyridin-2-yl, and -Q- represents
pyridin-2,6-diyl.
(B) Ligands of the general formula (IB):
R~ Q~
R -Q /N-~Q-N~-Q4 Ra
z 2 Qs
I
R3
(IB)
wherein
n = 1 or 2, whereby if n = 2, then each -Q3-R3 group is
independently defined;
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Rl, Rz, R3, R4 independently represent a group selected
from hydrogen, hydroxyl, halogen, -NH-C(NH)NH2, -R and -OR,
wherein R= alkyl, alkenyl, cycloalkyl, heterocycloalkyl,
aryl, heteroaryl or a carbonyl derivative group, R being
optionally substituted by one or more functional groups E,
Ql, Qa, Qa, Q4 and Q independently represent a group of
the formula:
5 7
b Y c
a n
R6 R$
wherein
5 > a+b+c > 1; a=0-5; b=0-5; c=0-5; n=1 or 2;
Y independently represents a group selected from -O-, -
S-, -SO-, -S02-, -C(O)-, arylene, alkylene, heteroarylene,
heterocycloalkylene, -(G)P-, -P(O)- and -(G)N- , wherein G
is selected from hydrogen, alkyl, aryl, arylalkyl,
cycloalkyl, each except hydrogen being optionally
substituted by one or more functional groups E;
R5, R6, R7, R8 independently represent a group selected
from hydrogen, hydroxyl, halogen, -R and -OR, wherein R
represents alkyl, alkenyl, cycloalkyl, heterocycloalkyl,
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aryl, heteroaryl or a carbonyl derivative group, R being
optionally substituted by one or more functional groups E,
or R5 together with R6, or R7 together with R8, or
both, represent oxygen,
or R5 together with R7 and/or independently R6 together
with R8, or R5 together with R8 and/or independently R6
together with R7, represent C,,_6-alkylene optionally
substituted by C1_4-alkyl, -F, -C1, -Br or -I,
provided that at least two of R1, R2, R3, R4 comprise
coordinating heteroatoms and no more than six heteroatoms
are coordinated to the same transition metal atom.
At least two, and preferably at least three, of R1, Rz, R3, R4
independently represent a group selected from carboxylate,
amido, -NH-C(NH)NHz, hydroxyphenyl, an optionally substituted
heterocyclic ring or an optionally substituted
heteroaromatic ring selected from pyridine, pyrimidine,
pyrazine, pyrazole, imidazole, benzimidazole, quinoline,
quinoxaline, triazole, isoquinoline, carbazole, indole,
isoindole, oxazole and thiazole.
Preferably, substituents for groups R1, Rz, R3, R4, when
representing a heterocyclic or heteroaromatic ring, are
selected from C1_4-alkyl, aryl, arylalkyl, heteroaryl,
methoxy, hydroxy, nitro, amino, carboxyl, halo, and
carbonyl.
The groups Q1, Q2, Q3, QQ preferably independently represent a
group selected from -CH2- and -CHzCH2- .
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Group Q is preferably a group selected from - (CHz) z-4-, -
CH2CH (OH) CHZ-,
optionally substituted by methyl or ethyl,
OH tV and
i i
wherein R represents -H or C1_4-alkyl.
Preferably, Q1, Qa, Qa, Q4 are defined such that a=b=0, c=1
and n=1, and Q is defined such that a=b=0, c=2 and n=1.
The groups R5, R6, R7, R8 preferably independently represent
a group selected from -H, hydroxy-Co-C2o-alkyl, halo-Co-Czo-
alkyl, nitroso, formyl-Co-C2o-alkyl, carboxyl-Co-C2o-alkyl and
esters and salts thereof, carbamoyl-Co-C2o-alkyl, sulfo-Co-
Czo-alkyl and esters and salts thereof, sulfamoyl-Co-C2o-
alkyl, amino-Co-CZO-alkyl, aryl-Co-Czo-alkyl, Co-CZO-alkyl,
alkoxy-Co-CB-alkyl, carbonyl-Co-C6-alkoxy, and Co-Czo-
alkylamide. Preferably, none of R5-R8 is linked together.
In a preferred aspect, the ligand is of the general formula
(IIB)
Ri Q~ Qa Ra
,N-Q-N
R2 Q2 Q3 R3
(IIB)
wherein
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Ql, Qa, Qa, QQ are defined such that a=b=0, c=1 or 2 and
n=1;
Q is defined such that a=b=0, c=2,3 or 4 and n=1; and
R1, R2, R3, R4, R7, R8 are independently defined as for
formula (I) .
Preferred classes of ligands according to this aspect, as
represented by formula (IIB) above, are as follows:
(i) ligands of the general formula (IIB) wherein:
R1, R2, R3, R4 each independently represent a
coordinating group selected from carboxylate, amido, -NH-
C(NH)NH2, hydroxyphenyl, an optionally substituted
heterocyclic ring or an optionally substituted
heteroaromatic ring selected from pyridine, pyrimidine,
pyrazine, pyrazole, imidazole, benzimidazole, quinoline,
quinoxaline, triazole, isoquinoline, carbazole, indole,
isoindole, oxazole and thiazole.
In this class, we prefer that:
Q is defined such that a=b=0, c=2 or 3 and n=1;
R1, R2, R3, R4 each independently represent a
coordinating group selected from optionally substituted
pyridin-2-yl, optionally substituted imidazol-2-yl,
optionally substituted imidazol-4-yl, optionally substituted
pyrazol-1-yl, and optionally substituted quinolin-2-yl.
(ii) ligands of the general formula (IIB) wherein:
R1, Rz, R3 each independently represent a coordinating
group selected from carboxylate, amido, -NH-C(NH)NH2,
hydroxyphenyl, an optionally substituted heterocyclic ring
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or an optionally substituted heteroaromatic ring selected
from pyridine, pyrimidine, pyrazine, pyrazole, imidazole,
benzimidazole, quinoline, quinoxaline, triazole,
isoquinoline, carbazole, indole, isoindole, oxazole and
thiazole; and
R4 represents a group selected from hydrogen, C1_zo
optionally substituted alkyl, C1_zo optionally substituted
arylalkyl, aryl, and C1_zo optionally substituted NR3+
(wherein R=C1_8-alkyl ) .
In this class, we prefer that:
Q is defined such that a=b=0, c=2 or 3 and n=1;
R1, Rz, R3 each independently represent a coordinating
group selected from optionally substituted pyridin-2-yl,
optionally substituted imidazol-2-yl, optionally substituted
imidazol-4-yl, optionally substituted pyrazol-1-yl, and
optionally substituted quinolin-2-yl; and
R4 represents a group selected from hydrogen, C1_lo
optionally substituted alkyl, C1_5-furanyl, C1_5 optionally
substituted benzylalkyl, benzyl, C1_5 optionally substituted
alkoxy, and C1_zo optionally substituted N+Me3.
(iii) ligands of the general formula (IIB) wherein:
R1, R4 each independently represent a coordinating group
selected from carboxylate, amido, -NH-C(NH)NHz,
hydroxyphenyl, an optionally substituted heterocyclic ring
or an optionally substituted heteroaromatic ring selected
from pyridine, pyrimidine, pyrazine, pyrazole, imidazole,
benzimidazole, quinoline, quinoxaline, triazole,
isoquinoline, carbazole, indole, isoindole, oxazole and
thiazole; and
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Rz, R3 each independently represent a group selected
from hydrogen, C1_zo optionally substituted alkyl, C1_zo
optionally substituted arylalkyl, aryl, and C1_zo optionally
substituted NR3+ (wherein R=C1_e-alkyl) .
In this class, we prefer that:
Q is defined such that a=b=0, c=2 or 3 and n=1;
R1, R4 each independently represent a coordinating group
selected from optionally substituted pyridin-2-yl,
optionally substituted imidazol-2-yl, optionally substituted
imidazol-4-yl, optionally substituted pyrazol-1-yl, and
optionally substituted quinolin-2-yl; and
Rz, R3 each independently represent a group selected
from hydrogen, C1_lo optionally substituted alkyl, C1_s-
furanyl, C1_5 optionally substituted benzylalkyl, benzyl, C1_5
optionally substituted alkoxy, and C1_zo optionally
substituted N+Me3.
Examples of preferred ligands in their simplest forms are:
N,N',N'-tris(3-methyl-pyridin-2-ylmethyl)-ethylenediamine;
N-trimethylammoniumpropyl-N,N',N'-tris(pyridin-2-ylmethyl)
ethylenediamine;
N-(2-hydroxyethylene)-N,N',N'-tris(pyridin-2-ylmethyl)-
ethylenediamine;
N,N,N',N'-tetrakis(3-methyl-pyridin-2-ylmethyl)-ethylene-
diamine;
N,N'-dimethyl-N,N'-bis(pyridin-2-ylmethyl)-cyclohexane-1,2-
diamine;
N-(2-hydroxyethylene)-N,N',N'-tris(3-methyl-pyridin-2-
ylmethyl)-ethylenediamine;
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N-methyl-N,N',N'-tris(pyridin-2-ylmethyl)-ethylenediamine;
N-methyl-N,N',N'-tris(5-ethyl-pyridin-2-ylmethyl)-
ethylenediamine;
N-methyl-N,N',N'-tris(5-methyl-pyridin-2-ylmethyl)-
ethylenediamine;
N-methyl-N,N',N'-tris(3-methyl-pyridin-2-ylmethyl)-
ethylenediamine;
N-benzyl-N,N',N'-tris(3-methyl-pyridin-2-ylmethyl)-
ethylenediamine;
N-ethyl-N,N',N'-tris(3-methyl-pyridin-2-ylmethyl)-
ethylenediamine;
N,N,N'-tris(3-methyl-pyridin-2-ylmethyl)-N'(2'-methoxy-
ethyl-1)-ethylenediamine;
N,N,N'-tris(1-methyl-benzimidazol-2-yl)-N'-methyl-
ethylenediamine;
N-(furan-2-yl)-N,N',N'-tris(3-methyl-pyridin-2-ylmethyl)-
ethylenediamine;
N-(2-hydroxyethylene)-N,N',N'-tris(3-ethyl-pyridin-2-
ylmethyl)-ethylenediamine;
N-methyl-N,N',N'-tris(3-methyl-pyridin-2-ylmethyl)ethylene-
1,2-diamine;
N-ethyl-N,N',N'-tris(3-methyl-pyridin-2-ylmethyl)ethylene-
1,2-diamine;
N-benzyl-N,N',N'-tris(3-methyl-pyridin-2-ylmethyl)ethylene-
1,2-diamine;
N-(2-hydroxyethyl)-N,N',N'-tris(3-methyl-pyridin-2-
ylmethyl)ethylene-1,2-diamine;
N-(2-methoxyethyl)-N,N',N'-tris(3-methyl-pyridin-2-
ylmethyl)ethylene-1,2-diamine;
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N-methyl-N,N',N'-tris(5-methyl-pyridin-2-ylmethyl)ethylene-
1,2-diamine;
N-ethyl-N,N',N'-tris(5-methyl-pyridin-2-ylmethyl)ethylene-
1,2-diamine;
N-benzyl-N,N',N'-tris(5-methyl-pyridin-2-ylmethyl)ethylene-
1,2-diamine;
N-(2-hydroxyethyl)-N,N',N'-tris(5-methyl-pyridin-2-
ylmethyl)ethylene-1,2-diamine;
N-(2-methoxyethyl)-N,N',N'-tris(5-methyl-pyridin-2-
ylmethyl)ethylene-1,2-diamine;
N-methyl-N,N',N'-tris(3-ethyl-pyridin-2-ylmethyl)ethylene-
1,2-diamine;
N-ethyl-N,N',N'-tris(3-ethyl-pyridin-2-ylmethyl)ethylene-
1,2-diamine;
N-benzyl-N,N',N'-tris(3-ethyl-pyridin-2-ylmethyl)ethylene-
1,2-diamine;
N-(2-hydroxyethyl)-N,N',N'-tris(3-ethyl-pyridin-2-
ylmethyl)ethylene-1,2-diamine;
N-(2-methoxyethyl)-N,N',N'-tris(3-ethyl-pyridin-2-
ylmethyl)ethylene-1,2-diamine;
N-methyl-N,N',N'-tris(5-ethyl-pyridin-2-ylmethyl)ethylene-
1,2-diamine;
N-ethyl-N,N',N'-tris(5-ethyl-pyridin-2-ylmethyl)ethylene-
1,2-diamine;
N-benzyl-N,N',N'-tris(5-ethyl-pyridin-2-ylmethyl)ethylene-
1,2-diamine; and
N-(2-methoxyethyl)-N,N',N'-tris(5-ethyl-pyridin-2-
ylmethyl)ethylene-1,2-diamine.
