Fabric bleaching composition

A fabric bleaching composition comprising a peroxy compound and a specified manganese complex is disclosed, as well as a process for bleaching and/or cleaning a fabric by contacting it with said fabric bleaching composition.

The present invention relates to fabric bleaching compositions comprising a 
peroxygen compound and, as bleach activator, a manganese complex. 
Bleaching compositions which contain a peroxide bleaching agent are well 
known. In such compositions, the bleaching agent functions to remove 
common domestic stains such as tea, coffee, fruit and wine stains from the 
soiled clothing at the boil. If the washing temperature is reduced to 
below 60.degree. C., however, the efficacy of the bleaching agent is 
correspondingly reduced. 
It is also well known that certain heavy metal ions, or complexes thereof, 
function to catalyse the decomposition of hydrogen peroxide, or of 
compounds which can liberate hydrogen peroxide, in order to render the 
peroxide compound effective at temperatures below 60.degree. C. 
For example, in U.S. Pat. No. 5,114,611, there is described the activation 
of a peroxy compound by a complex of a transition metal (Mn, Co, Fe or Cu) 
with a non-(macro) cyclic ligand, preferably 2,2-bispyridylamine or 
2,2-bispyridylmethane. 
Moreover, in U.S. Pat. No. 5,114,606, there is described a manganese 
complex, for use as a bleach catalyst for a peroxy compound, which is a 
water-soluble complex of manganese II, III or IV, or mixtures thereof, 
with a ligand which is a non-carboxylate polyhydroxy compound, having at 
least three consecutive C--OH groups in its molecular structure, 
preferably sorbitol. 
Other disclosures, relating to the use of metal complexes as activators for 
peroxy compounds in bleaches or detergents, include U.S. Pat. No. 
5,227,084, U.S. Pat. No. 5,194,416, U.S. Pat. No. 4,728,455, U.S. Pat. No. 
4,478,733, U.S. Pat. No. 4,430,243, EP-A-549 271, EP-A-549 272, EP-A-544 
519, EP-A-544 490, EP-A-544 440, EP-A-509 787, EP-A-458 397 and EP-A-458 
398. 
It has now been found, surprisingly, that certain other manganese complexes 
are excellent bleach catalysts for peroxy compounds and, relative to known 
bleach catalysts, provide enhanced bleach effects at low wash temperatures 
(e.g. at 15 to 40.degree. C.) and/or using shorter washing times. 
Accordingly, the present invention provides a fabric bleaching composition 
comprising 
a) a peroxy compound; and 
b) 0.0005 to 0.5, preferably 0.005 to 0.05%, by weight of manganese, of one 
or more water-soluble manganese complexes having one of the formulae (1), 
(2), (3), (4), (5), (6), (7) (8), (9), (10), (11), (12), (13), (14), (15), 
(16), (17) or (18): 
##STR1## 
in which R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are the same or different 
and each is hydrogen or optionally substituted alkyl, cycloalkyl or aryl; 
R.sub.5 is hydrogen, optionally substituted alkyl, optionally substituted 
alkoxy, halogen, cyano, N(optionally substituted alkyl).sub.2, 
N.sym.(optionally substituted alkyl).sub.3 or a water-solubilising group, 
especially SO.sub.3 M; R.sub.6 and R.sub.7 are the same or different and 
each is NH--CO--NH.sub.2, a group of formula 
##STR2## 
or a group of formula 
##STR3## 
Y is optionally substituted alkylene or cyclohexylene; X is OH, NH.sub.2, 
optionally substituted alkyl or optionally substituted aryl; n is 0, 1, 2 
or 3; M is hydrogen, an alkali metal atom, ammonium or a cation formed 
from an amine; m is 2 or 3; q is 0, 1, 2 or 3; and A is an anion. 
When one or more of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and X are 
optionally substituted alkyl, preferred alkyl groups are C.sub.1 -C.sub.12 
-, especially C.sub.1 -C.sub.4 -alkyl groups. The alkyl groups may be 
branched or unbranched and may be optionally substituted, e.g. by halogen 
such as fluorine, chlorine or bromine, by C.sub.1 -C.sub.4 -alkoxy such as 
methoxy or ethoxy, by phenyl or carboxyl, by C.sub.1 -C.sub.4 
-alkoxycarbonyl such as acetyl, or by a mono- or di-C.sub.1 -C.sub.4 
alkylated amino group. 
Optionally substituted alkoxy groups R.sub.5 are preferably C.sub.1 
-C.sub.8 -, especially C.sub.1 -C.sub.4 -alkoxy groups. The alkoxy groups 
may be branched or unbranched and may be optionally substituted, e.g. by 
halogen such as fluorine, chlorine or bromine, by C.sub.1 -C.sub.4 -alkoxy 
such as methoxy or ethoxy, by phenyl or carboxyl, by C.sub.1 -C.sub.4 
-alkoxycarbonyl such as acetyl, or by a mono- or di-alkylated amino group. 
Halogen atoms R.sub.5 are preferably bromo or, especially, chloro atoms. 
