U.S. patent application number 10/337516 was filed with the patent office on 2003-12-11 for composition and method for bleaching a substrate.
This patent application is currently assigned to Unilever Home & Personal Care USA, Division of Conopco, Inc.. Invention is credited to Hage, Ronald.
Application Number | 20030226999 10/337516 |
Document ID | / |
Family ID | 10867076 |
Filed Date | 2003-12-11 |
United States Patent
Application |
20030226999 |
Kind Code |
A1 |
Hage, Ronald |
December 11, 2003 |
Composition and method for bleaching a substrate
Abstract
The invention relates to catalytically bleaching substrates,
especially laundry fabrics, with atmospheric oxygen or air. A
method of bleaching a substrate is provided that comprises applying
to the substrate, in an aqueous medium, a specified organic
substance which forms a complex with a transition metal, the
complex catalysing bleaching of the substrate by atmospheric
oxygen. Also provided is a bleaching composition comprising, in an
aqueous medium atmospheric oxygen and an organic substance which
forms a complex with a transition metal, the complex catalysing
bleaching of the substrate by the atmospheric oxygen, wherein the
aqueous medium is substantially devoid of peroxygen bleach or a
peroxy-based or -generating bleach system.
Inventors: |
Hage, Ronald; (Vlaardingen,
NL) |
Correspondence
Address: |
UNILEVER
PATENT DEPARTMENT
45 RIVER ROAD
EDGEWATER
NJ
07020
US
|
Assignee: |
Unilever Home & Personal Care
USA, Division of Conopco, Inc.
|
Family ID: |
10867076 |
Appl. No.: |
10/337516 |
Filed: |
January 7, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10337516 |
Jan 7, 2003 |
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09740114 |
Dec 19, 2000 |
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6569354 |
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Current U.S.
Class: |
252/186.33 ;
510/302 |
Current CPC
Class: |
C11D 3/3932 20130101;
D06L 4/00 20170101 |
Class at
Publication: |
252/186.33 ;
510/302 |
International
Class: |
C11D 007/54 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 24, 1999 |
GB |
9930695.3 |
Claims
1. Use of an organic substance which forms a complex with a
transition metal in a process for the manufacture of a bleaching
composition for bleaching a substrate with atmospheric oxygen, the
bleaching composition upon addition to an aqueous medium providing
an aqueous bleaching medium substantially devoid of a peroxygen
bleach or a peroxy-based or peroxyl-generating bleach system,
wherein the organic substance forms a complex of a transition metal
coordinated with a macropolycyclic rigid ligand having at least 3
donor atoms, at least two of which are bridgehead donor atoms.
2. Use according to claim 1, wherein the ligand is a cross-bridged
macropolycyclic ligand.
3. Use according to claim 1, comprising: (a) a catalytically
effective amount of the complex and (b) the balance, to 100%, of
one or more adjunct materials.
4. Use according to claim 1, wherein the medium has a pH value in
the range rom pH 6 to 11, preferably in the range from pH 8 to
10.
5. Use according to claim 1, wherein the medium is substantially
devoid of a transition metal sequestrant.
6. Use according to claim 1, wherein the medium further comprises a
surfactant.
7. Use according to claim 1, wherein the medium further comprises a
builder.
8. Use according to claim 1, wherein the organic substance
comprises a preformed complex of a ligand and a transition
metal.
9. Use according to claim 1, wherein the organic substance
comprises a free ligand that complexes with a transition metal
present in the water.
10. Use according to claim 1, wherein the organic substance
comprises a free ligand that complexes with a transition metal
present in the substrate.
11. Use according to claim 1, wherein the organic substance
comprises a composition of a free ligand or a transition
metal-substitutable metal-ligand complex, and a source of
transition metal.
12. Use according to claim 1, wherein the macropolycyclic rigid
ligand is coordinated by four or five donor atoms to the same
transition metal and comprises: (i) an organic macrocycle ring
containing four or more donor atoms (preferably at least 3, more
preferably at least 4, of these donor atoms are N) separated from
each other by covalent linkages of at least one, preferably 2 or 3
non-donor atoms, two to five (preferably three or four, more
preferably four) of these donor atoms being coordinated to the same
transition metal in the complex; (ii) a linking moiety, preferably
a cross-bridging chain, which covalently connects at least 2
non-adjacent donor atoms of the organic macrocycle ring, said
covalently connected non-adjacent donor atoms being bridgehead
donor atoms which are coordinated to the same transition metal in
the complex, and wherein said linking moiety comprises from 2 to
about 10 atoms; and (iii) optionally, one or more
non-macropolycyclic ligands, preferably selected from the group
consisting of H.sub.2O, ROH, NR.sub.3, RCN, OH.sup.-, OOH.sup.-,
RS.sup.-, RO.sup.-, RCOO.sup.-, OCN.sup.-, SCN.sup.-,
N.sub.3.sup.-, CN.sup.-, F.sup.-, Cl.sup.-, Br.sup.-, I.sup.-,
O.sub.2.sup.-, NO.sub.3.sup.-, NO.sub.2.sup.-, SO.sub.4.sup.2-,
SO.sub.3.sup.2-, PO.sub.4.sup.3-, organic phosphates, organic
phosphonates, organic sulphates, organic sultanates, and aromatic N
donors such as pyridines, pyrazines, pyrazoles, imidazoles,
benzimidazoles, pyrimidines, triazoles and thiazoles with R being
H, optionally substituted alkyl, or optionally substituted
aryl.
13. Use according to claim 12, wherein the donor atoms in the
organic macrocycle ring of the macropolycyclic ligand are selected
from N, O, S and P, preferably N and O, and most preferably all
N.
14. Use according to claim 13, wherein the organic macropolycyclic
ligand comprises 4 or 5 donor atoms, all of which are coordinated
to the same transition metal.
15. Use according to claim 12, wherein the organic macropolycyclic
ligand comprises an organic macrocycle ring containing at least 12
atoms, preferably from 12 to 20 atoms.
16. Use according to claim 1, wherein the macropolycyclic rigid
ligand is selected from the group consisting of: (i) the
macropolycyclic rigid ligand of formula (I) having denticity of 3
or 4: 36(ii) the macropolycyclic rigid ligand of formula (II)
having denticity of 4 or 5 37(iii) the macropolycyclic rigid ligand
of formula (III) havind denticity of 5 or 6: 38(iv) the
macropolycyclic rigid ligand of formula (IV) having denticity of 6
or 7 39wherein in these formulas:- each "E" is the moiety
(CR.sub.n).sub.a-X-(CR.sub.n).sub.a', wherein X is selected from
the group consisting of O, S, NR and P, or a covalent bond, and
preferably X is a covalent bond and for each E the sum of a+a' is
independently selected from 1 to 5, more preferably 2 and 3,
wherein: each "G" is the moiety (CR.sub.n).sub.b; each "R" is
independently selected from H, alkyl, alkenyl, alkynyl, aryl,
alkylaryl and heteroaryl, or two or more R are covalently bonded to
form an aromatic, heteroaromatic, cycloalkyl, or heterocycloalkyl
ring; each "D" is a donor atom independently selected from the
group consisting of N, O, S, and P, and at least two D atoms are
bridgehead donor atoms coordinated to the transition metal; "B" is
a carbon atom or "D" donor atom, or a cycloalkyl or heterocyclic
ring; each "n" is an integer independently selected from 1 and 2,
completing the valence of the carbon atoms to which the R moieties
are covalently bonded; each "n"' is an integer independently
selected from 0 and 1, completing the valence of the D donor atoms
to which the R moieties are covalently bonded; each "n"" is an
integer independently selected from 0, 1, and 2 completing the
valence of the carbon atoms to which the R moieties are covalently
bonded; each "a" and "a'" is an integer independently selected from
0-5, preferably a+a' equals 2 or 3, wherein the sum of all "a" plus
"a'" in the ligand of formula (I) is within the range of from 7 to
11, the sum of all "a" plus "a'" in the ligand of formula (II) is
within the range of from 8 to 12, the sum of all "a" plus "a'" in
the ligand of formula (III) is within the range of from 10 to 15,
and the sum of all "a" plus "a'" in the ligand of formula (IV) is
within the range of from 12 to 18; each "b" is an integer
independently selected from 0-9 preferably 0-5, or in any of the
above formulas, one or more of the (CR.sub.n).sub.b moieties
covalently bonded from any D to the B atom is absent as long as at
least two (CR.sub.n).sub.b covalently bond two of the D donor atoms
to the B atom in the formula, and the sum of all "b" is within the
range of from about 1 to about 5.
17. Use according to claim 16, wherein in the macropolycyclic
ligand all "a" are independently selected from the integers 2 and
3, all X are selected from covalent bonds, all "a'" are 0, and all
"b" are independently selected from 0 or the integers 1 and 2, and
D is selected from the group consisting of N and O, and preferably
are N.
18. Use according to claim 17, wherein the molar ratio of
transition metal to macropolycyclic ligand is 1:1, and the
transition metal is manganese or iron.
19. Use according to claim 1, wherein the macropolycyclic rigid
ligand is a macropolycyclic moiety of formula: 40wherein each "a"
is independently selected from the integers 2 or 3, and each "b" is
independently selected from the integers 0,1 and 2.
20. Use according to claim 1, wherein the macropolycyclic rigid
ligand is a macropolycyclic moiety of formula: 41wherein: each "n"
is an integer independently selected from 1 and 2, completing the
valence of the carbon atom to which the R moieties are covalently
bonded; each "R" and "R.sup.I" is independently selected from H,
alkyl, alkenyl, alkynyl, aryl, alkylaryl (e.g., benzyl) and
heteroaryl, or R and/or R1 are covalently bonded to form an
aromatic, heteroaromatic, cycloalkyl, or heterocycloalkyl ring, and
wherein preferably all R are H and R.sup.1 are independently
selected from linear or branched, substituted or unsubstituted
C1-C20 alkyl, alkenyl or alkynyl; each "a" is an integer
independently selected from 2 or 3 all nitrogen atoms in the
cross-bridged macropolycycle rings are coordinated with the
transition metal.
21. Use according to claim 1, wherein the macropolycyclic rigid
ligand is of the formula 1.2; 42wherein m and n are 0 or integers
from 1 to 2, p is an integer from 1 to 6, preferably m and n are
both 0 or both 1 (preferably both 1), or m is 0 and n is at least
1; and p is 1; and A is a nonhydrogen moiety preferably having no
aromatic content; more particularly each A can vary independently
and is preferably selected from methyl, ethyl, propyl, isopropyl,
butyl, isobutyl, tert-butyl, C5-C20 alkyl, and one, but not both,
of the A moieties is benzyl, and combinations thereof.
22. Use according to claim 1, wherein the macropolycyclic ligand is
of the formula: 43wherein "R.sup.1" is independently selected from
H, and linear or branched, substituted or unsubstituted C1-C20
alkyl, alkylaryl, alkenyl or alkynyl; and all nitrogen atoms in the
macropolycyclic rings are coordinated with the transition
metal.
23. Use according to claim 1, wherein the macropolycyclic ligand is
of the formula: 44wherein: each "n" is an integer independently
selected from 1 and 2, completing the valence of the carbon atom to
which the R moieties are covalently bonded; each "R" and "R.sup.1"
is independently selected from H, alkyl, alkenyl, alkynyl, aryl,
alkylaryl, and heteroaryl, or R and/or R.sup.1 are covalently
bonded to form an aromatic, heteroaromatic, cycloalkyl, or
heterocycloalkyl ring, and wherein preferably all R and H and
R.sup.1 are independently selected from linear or branched,
substituted or unsubstituted C1-C20 alkyl, alkenyl or alkynyl; each
"a" is an integer independently selected from 2 or 3; all nitrogen
atoms in the macropolycyclic rings are coordinated with the
transition metal.