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More preferred ligands are:
N-methyl-N,N',N'-tris(3-methyl-pyridin-2-ylmethyl)ethylene-
1,2-diamine;
N-ethyl-N,N',N'-tris(3-methyl-pyridin-2-ylmethyl)ethylene-
1,2-diamine;
N-benzyl-N,N',N'-tris(3-methyl-pyridin-2-ylmethyl)ethylene-
1,2-diamine;
N-(2-hydroxyethyl)-N,N',N'-tris(3-methyl-pyridin-2-
ylmethyl)ethylene-1,2-diamine; and
N-(2-methoxyethyl)-N,N',N'-tris(3-methyl-pyridin-2-
ylmethyl)ethylene-1,2-diamine.
(C) Ligands of the general formula (IC):
Z3
Q3
Q1 Q2
Zz
(IC)
wherein
Z1, ZZ and Z3 independently represent a coordinating
group selected from carboxylate, amido, -NH-C(NH)NH2,
hydroxyphenyl, an optionally substituted heterocyclic ring
or an optionally substituted heteroaromatic ring selected
from pyridine, pyrimidine, pyrazine, pyrazole, imidazole,
benzimidazole, quinoline, quinoxaline, triazole,
isoquinoline, carbazole, indole, isoindole, oxazole and
thiazole;
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Q1, Qz, and Q3 independently represent a group of the
formula:
7
_ c
a n
R6 R8
5
wherein
5 > a+b+c > 1; a=0-5; b=0-5; c=0-5; n=1 or 2;
Y independently represents a group selected from -O-, -
S-, -SO-, -S02-, -C(O)-, arylene, alkylene, heteroarylene,
heterocycloalkylene, -(G)P-, -P(O)- and -(G)N- , wherein G
is selected from hydrogen, alkyl, aryl, arylalkyl,
cycloalkyl, each except hydrogen being optionally
substituted by one or more functional groups E; and
R5, R6, R7, R8 independently represent a group selected
from hydrogen, hydroxyl, halogen, -R and -OR, wherein R
represents alkyl, alkenyl, cycloalkyl, heterocycloalkyl,
aryl, heteroaryl or a carbonyl derivative group, R being
optionally substituted by one or more functional groups E,
or R5 together with R6, or R7 together with R8, or
both, represent oxygen,
or R5 together with R7 and/or independently R6 together
with R8, or R5 together with R8 and/or independently R6
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together with R7, represent C1_6-alkylene optionally
substituted by C1_4-alkyl, -F, -Cl, -Br or -I.
Z1, ZZ and Z3 each represent a coordinating group, preferably
selected from optionally substituted pyridin-2-yl,
optionally substituted imidazol-2-yl, optionally substituted
imidazol-4-yl, optionally substituted pyrazol-1-yl, and
optionally substituted quinolin-2-yl. Preferably, Z1, ZZ and
Z3 each represent optionally substituted pyridin-2-yl.
Optional substituents for the groups Z1, Zz and Z3 are
preferably selected from C1_4-alkyl, aryl, arylalkyl,
heteroaryl, methoxy, hydroxy, nitro, amino, carboxyl, halo,
and carbonyl, preferably methyl.
Also preferred is that Q1, Qz and Q3 are defined such that
a=b=0, c=1 or 2, and n=1.
Preferably, each Q1, Q2 and Q3 independently represent C1_4-
alkylene, more preferably a group selected from -CHz- and -
CHzCH2- .
The groups R5, R6, R7, R8 preferably independently represent
a group selected from -H, hydroxy-Co-CZO-alkyl, halo-Co-CZO-
alkyl, nitroso, formyl-Co-C2o-alkyl, carboxyl-Co-Czo-alkyl and
esters and salts thereof, carbamoyl-Co-C2o-alkyl, sulfo-Co-
CZO-alkyl and esters and salts thereof, sulfamoyl-Co-CZO-
alkyl, amino-Co-C2o-alkyl, aryl-Co-C2o-alkyl, Co-Czo-alkyl,
alkoxy-Co-Ce-alkyl, carbonyl-Co-C6-alkoxy, and Co-C2o-
alkylamide. Preferably, none of R5-R8 is linked together.
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Preferably, the ligand is selected from tris(pyridin-2-
ylmethyl)amine, tris(3-methyl-pyridin-2-ylmethyl)amine,
tris(5-methyl-pyridin-2-ylmethyl)amine, and tris(6-methyl-
pyridin-2-ylmethyl)amine.
(D) Ligands of the general formula (ID):
R~
Q,\N~Q~N~Qz RZ
I I
Q~N~Q
I
Q3
R3
(ID)
wherein
R1, R2, and R3 independently represent a group selected
from hydrogen, hydroxyl, halogen, -NH-C(NH)NHz, -R and -OR,
wherein R= alkyl, alkenyl, cycloalkyl, heterocycloalkyl,
aryl, heteroaryl or a carbonyl derivative group, R being
optionally substituted by one or more functional groups E;
Q independently represent a group selected from CZ-3-
alkylene optionally substituted by H, benzyl or C1_8-alkyl;
Q1, Qz and Q3 independently represent a group of the
formula:
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7
b Y c
a n
R6 R8
wherein
5 5 > a+b+c > l; a=0-5; b=0-5; c=0-5; n=1 or 2;
Y independently represents a group selected from -O-, -
S-, -SO-, -SOZ-, -C(O)-, arylene, alkylene, heteroarylene,
heterocycloalkylene, -(G)P-, -P(O)- and -(G)N- , wherein G
is selected from hydrogen, alkyl, aryl, arylalkyl,
cycloalkyl, each except hydrogen being optionally
substituted by one or more functional groups E; and
R5, R6, R7, R8 independently represent a group selected
from hydrogen, hydroxyl, halogen, -R and -OR, wherein R
represents alkyl, alkenyl, cycloalkyl, heterocycloalkyl,
aryl, heteroaryl or a carbonyl derivative group, R being
optionally substituted by one or more functional groups E,
or R5 together with R6, or R7 together with R8, or
both, represent oxygen,
or R5 together with R7 and/or independently R6 together
with R8, or R5 together with R8 and/or independently R6
together with R7, represent C1_6-alkylene optionally
substituted by C1_4-alkyl, -F, -C1, -Br or -I,
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provided that at least one, preferably at least two, of
R1, Rz and R3 is a coordinating group.
At least two, and preferably at least three, of Rl, Rz and R3
independently represent a group selected from carboxylate,
amido, -NH-C(NH)NH2, hydroxyphenyl, an optionally substituted
heterocyclic ring or an optionally substituted
heteroaromatic ring selected from pyridine, pyrimidine,
pyrazine, pyrazole, imidazole, benzimidazole, quinoline,
quinoxaline, triazole, isoquinoline, carbazole, indole,
isoindole, oxazole and thiazole. Preferably, at least two
of R1, R2, R3 each independently represent a coordinating
group selected from optionally substituted pyridin-2-yl,
optionally substituted imidazol-2-yl, optionally substituted
imidazol-4-yl, optionally substituted pyrazol-1-yl, and
optionally substituted quinolin-2-yl.
Preferably, substituents for groups R1, R2, R3, when
representing a heterocyclic or heteroaromatic ring, are
selected from C1_4-alkyl, aryl, arylalkyl, heteroaryl,
methoxy, hydroxy, nitro, amino, carboxyl, halo, and
carbonyl.
Preferably, Q1, Qz and Q3 are defined such that a=b=0,
c=1,2,3 or 4 and n=1. Preferably, the groups Q1, Q2 and Q3
independently represent a group selected from -CH2- and -
CHZCH2- .
Group Q is preferably a group selected from -CH2CH2- and -
CHzCH2CHz- .
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The groups R5, R6, R7, R8 preferably independently represent
a group selected from -H, hydroxy-Co-Czo-alkyl, halo-Co-Czo-
alkyl, nitroso, formyl-Co-Czo-alkyl, carboxyl-Co-Czo-alkyl and
esters and salts thereof, carbamoyl-Co-Czo-alkyl, sulfo-Co-
Czo-alkyl and esters and salts thereof, sulfamoyl-Co-Czo-
alkyl, amino-Co-Czo-alkyl, aryl-Co-Czo-alkyl, Co-Czo-alkyl,
alkoxy-Co-C8-alkyl, carbonyl-Co-C6-alkoxy, and Co-Czo-
alkylamide. Preferably, none of R5-R8 is linked together.
In a preferred aspect, the ligand is of the general formula
(IID)
ctz R2
N
R1-Q~N~
(IID)
wherein R1, R2, R3 are as defined previously for R1, Rz, R3,
and Q1, Qz, Q3 are as defined previously.
Preferred classes of ligands according to this preferred
aspect, as represented by formula (IID) above, are as
follows:
(i) ligands of the general formula (IID) wherein:
R1, R2, R3 each independently represent a coordinating
group selected from carboxylate, amido, -NH-C(NH)NHz,
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hydroxyphenyl, an optionally substituted heterocyclic ring
or an optionally substituted heteroaromatic ring selected
from pyridine, pyrimidine, pyrazine, pyrazole, imidazole,
benzimidazole, quinoline, quinoxaline, triazole,
isoquinoline, carbazole, indole, isoindole, oxazole and
thiazole.
In this class, we prefer that:
R1, R2, R3 each independently represent a coordinating
group selected from optionally substituted pyridin-2-yl,
optionally substituted imidazol-2-yl, optionally substituted
imidazol-4-yl, optionally substituted pyrazol-1-yl, and
optionally substituted quinolin-2-yl.
(ii) ligands of the general formula (IID) wherein:
two of R1, R2, R3 each independently represent a
coordinating group selected from carboxylate, amido, -NH-
C(NH)NHz, hydroxyphenyl, an optionally substituted
heterocyclic ring or an optionally substituted
heteroaromatic ring selected from pyridine, pyrimidine,
pyrazine, pyrazole, imidazole, benzimidazole, quinoline,
quinoxaline, triazole, isoquinoline, carbazole, indole,
isoindole, oxazole and thiazole; and
one of R1, R2, R3 represents a group selected from
hydrogen, C1_zo optionally substituted alkyl, C1_zo optionally
substituted arylalkyl, aryl, and C1_zo optionally substituted
NR3+ (wherein R=C1_8-alkyl ) .
In this class, we prefer that:
two of R1, R2, R3 each independently represent a
coordinating group selected from optionally substituted
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pyridin-2-yl, optionally substituted imidazol-2-yl,
optionally substituted imidazol-4-yl, optionally substituted
pyrazol-1-yl, and optionally substituted quinolin-2-yl; and
one of R1, R2, R3 represents a group selected from
hydrogen, C1_lo optionally substituted alkyl, Cl_5-furanyl, C1_s
optionally substituted benzylalkyl, benzyl, C1_5 optionally
substituted alkoxy, and C1_zo optionally substituted N+Me3.
In especially preferred embodiments, the ligand is selected
from:
Pz3
~N~~ Pz3
N
Pz3J
Pzl
~N~~Pzl ~~N~~Qu
N N
PzlJ
Py PZl
~N~~Py ~N~~PzI
N N
Fx Fx
wherein -Et represents ethyl, -Py represents pyridin-2-yl,
Pz3 represents pyrazol-3-yl, Pzl represents pyrazol-1-yl,
and Qu represents quinolin-2-yl.