N(optionally substituted alkyl).sub.2 groups R.sub.5 are preferably 
N(optionally substituted C.sub.1 -C.sub.4 alkyl).sub.2 groups, especially 
N(methyl).sub.2 or N(ethyl).sub.2. 
N.sym.(optionally substituted alkyl).sub.3 groups R.sub.5 are 
N.sym.(optionally substituted C.sub.1 -C.sub.4 alkyl).sub.3, especially 
N.sym.(methyl).sub.3 or N.sym.(ethyl).sub.3. 
When one or more of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are cycloalkyl, 
this may also be substituted, e.g. by C.sub.1 -C.sub.4 -alkyl or C.sub.1 
-C.sub.4 -alkoxy. 
When one or more of R.sub.1, R.sub.2, R.sub.3, R.sub.4 and X are optionally 
substituted aryl, they are preferably a phenyl or naphthyl group which may 
be substituted by C.sub.1 -C.sub.4 -alkyl, e.g. by methyl, ethyl, propyl, 
isopropyl, butyl, isobutyl, sec.-butyl or tert.-butyl, by C.sub.1 -C.sub.4 
-alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, 
sec.-butoxy or tert.-butoxy, by halogen such as fluorine, chlorine or 
bromine, by C.sub.2 -C.sub.5 -alkanoylamino, such as acetylamino, 
propionylamino or butyrylamino, by nitro, sulpho or by dialkylated amino. 
When Y is alkylene, it is preferably a C.sub.2 -C.sub.4 -alkylene residue, 
especially a --CH.sub.2 -CH.sub.2 - bridge. Y may also be a C.sub.2 
-C.sub.8 -alkylene residue which is interrupted by oxygen or, especially, 
by nitrogen, in particular the --(CH.sub.2).sub.3 -NH--(CH.sub.2).sub.3 -, 
--(CH.sub.2).sub.2 -NH--(CH.sub.2).sub.2 or --(CH.sub.2).sub.2 
-N(CH.sub.3)--(CH.sub.2).sub.2 - bridge. 
Anions A include halide, especially chloride, chlorate, sulphate, nitrate, 
hydroxy, methoxy, BF.sub.4, PF.sub.6, carboxylate, especially acetate, 
triflate or tosylate. 
With respect to the compounds of formula (1), preferably each R.sub.1 is 
hydrogen, Y is the ethylene bridge and n is 2, whereby one sulpho group is 
preferably present in each benzene ring, especially in para position to 
the oxygen atom. 
In relation to the compounds of formula (2), preferably R.sub.2 is hydrogen 
and X is OH. 
With respect to the compounds of formula (3), preferred compounds are those 
in which R.sub.3 is hydrogen and R.sub.4 is hydrogen, methyl or, 
especially, phenyl. Especially preferred compounds are those in which the 
SO.sub.3 M group is in para position to the oxygen atom. 
With respect to the compounds of formula (4), preferred compounds are those 
in which R.sub.1 is hydrogen , more especially those in which each 
SO.sub.3 M group is in para position to the respective oxygen atom. 
As to the compounds of formula (5), (6), (7) and (8), preferably R, is 
hydrogen or methyl, q is 1, R.sub.5 is hydrogen, methyl or SO.sub.3 Na and 
is preferably in p-position with respect to the oxygen atom, Y is 
--CH.sub.2 CH.sub.2 - or cyclohexylene and A is a chloride, chlorate, 
acetate, hydroxy, methoxy or PF.sub.6 anion. 
In relation to the compounds of formula (9), preferably R.sub.6 and R.sub.7 
are the same. The preferred anion, when present, is acetate. 
With respect to the compounds of formula (11) or (12), preferably R.sub.1 
is hydrogen , n is 0 and A is acetate. 
In relation to the compounds of formula (13), preferably R.sub.1 is 
hydrogen, m is 2 or 3 and A is acetate. 
With respect to the compounds of formula (14), preferred compounds are 
those in which R.sub.1 is hydrogen, m is 2 and A is Cl. 
With respect to the compounds of formula (15), preferred compounds are 
those in which m is 2 and A is chloride. 
As to the compounds of formula (16), preferably m is 2 and A is acetate. 
In the compounds of formula (17), A is preferably perchlorate. 
In each of the compounds of formula (1) to (18), it is preferred that they 
are used in neutral form, i.e. that M, when present, is other than 
hydrogen, preferably a cation formed from an alkali metal, in particular 
sodium, or from an amine. 
Moreover, in each of the compounds of formula (1) to (4), (9), (10), (11), 
(12), (13), (14) and (18), the respective benzene rings may contain, in 
addition to any sulpho group, one or more further substituents such as 
C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, halogen, cyano or 
nitro. 
The manganese complexes of formula (5) in which q is 2, 3 or 4 and those of 
formula (6), (7), (8) and (11) to (17) are believed to be new compounds 
and, as such, form a further aspect of the present invention. The 
compounds of formula (5) are described, at least in part in WO 93/03838. 
The compounds of formula (5), (6) and (10) to (18) may be produced by 
known methods, e.g. by the methods analogous to those disclosed in U.S. 
Pat. No. 4,655,785 relating to similar copper complexes. The compounds of 
formula (7) and (8) may be produced by oxidative coupling of the 
respective compound of formula (5) or (6). 