24. Use according to claim 1, wherein the macropolycyclic ligand is
of the formula: 45wherein "R.sup.1" is independently selected from
H and linear or branched, substituted or unsubstituted CI-C20
alkyl, alkenyl or alkynyl; and all nitrogen atoms in the
macropolycyclic rings are coordinated with the transition
metal.
25. A method of bleaching a substrate comprising applying to the
substrate, in an aqueous medium, an organic substance which forms a
complex with a transition metal, the complex catalysing bleaching
of the substrate by atmospheric oxygen, wherein the organic
substance is as defined in claim 1.
26. A method according to claim 25, wherein the majority of the
bleaching species in the medium (on an equivalent weight basis) is
derived from the atmospheric oxygen.
Description
[0001] This invention relates to compositions and methods for
catalytically bleaching substrates with atmospheric oxygen or
air.
[0002] Peroxygen bleaches are well known for their ability to
remove stains from substrates. Traditionally, the substrate is
subjected to hydrogen peroxide, or to substance 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.degree. C. or
higher. However, these high temperatures often lead to inefficient
cleaning, and can also cause premature damage to the substrate.
[0003] A preferred approach to generating hydroperoxyl bleach
radicals 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 perborate or sodium percarbonate, whereas in the United
States laundry bleach products are typically based on sodium
nonanoyloxybenzenesulphonat- e (SNOBS) as the organic precursor
coupled with sodium perborate.
[0004] 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.
[0005] 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 WO95/34628, or the ligand Tpen (i.e. N, N, N',
N'-tetra(pyridin-2-yl-methyl)ethylenediamine) disclosed in
WO97/48787. According to these publications, molecular oxygen may
be used as the oxidant as an alternative to peroxide generating
systems. However, no role in catalysing bleaching by atmospheric
oxygen or air in an aqueous medium is reported.
[0006] WO-A-98/39098 and WO-A-98/39406 disclose classes of
complexes of a transition metal coordinated to a macropolycyclic
ligand, used as oxidation catalysts in laundry or cleaning
compositions. The compositions preferably comprise an oxygen
bleaching agent, as part or all of the laundry or cleaning adjunct
materials, which can be any of the oxidizing agents known for
laundry, hard surface cleaning, automatic dishwashing or denture
cleaning purposes. Oxygen bleaches are preferred, though other
oxidant bleaches such as oxygen may be used. Again, however, no
role in catalysing bleaching by atmospheric oxygen or air in an
aqueous medium is reported.
[0007] It has long been thought desirable to be able to use
atmospheric oxygen (air) as the source for a bleaching species, as
this 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.
[0008] 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.
[0009] Accordingly, it would be desirable to be able to provide a
bleaching system based on atmospheric oxygen or air that 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.
[0010] We have now found, surprisingly, that classes of complexes
of the type disclosed in WO-A-98/39098 and WO-A-98/39406 can be
used in an aqueous medium with atmospheric oxygen or air to bleach
substrates, even in the absence of a conventional oxygen bleaching
agent.
[0011] Accordingly, in a first aspect, the present invention
provides a bleaching composition comprising, in an aqueous medium,
atmospheric oxygen and an organic substance which forms a complex
with a transition metal, the complex catalysing bleaching of a
substrate by the atmospheric oxygen, wherein the aqueous medium is
substantially devoid of peroxygen bleach or a peroxy-based or
-generating bleach system,
[0012] wherein the organic substance forms a complex of a
transition metal, preferably selected from Mn(II), Mn(III), Mn(IV),
Mn(V), Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III), Ni(I),
Ni(II), Ni(III), Cu(I), Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV),
Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV),
W(V), W(VI), Pd(II), Ru(II), Ru(III) and Ru(IV), coordinated with a
macropolycyclic rigid ligand having at least 3 donor atoms, at
least two of which are bridgehead donor atoms. The medium is
therefore preferably insensitive or stable to catalase, which acts
on peroxy species.
[0013] In a second aspect, the present invention provides a method
of bleaching a substrate comprising applying to the substrate, in
an aqueous medium, an organic substance which forms a complex with
a transition metal, the complex catalysing bleaching of the
substrate by atmospheric oxygen, as further specified in the claim
24.
[0014] Furthermore, in a third aspect, the present invention
provides the use of an organic substance which forms a complex with
a transition metal, as a catalytic bleaching agent for a substrate
in an aqueous medium substantially devoid of peroxygen bleach or a
peroxy-based or -generating bleach system, the complex catalysing
bleaching of the substrate by the atmospheric oxygen, as further
specified in claim 29.
[0015] Advantageously, the method according to the present
invention permits all or the majority of the bleaching species in
the medium (on an equivalent weight basis) to be derived from
atmospheric oxygen. Thus, the medium can be made wholly or
substantially devoid of peroxygen bleach or a peroxy-based or
-generating bleach system. Furthermore, 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. The
catalytically activated bleaching system of the type in accordance
with the present invention, which is based on atmospheric oxygen,
is therefore both cost-effective and environmentally friendly.
[0016] Moreover, the bleaching system is operable under
unfavourable wash conditions which include low temperatures, short
contact times and low dosage requirements.
[0017] Furthermore, the method is effective in 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.
[0018] The bleaching method may be carried out by simply leaving
the substrate in contact with the medium for a sufficient period of
time. Preferably, however, the aqueous medium on or containing the
substrate is agitated.
[0019] It has also been found that after bleaching if the treated
substrate is dried by a tumble drier, ironing process or any other
heat-generating process wherein the temperature of the process is
between 35.degree. C. and 80.degree. C. the bleaching effect is
accelerated in comparison to drying at ambient temperatures.
[0020] The organic substance may comprise a preformed complex of a
ligand and a transition metal. Alternatively, the organic substance
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 organic substance 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.
[0021] The organic substance 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 I-IV, copper I-III, cobalt I-III,
nickel I-III, chromium II-VII, silver I-II, titanium II-IV,
tungsten IV-VI, palladium II, ruthenium II-V, vanadium II-V and
molybdenum II-VI.
[0022] In a preferred embodiment, the organic substance forms a
complex of the general formula:
[M.sub.aL.sub.kX.sub.n]Y.sub.m
[0023] in which:
[0024] M represents a metal selected from Mn(II)-(III)-(IV)-(V),
Cu(I)-(II)-(III), Fe(I)-(II)-(III)-(IV), Co(I)-(II)-(III),
Ni(I)-(II)-(III), Cr(II)-(III)-(IV)-(V)-(VI)-(VII),
Ti(II)-(III)-(IV), V(II)-(III)-(IV)-(V),
Mo(II)-(III)-(IV)-(V)-(VI), W(IV)-(V)-(VI), Pd(II),
Ru(II)-(III)-(IV)-(V) and Ag(I)-(II), and preferably selected from
Mn(II)-(III)-(IV)-(V), Cu(I)-(II), Fe(II)-(III)-(IV) and
Co(I)-(II)-(III);
[0025] L represents a macropolycyclic rigid ligand as herein
defined, or its protonated or deprotonated analogue;
[0026] 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, bit or tridentate manner,
preferably selected from O.sup.2-, RBO.sub.2.sup.2-, RCOO.sup.-,
RCONR.sup.-, OH.sup.-, NO.sub.3.sup.-, NO.sub.2.sup.-, NO, CO,
S.sup.2-, RS.sup.-, PO.sub.3.sup.4-, STP-derived anions,
PO.sub.3OR.sup.3-, H.sub.2O, CO.sub.3.sup.2-, HCO.sub.3.sup.-, ROH,
NRR'R", RCN, Cl.sup.-, Br.sup.-, OCN.sup.-, SCN.sup.-, CN.sup.-,
N.sub.3.sup.-, F.sup.-, , RO.sup.-, ClO.sub.4.sup.-,
SO.sub.4.sup.2-, HSO.sub.4.sup.-, SO.sub.3.sup.2- and
RSO.sub.3.sup.-, and more preferably selected from O.sup.2-,
RBO.sub.2.sup.2-, RCOO.sup.-, OH.sup.-, NO.sub.3.sup.-,
NO.sub.2.sup.-, NO, CO, CN.sup.-, S.sup.2-, RS.sup.-,
PO.sub.3.sup.4-, H.sub.2O, CO.sub.3.sup.2-, HCO.sub.3.sup.-, ROH,
NRR'R", Cl.sup.-, Br.sup.-, OCN.sup.-, SCN.sup.-, RCN,
N.sub.3.sup.-, F.sup.-, I.sup.-, RO.sup.-, ClO.sub.4.sup.-,
SO.sub.4.sup.2-, HSO.sub.4.sup.-, SO.sub.3.sup.2- and
RSO.sub.3.sup.- (preferably CF.sub.3SO.sub.3.sup.-);
[0027] Y represents any non-coordinated counter ion, preferably
selected from ClO.sub.4.sup.-, BR.sub.4.sup.-, [FeCl.sub.4].sup.-,
PF.sub.6.sup.-, RCOO.sup.-, NO.sub.3.sup.-, NO.sub.2.sup.-,
RO.sup.-, N.sup.+RR'R"R"', Cl.sup.-, Br.sup.-, F.sup.-, I.sup.-,
RSO.sub.3.sup.-, S.sub.2O.sub.6.sup.2-, OCN.sup.-, SCN.sup.-,
Li.sup.-, Ba.sup.2-, Na.sup.+, Mg.sup.2-, K.sup.+, Ca.sup.2+,
Cs.sup.+, PR.sub.4.sup.+, RBO.sub.2.sup.2-, SO.sub.4.sup.2-,
HSO.sub.4.sup.-, SO.sub.3.sup.2-, SbCl.sub.6.sup.-,
CuCl.sub.4.sup.2-, CN, PO.sub.4.sup.3-, HPO.sub.4.sup.2-,
H.sub.2PO.sub.4.sup.-, STP-derived anions, CO.sub.3.sup.2-,
HCO.sub.3.sup.- and BF.sub.4.sup.-, and more preferably selected
from ClO.sub.4.sup.-, BR.sub.4.sup.-, [FeCl.sub.4].sup.-,
PF.sub.6.sup.-, RCOO.sup.-, NO.sub.3.sup.-, NO.sub.2.sup.-,
RO.sup.-, N.sup.+RR'R"R"', Cl.sup.-, Br.sup.-, F.sup.-, I.sup.-,
RSO.sub.3.sup.- (preferably CF.sub.3SO.sub.3.sup.-),
S.sub.2O.sub.6.sup.2-, OCN.sup.-, SCN.sup.-, Li.sup.+, Ba.sup.2+,
Na.sup.+, Mg.sup.2+, K.sup.+, Ca.sup.2+, PR.sub.4.sup.+,
SO.sub.4.sup.2-, HSO.sub.4.sup.-, SO.sub.3.sup.2-, and
BF.sub.4.sup.-;
[0028] R, R', R", R"' independently represent a group selected from
hydrogen, hydroxyl, --OR (wherein R=alkyl, alkenyl, cycloalkyl,
heterocycloalkyl, aryl, heteroaryl or carbonyl derivative group),
--OAr, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl,
heteroaryl and carbonyl derivative groups, each of R, Ar, alkyl,
alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and
carbonyl derivative groups being optionally substituted by one or
more functional groups E, or R6 together with R7 and independently
R8 together with R9 represent oxygen, wherein E is selected from
functional groups containing oxygen, sulphur, phosphorus, nitrogen,
selenium, halogens, and any electron donating and/or withdrawing
groups, and preferably R, R', R", R"' represent hydrogen,
optionally substituted alkyl or optionally substituted aryl, more
preferably hydrogen or optionally substituted phenyl, naphthyl or
C.sub.1-4-alkyl;
[0029] a represents an integer from 1 to 10, preferably from 1 to
4;
[0030] k represents an integer from 1 to 10,
[0031] n represents zero or an integer from 1 to 10, preferably
from 1 to 4;
[0032] m represents zero or an integer from 1 to 20, preferably
from 1 to 8.