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(E) Ligands of the general formula (IE):
T1-[-N-(Q1)r ]s N-(Q2)g T2
I I
R1 R2
(IE)
wherein
g represents zero or an integer from 1 to 6;
r represents an integer from 1 to 6;
s represents zero or an integer from 1 to 6;
Q1 and Q2 independently represent a group of the
formula
IR6 ~t8
- [-C-] d- [-Y 1-] a [
R7 R9
wherein
5 > d+e+f > 1; d=0-5; e=0-5; f=0-5;
each Y1 independently represents a group selected from
-O-, -S-, -SO-, -SOZ-, -C(O)-, arylene, alkylene,
heteroarylene, heterocycloalkylene, -(G)P-, -P(O)- and -
(G)N- , wherein G is selected from hydrogen, alkyl, aryl,
arylalkyl, cycloalkyl, each except hydrogen being optionally
substituted by one or more functional groups E;
if s>1, each - [-N(R1) - (Q1) r-] - group is independently
defined;
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R1, R2, R6, R7, R8, R9 independently represent a group
selected from hydrogen, hydroxyl, halogen, -R and -OR,
wherein R represents alkyl, alkenyl, cycloalkyl,
heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative
group, R being optionally substituted by one or more
functional groups E,
or R6 together with R7, or R8 together with R9, or
both, represent oxygen,
or R6 together with R8 and/or independently R7 together
with R9, or R6 together with R9 and/or independently R7
together with R8, represent C1_6-alkylene optionally
substituted by C1_4-alkyl, -F, -C1, -Br or -I;
or one of R1-R9 is a bridging group bound to another
moiety of the same general formula;
T1 and T2 independently represent groups R4 and R5,
wherein R4 and R5 are as defined for R1-R9, and if g=0 and
s>0, R1 together with R4, and/or R2 together with R5, may
optionally independently represent =CH-R10, wherein R10 is
as defined for R1-R9, or
T1 and T2 may together (-T2-T1-) represent a covalent
bond linkage when s>1 and g>0;
if T1 and T2 together represent a single bond linkage,
Q1 and/or Q2 may independently represent a group of the
formula: =CH-[-Y1-]e CH= provided R1 and/or R2 are
absent, and R1 and/or R2 may be absent provided Q1 and/or Q2
independently represent a group of the formula:
=CH- [-Y1-] a CH= .
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The groups R1-R9 are preferably independently selected from
-H, hydroxy-Co-CZO-alkyl, halo-Co-C2o-alkyl, nitroso, formyl-
Co-C2o-alkyl, carboxyl-Co-C2o-alkyl and esters and salts
thereof, carbamoyl-Co-CZO-alkyl, sulpho-Co-C2o-alkyl and
esters and salts thereof, sulphamoyl-Co-CZO-alkyl, amino-Co-
CZO-alkyl, aryl-Co-CZO-alkyl, heteroaryl-Co-C2o-alkyl, Co-C2o-
alkyl, alkoxy-Co-C8-alkyl, carbonyl-Co-C6-alkoxy, and aryl-Co-
C6-alkyl and Co-CZO-alkyl amide .
One of R1-R9 may be a bridging group which links the ligand
moiety to a second ligand moiety of preferably the same
general structure. In this case the bridging group is
independently defined according to the formula for Q1, Q2,
preferably being alkylene or hydroxy-alkylene or a
heteroaryl-containing bridge, more preferably C1_6-alkylene
optionally substituted by C1_4-alkyl, -F, -C1, -Br or -I.
In a first variant according to formula (IE), the groups T1
and T2 together form a single bond linkage and s>1,
according to general formula (IIE):
N --( )g
(~) -R2
~---cQik~ S
(IIE)
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wherein R3 independently represents a group as defined for
R1-R9; Q3 independently represents a group as defined for
Q1, Q2; h represents zero or an integer from 1 to 6; and
s=s-1.
In a first embodiment of the first variant, in general
formula (IIE), s=1, 2 or 3; r=g=h=1; d=2 or 3; e=f=0;
R6=R7=H, preferably such that the ligand has a general
formula selected from:
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R1~ R1~ R1~
N~ N ~ N
N-R3 N-R3 N-R3
N NJ N
R2 R2 R2
R1 N R1 ~ n ~R2 R1 ~ ~ ~R2
N N N N
N-R3
C
N N
1o N R4~N N~R3 R4~ U ~R3
R2
R1~ ~/R2
N N
R5~N N~R3
~N~
I
R4
In these preferred examples, R1, R2, R3 and R4 are
preferably independently selected from -H, alkyl, aryl,
heteroaryl, and/or one of R1-R4 represents a bridging group
bound to another moiety of the same general formula and/or
two or more of R1-R4 together represent a bridging group
linking N atoms in the same moiety, with the bridging group
being alkylene or hydroxy-alkylene or a heteroaryl-
containing bridge, preferably heteroarylene. More
preferably, Rl, R2, R3 and R4 are independently selected
from -H, methyl, ethyl, isopropyl, nitrogen-containing
heteroaryl, or a bridging group bound to another moiety of
the same general formula or linking N atoms in the same
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moiety with the bridging group being alkylene or hydroxy-
alkylene.
In a second embodiment of the first variant, in general
formula (IIE), s=2 and r=g=h=1, according to the general
formula
/~
Ra.. /
~N~R2
~N Ql
R1
In this second embodiment, preferably R1-R4 are absent; both
Q1 and Q3 represent =CH-[-Y1-]e CH= ; and both Q2 and Q4
represent -CHZ- [-Y1-] ri CHZ-.
Thus, preferably the ligand has the general formula:
A ,
H
wherein A represents optionally substituted alkylene
optionally interrupted by a heteroatom; and n is zero or an
integer from 1 to 5.
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Preferably, R1-R6 represent hydrogen, n=1 and A= -CHz-, -
CHOH- , -CHIN (R) CH2- or -CHzCH2N (R) CH2CH2- wherein R represents
hydrogen or alkyl, more preferably A= -CH2-, -CHOH- or -
CHzCH2NHCHzCH2- .
In a second variant according to formula (IE), T1 and T2
independently represent groups R4, R5 as defined for R1-R9,
according to the general formula (IIIE):
R4-[-~1-(Q1) r ] g ~T-(Q2)9 R5
R1 R2
(IIIE)
In a first embodiment of the second variant, in general
formula (IIIE), s=1; r=1; g=0; d=f=1; e=0-4; Y1= -CHz-; and
R1 together with R4, and/or R2 together with R5,
independently represent =CH-R10, wherein R10 is as defined
for R1-R9. In one example, R2 together with R5 represents
=CH-R10, with R1 and R4 being two separate groups.
Alternatively, both R1 together with R4, and R2 together
with R5 may independently represent =CH-R10. Thus,
preferred ligands may for example have a structure selected
f rom
R2 R3 R2 R3
R6-~-~C H2~--~-R5 R6~C H2~R5
--N N=~ R~ N N~
R~ Ra R~ Ra
wherein n = 0-4.
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Preferably, the ligand is selected from:
-N~N=~ R4-N~N=~
R~ R2 R3 R~
wherein Rland R2 are selected from optionally substituted
phenols, heteroaryl-Co-C2o-alkyls, R3 and R4 are selected
from -H, alkyl, aryl, optionally substituted phenols,
heteroaryl-Co-Czo-alkyls, alkylaryl, aminoalkyl, alkoxy, more
preferably R1 and R2 being selected from optionally
substituted phenols, heteroaryl-Co-Cz-alkyls, R3 and R4 are
selected from -H, alkyl, aryl, optionally substituted
phenols, nitrogen-heteroaryl-Co-Cz-alkyls.
In a second embodiment of the second variant, in general
formula (IIIE), s=1; r=1; g=0; d=f=1; e=1-4; Y1= -C(R')(R"),
wherein R' and R" are independently as defined for R1-R9.
Preferably, the ligand has the general formula:
R1 R2 R5 R3 R4
R7- i Rg N-R9
R$ R10
The groups R1, R2, R3, R4, R5 in this formula are preferably
-H or Co-C2o-alkyl, n=0 or 1, R6 is -H, alkyl, -OH or -SH,
and R7, R8, R9, R10 are preferably each independently
selected from -H, Co-C2o-alkyl, heteroaryl-Co-Czo-alkyl,
alkoxy-Co-CB-alkyl and amino-Co-CZO-alkyl.
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In a third embodiment of the second variant, in general
formula (IIIE), s=0; g=1; d=e=0; f=1-4. Preferably, the
ligand has the general formula:
R2
R1\I/R3
R4'N~RS
This class of ligand is particularly preferred according to
the invention.
More preferably, the ligand has the general formula:
R1 \
N N
R2'N~R3
wherein R1, R2, R3 are as defined for R2, R4, R5.
In a fourth embodiment of the second variant, the ligand is
a pentadentate ligand of the general formula (IVE):
1 R2
R3--- C N
2 0 Rl R2
(IVE)
wherein
each R1 , R2 independently represents -R4-R5,
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R3 represents hydrogen, optionally substituted alkyl,
aryl or arylalkyl, or -R4-RS,
each R4 independently represents a single bond or
optionally substituted alkylene, alkenylene, oxyalkylene,
aminoalkylene, alkylene ether, carboxylic ester or
carboxylic amide, and
each RS independently represents an optionally N-
substituted aminoalkyl group or an optionally substituted
heteroaryl group selected from pyridinyl, pyrazinyl,
pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl,
pyrimidinyl, triazolyl and thiazolyl.
Ligands of the class represented by general formula (IVE)
are also particularly preferred according to the invention.
The ligand having the general formula (IVE), as defined
above, is a pentadentate ligand. By 'pentadentate' herein
is meant that five hetero atoms can coordinate to the metal
M ion in the metal-complex.
In formula (IVE), one coordinating hetero atom is provided
by the nitrogen atom in the methylamine backbone, and
preferably one coordinating hetero atom is contained in each
of the four R1 and Rz side groups. Preferably, all the
coordinating hetero atoms are nitrogen atoms.
The ligand of formula (IVE) preferably comprises at least
two substituted or unsubstituted heteroaryl groups in the
four side groups. The heteroaryl group is preferably a
pyridin-2-yl group and, if substituted, preferably a methyl-
or ethyl-substituted pyridin-2-yl group. More preferably,
the heteroaryl group is an unsubstituted pyridin-2-yl group.
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Preferably, the heteroaryl group is linked to methylamine,
and preferably to the N atom thereof, via a methylene group.
Preferably, the ligand of formula (IVE) contains at least
one optionally substituted amino-alkyl side group, more
preferably two amino-ethyl side groups, in particular 2-(N-
alkyl)amino-ethyl or 2-(N,N-dialkyl)amino-ethyl.
Thus, in formula (IVE) preferably R1 represents pyridin-2-yl
or RZ represents pyridin-2-yl-methyl. Preferably R2 or R1
represents 2-amino-ethyl, 2-(N-(m)ethyl)amino-ethyl or 2-
(N,N-di(m)ethyl)amino-ethyl. If substituted, RS preferably
represents 3-methyl pyridin-2-yl. R3 preferably represents
hydrogen, benzyl or methyl.