The peroxy component a) of the fabric bleaching compositions of the present 
invention may be hydrogen peroxide, a compound which liberates hydrogen 
peroxide, a peroxyacid, a peroxyacid bleach precursor or a mixture 
thereof. 
Compounds which liberate hydrogen peroxide are well known and include, 
e.g., inorganic compounds such as alkali metal peroxides, -perborates, 
-percarbonates, -perphosphates and -persulfates and organic compounds such 
as peroxylauric acid, peroxybenzoic acid, 1,12-diperoxydodecanoic acid, 
diperoxyisophthalic acid and urea peroxide, as well as mixtures thereof. 
Sodium percarbonate and sodium perborate, in particular sodium perborate 
monohydrate, are preferred. 
Peroxyacid compounds and peroxyacid bleach precursors are also well known 
and a summary of references describing them is provided in the 
above-mentioned U.S. Pat. No. 5 114606. 
Examples of peroxyacid bleach precursors include benz(4H)-1,3-oxazin-4-one 
derivatives, especially substituted 2-phenyl-benz(4H)- 1,3-oxazin-4-one 
2-(N,N,N-trimethyl ammonium) ethyl sodium-4-sulfophenyl carbonate chloride 
(SPCC) N-octyl,N,N-dimethyl-N10-carbophenoxy decyl ammonium chloride (ODC) 
3-(N,N,N-trimethyl ammonium) propyl sodium 4-sulfophenyl carboxylate 
N,N,N-trimethyl ammonium toluyloxy benzene sulfonate sodium-4-benzoyloxy 
benzene sulfonate (SBOBS) N,N,N',N'-tetraacetyl ethylene diamine (TAED) 
sodium-1-methyl-2-benzoyloxy benzene-4-sulfonate 
sodium-4-methyl-3-benzoyloxy benzoate and sodium nonanoyloxybenzene 
sulfonate (NOBS). The substituted 2-phenyl-benz(4H)-1,3-oxazin-4-one, NOBS 
and TAED precursors are preferred 
Preferably, the amount of the peroxy compound in the fabric bleaching 
composition according to the invention ranges from 0.5 to 50%, especially 
from 2 to 20% by weight, based on the total weight of the composition. 
The fabric bleaching compositions of the present invention preferably also 
comprises a surfactant and a detergent builder component. 
The surfactant component is preferably an anionic surfactant, a nonionic 
surfactant or a mixture thereof and is preferably present in an amount of 
5 to 50%, especially 5 to 25% by weight, based on the total weight of the 
fabric bleaching composition. 
The anionic surfactant component may be, e.g., a sulphate, sulphonate or 
carboxylate surfactant, or a mixture of these. 
Preferred sulphates are alkyl sulphates having 12-22 carbon atoms in the 
alkyl radical, optionally in combination with alkyl ethoxy sulphates 
having 10-20 carbon atoms in the alkyl radical. 
Preferred sulphonates include alkyl benzene sulphonates having 9-15 carbon 
atoms in the alkyl radical. 
In each case, the cation is preferably an alkali metal, especially sodium. 
Preferred carboxylates are alkali metal sarcosinates of formula 
R--CO(R.sup.1)CH.sub.2 COOM.sup.1 in which R is alkyl or alkenyl having 
9-17 carbon atoms in the alkyl or alkenyl radical, R.sup.1 is C.sub.1 
-C.sub.4 alkyl and M.sup.1 is alkali metal. 
The nonionic surfactant component may be, e.g., a condensate of ethylene 
oxide with a C.sub.9 -C.sub.15 primary alcohol having 3-8 moles of 
ethylene oxide per mole. 
The detergent builder component is preferably present in an amount of 5 to 
80%, especially 10 to 60% by weight, based on the total weight of the 
fabric bleaching composition. It may be an alkali metal phosphate, 
especially a tripolyphosphate; a carbonate or bicarbonate, especially the 
sodium salts thereof; a silicate; an aluminosilicate; a polycarboxylate; a 
polycarboxylic acid; an organic phosphonate; or an aminoalkylene poly 
(alkylene phosphonate); or a mixture of these. 
Preferred silicates are crystalline layered sodium silicates of the formula 
EQU NaHSi.sub.m O.sub.2m+1.multidot. pH.sub.2 O or Na.sub.2 Si.sub.m 
O.sub.2m+1.multidot. pH.sub.2 O 
in which m is a number from 1.9 to 4 and p is 0 to 20. 
Preferred aluminosilicates are the commercially-available synthetic 
materials designated as Zeolites A, B, X, and HS, or mixtures of these. 
Zeolite A is preferred. 
Preferred polycarboxylates include hydroxypolycarboxylates, in particular 
citrates, polyacrylates and their copolymers with maleic anhydride. 
Preferred polycarboxylic acids include nitrilotriacetic acid and ethylene 
diamine tetra-acetic acid. 
Preferred organic phosphonates or aminoalkylene poly (alkylene 
phosphonates) are alkali metal ethane 1-hydroxy diphosphonates, nitrilo 
trimethylene phosphonates, ethylene diamine tetra methylene phosphonates 
and diethylene triamine penta methylene phosphonates. 