[0033] In a preferred embodiment, the present invention relates to
a method for oxidizing materials, said method comprising contacting
a material capable of being oxidized and a transition-metal
oxidation catalyst, in an aqueous medium essentially devoid of any
oxidation agent, wherein said transition metal oxidation catalyst
comprises a complex of a transition metal selected from the group
consisting of Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III),
Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I),
Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III),
V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II),
Ru(II), Ru(III), and Ru(IV), preferably Mn(II, Mn(III), Mn(IV),
Fe(II), Fe(III), Fe(IV), Cu(I), Cu(II), Cu(III), Co(I), Co(II),
Co(III), more preferably Mn(II), Mn(III), Fe(II), Fe(III), Cu(I),
Cu(II), Co(II), Co(III) coordinated with a macropolycyclic rigid
ligand, preferably a cross-bridged macropolycyclic ligand, having
at least 3 donor atoms, at least two of which are bridgehead donor
atoms.
[0034] The present invention also relates to catalytic systems
effective for oxidation of materials comprising: (a) a
catalytically effective amount, preferably from about 1 ppb to
about 99.9%, more typically from about 0.001 ppm to about 500 ppm,
more preferably from about 0.05 ppm to about 100 ppm (wherein "ppb"
denotes parts per billion by weight and "ppm" denotes parts per
million by weight), of a transition-metal oxidation catalyst,
wherein said transition-metal oxidation catalyst comprises a
complex of a transition metal selected from the group consisting of
Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(I),
Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III),
Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V),
Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III),
and Ru(IV) coordinated with a macropolycyclic rigid ligand,
preferably a cross-bridged macropolycyclic ligand, having at least
3 donor atoms, at least two of which are bridgehead donor atoms;
and (b) the balance, to 100%, of one or more adjunct materials.
[0035] Amounts of the essential transition-metal catalyst and
essential adjunct materials can vary widely depending on the
precise application. For example, the catalytic systems herein may
be provided as a concentrate, in which case the catalyst can be
present in a high proportion, for example 0.01%-80%, or more, of
the composition. The invention also encompasses catalytic systems
at their in-use levels; such systems include those in which the
catalyst is dilute, for example at ppb levels. Intermediate level
compositions, for example those comprising from about 0.01 ppm to
about 500 ppm, more preferably from about 0.05 ppm to about 50 ppm,
more preferably still from about 0.1 ppm to about 10 ppm of
transition-metal catalyst and the balance to 100%, preferably at
least about 0.1%, typically about 99% or more being solid-form or
liquid-form adjunct materials (for example fillers, solvents, and
adjuncts especially adapted to a particular use (for example paper
making adjuncts, detergent adjuncts, or the like).
[0036] The present invention preferably relates to catalytic
systems effective for oxidation of materials comprising: (a) a
catalytically effective amount, preferably from about 1 ppb to
about 49%, of a transition-metal oxidation catalyst, said catalyst
comprising a complex of a transition metal and a macropolycyclic
rigid ligand, preferably a cross-bridged macropolycyclic ligand,
wherein: (1) said transition metal is selected from the group
consisting of Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III),
Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I),
Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III),
V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II),
Ru(II), Ru(III), and Ru(IV); (2) said macropolycyclic rigid ligand
is coordinated by at least three, preferably at least four, more
preferably four or five donor atoms to the same transition metal
and comprises:
[0037] (i) an organic macrocycle ring containing three, preferably
four, or more donor atoms (preferably at least 3, more preferably
at least 4, of these donor atoms are N) separated from each other
by covalent linkages of at least one, preferably 2 or 3 non-donor
atoms, two to five (preferably three or four, more preferably four)
of these donor atoms being coordinated to the same transition metal
in the complex.
[0038] (ii) a linking moiety, preferably a cross-bridging chain,
which covalently connects at least 2 (preferably non-adjacent)
donor atoms of the organic macrocycle ring, said covalently
connected (preferably non-adjacent) donor atoms being bridgehead
donor atoms which are coordinated to the same transition metal in
the complex, and wherein said linking moiety (preferably a
cross-bridged chain) comprises from 2 to about 10 atoms (preferably
the cross-bridged chain is selected from 2, 3 or 4 non- donor
atoms, and 4-6 non-donor atoms with a further donor atom),
including for example, a cross-bridge which is the result of a
Mannich condensation of ammonia and formaldehyde; and
[0039] (iii) optionally, one or more non-macropolycyclic ligands,
preferably monodentate ligands, such as those selected from the
group consisting of H.sub.2O, ROH, NR.sub.3, RCN, OH.sup.-,
OOH.sup.-, RS.sup.-, RO.sup.-, RCOO.sup.-, OCN.sup.-, SCN.sup.-,
N.sub.3.sup.-, CN.sup.-, F.sup.-, Cl.sup.-, Br.sup.-, I.sup.-,
O.sub.2.sup.-, NO.sub.3.sup.-, NO.sub.2.sup.-, SO.sub.4.sup.2-,
SO.sub.3.sup.2-, PO.sub.4.sup.3-, organic phosphates, organic
phosphonates, organic sulphates, organic sultanates, and aromatic N
donors such as pyridines, pyrazines, pyrazoles, imidazoles,
benzimidazoles, pyrimidines, triazoles and thiazoles with R being
H, optionally substituted alkyl, optionally substituted aryl
(specific examples of monodentate ligands including phenolate,
acetate or the like); and (b) at least about 0.1%, preferably B%,
of one or more adjunct materials (where B%, the "balance" of the
composition expressed as a percentage, is obtained by subtracting
the weight of said component (a) from the weight of the total
composition and then expressing the result as a percentage by
weight of the total composition).
[0040] The present invention also preferably relates to catalytic
systems effective for oxidation of materials comprising: (a) a
catalytically effective amount, as identified supra, of a
transition-metal oxidation catalyst, said catalyst comprising a
complex of a transition metal and a macropolycyclic rigid ligand
(preferably a cross-bridged macropolycyclic ligand) wherein: (I)
said transition metal is selected from the group consisting of
Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(I),
Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III),
Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V),
Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III),
and Ru(IV), and (2) said macropolycyclic rigid ligand is selected
from the group consisting of: (i) the macropolycyclic rigid ligand
of formula (I) having denticity of 3 or 4: 1
[0041] (ii) the macropolycyclic rigid ligand of formula (II) having
denticity of 4 or 5 2
[0042] (iii) the macropolycyclic rigid ligand of formula (III)
having denticity of 5 or 6: 3
[0043] (iv) the macropolycyclic rigid ligand of formula (IV) having
denticity of 6 or 7 4
[0044] wherein in these formulas:- each "E" is the moiety
(CR.sub.n).sub.a-X-(CR.sub.n).sub.a', wherein X is selected from
the group consisting of O, S, NR and P, or a covalent bond, and
preferably X is a covalent bond and for each E the sum of a+a' is
independently selected from 1 to 5, more preferably 2 and 3.
[0045] each "G" is the moiety (CR.sub.n).sub.b.
[0046] each "R" is independently selected from H, alkyl, alkenyl,
alkynyl, aryl, alkylaryl
[0047] (e.g., benzyl), and heteroaryl, or two or more R are
covalently bonded to form an aromatic, heteroaromatic, cycloalkyl,
or heterocycloalkyl ring.
[0048] each "D" is a donor atom independently selected from the
group consisting of N, O, S, and P, and at least two D atoms are
bridgehead donor atoms coordinated to the transition metal (in the
preferred embodiments, all donor atoms designated D are donor atoms
which coordinate to the transition metal, in contrast with
heteroatoms in the structure which are not in D such as those which
may be present in E; the non-D heteroatoms can be non-coordinating
and indeed are non-coordinating whenever present in the preferred
embodiment).
[0049] "B" is a carbon atom or "D" donor atom, or a cycloalkyl or
heterocyclic ring.
[0050] each "n" is an integer independently selected from 1 and 2,
completing the valence of the carbon atoms to which the R moieties
are covalently bonded.
[0051] each "n"' is an integer independently selected from 0 and 1,
completing the valence of the D donor atoms to which the R moieties
are covalently bonded.
[0052] each "n"" is an integer independently selected from 0, 1,
and 2 completing the valence of the B atoms to which the R moieties
are covalently bonded.
[0053] each "a" and "a"' is an integer independently selected from
0-5, preferably a+a' equals 2 or 3, wherein the sum of all "a" plus
"a'" in the ligand of formula (I) is within the range of from about
7 to about 11. The sum of all "a" plus "a" in the ligand of formula
(II) is within the range of from about 6 (preferably 8) to about
12. The sum of all "a" plus "a'" in the ligand of formula (III) is
within the range of from about 8 (preferably 10) to about 15, and
the sum of all "a" plus "a'" in the ligand of formula (IV) is
within the range of from about 10 (preferably 12) to about 18.
[0054] each "b" is an integer independently selected from 0-9,
preferably 0-5 (wherein when b=0, (CR.sub.n).sub.0 represents a
covalent bond), or in any of the above formulas, one or more of the
(CR.sub.n).sub.b moieties covalently bonded from any D to the B
atom is absent as long as at least two (CR.sub.n).sub.b covalently
bond two of the D donor atoms to the B atom in the formula, and the
sum of all "b" is within the range of from about 1 to about 5;
and
[0055] (iii) optionally, one or more non-macropolycyclic ligands;
and
[0056] (b) adjunct materials at suitable levels, as identified
hereinabove.
[0057] The present invention also uses complexes formed by
transition metals selected from: Mn(II), Mn(III), Mn(IV), Mn(V),
Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II),
Ni(III), Cu(I), Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V),
Cr(VI), V(III), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V),
W(VI), Pd(II), Ru(II), Ru(III), and Ru(IV), preferably Mn(II,
Mn(III), Mn(IV), Fe(II), Fe(III), Fe(IV), Cu(I), Cu(II), Cu(III),
Co(II), Co(III) preferably Mn(II), Mn(III), Fe(II), Fe(III), Cu(I),
Cu(II), Co(II), Co(III) and the cross-bridged tetraazamacrocycle
and cross-bridged pentaazamacrocycle ligands; these complexes
include those in which the cross-bridging moiety is a C2-C4 alkyl
moiety and in which there is a mole ratio of macrocycle to metal of
1:1, and moreover these are most preferably monometallic
mononuclear complexes, though in general, dimetallic or
multimetallic complexes are not excluded.
[0058] A preferred sub-group of the transition-metal complexes
includes the Mn(II), Fe(II), and Cu(II) complexes of the ligand
1.2: 5
[0059] wherein m and n are integers from 0 to 2, p is an integer
from 1 to 6, preferably m and n are both 0 or both 1 (preferably
both 1), or m is 0 and n is at least 1; and p is 1;
[0060] and A is a nonhydrogen moiety preferably having no aromatic
content; more particularly each A can vary independently and is
preferably selected from methyl, ethyl, propyl, isopropyl, butyl,
isobutyl, tert-butyl, C5-C20 alkyl, and one, but not both, of the A
moieties is benzyl, and combinations thereof. In one such complex,
one A is methyl and one A is benzyl.