Examples of preferred ligands of formula (IVE) in their
simplest forms are:
(i) pyridin-2-yl containing ligands such as:
N,N-bis(pyridin-2-yl-methyl)-bis(pyridin-2-yl)methylamine;
N,N-bis(pyrazol-1-yl-methyl)-bis(pyridin-2-yl)methylamine;
N,N-bis(imidazol-2-yl-methyl)-bis(pyridin-2-yl)methylamine;
N,N-bis(1,2,4-triazol-1-yl-methyl)-bis(pyridin-2-
yl)methylamine;
N,N-bis(pyridin-2-yl-methyl)-bis(pyrazol-1-yl)methylamine;
N,N-bis(pyridin-2-yl-methyl)-bis(imidazol-2-yl)methylamine;
N,N-bis(pyridin-2-yl-methyl)-bis(1,2,4-triazol-1-
yl)methylamine;
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-1-
aminoethane;
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-phenyl-
1-aminoethane;
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N,N-bis(pyrazol-1-yl-methyl)-1,1-bis(pyridin-2-yl)-1-
aminoethane;
N,N-bis(pyrazol-1-yl-methyl)-1,1-bis(pyridin-2-yl)-2-phenyl-
1-aminoethane;
N,N-bis(imidazol-2-yl-methyl)-1,1-bis(pyridin-2-yl)-1-
aminoethane;
N,N-bis(imidazol-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-
phenyl-1-aminoethane;
N,N-bis(1,2,4-triazol-1-yl-methyl)-1,1-bis(pyridin-2-yl)-1-
aminoethane;
N,N-bis(1,2,4-triazol-1-yl-methyl)-1,1-bis(pyridin-2-yl)-2-
phenyl-1-aminoethane;
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyrazol-1-yl)-1-
aminoethane;
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyrazol-1-yl)-2-phenyl-
1-aminoethane;
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(imidazol-2-yl)-1-
aminoethane;
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(imidazol-2-yl)-2-
phenyl-1-aminoethane;
N,N-bis(pyridin-2-yl-methyl)-l,l-bis(1,2,4-triazol-1-yl)-1-
aminoethane;
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(1,2,4-triazol-1-yl)-1-
aminoethane;
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-1-
aminoethane;
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-1-
aminohexane;
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-phenyl-
1-aminoethane;
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N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-(4-
sulphonic acid-phenyl)-1-aminoethane;
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-
(pyridin-2-yl)-1-aminoethane;
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-
(pyridin-3-yl)-1-aminoethane;
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-
(pyridin-4-yl)-1-aminoethane;
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-(1-
alkyl-pyridinium-4-yl)-1-aminoethane;
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-(1-
alkyl-pyridinium-3-yl)-1-aminoethane;
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-(1-
alkyl-pyridinium-2-yl)-1-aminoethane;
(ii) 2-amino-ethyl containing ligands such as:
N,N-bis(2-(N-alkyl)amino-ethyl)-bis(pyridin-2-
yl)methylamine;
N,N-bis(2-(N-alkyl)amino-ethyl)-bis(pyrazol-1-
yl)methylamine;
N,N-bis(2-(N-alkyl)amino-ethyl)-bis(imidazol-2-
yl)methylamine;
N,N-bis(2-(N-alkyl)amino-ethyl)-bis(1,2,4-triazol-1-
yl)methylamine;
N,N-bis(2-(N,N-dialkyl)amino-ethyl)-bis(pyridin-2-
yl)methylamine;
N,N-bis(2-(N,N-dialkyl)amino-ethyl)-bis(pyrazol-1-
yl)methylamine;
N,N-bis(2-(N,N-dialkyl)amino-ethyl)-bis(imidazol-2-
yl)methylamine;
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N,N-bis(2-(N,N-dialkyl)amino-ethyl)-bis(1,2,4-triazol-1-
yl)methylamine;
N,N-bis(pyridin-2-yl-methyl)-bis(2-amino-ethyl)methylamine;
N,N-bis(pyrazol-1-yl-methyl)-bis(2-amino-ethyl)methylamine;
N,N-bis(imidazol-2-yl-methyl)-bis(2-amino-ethyl)methylamine;
N,N-bis(1,2,4-triazol-1-yl-methyl)-bis(2-amino-
ethyl)methylamine.
More preferred ligands are:
N,N-bis(pyridin-2-yl-methyl)-bis(pyridin-2-yl)methylamine,
hereafter referred to as N4Py.
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-1-
aminoethane, hereafter referred to as MeN4Py,
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-phenyl-
1-aminoethane, hereafter referred to as BzN4Py.
In a fifth embodiment of the second variant, the ligand
represents a pentadentate or hexadentate ligand of general
formula (VE):
R1R1N-W-NR1R2
(VE)
wherein
each R1 independently represents -R3-V, in which R3
represents optionally substituted alkylene, alkenylene,
oxyalkylene, aminoalkylene or alkylene ether, and
V represents an optionally substituted heteroaryl group
selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl,
imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and
thiazolyl;
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W represents an optionally substituted alkylene
bridging group selected from
-CHZCHz-, -CH2CH2CH2-, -CHzCH2CHzCH2-, -CHZ-C6H4-CH2-, -CH2-C6Hio-
CHZ- , and -CHZ-CloH6-CHZ- ; and
R2 represents a group selected from Rl, and alkyl, aryl
and arylalkyl groups optionally substituted with a
substituent selected from hydroxy, alkoxy, phenoxy,
carboxylate, carboxamide, carboxylic ester, sulphonate,
amine, alkylamine and N+(R4)3, wherein R4 is selected from
hydrogen, alkanyl, alkenyl, arylalkanyl, arylalkenyl,
oxyalkanyl, oxyalkenyl, aminoalkanyl, aminoalkenyl, alkanyl
ether and alkenyl ether.
The ligand having the general formula (VE), as defined
above, is a pentadentate ligand or, if R1=R2, can be a
hexadentate ligand. As mentioned above, by 'pentadentate'
is meant that five hetero atoms can coordinate to the metal
M ion in the metal-complex. Similarly, by 'hexadentate' is
meant that six hetero atoms can in principle coordinate to
the metal M ion. However, in this case it is believed that
one of the arms will not be bound in the complex, so that
the hexadentate ligand will be penta coordinating.
In the formula (VE), two hetero atoms are linked by the
bridging group W and one coordinating hetero atom is
contained in each of the three R1 groups. Preferably, the
coordinating hetero atoms are nitrogen atoms.
The ligand of formula (VE) comprises at least one optionally
substituted heteroaryl group in each of the three R1 groups.
Preferably, the heteroaryl group is a pyridin-2-yl group, in
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particular a methyl- or ethyl-substituted pyridin-2-yl
group. The heteroaryl group is linked to an N atom in
formula (VE), preferably via an alkylene group, more
preferably a methylene group. Most preferably, the
heteroaryl group is a 3-methyl-pyridin-2-yl group linked to
an N atom via methylene.
The group R2 in formula (VE) is a substituted or
unsubstituted alkyl, aryl or arylalkyl group, or a group Rl.
However, preferably RZ is different from each of the groups
R1 in the formula above. Preferably, RZ is methyl, ethyl,
benzyl, 2-hydroxyethyl or 2-methoxyethyl. More preferably,
Rz is methyl or ethyl.
The bridging group W may be a substituted or unsubstituted
alkylene group selected from -CHzCH2-, -CHZCHZCH2-, -CHzCH2CH-
ZCHz-, -CHZ-C6H4-CH2-, -CHZ-C6Hlo-CHZ-, and -CHz-Cloths-CHz_
(wherein -C6H4-, -C6Hlo-, -Cloths- can be ortho-, para-, or
meta-C6H4-, -C6Hlo-, -Cloths-) . Preferably, the bridging group
W is an ethylene or 1,4-butylene group, more preferably an
ethylene group.
Preferably, V represents substituted pyridin-2-yl,
especially methyl-substituted or ethyl-substituted pyridin-
2-yl, and most preferably V represents 3-methyl pyridin-2-
y1.
(F) Ligands of the classes disclosed in WO-A-98/39098 and
4d0-A-98/39406.
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The counter ions Y in formula (Al) balance the charge z on
the complex formed by the ligand L, metal M and coordinating
species X. Thus, if the charge z is positive, Y may be an
anion such as RCOO-, BPh4-, C104-, BF4-, PF6-, RS03-, RS04-, SO42-
, N03-, F-, Cl-, Br-, or I-, with R being hydrogen,
optionally substituted alkyl or optionally substituted aryl.
If z is negative, Y may be a common cation such as an alkali
metal, alkaline earth metal or (alkyl)ammonium cation.
Suitable counter ions Y include those which give rise to the
formation of storage-stable solids. Preferred counter ions
for the preferred metal complexes are selected from R'COO-,
C104-, BF4-, PF6-, RS03- (in particular CF3S03-) , RS04-, SO4a-,
N03-, F-, C1-, Br-, and I-, wherein R represents hydrogen or
optionally substituted phenyl, naphthyl or C1-C4 alkyl.
It will be appreciated that the complex (A1) can be formed
by any appropriate means, including in situ formation
whereby precursors of the complex are transformed into the
active complex of general formula (A1) under conditions of
storage or use. Preferably, the complex is formed as a
well-defined complex or in a solvent mixture comprising a
salt of the metal M and the ligand L or ligand L-generating
species. Alternatively, the catalyst may be formed in situ
from suitable precursors for the complex, for example in a
solution or dispersion containing the precursor materials.
In one such example, the active catalyst may be formed in
situ in a mixture comprising a salt of the metal M and the
ligand L, or a ligand L-generating species, in a suitable
solvent. Thus, for example, if M is iron, an iron salt such
as FeS04 can be mixed in solution with the ligand L, or a
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ligand L-generating species, to form the active complex.
Thus, for example, the composition may formed from a mixture
of the ligand L and a metal salt MXn in which preferably n=1-
5, more preferably 1-3. In another such example, the ligand
L, or a ligand L-generating species, can be mixed with metal
M ions present in the substrate or wash liquor to form the
active catalyst in situ. Suitable ligand L-generating
species include metal-free compounds or metal coordination
complexes that comprise the ligand L and can be substituted
by metal M ions to form the active complex according the
formula (A1) .
Throughout the description and claims generic groups have
been used, for example alkyl, alkoxy, aryl. Unless
otherwise specified the following are preferred group
restrictions that may be applied to generic groups found
within compounds disclosed herein:
alkyl: C1-C6-alkyl,
alkenyl: C2-C6-alkenyl,
cycloalkyl: C3-C8-cycloalkyl,
alkoxy: C1-C6-alkoxy,
alkylene: selected from the group consisting of: methylene;
1,1-ethylene; 1,2-ethylene; 1,1-propylene; 1,2-propylene;
1,3-propylene; 2,2-propylene; butan-2-ol-1,4-diyl; propan-2-
0l-1,3-diyl; and 1,4-butylene,
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aryl: selected from homoaromatic compounds having a
molecular weight under 300,
arylene: selected from the group consisting of: 1,2-
benzene; 1,3-benzene; 1,4-benzene; 1,2-naphthalene; 1,3-
naphthalene; 1,4-naphthalene; 2,3-naphthalene; phenol-2,3-
diyl; phenol-2,4-diyl; phenol-2,5-diyl; and phenol-2,-6-
diyl,
heteroaryl: selected from the group consisting of:
pyridinyl; pyrimidinyl; pyrazinyl; triazolyl, pyridazinyl;
1,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl;
imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl;
oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl,
heteroarylene: selected from the group consisting of:
pyridin-2,3-diyl; pyridin-2,4-diyl; pyridin-2,5-diyl;
pyridin-2,6-diyl; pyridin-3,4-diyl; pyridin-3,5-diyl;
quinolin-2,3-diyl; quinolin-2,4-diyl; quinolin-2,8-diyl;
isoquinolin-1,3-diyl; isoquinolin-1,4-diyl; pyrazol-1,3-
diyl; pyrazol-3,5-diyl; triazole-3,5-diyl; triazole-1,3-
diyl; pyrazin-2,5-diyl; and imidazole-2,4-diyl,
heterocycloalkyl: selected from the group consisting of:
pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl;
piperazinyl; hexamethylene imine; and oxazolidinyl,
amine: the group -N(R)2 wherein each R is independently
selected from: hydrogen; C1-C6-alkyl; C1-C6-alkyl-C6H5; and
phenyl, wherein when both R are C1-C6-alkyl both R together
may form an -NC3 to an -NC5 heterocyclic ring with any
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remaining alkyl chain forming an alkyl substituent to the
heterocyclic ring,
halogen: selected from the group consisting of: F; Cl; Br
and I,
sulphonate: the group -S(O)ZOR, wherein R is selected
from: hydrogen; C1-C6-alkyl; phenyl; C1-C6-alkyl-C6H5; Li;
Na; K; Cs; Mg; and Ca,
sulphate: the group -OS(O)20R, wherein R is selected from:
hydrogen; C1-C6-alkyl; phenyl; C1-C6-alkyl-C6H5; Li; Na; K;
Cs; Mg; and Ca,
sulphone: the group -S(O)ZR, wherein R is selected from:
hydrogen; C1-C6-alkyl; phenyl; C1-C6-alkyl-C6H5 and amine
(to give sulphonamide) selected from the group: -NR'2,
wherein each R' is independently selected from: hydrogen;
C1-C6-alkyl; C1-C6-alkyl-C6H5; and phenyl, wherein when both
R' are C1-C6-alkyl both R' together may form an -NC3 to an -
NC5 heterocyclic ring with any remaining alkyl chain forming
an alkyl substituent to the heterocyclic ring,
carboxylate derivative: the group -C(O)OR, wherein R is
selected from: hydrogen, C1-C6-alkyl; phenyl; C1-C6-alkyl-
C6H5, Li; Na; K; Cs; Mg; and Ca,
carbonyl derivative: the group -C(O)R, wherein R is
selected from: hydrogen; C1-C6-alkyl; phenyl; C1-C6-alkyl-
C6H5 and amine (to give amide) selected from the group:
NR'2, wherein each R' is independently selected from:
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hydrogen; C1-C6-alkyl; C1-C6-alkyl-C6H5; and phenyl, wherein
when both R' are C1-C6-alkyl both R' together may form an -
NC3 to an -NC5 heterocyclic ring with any remaining alkyl
chain forming an alkyl substituent to the heterocyclic ring,
phosphonate: the group -P(O)(OR)2, wherein each R is
independently selected from: hydrogen; C1-C6-alkyl; phenyl;
C1-C6-alkyl-C6H5; Li; Na; K; Cs; Mg; and Ca,
phosphate: the group -OP(O)(OR)2, wherein each R is
independently selected from: hydrogen; C1-C6-alkyl; phenyl;
C1-C6-alkyl-C6H5; Li; Na; K; Cs; Mg; and Ca,
phosphine: the group -P(R)2, wherein each R is
independently selected from: hydrogen; C1-C6-alkyl; phenyl;
and C1-C6-alkyl-C6H5,
phosphine oxide: the group -P(O)R2, wherein R is
independently selected from: hydrogen; C1-C6-alkyl; phenyl;
and C1-C6-alkyl-C6H5; and amine (to give phosphonamidate)
selected from the group: -NR'2, wherein each R' is
independently selected from: hydrogen; C1-C6-alkyl; C1-C6-
alkyl-C6H5; and phenyl, wherein when both R' are C1-C6-alkyl
both R' together may form an -NC3 to an -NC5 heterocyclic
ring with any remaining alkyl chain forming an alkyl
substituent to the heterocyclic ring.