The fabric bleaching compositions of the invention may contain, in addition 
to the components already mentioned, one or more of fluorescent whitening 
agents, such as a bis-triazinylamino-stilbene-disulphonic acid, a 
bis-triazolyl-stilbene-disulphonic acid, a bis-styryl-biphenyl, a 
bis-benzofuranylbiphenyl, a bis-benzoxalyl derivative, a 
bis-benzimidazolyl derivative, a coumarine derivative or a pyrazoline 
derivative; soil suspending agents, for example sodium 
carboxymethylcellulose; salts for adjusting the pH, for example alkali or 
alkaline earth metal silicates; foam regulators, for example soap; salts 
for adjusting the spray drying and granulating properties, for example 
sodium sulphate; perfumes; and also, if appropriate, antistatic and 
softening agents; such as smectite clays; enzymes, such as proteases, 
cellulases, lipases, oxidases and amylases; photobleaching agents; 
pigments; and/or shading agents. These constituents should, of course, be 
stable to the bleaching system employed. 
A particularly preferred fabric bleaching composition co-additive is a 
polymer known to be useful in preventing the transfer of labile dyes 
between fabrics during the washing cycle. Preferred examples of such 
polymers are polyvinyl pyrrolidones, optionally modified by the inclusion 
of an anionic or cationic substituent, especially those having a molecular 
weight in the range from 5000 to 60,000, in particular from 10,00 to 
50,000. Preferably, such polymer is used in an amount ranging from 0.05 to 
5%, preferably 0.2-1.7% by weight, based on the weight of the detergent. 
The formulation of the fabric bleaching compositions of the invention may 
be conducted by any conventional technique. 
The fabric bleaching composition may be formulated as a solid; or as a 
non-aqueous liquid fabric bleaching composition, containing not more than 
5, preferably 0-1 wt. % of water, and based on a suspension of a builder 
in a non-ionic surfactant, as described, e.g., in GB-A-2158454. 
Preferably, the fabric bleaching composition is in powder or granulate 
form. 
Such powder or granulate forms may be produced by firstly forming a base 
powder by spray-drying an aqueous slurry containing all the said 
components, apart from the components a) and b); then adding the 
components a) and b) by dry-blending them into the base powder. In a 
further process, the component b) may be added to an aqueous slurry 
containing the surfactant and builder components, followed by spray-drying 
the slurry prior to dry-blending component a) into the mixture. In a still 
further process, a nonionic component is not present, or is only partly 
present in an aqueous slurry containing anionic surfactant and builder 
components; component b) is incorporated into the nonionic surfactant 
component, which is then added to the spray-dried base powder; and finally 
component a) is dry-blended into the mixture. 
The present invention also comprises a bleaching and/or cleaning process 
comprising contacting a fabric to be bleached and/or cleaned with an 
effective amount of a fabric bleaching composition according to the 
present invention. Preferably the amount of the fabric bleaching 
composition used is such that the amount of manganese complex b) provides 
from 0.001 to 100 ppm, preferably from 0.01 to 20 ppm of manganese in the 
bleaching and/or cleaning bath. 
The following Examples serve to illustrate the invention; parts and 
percentages are by weight, unless otherwise stated.

EXAMPLE 1 
6 g of ethylenediamine are dropped into a solution of 34.5 g of 
3-isopropylsalicylaldehyde in 500 ml of ethanol over 1 hour at 60.degree. 
C. Stirring is continued at 60.degree. C. for a further 2 hours and the 
precipitate so formed is filtered off. There are obtained 34.5 g of a 
yellow liquid compound having the formula: 
##STR4## 
corresponding to a yield of 98% of theory. 
To 10.6 g of the compound of formula (101) dissolved in 350 ml of ethanol 
there are added 7.4 g of manganese-(II)-acetate.4H.sub.2 O. The dark brown 
solution so produced is stirred at 65.degree. C. for 3 hours and then 
evaporated to dryness. There are obtained 10.5 g of the compound having 
the formula: 
##STR5## 
corresponding to a yield of 75% of theory. 
Elemental analysis of the compound having the formula (102) and having the 
empirical formula C.sub.24 H.sub.29 MnN.sub.2 O.sub.4. 0.8 
3-isopropylsalicylaldehyde gives: 
Req. % C 64.47; H 6.48; N 4.70; Mn 9.23. 
Found % C 64.5; H 6.7; N 5.0; Mn 9.46. 
EXAMPLE 2 
Using the procedure described in Example 1 but with appropriate 
modification of the salicylaldehyde starting material, the compound of 
formula: 
##STR6## 
is obtained as a dark brown product in a yield of 91% of theory. 
Elemental analysis of the compound having the formula (103) and having the 
empirical formula C.sub.34 H.sub.49 MnN.sub.2 O.sub.4. 1.0 acetic acid 
gives: 
Req. % C 65.05; H 7.97; N 4.21; Mn 8.27. 
Found % C 64.3; H 8.1; N 4.2; Mn 8.44. 
EXAMPLE 3 
Using the procedure described in Example 1 but with appropriate 
modification of the salicylaldehyde starting material and the salt 
formation step, the compound of formula: 
##STR7## 
is obtained as a red brown product in a yield of 63% of theory. 