[0061] All parts, percentages and ratios used herein are expressed
as percent weight unless otherwise specified.
[0062] The catalytic systems of the present invention comprise a
particularly selected transition metal oxidation catalyst which is
a complex of a transition metal and a macropolycyclic rigid ligand,
preferably one which is cross-bridged. The catalytic systems do not
contain any added oxidants such as hydrogen peroxide sources,
peroxy acids, peroxy acid precursors, monoperoxysulphate (e.g.
Oxone.sup.(.TM.), manufactured by DuPont), chlorine, ClO.sub.2 or
hypochlorite. Therefore, the aqueous medium of the catalytic
systems described herein are essentially devoid of conventional
oxidation agents.
[0063] To secure the benefits of the invention, a substrate
material, such as a chemical compound to be oxidized, or a
commercial mixture of materials such as a paper pulp, or a soiled
material such as a textile containing one or more materials or
soils to be oxidized, is added to the catalytic system under widely
ranging conditions further described hereinafter.
[0064] The present invention catalytic systems also have utility in
the area of oxidizing (preferably including bleaching) wood pulp
for use in, for example, paper making processes. Other utilities
include oxidative destruction of waste materials or effluents.
[0065] Effective Amounts of Catalyst Materials
[0066] The term "catalytically effective amount", as used herein,
refers to an amount of the transition-metal oxidation catalyst
present in the present invention catalytic systems, or during use
according to the present invention methods, that is sufficient,
under whatever comparative or use conditions are employed, to
result in at least partial oxidation of the material sought to be
oxidized by the catalytic systems or method. For example, in the
synthesis of epoxides from alkenes, the catalytic amount is that
amount which is sufficient to catalyze the desired epoxidation
reaction. As note, the invention encompasses catalytic systems both
at their in-use levels and at the levels which may commercially be
provided for sale as "concentrates"; thus "catalytic systems"
herein include both those in which the catalyst is highly dilute
and ready to use, for example at ppb levels, and compositions
having rather higher concentrations of catalyst and adjunct
materials, intermediate level compositions, as noted in summary,
can include those comprising from about 0.01 ppm to about 500 ppm,
more preferably from about 0.05 ppm to about 50 ppm, more
preferably still from about 0.1 ppm to about 10 ppm of
transition-metal catalyst and the balance to 100%, typically about
99% or more, being solid-form or liquid-form adjunct materials (for
example fillers, solvents, and adjuncts especially adapted to a
particular use, such as papermaking adjuncts, detergent adjuncts,
or the like). In terms of amounts of materials, the invention also
encompasses a large number of novel transition-metal catalysts
per-se, especially including their substantially pure (100% active)
forms. Other amounts, for example of oxidant materials and other
adjuncts for specialized uses are illustrated in more detail
hereinafter.
[0067] Transition-Metal Oxidation Catalysts:
[0068] The present invention catalytic systems comprise a
transition-metal oxidation catalyst. In general, the catalyst
contains an at least partially covalently bonded transition metal,
and bonded thereto at least one particularly defined
macropolycyclic rigid ligand, preferably one having four or more
donor atoms and which is cross-bridged or otherwise tied so that
the primary macrocycle ring complexes in a folded conformation
about the metal. Catalysts herein are thus neither of the more
conventional macrocyclic type: e.g., porphyrin complexes, in which
the metal can readily adopt square-planar configuration; nor are
they complexes in which the metal is fully encrypted in a ligand.
Rather, the presently useful catalysts represent a selection of all
the many complexes, hitherto largely unrecognized, which have an
intermediate state in which the metal is bound in a "cleft".
Further, there can be present in the catalyst one or more
additional ligands, of generally conventional type such as chloride
covalently bound to the metal; and, if needed, one or more
counter-ions, most commonly anions such as chloride,
hexafluorophosphate, perchlorate or the like; and additional
molecules to complete crystal formation as needed, such as water of
crystallization. Only the transition-metal and macropolycyclic
rigid ligand are, in general, essential.
[0069] Transition-metal oxidation catalysts useful in the invention
catalytic systems can in general include known compounds where they
conform with the invention definition, as well as, more preferably,
any of a large number of novel compounds expressly designed for the
present oxidation catalysis uses and non-limitingly illustrated by
any of the following:
[0070]
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicycle[6.6.2]hexadecane
Manganese (II)
[0071]
Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane
Manganese(II)
[0072]
Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(II) Hexafluorophosphate
[0073]
Aquo-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexacieca-
ne Manganese(III) Hexafluorophosphate
[0074]
Diaquo-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane
Manganese(II) Hexafluorophosphate
[0075]
Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(II) Tetrafluoroborate
[0076] Diaquo-4,10-dimethyl-1,4,7,10-tetraazabicyclo
[5.5.2]tetradecane Manganese(II) Tetrafluoroborate
[0077]
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(III) Hexafluorophosphate
[0078]
Dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(II)
[0079] Dichloro-5,I 2-dibenzyl-1,5,8, I 2-tetraazabicyclo[6.
6.2]hexadecane Manganese(II)
[0080]
Ddichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexade-
cane Manganese(II)
[0081] Dichloro-5-n-octyl-12-methyl- I,5,8, I
2-tetraazabicyclo[6.6.2]hexa- decane Manganese(II)
Dichloro-5-n-butyl-12-methyl-I,
5,8,12-tetraaza-bicyclo[6.6.2]hexadecane Manganese(II)
[0082]
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Iron(II)
[0083]
Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane
Iron(II)
[0084]
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Copper(II)
[0085]
Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane
Copper(II)
[0086]
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadacane
Cobalt(II)
[0087]
Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane
Cobalt(II)
[0088] Dichloro
5,12-dimethyl-4-phenyl-1,5,8,12-tetraazabicyclo[6.6.2]hexa- decane
Manganese(II)
[0089]
Dichloro-4,10-dimethyl-3-phenyl-1,4,7,10-tetraazabicyclo[5.5.2]tetr-
adecane Manganese(II)
[0090]
Dichloro-5,12-dimethyl-4,9-diphenyl-1,5,8,12-tetraazabicyclo[6.6.2]-
hexadecane Manganese(II)
[0091]
Dichloro-4,10-dimethyl-3,8-diphenyl-1,4,7,10-tetraazabicyclo[5.5.2]-
tetradecane Manganese(II)
[0092]
Dichloro-5,12-dimethyl-2,11-diphenyl-1,5,8,12-tetraazabicyclo[6.6.2-
]hexadecane Manganese(II)
[0093]
Dichloro-4,10-dimethyl-4,9-diphenyl-1,4,7,10-tetraazabicyclo[5.5.2]-
tetradecane Manganese(II)
[0094] Dichloro-2,4,5,9, 11,12-hexamethyl-1,5,
8,12-tetraazabicyclo[6.6.2]- hexadecane Manganese(II)
[0095]
Dichloro-2,3,5,9,10,12-hexamethyl-1,5,8,12-tetraazabicyclo[6.6.2]he-
xadecane Manganese(II)
[0096]
Dichloro-2,2,4,5,9,9,11,12-octamethyl-1,5,8,12-tetraazabicyclo[6.6.-
2]hexadecane Manganese(II)
[0097]
Dichloro-2,2,4,5,9,11,11,12-octamethyl-1,5,8,12-tetraazabicyclo[6.6-
.2]hexadecane Manganese(II)
[0098]
Dichloro-3,3,5,10,10,12-hexamethyl-1,5,8,12-tetraazabicyclo[6.6.2]h-
exadecane Manganese(II)
[0099]
Dichloro-3,5,10,12-tetramethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexad-
ecane Manganese(II)
[0100]
Dichloro-3-butyl-5,10,12-trimethyl-1,5,8,12-tetraazabicyclo[6.6.2]h-
exadecane Manganese(II)
[0101] Dichloro-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(II)
[0102] Dichloro-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane
Manganese (II)
[0103] Dichloro-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Iron(II)
[0104] Dichloro-1,4,7,10-tetraazablcyclo[5.5.2]tetradecane
Iron(II)
[0105]
Aquo-chloro-2-(2-hydroxyphenyl)-5,12-dimethyl,5,8,12-tetraazabicycl-
o[6.6.2]hexadecane Manganese(II)
[0106]
Aquo-chloro-10-(2-hydroxybenzyl)-4,10-dimethyl-1,4,7,10-tetraazabic-
yclo[5.5.2)tetradecane Manganese(II)
[0107] Chloro-2-(2-hydroxybenzyl)-5-methy
1,5,8,12-tetraazabicyclo[6.6.2]h- exadecane Manganese(II)
[0108]
Chloro-10-(2-hydroxybenzyl)-4-methyl-1,4,7,10-tetraazabicyclo[5.5.2-
]tetradecane Manganese(II)
[0109]
Chloro-5-methyl-12-(2-picolyl)-1,5,8,12-tetraazabicyclo[6.6.2]hexad-
ecane Manganese(II) Chloride
[0110]
Chloro-4-methyl-10-(2-picolyl)-1,4,7,10-tetraazabicyclo[5.5.2]tetra-
decane Manganese(II) Chloride
[0111] Dichloro-5-(2-sulphato)dodecyl-12-methyl-I 5,8
12-tetraazabicyclo[6.6.2]hexadecane Manganese(III)
[0112]
Aquo-Chloro-5-(2-sulphato)dodecyl-12-methyl-1,5,8,12-tetraazabicycl-
o[6.6.2]hexadecane Manganese(II)
[0113]
Aquo-Chloro-5-(3-sulphonopropyl)-12-methyl-1,5,8,12-tetraazabicyclo-
[6.6.2]hexadecane Manganese(II)
[0114]
Dichloro-5-(Trimethylammoniopropyl)dodecyl-12-methyl-1,5,8,12-tetra-
azabicyclo[6.6.2]hexadecane Manganese(III) Chloride
[0115] Dichloro-5,12-dimethyl-1,4,7, 10,13-pentaazabicyclo[8.
5.2]heptadecane Manganese(II)
[0116]
Dichloro-14,20-dimethyl-1,10,14,20-tetraazatriyclo[8.6.6]docosa-3(8-
),4,6-triene Manganese(II)
[0117]
Dichloro-4.11-dimethyl-1,4,7,11-tetraazabicyclo[6.5.2]pentadecane
Manganese(II)
[0118]
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[7.6.2]heptadecane
Manganese(II)
[0119]
Dichloro-5.13-dimethyl-1,5,9,13-tetraazabicyclo[7.7.2]heptadecane
Manganese(II)
[0120]
Dichloro-3,10-bis(butylcarboxy)-5,12-dimethyl-1,5,8,12-tetraazabicy-
clo[6.6.2]hexadecane Manganese(II)
[0121] Diaquo-3,
10-dicarboxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2-
]hexadecane Manganese(II)
[0122] Chloro-20-methyl-1,9,20,24,25-pentaaza-tetracyclo[7.