Unless otherwise specified the following are more preferred
group restrictions that may be applied to groups found
within compounds disclosed herein:
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alkyl: C1-C4-alkyl,
alkenyl: C3-C6-alkenyl,
cycloalkyl: C6-C8-cycloalkyl,
alkoxy: C1-C4-alkoxy,
alkylene: selected from the group consisting of: methylene;
1,2-ethylene; 1,3-propylene; butan-2-ol-1,4-diyl; and 1,4-
butylene,
aryl: selected from group consisting of: phenyl;
biphenyl, naphthalenyl; anthracenyl; and phenanthrenyl,
arylene: selected from the group consisting of: 1,2-
benzene, 1,3-benzene, 1,4-benzene, 1,2-naphthalene, 1,4-
naphthalene, 2,3-naphthalene and phenol-2,6-diyl,
heteroaryl: selected from the group consisting of:
pyridinyl; pyrimidinyl; quinolinyl; pyrazolyl; triazolyl;
isoquinolinyl; imidazolyl; and oxazolidinyl,
heteroarylene: selected from the group consisting of:
pyridin-2,3-diyl; pyridin-2,4-diyl; pyridin-2,6-diyl;
pyridin-3,5-diyl; quinolin-2,3-diyl; quinolin-2,4-diyl;
isoquinolin-1,3-diyl; isoquinolin-1,4-diyl; pyrazol-3,5-
diyl; and imidazole-2,4-diyl,
heterocycloalkyl: selected from the group consisting of:
pyrrolidinyl; morpholinyl; piperidinyl; and piperazinyl,
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amine: the group -N(R)2, wherein each R is independently
selected from: hydrogen; C1-C6-alkyl; and benzyl,
halogen: selected from the group consisting of: F and Cl,
sulphonate: the group -S(O)ZOR, wherein R is selected
from: hydrogen; C1-C6-alkyl; Na; K; Mg; and Ca,
sulphate: the group -OS(O)ZOR, wherein R is selected from:
hydrogen; C1-C6-alkyl; Na; K; Mg; and Ca,
sulphone: the group -S(O)2R, wherein R is selected from:
hydrogen; C1-C6-alkyl; benzyl and amine selected from the
group: -NR'2, wherein each R' is independently selected
from: hydrogen; C1-C6-alkyl; and benzyl,
carboxylate derivative: the group -C(O)OR, wherein R is
selected from hydrogen; Na; K; Mg; Ca; C1-C6-alkyl; and
benzyl,
carbonyl derivative: the group: -C(O)R, wherein R is
selected from: hydrogen; C1-C6-alkyl; benzyl and amine
selected from the group: -NR'2, wherein each R' is
independently selected from: hydrogen; C1-C6-alkyl; and
benzyl,
phosphonate: the group -P(O)(OR)2, wherein each R is
independently selected from: hydrogen; C1-C6-alkyl, benzyl;
Na; K; Mg; and Ca,
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phosphate: the group -OP(O)(OR)2, wherein each R is
independently selected from: hydrogen; C1-C6-alkyl; benzyl;
Na; K; Mg; and Ca,
phosphine: the group -P(R)z, wherein each R is
independently selected from: hydrogen; C1-C6-alkyl; and
benzyl,
phosphine oxide: the group -P(O)R2, wherein R is
independently selected from: hydrogen; C1-C6-alkyl; benzyl
and amine selected from the group: -NR'2, wherein each R' is
independently selected from: hydrogen; C1-C6-alkyl; and
benzyl.
Other compounds or ligands forming complexes with transition
metals, and which are capable of catalysing bleaching by
atmospheric oxygen, are suitable as organic substances in
the liquid bleaching compositions of the present invention.
These include the classes of complexes of a transition metal
coordinated to a macropolycyclic ligand disclosed in WO-A-
98/39098 and WO-A-98/39406.
The liquid bleaching compositions according to the present
invention may be used for laundry cleaning, hard surface
cleaning (including cleaning of lavatories, kitchen work
surfaces, floors, mechanical ware washing etc.). As is
generally known in the art, bleaching compositions are also
employed in waste-water treatment, pulp bleaching during the
manufacture of paper, leather manufacture, dye transfer
inhibition, food processing, starch bleaching, sterilisation,
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whitening in oral hygiene preparations and/or contact lens
disinfection.
In the context of the present invention bleaching should be
understood as relating generally to the decolourisation of
stains or of other materials attached to or associated with a
substrate. However, it is envisaged that the present
invention can be applied where a requirement is the removal
and/or neutralisation by an oxidative bleaching reaction of
malodours or other undesirable components attached to or
otherwise associated with a substrate. Furthermore, in the
context of the present invention bleaching is to be understood
as being restricted to any bleaching mechanism or process that
does not require the presence of light or activation by light.
Thus, photobleaching compositions and processes relying on the
use of photobleach catalysts or photobleach activators and the
presence of light are excluded from the present invention.
In typical washing compositions the level of the organic
substance is such that the in-use level is from 0.05 ~.M to
50 mM, with preferred in-use levels for domestic laundry
operations falling in the range 1 to 100 ~,M. Higher levels
may be desired and applied in industrial bleaching
processes, such as textile and paper pulp bleaching.
Preferably, the aqueous medium has a pH in the range from pH
6 to 13, more preferably from pH 6 to 11, and most
preferably from 7 to 10.
The liquid bleaching composition of the present invention
has particular application in detergent formulations,
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especially for laundry cleaning. Accordingly, in another
preferred embodiment, the present invention provides a
liquid detergent bleach composition comprising a liquid
bleaching composition as defined above and additionally a
surface-active material, optionally together with detergency
builder. In addition, the liquid bleaching composition may
optionally contain soluble and non-soluble enzymes, enzyme
stabiliser systems, functional polymers, polymers to modify
the appearance and sensory properties of the liquid
bleaching composition and optionally other minors such as a
perfume or a fluorescer.
The liquid bleach composition according to the present
invention may for example contain a surface-active material
in an amount of from 10 to 50~ by weight. The surface-
active material may be naturally derived, such as soap, or a
synthetic material selected from anionic, nonionic,
amphoteric, zwitterionic, cationic actives and mixtures
thereof. Many suitable actives are commercially available
and are fully described in the literature, for example in
"Surface Active Agents and Detergents", Volumes I and II, by
Schwartz, Perry and Berch.
Typical synthetic anionic surface-actives are usually water-
soluble alkali metal salts of organic sulphates and
sulphonates having alkyl groups containing from about 8 to
about 22 carbon atoms, the term "alkyl" being used to
include the alkyl portion of higher aryl groups. Examples
of suitable synthetic anionic detergent compounds are sodium
and ammonium alkyl sulphates, especially those obtained by
sulphating higher (C8-C18) alcohols produced, for example,
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from tallow or coconut oil; sodium and ammonium alkyl (C9-
CZO) benzene sulphonates, particularly sodium linear
secondary alkyl (Clo-Cls) benzene sulphonates; sodium alkyl
glyceryl ether sulphates, especially those ethers of the
higher alcohols derived from tallow or coconut oil fatty
acid monoglyceride sulphates and sulphonates; sodium and
ammonium salts of sulphuric acid esters of higher (C9-C18)
fatty alcohol alkylene oxide, particularly ethylene oxide,
reaction products; the reaction products of fatty acids such
as coconut fatty acids esterified with isethionic acid and
neutralised with sodium hydroxide; sodium and ammonium salts
of fatty acid amides of methyl taurine; alkane
monosulphonates such as those derived by reacting alpha-
olefins (C8-CZO) with sodium bisulphate and those derived by
reacting paraffins with S02 and C1z and then hydrolysing with
a base to produce a random sulphonate; sodium and ammonium
(C7-C12) dialkyl sulphosuccinates; and olefin sulphonates,
which term is used to describe material made by reacting
olefins, particularly (Clo-C2o) alpha-olefins, with S03 and
then neutralising and hydrolysing the reaction product. The
preferred anionic detergent compounds are sodium (Clo-Cls)
alkylbenzene sulphonates, and sodium (C16-Cla) alkyl ether
sulphates.
Examples of suitable nonionic surface-active compounds which
may be used, preferably together with the anionic surface-
active compounds, include, in particular, the reaction
products of alkylene oxides, usually ethylene oxide, with
alkyl (C6-CZ2) phenols, generally 5-25 EO, i.e. 5-25 units of
ethylene oxides per molecule; and the condensation products
of aliphatic (C8-C18) primary or secondary linear or branched
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alcohols with ethylene oxide, generally 2-30 EO. Other so-
called nonionic surface-actives include alkyl
polyglycosides, sugar esters, long-chain tertiary amine
oxides, long-chain tertiary phosphine oxides and dialkyl
sulphoxides. The non-ionic surfactant liquid may be applied/
added in the form of a water-soluble sachet.
Amphoteric or zwitterionic surface-active compounds can also
be used in the compositions of the invention. If any
amphoteric or zwitterionic detergent compounds are used, it
is generally in small amounts in compositions based on the
much more commonly used synthetic anionic and nonionic
actives.
The liquid detergent bleach composition of the invention may
comprise from 1 to 40 % wt of anionic surfactant and from 0
to 40 % by weight of nonionic surfactant. The liquid
detergent may contain any mixture of non-ionic, anionic,
cationic zwitterionic or combination thereof. Optionally,
fatty acid soaps (0-30%) may be present. The liquid
detergent bleach composition of the present invention may
also contains a detergency builder, for example in an amount
of from about 5 to 80 % by weight, preferably from about 10
to 60 % by weight.