Elemental analysis of the compound having the formula (104) and having the 
empirical formula C.sub.24 H.sub.32 ClMnN.sub.4 O.sub.2. 0.75 H.sub.2 O 
gives: 
Req. % C 56.41; H 6.55; N 10.96; Cl 6.94; Mn 10.76. 
Found % C 56.5; H 6.6; N 10.9; Cl 6.8; Mn 9.9. 
EXAMPLE 4 
Using the procedure described in Example 1 but with appropriate 
modification of the salicylaldehyde starting material, the compound of 
formula: 
##STR8## 
is obtained as a red product in a yield of 61% of theory. 
Elemental analysis of the compound having the formula (105) and having the 
empirical formula C.sub.30 H.sub.47 MnN.sub.4 O.sub.12 S.sub.2. 2.5 
H.sub.2 O gives: 
Req. % C 43.90; H 6.34; N 6.83; S 7.80; Mn 6.70. 
Found % C 44.20; H 6.7; N 6.6; S 7.1; Mn 5.71. 
EXAMPLE 5 
60 g of ethylenediamine are dropped into a solution of 277 g of 
salicylaldehyde in 500 ml of ethanol over 1 hour at 60.degree. C. Stirring 
is continued at 60.degree. C. for a further 2 hours and the precipitate so 
formed is filtered off. There are obtained 260 g of a yellow compound 
having the formula: 
##STR9## 
corresponding to a yield of 97% of theory. 
16 g. of this compound are dissolved in 500 mls. of ethanol and treated 
with 11.9 g. of manganese-II-chloride.4H.sub.2 O and with 11.9 g. of 
potassium hexafluorophosphate. The solution is stirred for 20 minutes at 
25.degree. C., then cooled to 5.degree. C. and treated with a mixture of 
12 mls. of 30% caustic soda solution, 6.8 mls. of a 30% hydrogen peroxide 
solution and 300 mls. of water. The pH of the solution is adjusted to 8-9 
using 2N H.sub.2 SO.sub.4 and filtered. After concentration of the 
filtrate, 8 g. of a brown-violet crystalline product of formula (107) are 
obtained, corresponding to a yield of 32% of theory: 
##STR10## 
Elemental analysis of the compound having the formula (107) and having the 
empirical formula C.sub.32 H.sub.28 F.sub.12 Mn.sub.2 N.sub.4 O.sub.5 
P.sub.2 gives: 
Req. % C 40.53; H 2.99; N 5.91; F 24.04; Mn 11.59. 
Found % C 40.8; H 3.3; N 6.0; F 22.3; Mn 11.1. 
EXAMPLE 6 
The compound of formula (106) described in Example 5 is dissolved in 
tetrahydrofuran solvent and hydrogenated at 25.degree. C. and under normal 
pressure in the presence of a 5% Pd/C catalyst. The compound of the 
following formula is obtained in 86% of the theoretical yield: 
##STR11## 
Using the procedure described in Example 1, the compound (108) is converted 
into the dark brown compound having the following formula in a yield of 
12% of the theoretical yield: 
##STR12## 
Elemental analysis of the compound having the formula (109) and having the 
empirical formula C.sub.16 H.sub.18 ClMnN.sub.2 O.sub.2.1.5 H.sub.2 O. 
0.33 compound (108) gives: 
Req. % C 53.53; H 5.16; N 7.81; Cl 7.43; Mn 11.53. 
Found % C 53.1; H 5.6; N 7.4; Cl 7.8; Mn 11.7. 
EXAMPLE 7 
Using the procedure described in Example 1, the following compound of 
formula (110) is obtained: 
##STR13## 
Elemental analysis of the compound having the formula (110) and having the 
empirical formula C.sub.16 H.sub.14 ClMnN.sub.2 O.sub.2. 1.92 H.sub.2 O 
gives: 
Req. % C 49.11; H 4.60; N 7.16; Cl 9.06; Mn 14.04. 
Found % C 49.4; H 4.6; N 7.1; Cl 8.9; Mn 13.9. 
EXAMPLE 8 
To 26.8 g of the compound of formula (106), as described in Example 5, 
dissolved in 450 ml of water there are added 24.5 g of 
manganese-(II)-acetate.4H.sub.2 O and 26.2 g of 30% caustic soda solution. 
The dark brown solution so produced is stirred at 70.degree. C. for 2 
hours and then cooled to 5.degree. C. The precipitated dark brown product 
is filtered off and dried in vacuum. There are obtained 25 g of the 
compound having the formula (111) (92% of theory): 
##STR14## 
Elemental analysis of the compound having the formula (111) and having the 
empirical formula C.sub.16 H.sub.13 MnN.sub.2 Na.sub.2 O.sub.9 S.sub.2. 
1.0H.sub.2 O gives: 
Req. % C 34.2; H 3.03; N 5.0; Mn 9.8. 
Found % C 34.2; H 3.3; N 5.6; Mn 9.3. 