7.7.1.sup.3,7.1.sup.11,15]pentacosa-3,5,7(24),11,1315(25)-hexaene
manganese (II) Hexafluorophosphate
[0123]
Trifluoromethanesulphono-20-methyl-1,9,20,24,25-peritaazatetracyclo-
[7.7.7.1.sup.3,7.1.sup.11,15]pentacosa-3,5,7(24),11,13,15(25)-hexaene
Manganese(II) trifluoromethanesulphonate
[0124]
Trifluoromethanesulphono-20-methyl-1,9,20,24,25-pentaazatetracyclo[-
7.7.7.1.sup.3,7.1.sup.11,15.]pentacosa-3,5,7(24),11,13,15(25)-hexaene
Iron(II) trifluoromethanesulphonate
[0125]
Chloro-5,12,17-trimethyl-1,5,8,12,17-pentaazabicyclo[6.6.5]nonadeca-
ne Manganese(II) hexafluorophosphate
[0126]
Chloro-4,10,15-trimethyl-1,4,7,10,15-pentaazabicyclo[5.5.5.]heptade-
cane Manganese(II) hexafluorophosphate
[0127]
Chloro-5,12,17-trlmethyl-1,5,8,12,17-pentaazabicyclo[6.6.5]nonadeca-
ne Manganese(II) chloride
[0128]
Chloro-4,10,15-trimethyl-1,4,7,10,15-pentaazabicyclo[5.5.5]heptadec-
ane Manganese(II) chloride
[0129] Preferred complexes useful as transition-metal oxidation
catalysts more generally include not only monometallic, mononuclear
kinds such as those illustrated hereinabove but also
bimetallic,trimetallic or cluster kinds, especially when the
polymetallic kinds transform chemically in the presence of medium
(water, hydroxyl anions, surfactants, etc) to form a mononuclear,
monometallic active species. Monometallic, mononuclear complexes
are preferred. As defined herein, a monometallic transition-metal
oxidation catalyst contains only one transition metal atom per mole
of complex. A monometallic, mononuclear complex is one in which any
donor atoms of the essential macrocyclic ligand are bonded to the
same transition metal atom, that is, the essential ligand does not
"bridge" across two or more transition-metal atoms transition
metals of the catalyst. Just as the macropolycyclic ligand cannot
vary indeterminately for the present useful purposes, nor can the
metal. An important part of the invention is to arrive at a match
between ligand selection and metal selection which results in
excellent oxidation catalysis. In general, transition-metal
oxidation catalysts therein comprise a transition metal selected
from the group consisting of Mn(II), Mn(III), Mn(IV), Mn(V),
Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II),
Ni(III), Cu(I), Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V),
Cr(VI), V(III) , V(IV),V(V), Mo(IV), Mo(V), Mo(VI) ,W(IV), W(V),
W(VI) , Pd(II), Ru(II), Ru(III), and Ru(IV). Preferred
transition-metals in the instant transition-metal oxidation
catalyst include manganese, iron, copper, and cobalt. Preferred
oxidation states include the (II) and (III) oxidation states.
Manganese(II) in both the low-spin configuration and high spin
complexes are included. It is to be noted that complexes such as
low-spin Mn(II) complexes are rather rare in all of coordination
chemistry. The designation (II) or (III) denotes a coordinated
transition metal having the requisite oxidation state; the
coordinated metal atom is not a free ion or one having only water
as a ligand.
[0130] Ligands
[0131] In general, as used herein, a "ligand" is any moiety capable
of direct covalent bonding to a metal ion. Ligands can be charged
or neutral and may range widely, including simple monovalent
donors, such as chloride, or simple amines which form a single
coordinate bond and a single point of attachment to a metal; to
oxygen or ethylene, which can form a three-membered ring with a
metal and thus can be said to have two potential points of
attachment, to larger moieties such as ethylenediamine or aza
macrocycles, which form up to the maximum number of single bonds to
one or more metals that are allowed by the available sites on the
metal and the number of lone pairs or alternate bonding sites of
the free ligand. Numerous ligands can form bonds other than simple
donor bonds, and can have multiple points of attachment.
[0132] Ligands useful herein can fall into several groups: the
essential macropolycyclic rigid ligand, preferably a cross-bridged
macropolycycle (preferably there will be one such ligand in a
useful transition-metal complex, but more, for example two, can be
present, but not in preferred mononuclear complexes); other,
optional ligands, which in general are different from the essential
cross-bridged macropolycycle (generally there will be from 0 to 4,
preferably from 1 to 3 such ligands); and ligands associated
transiently with the metal as part of the catalytic cycle, these
latter typically being related to water, hydroxide, oxygen, water,
hydroxide, or peroxides. Ligands of the third group are not
essential for defining the metal oxidation catalyst, which is a
stable, isolable chemical compound that can be fully characterized.
Ligands which bind to metals through donor atoms each having at
least a single lone pair of electrons available for donation to a
metal have a donor capability, or potential denticity, at least
equal to the number of donor atoms. in general, that donor
capability may be fully or only partially exercised.
[0133] Macropolycyclic Rigid Ligands
[0134] To arrive at the instant transition-metal catalysts, a
macropolycyclic rigid ligand is essential. This is coordinated
(covalently connected to any of the above-identified
transition-metals) by at least three, preferably at least four, and
most preferably four or five, donor atoms to the same transition
metal.
[0135] Generally, the macropolycyclic rigid ligands herein can be
viewed as the result of imposing additional structural rigidity on
specifically selected "parent macrocycles". The term "rigid" herein
has been defined as the constrained converse of flexibility: see D.
H. Busch, Chemical Reviews (1993), p 847-860, incorporated by
reference. More particularly, "rigid" as used herein means that the
essential ligand, to be suitable for the purposes of the invention,
must be determinably more rigid than a macrocycle ("parent
macrocycle") which is otherwise identical (having the same ring
size and type and number of atoms in the main ring) but lacks the
superstructure (especially linking moieties or, preferably
cross-bridging moieties) of the present ligands. In determining the
comparative rigidity of the macrocycles with and without
superstructures, the practitioner will use the free form (not the
metal-bound form) of the macrocycles. Rigidity is well-known to be
useful in comparing macrocycles; suitable tools for determining,
measuring or comparing rigidity include computational methods (see,
for example, Zimmer, Chemical Review, (1995), 95(38), 2629-2648 or
Hancock et al., Inorganica Chimica Acta (1989), 164, 73-84). A
determination of whether one macrocycle is more rigid than another
can be often made by simply making a molecular model, thus it is
not in general essential to know configurational energies in
absolute terms or to precisely compute them. Excellent comparative
determinations of rigidity of one macrocycle vs. another can be
made using inexpensive personal computer-based computational tools,
such as ALCHEMY III, commercially available from Tripos Associates.
Tripos also has available more expensive software permitting not
only comparative, but absolute determinations; ultimately, SHAPES
can be used (see Zimmer cited supra). One observation which is
significant in the context of the present invention is that there
is an optimum for the present purposes when the parent macrocycle
is distinctly flexible as compared to the cross-bridged form. Thus,
unexpectedly, it is preferred to use parent macrocycles containing
at least four donor atoms, such as cyclam derivatives, and to
cross-bridge them, rather than to start with a more rigid parent
macrocycle. Another observation is that cross-bridged macrocycles
are significantly preferred over macrocycles which are bridged in
other manners.
[0136] The macrocyclic rigid ligands herein are of course not
limited to being synthesised from any performed macrocycle plus
performed "rigidizing" or "conformation-modifying" element: rather,
a wide variety of synthetic means, such as template syntheses, are
useful. See for example Busch et al., reviewed in "Heterocyclic
compounds: Aza-crown macrocycles", J. S. Bradshaw et. al., referred
to in the Background Section hereinbefore for synthetic
methods.
[0137] In an embodiment of the present invention, the
macropolycyclic rigid ligands herein include those comprising:
[0138] (i) an organic macrocycle ring containing three, preferably
four, or more donor atoms (preferably at least 3, more preferably
at leas 4, of these donor atoms are N) separated from each other by
covalent linkages of at least one, preferably 2 or 3, non-donor
atoms, two to five (preferably three to four, more preferably four)
of these donor atoms being coordinated to the same transition metal
in the complex; and p1 (ii) a linking moiety, preferably a
cross-bridging chain, which covalently connects at least 2
(preferably non-adjacent) donor atoms of the organic macrocycle
ring, said covalently connected (preferably nonadjacent) donor
atoms being bridgehead donor atoms Which are coordinated to the
same transition metal in the complex, and wherein said linking
moiety (preferably a cross-bridged chain) comprises from 2 to about
10 atoms (preferably the cross-bridged chain is selected from 2, 3
or 4 non-donor atoms, and 4-6 non-donor atoms with a further donor
atom).
[0139] While clear from the various contexts and illustrations
already presented, the practitioner may further benefit if certain
terms receive additional definition and illustration. As used
herein, "macrocyclic rings" are covalently connected rings formed
from three or more, preferably four or more, donor atoms (i.e.,
heteroatoms such as nitrogen or oxygen) with carbon chains
connecting them, and any macrocycle ring as defined herein must
contain a total of at least ten, preferably at least twelve, atoms
in the macrocycle ring. A macropolycyclic rigid ligand herein may
contain more than one ring of any sort per ligand, but at least one
macrocycle ring must be identifiable. Moreover, in the preferred
embodiments, no two hetero- atoms are directly connected. Preferred
transition-metal oxidation catalysts are those wherein the
macropolycyclic rigid ligand comprises an organic macrocycle ring
(main ring) containing at least 10-20 atoms, preferably 12-18
atoms, more preferably from about 12 to about 20 atoms, most
preferably 12 to 16 atoms.
[0140] "Donor atoms" herein are heteroatoms such as nitrogen,
oxygen, phosphorus or sulphur, which when incorporated into a
ligand still have at least one lone pair of electrons available for
forming a donor-acceptor bond with a metal. Preferred
transition-metal oxidation catalyst are those wherein the donor
atoms in the organic macrocycle ring of the cross-bridged
macropolycyclic ligand are selected from the group consisting of N,
O; S, and P, preferably N and O, and most preferably all N. Also
preferred are cross-bridged macropolycyclic ligands comprising 4 or
5 donor atoms, all of which are coordinated to the same transition
metal. Most preferred transition-metal oxidation catalysts are
those wherein the cross-bridged macropolycyclic ligand comprises 4
nitrogen donor atoms all coordinated to the same transition metal,
and those wherein the cross-bridged macropolycyclic ligand
comprises 5 nitrogen atoms all coordinated to the same transition
metal.
[0141] "Non-donor atoms" of the macropolycyclic rigid ligand herein
are most commonly carbon, though a number of atom types can be
included, especially in optional exocyclic substituents (such as
"pendant" moieties, illustrated hereinafter) of the macrocycles,
which are neither donor atoms for purposes essential to form the
metal catalysts, nor are they carbon. Thus, in the broadest sense,
the term "non- donor atoms" can refer to any atom not essential to
forming donor bonds with the metal of the catalyst. Examples of
such atoms could include heteroatoms such as sulphur as
incorporated in a non-coordinatable sulphonate group, phosphorus as
incorporated into a phosphonium salt moiety, phosphorus as
incorporated into a V(V) oxide, a non-transition metal, or the
like. In certain preferred embodiments, all non-donor atoms are
carbon.
[0142] The term "macropolycyclic ligand" is used herein to refer to
the essential ligand required for forming the essential metal
catalyst. As indicated by the term, such a ligand is both a
macrocycle and is polycyclic. "Polycyclic" means at least bicyclic
in the conventional sense. The essential macropolycyclic ligands
must be rigid, and preferred ligands must also cross-bridged.