Builder materials may be selected from 1) calcium
sequestrant materials, 2) precipitating materials, 3)
calcium ion-exchange materials and 4) mixtures thereof.
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Examples of calcium sequestrant builder materials include
alkali metal polyphosphates, such as sodium
tripolyphosphate; nitrilotriacetic acid and its water-
soluble salts; the alkali metal salts of carboxymethyloxy
succinic acid, ethylene diamine tetraacetic acid,
oxydisuccinic acid, mellitic acid, benzene polycarboxylic
acids, citric acid; and polyacetal carboxylates as disclosed
in US-A-4,144,226 and US-A-4,146,495.
Examples of precipitating builder materials include sodium
orthophosphate and sodium carbonate.
Examples of calcium ion-exchange builder materials include
the various types of water-insoluble crystalline or
amorphous aluminosilicates, of which zeolites are the best
known representatives, e.g. zeolite A, zeolite B (also known
as zeolite P), zeolite C, zeolite X, zeolite Y and also the
zeolite P-type as described in EP-A-0,384,070.
In particular, the liquid bleaching compositions of the
invention may contain any one of the organic and inorganic
builder materials, though, for environmental reasons,
phosphate builders are preferably omitted or only used in
very small amounts. Typical builders usable in the present
invention are, for example, sodium carbonate,
calcite/carbonate, the sodium salt of nitrilotriacetic acid,
sodium citrate, carboxymethyloxy malonate, carboxymethyloxy
succinate and water-insoluble crystalline or amorphous
aluminosilicate builder materials, each of which can be used
as the main builder, either alone or in admixture with minor
amounts of other builders or polymers as co-builder.
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It is preferred that the liquid bleaching composition
contains not more than 5% by weight of a carbonate builder,
expressed as sodium carbonate, more preferably not more than
2.5 % by weight to substantially nil, if the composition pH
lies in the lower alkaline region of up to 10.
a
Apart from the components already mentioned, the liquid
bleaching composition of the present invention can contain
any of the conventional additives in amounts of which such
materials are normally employed in fabric washing detergent
compositions. Examples of these additives include buffers
such as carbonates, lather boosters, such as alkanolamides,
particularly the monoethanol amides derived from palmkernel
fatty acids and coconut fatty acids; lather depressants,
such as alkyl phosphates and silicones; anti-redeposition
agents, such as sodium carboxymethyl cellulose and alkyl or
substituted alkyl cellulose ethers; stabilisers, such as
phosphonic acid derivatives (i.e. Dequest° types); fabric
softening agents; inorganic salts and alkaline buffering
agents, such as sodium sulphate and sodium silicate; and,
usually in very small amounts, fluorescent agents; perfumes;
enzymes, such as proteases, cellulases, lipases, amylases
and oxidases; germicides and colourants.
Transition metal sequestrants such as EDTA, and phosphonic
acid derivatives such as EDTMP (ethylene diamine
tetra(methylene phosphonate)) may also be included, in
addition to the organic substance specified, for example to
improve the stability sensitive ingredients such as enzymes,
fluorescent agents and perfumes, but provided the
composition remains bleaching effective. However, the
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liquid bleaching composition according to the present
invention containing the organic substance, is preferably
substantially, and more preferably completely, devoid of
transition metal sequestrants (other than the organic
substance).
Whilst the present invention is based on the catalytic
bleaching of a substrate by atmospheric oxygen or air, it
will be appreciated that small amounts of hydrogen peroxide
or peroxy-based or -generating systems may be included in
the liquid composition, if desired, provided that the
chemical and physical stability of the composition is not
thereby adversely affected to an unacceptable level.
Therefore, by "substantially devoid of peroxygen bleach or
peroxy-based or -generating bleach systems" is meant that
the liquid bleaching composition contains from 0 to 50 %,
preferably from 0 to 10 %, more preferably from 0 to 5 %,
and optimally from 0 to 2 % by molar weight on an oxygen
basis, of peroxygen bleach or peroxy-based or -generating
bleach systems. Preferably, however, the liquid bleaching
composition will be wholly devoid of peroxygen bleach or
peroxy-based or -generating bleach systems.
Thus, at least 10 %, preferably at least 50 % and optimally at
least 90 % of any bleaching of the substrate is effected by
oxygen sourced from the air.
According to the fourth aspect, the organic substance in the
liquid bleaching composition may be contacted to the textile
fabric in any suitable manner. For example, it may be
applied in a liquor that is then dried, for example as an
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aqueous spray-on fabric treatment fluid or a wash liquor for
laundry cleaning, or a non-aqueous dry cleaning fluid or
spray-on aerosol fluid. Other suitable means of contacting
the organic substance in liquid form to the textile may be
used, as further explained below.
Any suitable textile that is susceptible to bleaching or one
that one might wish to subject to bleaching may be used.
Preferably the textile is a laundry fabric or garment.
In a preferred embodiment of the fourth aspect, the method
is carried out on a laundry fabric using an aqueous
treatment liquor. In particular, the treatment may be
effected in a wash cycle for cleaning laundry. More
preferably, the treatment is carried out in an aqueous
detergent bleach wash liquid. In a preferred embodiment, the
treated textile is dried, by allowing it to dry under
ambient temperature or at elevated temperatures.
The bleaching method of the fourth aspect may be carried out
by simply leaving the substrate in contact with the organic
substance in the liquid bleaching composition for a sufficient
period of time. Preferably, however, the organic substance is
in an aqueous medium, and the aqueous medium on or containing
the substrate is agitated.
In a preferred embodiment of the fourth aspect, the treated
textile is dried, by allowing it to dry under ambient
temperature or at elevated temperatures.
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In a particularly preferred embodiment the method according
to the fourth aspect is carried out on a laundry fabric
using aqueous treatment liquor. In particular the treatment
may be effected in, or as an adjunct to, an essentially
conventional wash cycle for cleaning laundry. More
preferably, the treatment is carried out in an aqueous
detergent wash liquor. Preferably, the organic substance is
delivered into the wash liquor from a liquid concentrate.
It is particularly advantageous that the organic substance
in liquid composition used in the method of the fourth
aspect makes use of atmospheric oxygen in its bleaching
activity. This avoids the requirement that peroxygen
bleaches and/or other relatively large quantities of
reactive substances need be used in the treatment process.
Consequently, only a relatively small quantity of bleach
active substance in liquid composition need be employed and
this allows dosage routes to be exploited, which could
previously not be used. Thus, while it is preferable to
include the organic substance in a liquid composition that
is normally used in a washing process, such as a pre-
treatment, main-wash, conditioning composition or ironing
aid, other means for ensuring that the organic substance is
present in the wash liquor may be envisaged.
For example, it is envisaged that the organic substance in
the liquid composition can be presented in the form of a
body from which it is slowly released during the whole or
part of the laundry process. Such release can occur over the
course of a single wash or over the course of a plurality of
washes. In the latter case it is envisaged that the organic
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substance in liquid composition can be released from a
carrier substrate used in association with the wash process,
e.g. from a body placed in the dispenser drawer of a washing
machine, elsewhere in the delivery system or in the drum of
the washing machine. When used in the drum of the washing
machine the carrier can be freely moving or fixed relative
to the drum. Such fixing can be achieved by mechanical
means, for example by barbs that interact with the drum
wall, or employ other forces, for example a magnetic force.
The modification of a washing machine to provide for means
to hold and retain such a carrier is envisaged similar means
being known from the analogous art of toilet block
manufacture. Freely moving carriers such as shuttles for
dosage of surfactant materials and/or other detergent
ingredients into the wash can comprise means for the release
of the organic substance in the liquid composition into the
wash.
In the alternative, the organic substance can be presented
in the form of a liquid wash additive that preferably is
soluble. Dosage of the additive can be unitary or in a
quantity determined by the user. While it is envisaged that
such additives can be used in the main washing cycle, the
use of them in the conditioning or drying cycle is not
hereby excluded.
The present invention is not limited to those circumstances
in which a washing machine is employed, but can be applied
where washing is performed in some alternative vessel. In
these circumstances it is envisaged that the organic
substance in liquid composition can be delivered by means of
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slow release from the bowl, bucket or other vessel which is
being employed, or from any implement which is being
employed, such as a brush, bat or dolly, or from any
suitable applicator for liquid compositions.
Suitable pre-treatment means for application of the organic
substance from the liquid composition to the textile
material prior to the main wash include sprays, pens,
roller-ball devices and impregnated cloths or cloths
containing microcapsules. Such means are well known in the
analogous art of deodorant application and/or in spot
treatment of textiles. Similar means for application are
employed in those embodiments where the organic substance in
liquid composition is applied after the main washing and/or
conditioning steps have been performed, e.g. prior to or
after ironing or drying of the cloth. For example, the
organic substance in liquid composition may be applied using
tapes, sheets or sticking plasters coated or impregnated
with the substance, or containing microcapsules of the
substance. The organic substance in liquid composition may
for example be incorporated into a drier sheet so as to be
activated or released during a tumble-drier cycle, or the
organic substance in liquid composition can be provided in
an impregnated or microcapsule-containing sheet so as to be
delivered to the textile when ironed.
The invention will now be further illustrated by way of the
following non-limiting examples:
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wTmrr~r z,e
Example 1
This example describes a synthesis of the catalyst as
employed in Example 2:
(i) Preparation of MeN4Py ligand:
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-1-
aminoethane, MeN4Py, was prepared according to the procedure
found in EP 0 909 809 A.
(ii) Synthesis of the complex FeMeN4PyClz:
MeN4Py ligand (33.7 g; 88.5mmoles) was dissolved in 500m1
dry methanol. Small portions of FeC12.4H20 (0.95eq; 16.7g;
84.Ommoles) were added, yielding a clear red solution. After
addition, the solution was stirred for 30 minutes at room
temperature, after which the methanol was removed (rotary-
evaporator). The dry solid was ground and 150 ml of
ethylacetate was added and the mixture was stirred until a
fine red powder was obtained. This powder was washed twice
with ethyl acetate, dried in the air and further dried under
vacuum (40 oC) . E1 . Anal . Calc. for [Fe (MeN4py) C1] C1 .2H20: C
53.03; H 5.16; N 12.89; C1 13.07; Fe 10.01%. Found C 52.29/
52.03; H 5.05/5.03; N 12.55/12.61; C1: 12.73/12.69; Fe:
10.06/10.01%.
Example 2:
Experiments with the FeMeN4PyC12 complex in a variety of
liquid detergents were performed to establish bleaching
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activity in various liquid detergent formulations and to
determine stability upon storage.
FeMeN4PyC12 complex was added to several liquid detergent
products and the stability and activity observed during
storage.
The following commercially available liquid detergent
compositions were used as base liquids: a) WISKTM liquid USA,
1999; b) OMOTM liquid NL, 1999; c) OMO-liquidoTM Brazil,
1999; and d) Rinse conditioner (RobijnTM - NL).
Incorporation of FeMeN4PyC12 in liquid detergents:
FeMeN4PyC12 was incorporated by post dosing a stock solution
of 0.01 g/ml using an electrical stirrer (125 rpm, Heidolph
RZR 2101). The final concentration in the product was 0.1~
for all products. To the reference a same amount of water
was added by post dosing to compensate for the post dose
volume of the stock solution.
The activity of FeMeN4PyC12 was measured by washing tomato
oil (TO) cloth samples in mini bottles for 15 minutes at a
temperature of 25 °C and a dosage of 2 g/1 product at 10
°FH. All of the liquids prepared were initially stable and
homogeneous.
The following table lists compositions prepared. As
detailed above base liquids a) to d) have had FeMeN4PyClz
incorporated therein. Compositions 5 to 8 are control
liquids without added FeMeN4PyC12.
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Composition No. Liquids
1 WiskTMliquid USA, 1999
2 OMOTM liquid NL, 1999
3 OMO-liquidoTM
Brazil,
1999
4 Rinse conditioner (RobijnTM - NL)
Reference Liquids
WiskTMliquid USA, 1999
6 OMOTM 1 i qu i d NL , 19 9 9
7 OMOTM -liquidoTM Brazil, 1999
Rinse conditioner (RobijnTM - NL)
Cloth samples were washed in mini bottles with a
liquid:cloth ratio of 1:20 and the samples were dried in a
5 tumble dryer.