EXAMPLE 9 
Using the procedure described in Example 1, the following compound of 
formula (112) is prepared: 
##STR15## 
Elemental analysis of the compound having the formula (112) and having the 
empirical formula C.sub.18 H.sub.17 MnN.sub.2 O.sub.4 gives: 
Req. % C 56.8; H 4.5; N 7.4; Mn 14.5. 
Found % C 56.7; H 4.6; N 7.3; Mn 14.6. 
EXAMPLE 10 
Using the procedure described in Example 1, the following compound of 
formula (113) is prepared: 
##STR16## 
Elemental analysis of the compound having the formula (113) and having the 
empirical formula C.sub.16 H.sub.14 F.sub.6 MnN.sub.2 O.sub.2 P. 
2.12H.sub.2 O gives: 
Req. % C 38.1; H 3.6; N 5.6; H.sub.2 O 7.6; Mn 10.9. 
Found % C 38.5; H 3.5; N 5.7; H.sub.2 O 7.6; Mn 11.0. 
EXAMPLE 11 
Using the procedure described in Example 1, the following compound of 
formula (114) is prepared: 
##STR17## 
Elemental analysis of the compound having the formula (114) and having the 
empirical formula C.sub.22 H.sub.23 MnN.sub.2 O.sub.4.1.9H.sub.2 O gives: 
Req. % C 56.4; H 5.8; N 6.0; H.sub.2 O 7.3; Mn 11.7. 
Found % C 56.2; H 5.8; N 5.9; H.sub.2 O 7.3; Mn 11.5. 
EXAMPLE 12 
Using the procedure described in Example 1, the following compound of 
formula (115) is prepared: 
##STR18## 
Elemental analysis of the compound having the formula (115) having the 
empirical formula C.sub.18 H.sub.18 ClMnN.sub.2 O.sub.4 gives: 
Req. % C 56.2; H 4.7; N 7.3; Mn 17.3. 
Found % C 56.3; H 4.6; N 7.1; Mn 17.1. 
EXAMPLE 13 
Using the procedure described in Example 1, the following compound of 
formula (116) is prepared: 
##STR19## 
Elemental analysis of the compound having the formula (116) having the 
empirical formula C.sub.2O H.sub.22 ClMnN.sub.2 O.sub.2.4.25 H.sub.2 
O.0.33 NaCl gives: 
Req. % C 49.1; H 5.8; N 5.72; Cl 9.65; Mn 11.23. 
Found % C 49.1; H 5.9; N 5.6; Cl 9.8; Mn 10.8. 
EXAMPLE 14 
Using the procedure described in Example 1, the following compound of 
formula (117) is prepared: 
##STR20## 
Elemental analysis of the compound having the formula (117) having the 
empirical formula C.sub.16 H.sub.12 ClMnN.sub.2 Na.sub.2 O.sub.8 S.sub.2. 
3H.sub.2 O. 1.2NaCl gives: 
Req. % C 28.0; H 2.6; N 4.1; Mn 8.0; S 9.3. 
Found % C28.0;H2.6;N4.1;Mn7.8;S9.1. 
EXAMPLE 15 
Using the procedure described in Example 1, the following compound of 
formula (118) is prepared: 
##STR21## 
Elemental analysis of the compound having the formula (118) and having the 
empirical formula C.sub.17 H.sub.15 MnN.sub.2 Na.sub.2 O.sub.9 S.sub.2 
gives: 
Req. % C 34.0; H 2.7; N 5.0; Mn 9.9; S 11.5. 
Found % C 34.8; H 3.3; N 5.0; Mn 10.1; S 11.2. 
EXAMPLE 16 
Using the procedure described in Example 1, the following compound of 
formula (119) is prepared: 
##STR22## 
Elemental analysis of the compound having the formula (119) and having the 
empirical formula C.sub.22 H.sub.21 MnN.sub.2 Na.sub.2 O.sub.10 S.sub.2. 
1.56H.sub.2 O gives: 
Req. % C 39.6; H 3.6; N 4.2; Mn 8.2; S 9.6. 
Found % C 39.6; H 4.2; N 4.9; Mn 8.7; S 9.6. 
EXAMPLE 17 
Using the procedure described in Example 1, the following compound of 
formula (120) is prepared: 
##STR23## 
Elemental analysis of the compound having the formula (120) having the 
empirical formula C.sub.20 H.sub.18 ClMnN.sub.2 Na.sub.2 O.sub.8 S.sub.2. 
2.5H.sub.2 O. 1.45NaCl gives: 
Req. % C 32.2; H 3.1; N 3.8; Mn 7.4. 
Found % C 32.2; H 3.1; N 3.8; Mn 7.2. 
EXAMPLE 18 
##STR24## 
A) To a solution of 18.8 g. of 2-aminopyridine in 300 ml. of ethanol, there 
are added 24.4 g. of salicylaldehyde. The mixture is heated to 
70-75.degree. C. and stirred for 7 hours. The mixture is concentrated to 
one third of its volume and then cooled to 5.degree. C., whereupon an 
orange product having the formula: 
##STR25## 
crystallised out. The product is filtered off with suction and allowed to 
dry in the air, giving a yield of 25.5 g. (65% of theory). 
Elemental analysis of the compound having the formula (121a) having the 
empirical formula C.sub.12 H.sub.10 N.sub.2 O gives: 
Req. % C 72.71; H 5.08; N 14.13. 