[0143] Non-limiting examples of macropolycyclic rigid ligands, as
defined herein, include 1.3-1.7: 6
[0144] Ligand 1.3 is a macropolycyclic rigid ligand in accordance
with the invention which is a highly preferred, cross-bridged,
methyl-substituted (all nitrogen atoms tertiary) derivative of
cyclam. Formally, this ligand is named
5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane using the
extended von Baeyer system. see "A Guide to IUPAC Nomenclature of
Organic Compounds: recommendations 1993", R. Panico, W. H. Powell
and J-C Richer {Eds.}, Blackwell Scientific Publications, Boston,
1993; see especially section R-2.4.2.1. According to conventional
terminology, N1 and N8 are "bridgehead atoms"; as defined herein,
more particularly "bridgehead donor atoms" since they have lone
pairs capable of donation to a metal. N1 is connected to two
non-bridgehead donor atoms, N5 and N12, by distinct saturated
carbon chains 2,3,4 and 14,13 and to bridgehead donor atom N8 by a
"linking moiety" a,b which here is a saturated carbon chain of two
carbon atoms. N8 is connected to two non-bridgehead donor atoms, N5
and N12, by distinct chains 6,7 and 9,10,11. Chain a,b is a
"linking moiety" as defined herein, and is of the special,
preferred type referred to as a "cross-bridging" moiety. The
"macrocyclic ring" of the ligand supra, or "main ring" (IUPAC),
includes all four donor atoms and chains 2,3,4; 6,7; 9,10,11 and
13,14 but not a,b. This ligand is conventionally bicyclic. The
short bridge or "linking moiety" a,b is a "cross-bridge" as defined
herein, with a,b bisecting the macrocyclic ring. 7
[0145] Ligand 1.4 lies within the general definition of
macropolycyclic rigid ligands as defined herein, but is not a
preferred ligand since it is not "cross-bridged" as defined herein.
Specifically, the "linking moiety" a,b connects "adjacent" donor
atoms N1 and N12, which is outside the preferred embodiment of the
present invention: see for comparison the preceding macrocyclic
rigid ligand, in which the linking moiety a,b is a cross-bridging
moiety and connects "nonadjacent" donor atoms. 8
[0146] Ligand 1.5 lies within the general definition of
macropolycyclic rigid ligands as defined herein, but is not a
preferred ligand since it contains only three donor atoms, all of
which are bridgehead donor atoms. 9
[0147] Ligand 1.6 lies within the general definition of
macropolycyclic rigid ligands as defined herein. This ligand can be
viewed as a "main ring" which is a tetraazamacrocycle having three
bridgehead donor atoms. This macrocycle is bridged by a "linking
moiety" having a structure more complex than a simple chain,
containing as it does a secondary ring. The linking moiety includes
both a "cross-bridging" mode of bonding, and a non-cross-bridging
mode. 10
[0148] Ligand 1.7 lies within the general definition of
macropolycyclic rigid ligands. Five donor atoms are present; two
being bridgehead donor atoms. This ligand is a preferred
cross-bridged ligand. It contains no exocyclic or pendant
substituents which have aromatic content.
[0149] In contrast, for purposes of comparison, the following
ligands (1.8 and 1.9) conform neither with the broad definition of
macropolycyclic rigid ligands in the present invention, nor with
the preferred cross-bridged sub-family thereof and therefore are
completely outside the present invention: 11
[0150] In the ligand supra, neither nitrogen atom is a bridgehead
donor atom. There are insufficient donor atoms. 12
[0151] The ligand supra is also outside the present invention. The
nitrogen atoms are not bridgehead donor atoms, and the two-carbon
linkage between the two main rings does not meet the invention
definition of a "linking moiety" since, instead of linking across a
single macrocycle ring, it links two different rings. The linkage
therefore does not confer rigidity as used in the term
"macropolycyclic rigid ligand". See the definition of "linking
moiety" hereinafter.
[0152] Generally, the essential macropolycyclic rigid ligands (and
the corresponding transition-metal catalysts) herein comprise:
[0153] (a) at least one macrocycle main ring comprising three or
more heteroatoms; and
[0154] (b) a covalently connected non-metal superstructure capable
of increasing the rigidity of the macrocycle, preferably selected
from
[0155] (i) a bridging superstructure, such as a linking moiety;
[0156] (ii) a cross-bridging superstructure, such as a
cross-bridging linking moiety; and
[0157] (iii) combinations thereof.
[0158] The term "superstructure" is used herein as defined by Busch
et al., in the Chemical Reviews article incorporated
hereinabove.
[0159] Preferred superstructures herein not only enhance the
rigidity of the parent macrocycle, but also favor folding of the
macrocycle so that it co-ordinates to a metal in a cleft. Suitable
superstructures can be remarkably simple, for example a linking
moiety such as any of those illustrated in 1.10 and 1.11 below, can
be used. 13
[0160] wherein n is an integer, for example from 2 to 8, preferably
less than 6, typically 2 to 4, or 14
[0161] wherein m and n are integers from about 1 to 8, more
preferably from 1 to 3; Z is N or CH; and T is a compatible
substituent, for example H, alkyl, trialkylammonium, halogen,
nitro, sulphonate, or the like. The aromatic ring in I. 1 1 can be
replaced by a saturated ring, in which the atom in Z connecting
into the ring can contain N, O, S or C.
[0162] Without intending to be limited by theory, it is believed
that the preorganization built into the macropolycyclic ligands
herein that leads to extra kinetic and/or thermodynamic stability
of their metal complexes arises from either or both of topological
constraints and enhanced rigidity (loss of flexibility) compared to
the free parent macrocycle which has no superstructure. The
macropolycyclic rigid ligands as defined herein and their preferred
cross-bridged sub-family, which can be said to be "ultra-rigid",
combine two sources of fixed preorganization. In preferred ligands
herein, the linking moieties and parent macrocycle rings are
combined to form ligands which have a significant extent of "fold",
typically greater than in many known superstructured ligands in
which a superstructure is attached to a largely planar, often
unsaturated macrocycle. See, for example, D. H. Busch, Chemical
Reviews. (1993), 93, 847-880. Further, the preferred ligands herein
have a number of particular properties, including (1) they are
characterized by very high proton affinities, as in so-called
"proton sponges"; (2) they tend to react slowly with multivalent
transition metals, which when combined with (1) above, renders
synthesis of their complexes with certain hydrolyzable metal ions
difficult in hydroxylic solvents; (3) when they are coordinated to
transition metal atoms as identified herein, the ligands result in
complexes that have exceptional kinetic stability such that the
metal ions only dissociate extremely slowly under conditions that
would destroy complexes with ordinary ligands; and (4) these
complexes have exceptional thermodynamic stability; however, the
unusual kinetics of ligand dissociation from the transition metal
may defeat conventional equilibrium measurements that might
quantitate this property.
[0163] Other usable but more complex superstructures suitable for
the present invention purposes include those containing an
additional ring, such as in 1.6. Other bridging superstructures
when added to a macrocycle include, for example, 1.4. In contrast,
cross-bridging superstructures unexpectedly produce a substantial
improvement in the utility of a macrocyclic ligand for use in
oxidation catalysis: a preferred cross-bridging superstructure is
1.3.
[0164] A superstructure illustrative of a bridging plus
cross-bridging combination is 1.12: 15
[0165] in 1.12, linking moiety (i) is cross-bridging, while linking
moiety (ii) is not.1.12 is less preferred than 1.3.
[0166] More generally, a "linking moiety", as defined herein, is a
covalently linked moiety comprising a plurality of atoms which has
at least two points of covalent attachment to a macrocycle ring and
which does not form part of the main ring or rings of the parent
macrocycle. In other terms, with the exception of the bonds formed
by attaching it to the parent macrocycle, a linking moiety is
wholly in a superstructure.
[0167] The terms "cross-bridged" or "cross-bridging", as used
herein, refers to covalent ligation, bisection or "tying" of a
macrocycle ring in which two donor atoms of the macrocycle ring are
covalently connected by a linking moiety, for example an additional
chain distinct from the macrocycle ring, and further, preferably,
in which there is at least one donor atom of the macrocycle ring in
each of the sections of the macrocycle ring separated by the
ligation, bisection or tying, cross-bridging is not present in
structure 1.4 hereinabove; it is present in 1.3, where two donor
atoms of a preferred macrocycle ring are connected in such manner
that there is not a donor atom in each of the bisection rings. Of
course, provided that cross-bridging is present, any other kind of
bridging can optionally be added and the bridged macrocycle will
retain the preferred property of being "cross-bridged": see
structure 1.12. A "cross-bridged chain" or "cross-bridging chain",
as defined herein, is thus a highly preferred type of linking
moiety comprising a plurality of atoms which has at least two
points of covalent attachment to a macrocycle ring and which does
not form part of the original macrocycle ring (main ring), and
further, which is connected to the main ring using the rule
identified in defining the term "cross-bridging".
[0168] The term "adjacent" as used herein in connection with donor
atoms in a macrocycle ring means that there are no donor atoms
intervening between a first donor atom and another donor atom
within the macrocycle ring; all intervening atoms in the ring are
nor-donor atoms, typically they are carbon atoms. The complementary
term "non-adjacent" as used herein in connection with donor atoms
in a macrocycle ring means that there is at least one donor atom
intervening between a first donor atom and another that is being
referred to. In preferred cases such as a cross-bridged
tetraazamacrocycle, there will be at least a pair of non-adjacent
donor atoms which are bridgehead atoms, and a further pair of
non-bridgehead donor atoms.
[0169] "Bridgehead" atoms herein are atoms of a macropolycyclic
ligand which are connected into the structure of the macrocycle in
such manner that each non-donor bond to such an atom is a covalent
single bond and there are sufficient covalent single bonds to
connect the atom termed "bridgehead" such that it forms a junction
of at least two rings, this number being the maximum observable by
visual inspection in the un-coordinated ligand.
[0170] In general, the metal oxidation catalysts herein may contain
bridgehead atoms which are carbon, however, and importantly, in
certain preferred embodiments, all essential bridgehead atoms are
heteroatoms, all heteroatoms are tertiary, and further, they each
co-ordinate through lone pair donation to the metal. Thus,
bridgehead atoms are junction points not only of rings in the
macrocycle, but also of chelate rings.
[0171] The term "a further donor atom" unless otherwise
specifically indicated, as used herein, refers to a donor atom
other than a donor atom contained in the macrocycle ring of an
essential macropolycycle. For example, a "further donor atom" may
be present in an optional exocyclic substituent of a macrocyclic
ligand, or in a cross-bridged chain thereof. In certain preferred
embodiments, a "further donor atom" is present only in a
cross-bridged chain.
[0172] The term "coordinated with the same transition metal" as
used herein is used to emphasize that a particular donor atom or
ligand does not bind to two or more distinct metal atoms, but
rather, to only one.
[0173] Optional Ligands
[0174] It is to be recognized for the transition-metal oxidation
catalysts useful in the present invention catalytic systems that
additional non-macropolycyclic ligands may optionally also be
coordinated to the metal, as necessary to complete the coordination
number of the metal complexes. Such ligands may have any number of
atoms capable of donating electrons to the catalyst complex, but
preferred optional ligands have a denticity of 1 to 3, preferably
1. Examples of such ligands are H.sub.2O, ROH, NR.sub.3, RCN,
OH.sup.-, OOH.sup.-, RS.sup.-, RO.sup.-, RCOO.sup.-, OCN.sup.-,
SCN.sup.-, N.sub.3.sup.-, CN.sup.-, F.sup.-, CI.sup.-, Br.sup.-,
I.sup.-, O.sub.2.sup.-, NO.sub.3.sup.-, NO.sub.2.sup.-,
SO.sub.4.sup.2-, SO.sub.3.sup.2-, PO.sub.4.sup.3-, organic
phosphates, organic phosphonates, organic sulphates, organic
sulphonates, and aromatic N donors such as pyridines, pyrazines,
pyrazoles, imidazoles, benzimidazoles, pyrimidines, triazoles and
thiazoles with R being H, optionally substituted alkyl, optionally
substituted aryl. Preferred transition-metal oxidation catalysts
comprise one or two non-macropolycyclic ligands.