Bleaching activity was measured directly after the wash (after
2 hours), and after 1 one-day (24 hours) storage in the dark
in order to establish post wash bleach effects. The five
liquid formulations were stored under ambient conditions and
the cleaning activity of the formulations without and with
FeMeN4PyClz was determined after certain periods of times. The
times were immediately after preparation, and after 1, 2, 3, 4
and 6 weeks of storage. After the wash, the cloths were dried
in a tumble drier and the reflectance was measured with a
MinoltaTM 3700d spectrophotometer at 460 nm. The difference in
reflectance before and after the wash is defined as a OR460
value.
Tabulated results are shown in Tables 1 to 6 below.
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Table 1
Directly after preparation TO-stain T0-stain
DR 460 0R
460
FH, 2 g/1, T=25 C 2 hours 1 day after
after washing
washing
Triplicate measurements average stdv average Stdv
Composition 5 14.3 1.6 26.6 3.1
Composition 1 16.5 1.4 34.6 0.6
Composition 6 12.9 0.7 20.0 2.9
Composition 2 17.2 1.4 35.7 0.8
Composition 7 16.2 0.6 24.4 5.2
Composition 3 23.8 1.6 37.1 1.0
Composition 8 4.8 1.1 6.6 0.8
Composition 4 5.9 0.9 15:5 1.0
Table 2
1 week after preparation TO-stain TO-stain
OR 460 0R
460
10 FH, 2 g/1, T=25 C 2 hours 1 day after
after washing
washing
Triplicate measurements average stdv average Stdv
Composition 5 11.8 1.3 13.1
Composition 1 18.5 0.7 36.6
Composition 6 11.2 0.4 12.8
Composition 2 14.9 0.4 37.4
Composition 7 13.6 0.4 18.9
Composition 3 19.9 2.7 39.3
Composition 8 4.1 1.0 5.5
Composition 4 3.7 0.8 12.6
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Table 3
2 weeks after preparation TO-stain TO-stain
OR 460 0R
460
FH, 2 g/1, T=25 C 2 hours 1 day after
after washing
washing
Triplicate measurements average stdv average Stdv
'Composition 5 11.7 1.4 16.5 1.3
Composition 1 20.2 0.9 34.0 0.8
Composition 6 12.1 0.3 16.2 3.3
Composition 2 14.8 0.1 34.5 0.7
Composition 7 14.7 0.1 17.6 1.5
Composition 3 19.7 2.4 35.2 1.3
Composition 8 3.9 0.8 5.4 0.7
Composition 4 4.1 0.3 ~ 11.4 ~
0.8
Table 4
3 weeks after preparation TO-stain TO-stain
OR 460 ~R
460
10 FH, 2 g/1, T=25 C 2 hours 1 day after
after washing
washing
Triplicate measurements average stdv average Stdv
Composition 5 13.5 0.6 16.9 2.5
Composition 1 14.1 1.7 33.8 1.0
Composition 6 12.8 0.5 17.6 3.2
Composition 2 14.5 0.5 34.1 1.4
Composition 7 16.1 1.8 18.8 4.5
Composition 3 16.6 0.9 33.9 0.3
Composition 8 3.1 0.7 4.2 1.6
Composition 4 ~3.9 0.8 7.8 1.2
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Table 5
'4 weeks after preparation TO-stain TO-stain
DR 460 DR
460
FH, 2 g/1, T=25 C 2 hours 1 day after
after washing
washing
Triplicate measurements average stdv average Stdv
Composition 5 12.1 1.1 15.0 2.2
Composition 1 17.8 1.7 34.5 1.2
Composition 6 12.3 0.8 15.2 1.9
Composition 2 16.5 1.7 34.2 1.5
Composition 7 14.1 1.9 16.7 1.6
Composition 3 14.5 0.1 28.3 1.3
Composition 8 3.5 0.6 5.0 1.0
Composition 4 3.4 2.1 9.5 1.9
5 Table 6
6 weeks after preparation TO-stain TO-stain
0R 460 0R
460
10 FH, 2 g/1, T=25 C 2 hours 1 day after
after washing
washing
Triplicate measurements average stdv average Stdv
Composition 5 14.8 0.9 15.8 1.5
Composition 1 18.7 1.6 34.3 1.4
Composition 6 15.2 1.0 15.5 1.3
Composition 2 16.8 0.7 31.0 1.4
Composition 7 19.1 0.7 19.8 1.5
Composition 3 16.9 0.7 17.1 0.6
Composition 8 6.2 0.7 7.1 0.5
Composition 4 6.1 0.3 7.3 0.5
Example 3
10 Composition 5 WiskTM liquid USA, 1999
Composition 6 OMOTM liquid NL, 1999
Composition 7 OMO-liquidoTM Brazil, 1999
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Composition 9 non-aqueous liquid formulation:
Ingredient Wt%
Nonionic surfactant 26.6
Monopropylene glycol 5.5
Pigment premix 0.017
Glycerol 21.36
Monoethanolamine 7.56
Oleic fatty acid 13.10
Water Up to 100
Linear alkyl benzene 20.1
sulfonate
Perfume 1. 6
Protease Enzyme 1.0
In all experiments, 2 g/1 of the above formulation was used,
with either 2.5 or 5 microM of metal complex 1-8, or 2.5 or
5 microM of the ligand 1-8 dissolved in the wash liquor. In
all cases tomato stains were used and treated further as
described for Example 3. The cloths were measured
immediately after drying and after 24 h storage (expressed
as OR 460 bleaching value (a higher value indicates a
cleaner cloth).
Ligand 1: N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-
yl)-1-aminoethane (MeN4py).
Ligand 2: N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-
yl)-1-amino-2-phenylethane (BzN4py). The synthesis of
ligand 2 has been disclosed in EP 0909 809.
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Ligand 3: N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-
yl)-aminomethane (N4py). The synthesis of ligand 3 has been
disclosed in Wo-A-9534628.
Ligand 4: N,N,N',N'-tetrakis(pyridin-2ylmethyl)ethane-
diamine (tpen). Ligand 4 was synthesised according to a
modified literature procedure (see G. Anderegg, F. Wenk,
Helv. Chim. Acta, 50(8), 2330 (1967).
Trispicen-NH (5.95 g, 17.9 mmol) and 1.67 g (18.4 mmol) of
2-pyridinecarboxaldehyde were dissolved in 120 ml 1,2-
dichloroethane. To this mixture NaBH(OAc)3 (18 mmol) was
added and the mixture was refluxed for 16 h. Subsequently
50 ml of 5 N NaOH and after 1 h stirring the organic layer
was separated and the water layer was further extracted with
dichloromethane. After drying the organic layers over sodium
sulfate, filtration and evaporation of the solvents, a semi-
solid paste was obtained that was purified over an alumina
column (elutant: ethyl acetate/ hexane/ triethylamine
9:10:1). The oil isolated become now solid and could be
crystallised from ethyl acetate/hexane (1/1) yielding a
pale-brown powder (4.45 g, 10.5 mmol; 58.6%). 1H-nmr (CDC13):
b 2.78 (s, 4H) ; 3.75 (s, 8H) ; 7.0 (m, 4H) ; 7.38 (m, 4H) ;
7.50 (m, 4H); 8.43 (m, 4H).
Ligand 5: N-methyl-N,N',N'-tris(3-methyl-pyridin-
2ylmethyl)ethane-diamine (trilen). The synthesis of ligand 5
has been disclosed in EP 1001 009.
Ligand 6: N,N,N'-tris(pyridin-2ylmethyl)ethane-diamine
(trispicen-NH) .
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First N,N'-bis(pyridin-2ylmethyl)-ethanediamine (bispicen)
was synthesised by the following procedure. Ethylenediamine
(26 ml, 0.38 mol) was dissolved in 200 ml dry methanol. To
this mixture 74 ml (0.76 mol) pyridincarboxaldehyde was
added. The mixture was refluxed for 2 h, after which the
mixture was left to cool to RT and in small portions 40 g of
NaBH4 was added. The mixture was subsequently stirred for 16
h at RT. The methanol was evaporated and 500 ml of water was
added. The aqueous mixture was extracted by three portions
of dichloromethane (100 ml) and the dichloromethane solution
was dried over sodium sulfate, filtered off and the solvent
was removed. The dark oil containing N,N'-bis(pyridin-
2ylmethyl)-ethanediamine (73.7 g; 81%) was analysed by NMR
and used without further purification. 1H-nmr (CDC13): 8 2.20
(br, NH); 2.78 (s, 4H); 3.85 (s, 4H); 7.00-7,7.40 (m, 4H);
7.58 (m, 2H) ; 8.45 (m, 2H) .
In the second step the aminal of bispicen with 2-
pyridincarboxaldehyde was synthesised. 73,7 g of the
unpurified bispicen material (see above) was under argon
dissolved in 750 ml of dry diethyether (distilled over P205.
To this solution 32.8 of 2-pyridincarboxaldehyde was added,
the reaction mixture was stirred and cooled in an ice/water
bath. After 20 min a white precipitate was formed that was
filtered off (P4-glass filter) and dried with dry ether. The
yield was 66.6 g (66%) and was used without further
purification. 1H-nmr (CDC13) : 8 2.75 (m, 2H) ; 3.13 (m, 2H) ;
3.65 (d, 2H); 4.93 (d, 2H); 4.23 (s, 1H); 7.00-7.90 (m, 9H);
8.43 (m, 3H) .
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In the third step the desired ligand was obtained (N,N,N'-
tris(pyridin-2ylmethyl)ethane-diamine - trispicen-NH). The
aminal (45.0 g; 0.135 mol), obtained as described as above,
was dissolved in 1.2 1 of dry methanol (distilled over Mg),
and to this mixture 8.61 g (0.137 mol) of NaBCNH3 was added
in small portions. Subsequently 21 ml of trifluoroacetic
acid was added dropwise in the solution. The mixture was
stirred for 16 h at RT and subsequently 1.05 L of 5N NaOH
was added and the mixture was stirred for 6 h. Extraction
with dichloromethane yielded after drying, filtration and
removal of the solvent a yellow oil as product (42.7 g ,
0.128 mol; 95%. 1H-nmr (CDC13) : 8 2.15 (br, NH) ; 2.75 (s,
4H); 3.80 (s, 4H); 3.82(s, 2H); 7.0-7.8 (m, 3H); 7.45-7.70
(m, 6H) ; 8 .40-8 . 60 (m, 3H) . 13C-nmr (CDC13) : 8 53 . 9 (t) ; 54.7
(t); 60.4 (t); 121.7 (d); 121.9 (d); 122.1 (d); 123.0 (d);
136.3 (d) ; 136.4 (d) ; 148.9 (d) ; 149.1 (d) ; 159.3 (s) ; 159.6
(s) .
Ligand 7: N-methyl-,N,N'N'-tris(pyridin-2ylmethyl)ethane-
diamine (trispicen-NMe). Ligand 7 was prepared according to
a modified procedure described by Bernal et al (J. Chem.
Soc., Dalton Trans, 22, 3667 (1995)).
Trispicen-NH (10g, 30 mmol) was dissolved in 25 ml formic
acid and 10 ml water. To this mixture 36 % formaldehyde
solution was added (16 ml, 90 mmol) and the mixture was
warmed up till 90 °C for 3 h. Formic acid was evaporated and
the 2.5 N NaOH solution was added until the pH was higher
than 9. Extraction by dichloromethane and drying over sodium
sulfate, filtration of the solution and subsequently drying
yielded a dark-coloured oil (8.85g). The oil was purified
over a alumina column (elutant: ethyl acetate/ hexane/
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triethylamine 9:10:1). Yield 7,058 pale yellow oil
(20, 3mmoles; 68%) . 1H-nmr (CDC13) : 8 2 . 18 (s, 3H) ; 2 .65 (m,
2H); 2.75 (m, 2H); 3.60 (s; 2H); 3.83 (s; 4H); 7.10 (m, 3H);
7.3-7.6 (m, 6H); 8.5 (d, 3H).