Found % C 72.6; H 5.1; N 14.1. 
B) To a solution of 5.9 g. of the compound of formula (121a) obtained in 
Part A), in 200 ml. of ethanol, there are added 8.5 g. of 
manganese-III-acetate dihydrate. The resulting dark brown solution is 
stirred for 5 hours at 60-65.degree. C. and evaporated to dryness. The 
residue is dried in vacuum giving a yield of 6.3 g. (68% of theory) of a 
light brown compound having the formula (121). 
Elemental analysis of the compound having the formula (121) having the 
empirrical formula C.sub.14 H.sub.12 MnN.sub.2 O.sub.3. CH.sub.3 COOH 
gives: 
Req. % C 49.48; H 4.38; N 7.22; Mn 14.17. 
Found % C 50.18; H 4.45; N 7.40; Mn 14.4. 
EXAMPLE 19 
##STR26## 
A) To a solution of 26.8 g. phthaldialdehyde in 1000 ml. of ethanol there 
are added 21.5 ml. of diethylenetriamine and the mixture is stirred for 20 
hours at 25.degree. C. The resulting solution becomes brown-green in 
colour and is evaporated to dryness giving 40 g. (100% theory) of a thick 
brown liquid having the formula: 
##STR27## 
B) To a solution of 19.8 g. of manganese-II-chloride tetrahydrate in 250 
ml. of ethanol, there is added a solution of 20.1 g. of the product of 
formula (122a) in 250 ml. of ethanol. An ochre yellow suspension is formed 
and this is stirred for 18 hours at 25.degree. C. The product is filtered 
off with suction, washed with ethanol and dried in vacuum at 25.degree. C. 
giving 28 g. (85% theory) of an ochre yellow of formula (122). 
Elemental analysis of the compound having the formula (122) and having the 
empirical formula C.sub.12 H.sub.14 Cl.sub.2 MnN.sub.3 gives: 
Req. % C 37.81; H 5.55; N 11.02; Cl 18.60; Mn 14.41. 
Found % C 38.0; H 5.0; N 10.5; Cl 19; Mn 15.4. 
EXAMPLE 20 
##STR28## 
To a solution of 5.1 g. of 2,2'-dipyridylamine in 50 ml. of ethanol there 
are added 7.4 g. of manganese-II-acetate tetrahydrate and the mixture is 
stirred for 18 hours at 25.degree. C. The product is filtered off with 
suction, washed with methanol and dried in vacuum at 25.degree. C. giving 
6.6 g. (58% theory) of a white product having the formula (123). 
Elemental analysis of the compound having the formula (123) having the 
empirical formula C.sub.32 H.sub.36 Mn.sub.3 N.sub.6 O.sub.12 gives: 
Req. % C 44.62; H 4.21; N 9.76; Mn 19.13. 
Found % C 44.70; H 4.15; N 9.72; Mn 19.8. 
EXAMPLE 21 
##STR29## 
8.2 g. of 1,2-bis(3,5-di-tert.butylsalicylidamino)cyclohexane are added to 
400 ml. of ethanol, the mixture is heated to 65.degree. C. and 3.7 g. of 
manganese-II-acetate tetrahydrate are added to the yellow suspension. 
After a short time, a dark brown solution is formed which is stirred for 
15 hours and then evaporated to dryness. 9.5 g. (92.8% theory) of a dark 
brown powder having the formula (124) are obtained. 
Elemental analysis of the compound having the formula (124) having the 
empirical formula C.sub.38 H.sub.55 MnN.sub.2 O.sub.4. 1.33 H.sub.2 O 
gives: 
Req. % C 66.85; H 8.43; N 4.10; Mn 8.05. 
Found % C 66.98; H 8.53; N 4.00; Mn 7.82. 
EXAMPLE 22 
##STR30## 
10.9 g. of o-aminophenol and 10.7 g. of pyridine-2-aldehyde are stirred in 
200 ml. of ethanol for 5 hours at 60-65.degree. C. The solution is then 
treated with 24.5 g. of manganese-II-acetate tetrahydrate and stirred for 
5 hours at 60-65.degree. C. The solution is evaporated and the residue is 
dried in vacuum giving 31 g. (95% theory) of a red-brown product having 
the formula (125). 
Elemental analysis of the compound having the formula (125) and having the 
empirical formula C.sub.14 H.sub.12 MnN.sub.2 O.sub.3. 0.83 H.sub.2 O 
gives: 
Req. % C 51.58; H 4.22; N 8.59; Mn 16.87. 
Found% C51.76;H3.91;N8.11;Mn 16.80. 
EXAMPLE 23 
##STR31## 
A) To a solution of 405 ml. of diaminoethane in 1000 ml. of toluene there 
are added 20 ml. of formic acid and 63.4 g. of copper dust. The suspension 
is heated to 100.degree. C. and is treated, dropwise, over 2 hours, with a 
solution of 111 ml. of o-chlorobenzaldehyde in 115 ml. of toluene. After 4 
hours at 100.degree. C., the mixture is cooled to 75.degree. C. and some 
copper dust is filtered off. 