[0175] The term "non-macrpolycyclic ligands" is used herein to
refer to ligands such as those illustrated immediately hereinabove
which in general are not essential for forming the metal catalyst,
and are not cross-bridged macropolycycles. "Not essential", with
reference to such non-macropolycyclic ligands means that, in the
invention as broadly defined, they can be substituted by a variety
of common alternate ligands. In highly preferred embodiments in
which metal, macropolycyclic and non-macropolycyclic ligands are
finely tuned into a transition-metal oxidation catalyst, there may
of course be significant differences in performance when the
indicated non-macropolycyclic ligand(s) are replaced by further,
especially non- illustrated, alternative ligands.
[0176] The term "metal catalyst" or "transition-metal oxidation
catalyst" is used herein to refer to the essential catalyst
compound of the invention and is commonly used with the "metal"
qualifier unless absolutely clear from the context. Note that there
is a disclosure hereinafter pertaining specifically to optional
catalyst materials. Therein the term "bleach catalyst" may be used
unqualified to refer to optional organic (metal-free) catalyst
materials, or to optional metal-containing catalysts that lack the
advantages of the essential catalyst: such optional materials, for
example, include known metal porphyrins or metal-containing
photobleaches. Other optional catalytic materials herein include
enzymes.
[0177] The macropolycyclic rigid ligands of the inventive
compositions and methods also include ligands selected from the
group consisting of:
[0178] (i) the macropolycyclic rigid ligand of formula (I) having
denticity of 3 or, preferably, 4: 16
[0179] (ii) the macropolycyclic rigid ligand of formula (II) having
denticity of 4 or 5 17
[0180] (iii) the macropolycyclic rigid ligand of formula (III)
having denticity of 5 or 6 18
[0181] (iv) the macropolycyclic rigid ligand of formula (IV) having
denticity of 6 or 7 19
[0182] wherein in these formulas:
[0183] each "E" is the moiety (CR.sub.n).sub.a-X-(CR.sub.n).sub.a',
wherein X is selected from the group consisting of O, S, NR, and P,
or a covalent bond, and preferably X is a covalent bond and for
each E the sum of a+a' is independently selected from I to 5, more
preferably 2 and 3;
[0184] each "G" is the moiety (CR.sub.n).sub.b;
[0185] each "R" is independently selected from H, alkyl, alkenyl,
alkynyl, aryl, alkylaryl
[0186] (e.g., benzyl), and heteroaryl, or two or more R are
covalently bonded to form an aromatic, heteroaromatic, cycloalkyl,
or heterocycloalkyl ring;
[0187] each "D" is a donor atom independently selected from the
group consisting of N, O, S, and P, and at least two D atoms are
bridgehead donor atoms coordinated to the transition metal;
[0188] "B" is a carbon atom or "D" donor atom, or a cycloalkyl or
heterocyclic ring;
[0189] each "n" is an integer independently selected from 1 and 2,
completing the valence of the carbon atoms to which the R moieties
are covalently bonded;
[0190] each "n"' is an integer independently selected from 0 and 1,
completing the valence of the D donor atoms to which the R moieties
are covalently bonded;
[0191] each "n"" is an integer independently selected from 0, 1,
and 2 completing the valence of the B atoms to which the R moieties
are covalently bonded;
[0192] each "a" and "a"' is an integer independently selected from
0-5, preferably a+a' equals 2 or 3, wherein the sum of all "a" plus
"a" in the ligand of formula (I) is within the range of from about
7 to about 12, the sum of all "a" plus "a"' in the ligand of
formula (II) is within the range of from about 6 (preferably 8) to
about 12, the sum of all "a" plus "a'" in the ligand of formula
(III) is within the range of from about 8 (preferably 10) to about
15, and the sum of all "a" plus "a"' in the ligand of formula (IV)
is within the range of from about 10 (preferably 12) to about
18;
[0193] each "b" is an integer independently selected from 0-5, or
in any of the above formulas, one or more of the (CR.sub.n).sub.b
moieties covalently bonded from any D to the b atom is absent as
long as at least two (CR.sub.n).sub.b covalently bond two of he D
donor
[0194] atoms to the B atom in the formula, and the sum of all "b"
is within the range of from about 1 to about 5. Preferred ligands
of the above formulas are those which are cross-bridged
macropolycyclic ligands having Formulas (II), (III) or (IV).
[0195] It is to be noted herein that for the above formulas wherein
"a" or "a'" is 1 these ligands are not preferred for potential
instability reasons in selected solvents, but are still within the
scope of the present invention.
[0196] Preferred are the transition-metal oxidation catalysts
wherein in the cross- bridged macropolycyclic ligand the D and B
are selected from the group consisting of N and O, and preferably
all D are N. Also preferred are wherein in the cross-bridged
macropolycyclic ligand all "a" are independently selected from the
integers 2 and 3, all X are selected from covalent bonds, all "a"'
are 0, and all "b" are independently selected from the integers 0,
1, and 2. Tetradentate and pentadentate cross-bridged
macropolycyclic ligands are most preferred.
[0197] Unless otherwise specified, the convention herein when
referring to denticity, as in "the macropolycycle has a denticity
of four" will be to refer to a characteristic of the ligand:
namely, the maximum number of donor bonds that it is capable of
forming when it coordinates to a metal. Such a ligand is identified
as "tetradentate". Similarly, a macropolycycle containing five
nitrogen atoms each with a lone pair is preferred to as
"pentadentate". The present invention encompasses catalystic
systems in which the macrocyclic rigid ligand exerts its full
denticity, as stated, in the transition-metal catalyst complexes;
moreover, the invention also encompasses any equivalents which can
be formed, for example, if one or more donor sites are not directly
coordinated to the metal. This can happen, for example, when a
pentadentate ligand coordinates through four donor atoms to the
transition metal and one donor atom is protonated.
[0198] To further illustrate, preferred catalytic systems may
contain metal catalysts wherein the cross-bridged macropolycyclic
ligand is a bicyclic ligand; preferably the cross-bridged
macropolycyclic ligand is a macropolycyclic moiety of the formula:
20
[0199] wherein each "a" is independently selected from the integers
2 or 3 and each "b" is independently selected from the integers 0,
1 and 2.
[0200] Further preferred are the compositions containing
cross-bridged macropoly- cyclic ligands having the formula: 21
[0201] wherein in this formula:
[0202] each "n" is an integer independently selected from 1 and 2,
completing the valence of the carbon atom to which the R moieties
are covalently bonded;
[0203] each "R" and "RI" is independently selected from H, alkyl,
alkenyl, alkynyl, aryl, alkylaryl (e.g., benzyl) and heteroaryl. or
R and/or R1 are covalently bonded to form an aromatic,
heteroaromatic, cycloalkyl, or heterocycloalkyl ring, and wherein
preferably all R are H and R1 are independently selected from
linear or branched, substituted or unsubstituted C1-C20 alkyl,
alkenyl or alkynyl;
[0204] each "a" is an integer independently selected from 2 or
3;
[0205] preferably all nitrogen atoms in the cross-bridged
macropolycycle rings are coordinated with the transition metal.
[0206] The invention further includes the methods and compositions
which include the transition-metal complexes, preferably the Mn,
Fe, Cu and Co complexes, or preferred cross-bridged macropolycyclic
ligands having the formula: 22
[0207] wherein in this formula "R1" is independently selected from
H, and linear or branched, substituted or unsubstituted C1-C20
alkyl, alkylaryl, alkenyl or alkynyl, more preferably RI is alkyl
or alkylaryl; and preferably all nitrogen atoms in the
macropolycyclic rings are coordinated with the transition
metal.
[0208] Also preferred are cross-bridged macropolycyclic ligands
having the formula: 23
[0209] wherein in this formula:
[0210] each "n" is an integer independently selected from 1 and 2,
completing the valence of the carbon atom to which the R moieties
are covalently bonded;
[0211] each "R" and "R1" is independently selected from H, alkyl,
alkenyl, alkynyl, aryl, alkylaryl (e.g., benzyl), and heteroaryl,
or R and/or R1 are covalently bonded to form an aromatic,
heteroaromatic, cycloalkyl, or heterocycloalkyl ring, and wherein
preferably all R are H and R1 are independently selected from
linear or branched, substituted or unsubstituted C1-C20 alkyl,
alkenyl or alkynyl;
[0212] each "a" is an integer independently selected from 2 or
3;
[0213] preferably all nitrogen atoms in the macropolycyclic rings
are coordinated with the transition metal. In terms of the present
invention, even though any of such ligands are known, the invention
encompasses the use of these ligands in the form of their
transition-metal complexes as oxidation catalysts, or in the form
of the defined catalytic systems. in like manner, included in the
definition or the preferred cross-bridged macropolycyclic ligands
are those having the formula: 24
[0214] wherein in either of these formulae, "R.sup.1" is
independently selected from H, or, preferably, linear or branched,
substituted or unsubstituted C1-C20 alkyl, alkenyl or alkynyl; and
preferably all nitrogen atoms in the macropolycyclic rings are
coordinated with the transition metal.
[0215] The present invention has numerous variations and alternate
embodiments. This, in the foregoing catalytic systems, the
macropolycyclic ligand can be replaced by any of the following:
2526
[0216] In the above, the R, R', R", R'" moieties can, for example,
be methyl, ethyl or propyl. (Note that in the above formalism, the
short straight strokes attached to certain N atoms are an alternate
representation for a methyl group).
[0217] While the above illustrative structures involve tetra-aza
derivatives (four donor nitrogen atoms), ligands and the
corresponding complexes in accordance with the present invention
can also be made, for example from any of the following: 27
[0218] Moreover, using only a single organic macropolycycle,
preferably a cross-bridged derivative of cyclam, a wide range of
oxidation catalyst compounds of the invention may be prepared;
numerous of these are believed to be novel chemical compounds.
Preferred transition-metal catalysts of both cyclam-derived and
non- cyclam-derived cross-bridged kinds are illustrated, but not
limited, by the following: 28
[0219] In other embodiments of the invention, transition-metal
complexes, such as the Mn, Fe, Co, or Cu complexes, especially (II)
and/or (III) oxidation state complexes, of the
hereinabove-identified metals with any of the following ligands are
also included: 29
[0220] wherein R1 is independently selected from H (preferably
non-H) and linear or branched, substituted or unsubstituted C1-C20
alkyl, alkenyl or alkynyl and L is any of the linking moieties
given herein, for example 1.10 or 1.11; 30
[0221] wherein R1 is as defined supra; m,n,o and p can vary
independently and are integers which can be zero or a positive
integer and can vary independently while respecting the provision
that the sum m+n+o+p is from 0 to 8 and L is any of the linking
moieties defined herein; 31
[0222] wherein X and Y can be any of the R1 defined supra, m,n,o
and p are as defined supra and q is an integer, preferably from 1
to 4; or, more generally, 32
[0223] wherein L is any of the linking moieties herein, X and Y can
be any of the RI defined supra, and m,n,o and p are as defined
supra. Alternately, another useful ligand is: 33
[0224] wherein RI is any of the RI moieties defined supra.