Ligand 8: tris(pyridin-2-ylmethyl)amine (tpa)
Ligand 8 was prepared according to literature procedures
(see G. Anderegg, F. Wenk " Helv. Chim. Acta, 50(8), 2330
(1967) .
Complex 1: [(MeN4Py)FeCl]C1
The synthesis of Complex 1 is described in Example 1.
Complex 2 : [ (BzN4Py) Fe (CH3CN) ] (C104) s
The synthesis of Complex 2 is described in EP 0909 809. An
optimised synthetic procedure is given below: 3.0 g (6.56
mmol) of BzN4Py was dissolved in 30m1 methanol and 30m1
acetonitrile. 2.26 g (6.23 mmol) of Fe (C104) .6H20 (Aldrich)
was added to solution containing the ligand in small
portions. To the dark-red coloured solution in total 100 ml
of ethyl acetate was added to facilitate the crystallisation
procedure. After 18 h stirring, the red powder was filtered
off, washed with ethyl acetate and dried, yielding 3.85 g of
the desired complex (anal: see EP 0909 809).
Complex 3: [(N4Py)FeCl]C1
Complex 3 was synthesised according to the procedure as
described for the analogous MeN4py complex using now N4py as
ligand (see example 1).
Complex 4 : ( (tpen) Fe] (C104) a
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Complex 4 was prepared according to the procedure found in
H. Toftlund et al., J.Am. Chem. Soc., 112, 6814 (1990)
Complex 5 : [ (trilen) FeCl] PF6
Complex 5 was prepared according to EP 1001 009
Complex 6: [(trispicen-NH)FeCl]PF6
Trispicen-NH (8.0 g; 24.0 mmol) was dissolved in 60 ml
methanol/water 1/1 v/v) and was heated till 50 °C. FeC12.4H20
4,788; 24,Ommoles)was added in small portions. The dark
blue-purple solution was stirred for 10 min at 50 °C.
Subsequently 4.42 g (24 mmol) of KPF6 was added and the
solution was stirred for 2 days at RT. The dark powder was
filtered, washed with methanol/water and then with ethyl
acetate. The powder was dried in the air. Yield 11.6 g.
Complex 7: [(trispicen-NMe)FeCl]PF6
TrispicenNMe (6,0g; 17,3mmoles) was dissolved in 15 ml
methanol/water 1/1 v/v) and was heated till 50 °C. FeC12.4H20
3,438; l7,Ommoles), dissolved in 20 ml water/methanol 1/1),
was added. The dark solution was stirred for 20 min at 50
°C. Subsequently 3.17 g (17 mmol) of KPF6 dissolved in 10 ml
water, was added and the solution was stirred for 15 h to
yield a yellow precipitation. The solid was filtered off,
wasged with methanol/water 1/1, v/v) and ethyl acetate.
Drying yielded 8.25 g of a pale-yellow powder.
Complex 8 : [Fe2 (tpa) 2 (H20) 2] (C104) s
Complex 8 was kindly donated by Prof. L. Que, University of
Minnesota, USA (references: L. Que et al., Inorg Chim. Acta,
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273, 393 (1998) and H. Toftlund et al., Inorg. Chem., 33,
3127 (1994).
Table 7. Bleaching results obtained on tomato stains for the
different complexes (5 microM) in solutions containing the
four liquid formulations (compositions 5, 6, 7 and 9). The
bleaching results obtained immediately after drying (t=0)
and after 1 day storage are shown. All values expressed in
0R 460 values; typical errors are in the order of 2 points.
Comp Comp Comp Comp
5 t=1 6 t=1 7 t=1 9 t=1
t=0 t=0 t=0 t=0
Complex 1 20 50 41 47 35 55 42 49
Complex 2 20 48 42 50 31 51 42 52
Complex 3 31 49 35 50 31 53 44 52
Complex 4 16 39 16 23 26 48 29 42
Complex 5 33 47 36 46 39 52 43 50
Complex 6 15 22 12 15 16 23 15 18
Complex 7 19 39 17 20 25 46 27 33
Blank 11 13 15 19 13 14 15 18
From these results is clear that especially complexes 1, 2,
3, and 5 give a good tomato stain bleaching with air,
although the exact amount depends on the formulation
employed. Complexes 4, 6, and 7 give somewhat lower
bleaching activity, but still in most cases more than the
blanks.
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Table 8. Bleaching results obtained on tomato stains for the
different ligands (5 microM) in solutions containing the
four liquid formulations (compositions 5, 6, 7 and 9). The
bleaching results obtained immediately after drying (t=0)
and after 1 day storage are shown. All values expressed in
0R 460 values; typical errors are in the order of 2 points.
Comp Comp Comp Comp
5 t=1 6 t=1 7 t=1 9 t=1
t=0 t=0 t=0 t=0
Ligand 1 16 42 22 44 18 32 33 52
Ligand 2 16 40 26 47 16 34 32 51
Ligand 3 18 37 19 39 18 39 33 53
Ligand 5 22 40 26 36 19 36 41 52
Ligand 6 14 16 14 16 14 20 18 20
Ligand 7 16 20 16 19 19 28 19 22
Blank 11 13 14 19 12 14 15 18
All ligands in the wash liquor containing the four
formulations give significant enhancement of the tomato
stain bleaching in the air. This effect is especially clear
for ligands 1, 2, 3 and 5.
Table 9. Bleaching results obtained on tomato stains for the
different complexes (2.5 microM) in solutions containing the
four liquid formulations (compositions 5, 6, 7 and 9). The
bleaching results obtained immediately after drying (t=0)
and after 1 day storage are shown. All values expressed in
OR 460 values; typical errors are in the order of 2 points.
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Comp Comp Comp Comp
5 t=1 6 t=1 7 t=1 9 t=1
t=0 t=0 t=0 t=0
Complex 1 15 46 38 48 27 49 22 44
Complex 2 22 46 15 35 28 47 18 38
Complex 3 20 46 24 43 27 44 24 47
Complex 4 12 19 9 11 18 24 12 19
Complex 5 30 43 23 33 27 36 23 40
Complex 6 9 10 8 9 16 23 13 14
Complex 7 15 18 9 10 23 32 17 21
Complex 8 10 13 11 12 11 13 12 15
Blank 10 11 9 10 12 14 11 12
Table 10. Bleaching results obtained on tomato stains for
the different ligands (2.5 microM) in solutions containing
the four liquid formulations (compositions 5, 6, 7 and 9).
The bleaching results obtained immediately after drying
(t=0) and after 1 day storage are shown. All values
expressed in OR 460 values; typical errors are in the order
of 2 points.
Comp 5 Comp Comp Comp
t=0 t=1 6 t=1 7 t=1 9 t=1
t=0 t=0 t=0
Ligand 1 13 26 9 13 11 13 11 15
Ligand 2 11 19 10 14 10 13 13 21
Ligand 3 13 26 9 11 12 14 13 17
Ligand 5 13 20 9 11 12 16 14 19
Ligand 6 11 12 10 12 10 11 10 12
Ligand 7 12 15 9 11 10 12 13 15
Ligand 8 8 9 9 11 13 15 11 14
Blank 10 11 9 10 11 14 11 12
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Discussion of Results:
The results show that the activity of FeMeN4PyClz is stable
for six weeks in the detergent Compositions 1 and 2.
However, the activity of FeMeN4PyC12 in composition 4 and in
composition 3 after more than four weeks storage decreased.
Without being bound by theory, it is more than likely that
STP present in a liquid composition gives the negative
effect on the storage stability and that addition of iron
salt restores the activity. The results show that by adding
a liquid composition containing a ligand or transition metal
complex thereof to the wash liquor a bleaching capacity is
provided without the presence of an added peroxyl species or
precursor thereof. In addition, the bleaching capacity is
provided at a low concentration of a ligand or transition
metal complex thereof in the wash liquor.
1) FeMeN4PyC12, amongst others, gives clear bleach benefits
in a variety of liquid formulations (incl. rinse
conditioner) on tomato-oil stains.
2) The bleach effect upon 24 hr storage of the cloths in
the dark is much larger then 2 h after the wash.
3) No visual change in structural phase after two weeks.
4) Immediate colour change upon addition of FeMeN4PyC12 of
the liquid observed.
5) Similar bleach performance upon 6 weeks of storage as
found immediately after mixing for the detergent
Compositions 1 and 2, implying a stable system.
6) No bleach effects were more observed after 6 weeks of
storage for detergent Composition 3 and rinse conditioner
Composition 4.
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Complex 8 and ligand 8 show significant decreased bleach
benefit in a liquid bleach composition. As is known from
inorganic chemistry, in general pentadentate ligands give
rise to more stable complexes than tetradenate ligands; this
is known as the chelate effect. (see Huheey, inorganic
chemistry, 2nd edition, Harper and Row). The decreased
stability is especially noted in basic aqueous media, where
formation of insoluble iron Hydroxide species are often
encountered. The decreased stability of the iron tpa
complexes/species gives rise to a poorer performance in the
liquid detergent formulations.
There are many liquid formulations for detergents and rinse
conditioners or other liquid products that may be enhanced
by conferring a bleaching ability to the liquid formulation.
As will be evident to one skilled in the art the present
invention is applicable to known liquid formulations and
liquid formulations to be developed.
As one skilled in the art will appreciate determining the
suitability of a particular catalyst for bleaching of a
substrate by atmospheric oxygen in a particular liquid
formulation is a matter of routine experimentation. The
present invention extends to both isotropic and complex
liquid compositions and formulations a brief discussion of
which follows. Some isotropic formulations are termed
'micro-emulsion' liquids that are clear and
thermodynamically stable over a specified temperature range.
The 'micro-emulsion' formulation may be water in oil, or oil
in water emulsions. Some liquid formulations are macro-
emulsions that are not clear and isotropic. Emulsions are
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considered meta-stable. Concentrated, clear compositions
containing fabric softening actives have been disclosed in
WO 98/08924 and WO 98/4799, both Procter & Gamble. Such
compositions comprise bio-degradable fabric conditioners.
However, both disclose compositions comprising water
miscible solvents that do not form water-in-oil micro-
emulsions. Clear fabric conditioning compositions have also
been disclosed in EP 730023 (Colgate Palmolive), WO 96/19552
(Colgate Palmolive), WO 96/33800 (Witco Co.), WO 97/03170
(Procter & Gamble), WO 97/03172 (Procter & Gamble), WO
97/03169 (Procter & Gamble), US 5492636 (Quest Int.) and US
5427697 (Procter & Gamble). Liquid formulations of the
present invention may contain for example; monoethoxy quats;
AQAs and bis-AQAs; cationic amides; cationic esters;
amino/diamino quats; glucamide; amine oxides; ethoxylated
polyethyleneimines; enhancement polymers of the form linear
amine based polymers, e.g. bis-hexamethylenetriamine;
polyamines e.g. TETA, TEPA or PEI polymers.
Experimentation to determine catalyst-liquid stability, as
detailed above, may be varied. The aforementioned method
determined the catalyst-liquid stability/compatibility by
examining how the oxygen bleaching ability of a particular
catalyst-liquid formulation varied with time.
Alternatively, the determination may be conducted by
monitoring the concentration of a particular catalyst in a
liquid formulation by known techniques, for example NMR,
HPLC, Liquid Chromatography-Mass Spectroscopy, Infra Red,
UV-visible measurements, etc, over a period of time.
Alternatively, another possible method of determining
catalyst-liquid stability would be to analyse the activity
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of a certain transition metal compound by oxidation activity
studies using a dye/compound that gives a colour change upon
oxidation. An example of a dye/compound that gives a colour
change upon oxidation is 2,2'-azinobis(3-
ethylbenzothiazoline-6-sulfonate) and many other
dyes/compounds that give a colour change upon oxidation are
known. Methods for using a dye/compound that gives a colour
change upon oxidation are known in the art for establishing
activity of a variety of redox enzymes.