[0225] Pendant Moieties
[0226] Macropolycyclic rigid ligands and the corresponding
transition-metal complexes and oxidation catalytic systems herein
may also incorporate one or more pendant moieties, in addition to,
or as a replacement for, R 1 moieties. Such pendant moieties are
nonlimitingly illustrated by any of the following:
[0227] --(CH.sub.2).sub.n--CH.sub.3
--(CH.sub.2).sub.n--C(O)NH.sub.2
[0228] --(CH.sub.2).sub.n--CN --(CH.sub.2).sub.n--C(O)OH
[0229] --(CH.sub.2).sub.n--C(O)NR.sub.2 --(CH.sub.2).sub.n--OH
[0230] --(CH.sub.2).sub.n--C(O)OR 34
[0231] wherein R is, for example, a C1-C12 alkyl, more typically a
C1-C4 alkyl, and Z and t are as defined in 1.11. Pendant moieties
may be useful, for example, if it is desired to adjust the
solubility of the catalyst in a particular solvent adjunct.
[0232] Alternatively, complexes of any of the foregoing highly
rigid, cross-bridged macropolycyclic ligands with any of the metals
indicated are equally within the invention.
[0233] Preferred are catalysts wherein the transition metal is
selected from manganese and iron, and most preferably manganese.
Also preferred are catalysts wherein the molar ratio of transition
metal to macropolycyclic ligand in the oxidation catalyst is 1:1,
and more preferably wherein the catalyst comprises only one metal
per oxidation catalyst complex. Further preferred transition-metal
oxidation catalysts are monmetallic, mononuclear complexes. The
term "monometallic, mononuclear complex" is used herein in
referring to an essential transition-metal oxidation catalyst
compound to identify and distinguish a preferred class of compounds
containing only one metal atom per mole of compound and only one
metal atom per mole of cross-bridged macropolycyclic ligand.
[0234] Preferred transition-metal oxidation catalysts also include
those wherein at least four of the donor atoms in the
macropolycyclic rigid ligand, preferably at least four nitrogen
donor atoms, two of which form an apical bond angle with the same
transition metal of 180.+-.50.degree. and two of which form at
least one equatorial bond angle of 90.+-.20.degree.. Such catalysts
preferably have four or five nitrogen donor atoms in total and also
have coordination geometry selected from distorted octahedral
(including trigonal antiprismatic and general tetragonal
distortion) and distorted trigonal prismatic, and preferably
wherein further the cross-bridged macropolycyclic ligand is in the
folded conformation as described, for example, in Hancock and
Martell, Chem. Rev., 1989, 89, at page 1894). A folded conformation
of a cross-bridged macropolycyclic ligand in a transition-metal
complex is further illustrated below: 35
[0235] This catalyst is the complex of the Examples hereinafter.
The centre atom is Mn; the two ligands to the right are chloride;
and a Bcyclam ligand occupies the left side of the distorted
octahedral structure. The complex contains an angle N--Mn--N of
158.degree. incorporating the two mutually Trans-donor atoms in
"axial" positions; the corresponding angle N--Mn--N for the
nitrogen donor atoms in plane with the two chloride ligands in
83.2.degree..
[0236] Stated alternatively, the preferred synthetic, laundry,
cleaning, papermaking, or effluent-treating catalytic systems
herein contain transition-metal complexes of a macropolycyclic
ligand in which there is a major energetic preference of the ligand
for a folded, as distinct from an "open" and/or "planar" and or
"flat" conformation. for comparison, a disfavored conformation is,
for example, either of the trans- structures shown in Hancock and
Martell, Chemical Review, (1989), 89 at page 1894 (see FIG. 18),
incorporated by reference.
[0237] In light of the foregoing coordination description, the
present invention includes oxidation catalytic systems comprising a
transition-metal oxidation catalyst, especially based on Mn(II) or
Mn(III) or correspondingly, Fe(II) or Fe(III) or Cr(II) or Cr(III),
wherein two of the donor atoms in the macropolycyclic rigid ligand,
preferably two nitrogen donor atoms, occupy mutually trans-
positions of the coordination geometry, and at least two of the
donor atoms in the macropolycyclic rigid ligand, preferably at
least two nitrogen donor atoms, occupy cis- equatorial positions of
the coordination geometry including particularly the cases in which
there is substantial distortion as illustrated hereinabove.
[0238] The present catalytic systems can furthermore, include
transition metal oxidation catalysts in which the number of
asymmetric sites can vary widely; thus both S- and R-absolute
conformations can Me included for any stereochemically active site.
Other types of isomerism, such as geometric isomerism, are also
included. The transition-metal oxidation catalyst can further
include mixtures of geometric or stereoisomers.
[0239] The 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 well as other uses where a
bleach is needed, for example waste water treatment or pulp
bleaching during manufacture of paper, dye transfer inhibition,
starch bleaching, sterilisation and/or whitening in oral hygiene
preparation, or contact lens disinfection.
[0240] In typical washing compositions the level of the organic
substance is such that the in-use level is from 1 .mu.M to 50 mM,
with preferred in-use levels for domestic laundry operations
falling in the range 10 to 100 .mu.M. Higher levels may be desired
and applied in industrial bleaching processes, such as textile and
paper pulp bleaching.
[0241] Preferably, the aqueous medium has a pH in the range from pH
6 to 13, more preferably from pH 6 to 11, still more preferably
from pH 8 to 11, and most preferably from pH 8 to 10, in particular
from pH 9 to 10.
[0242] The bleaching composition of the present invention has
particular application in detergent formulations, especially for
laundry cleaning. Accordingly, in another preferred embodiment, the
present invention provides a detergent bleach composition
comprising a bleaching composition as defined above and
additionally a surface-active material, optionally together with
detergency builder.
[0243] The 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.
[0244] 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
(C.sub.8-C.sub.18) alcohols produced, for examples, from tallow or
coconut oil; sodium and ammonium alkyl (C.sub.9-C.sub.20) benzene
sulphonates, particularly sodium linear secondary alkyl
(C.sub.10-C.sub.15) benzene sulphonates; sodium alkyl glyceryl
either 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 (C.sub.9-C.sub.18) 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
(C.sub.8-C.sub.20) with sodium bisulphite and those derived by
reacting paraffins with SO.sub.2 and Cl.sub.2 and then hydrolysing
with a base to produce a random sulphonate; sodium and ammonium
(C.sub.7-C.sub.12) dialkyl sulphosuccinates; and olefin
sulphonates, which term is used to describe material made by
reacting olefins, particularly (C.sub.10-C.sub.20) alpha-olefins,
with SO.sub.3 and then neutralising and hydrolysing, the reaction
product. The preferred anionic detergent compounds are sodium
(C.sub.10-C.sub.15) alkylbenzene sulphonates, and sodium
(C.sub.16-C.sub.18) alkyl ether sulphates.
[0245] 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
(C.sub.6-C.sub.22) phenols, generally 5-25 EO, i.e. 5-25 units of
ethylene oxides per molecule; and the condensation products of
aliphatic (C.sub.8-C.sub.18) primary or secondary linear or
branched 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.
[0246] Amphoteric or zwtterionic surface-active compounds can also
be used in the compositions of the invention but this is not
normally desired owing to their relatively high cost. 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.
[0247] The detergent bleach composition of the invention will
preferably comprise from 1 to 15% wt of anionic surfactant and from
10 to 40% by weight of nonionic surfactant. In a further preferred
embodiment, the detergent active system is free from
C.sub.16-C.sub.12 fatty acid soaps.
[0248] The 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.
[0249] Builder materials may be selected from 1) calcium
sequestrant materials, 2) precipitating materials, 3) calcium
ion-exchange materials and 4) mixtures thereof.
[0250] 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 U.S. Pat. No. 4,144,226 and U.S. Pat. No.
4,146,495.
[0251] Examples of precipitating builder materials include sodium
orthophosphate and sodium carbonate.
[0252] 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.
[0253] In particular, the 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 or other builders or
polymers as co-builder.
[0254] It is preferred that the 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.
[0255] Apart from the components already mentioned, the bleach
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.RTM.
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.
[0256] 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
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.
[0257] 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 composition, if
desired. Therefore, by "substantially devoid of peroxygen bleach or
peroxy-based or -generating bleach systems" is meant that the
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 composition
will be wholly devoid of peroxygen bleach or peroxy-based or
-generating bleach systems.
[0258] 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.
[0259] The invention will now be further illustrated by way of the
following non-limiting examples:
EXAMPLES
[0260] Compound 1: [Mn(Bcyclam)Cl.sub.2] was synthesised according
to prior art (WO98/39098).
Example 1
[0261] Stain: tomato oil stain. Washed for 30 min at 30.degree. C.,
rinsed, dried and measured immediately ("t=0" and after 1 day
storage ("t=1"). In all cases 10 .mu.M of metal complex is added to
the wash liquor (except for blank). The wash liquor contains either
buffer only (10 mM borate pH 8 or 10 mM carbonate pH 10) or the
same buffers with 0.6 g/l NaLAS (Albright & Wilson). Bleach
values expressed in .DELTA.E (a higher value means a cleaner cloth)
are shown in Table 1 below.
1 TABLE 1 pH 5 + LAS pH 8 - LAS PH 8 + LAS pH 10 - LAS pH 10 + LAS
t = 0 t = 0 t = 0 t = 0 t = 0 t = 1 t = 1 t = 1 t = 1 t = 1 Blank 3
2 4 4 5 3 2 4 3 4 Compound 9 2 9 6 8 1 22 7 21 16 21
[0262] The results presented in Table 1 show that this compound
bleaches tomato stains at wide range of conditions (pH 5-10 without
and with LAS). Further the results show that upon storage the
cloths become very clean upon storage for 1 day.
Example 2
[0263] Stain: tomato oil stain. Washed for 30 min at 30.degree. C.,
rinsed, dried and measured immediately ("t=0" and after 1 day
storage ("t=1"). In all cases 10 .mu.M of metal complex is added to
the wash liquor (except for blank). The wash liquor contains buffer
(10 mM borate pH 8 or 10 mM carbonate pH 10) with 0.3 g/l
Synperonic A7 (Surphos Chemicals, BV) and 0.3 g/l Synperonic A3
(Ellis and Everard PLC). Bleach values expressed in .DELTA.E are
shown in Table 2 below.
2 TABLE 2 pH 8 + pH 10 + EO7/EO3 EO7/EO3 t = 0 t = 1 t = 0 t = 1
Blank 3 3 4 4 Compound 1 14 20 14 19
[0264] The results presented in Table 2 snow that this compound
bleaches tomato stains by air also in the presence of EO3/EO7
non-ionics.
Example 3
[0265] Stain: tomato oil stain. Washed for 30 min at 30.degree. C.,
rinsed, dried and measured immediately ("t=0" and after 1 day
storage ("t=1"). In all cases 10 .mu.M of metal complex is added to
the wash liquor (except for blank). The wash liquor contains buffer
(10 mM borate pH 8 or 10 mM carbonate pH 10) with 0.6 g/l NaLAS,
0.6 mM SSTP and 0.7 mM CaCl.sub.2. Bleach values expressed in
.DELTA.E are shown in Table 3 below.
3 TABLE 3 pH 8 pH 10 t = 0 t = 1 t = 0 t = 1 Blank 3 3 3 3 Compound
1 14 19 17 22
[0266] The results presented in Table 3 show that this compound
bleaches tomato stains by air also in the presence of LAS/STP with
CaCl.sub.2.
[0267] The results presented in Table 1-3 show that compound 1
bleaches tomato stains by air under a variety of conditions, that
mimic the performance of a wide range of detergent powders
(LAS/SSTP and LAS/non-ionic based detergents).
* * * * *