The filtrate forms two phases. The upper toluene phase is separated and 
concentrated to 100 ml. This concentrate is diluted with 200 ml. of 
ethanol and allowed to stand for 48 hours at 25.degree. C. The product 
which crystallises out is filtered with suction and dried in vacuum at 
40.degree. C. giving 24 g. (16% theory) of a yellow product having the 
formula: 
##STR32## 
B) 5.8 g. of the compound of formula (126a) obtained in Part A) and 5 g. of 
manganese-II-acetate tetrahydrate are stirred for 12 hours in 200 ml. of 
ethanol, filtered with suction, washed with ethanol and dried in vacuum, 
giving 7.5 g. of the compound of formula (126). 
Elemental analysis of the compound having the formula (126) having the 
empirical formula C.sub.22 H.sub.26 MnN.sub.4 O.sub.4. 0.14 MnO.sub.2 
gives: 
Req. % C 55.30; H 5.48; N 11.72; Mn 13.12. 
Found % C 55.34; H 5.55; N 11.80; Mn 12.70. 
EXAMPLE 24 
##STR33## 
To a solution of 19.8 g. of manganese-II-chlorride in 200 ml. of methanol 
there are added 14 g. of hexamethylenetetrmrlne. After siring at 
25.degree. C. for 20 hours, the precipitated product is filtered with 
suction and dried in vacuum at 25.degree. C., giving 18.5 g. (91% theory) 
of a light grey product having the formula (127). 
Elemental analysis of the compound having the formula (127) and having the 
empirical formula C.sub.12 H.sub.24 Cl.sub.2 MnN.sub.8 2 H.sub.2 O gives: 
Req. % C 32.59; H 6.38; N 25.34; Cl 16.03; Mn 12.42. 
Found % C 32.2; H 6.5; N 24.8; Cl 16.2; Mn 12.4. 
EXAMPLE 25 
##STR34## 
To a solution of 3 g. of triazacyclononane in 80 ml. of methanol there are 
added 2 g. of manganese perchlorate hexahydrate. A white suspension is 
formed immediately. After 30 minutes, 1 g. of sodium acetate is added and 
the mixture is sted for 24 hours at 25.degree. C. The product is filtered 
with suction, washed with methanol and dried in vacuum at 25.degree. C., 
giving 1.8 g. (65% theory) of a white product having the formula (128). 
Elemental analysis of the compound having the formula (128) and having the 
empirical formula C.sub.12 H.sub.30 Cl.sub.2 MnN.sub.6 O.sub.8 gives: 
Req. % C 28.12; H 5.86; N 16.41; Cl 13.87; Mn 10.74. 
Found % C 28.1; H 6.2; N 16.3; Cl 13.6; Mn 11.0. 
EXAMPLE 26 
##STR35## 
To a solution of 13.8 g. of phthalocyanine tetrasulphonic acid in 140 ml. 
of water there are added 4.2 g. of manganese-III-acetate dihydrate. The 
mixture is heated to 70-75.degree. C. and stirred for 12 hours. 20 g. of 
sodium chloride are added, the mixture is stirred for a further 6 hours, 
cooled to 5.degree. C. and filtered with suction. The material filtered 
off is dissolved in 200 ml. of water and dialysed for 40 hours. The 
solution remaining is evaporated to dryness and the residue is dried in 
vacuum, giving 3.5 g. (20% theory) of a black product having the formula 
(129). 
Elemental analysis of the compound having the formula (129) having the 
empirical formula C.sub.64 H.sub.40 Mn.sub.3 N.sub.16 O.sub.24 S.sub.8.2.2 
H.sub.2 O gives: 
Req. % C 31.78; H 3.50; N 9.27; S 10.61; Mn 6.81. 
Found % C 32.1; H 3.2; N 9.4; S 10.7; Mn 6.79. 
EXAMPLE 27 
A standard (ECE) washing powder is made up from the following components in 
the indicated proportions: 
8.0% Sodium (C.sub.11.5)alkylbenzenesulphonate; 
2.9% Tallow-alcohol-tetradecane-ethyleneglycolether (14 moles EO); 
3.5% Sodium soap; 
43.8% Sodium triphosphate; 
7.5% Sodium silicate; 
1.9% Magnesium silicate; 
1.2% Carboxymethylcellulose; 
0.2% EDTA; 
21.2% Sodium sulphate; and 
9.8% Water. 
An aqueous wash liquid is then made up and contains 7.5 g/l of the ECE 
powder, 1.13 g/l of sodium perborate monohydrate and 0.015 g/l of the 
compound of formula (111) as described in Example 8. 
Into 400 ml of the aqueous wash liquid (made up using town water of 12 
degrees of hardness), there are placed 12.5 g. of test cotton fabric 
soiled with red wine, tea, coffee or blackberry stains, as well 37.5 g. of 
bleached cotton (i.e. giving a liquor ratio of 1:8). 
The respective wash baths are each heated from 15.degree. C. to the test 
temperature of 25.degree. C., 40.degree. C. or 60.degree. C. over a period 
of 10 minutes; and held at the respective test temperature for a further 
10 minutes. The respective swatches are then rinsed under flowing, cold 
town water, spun dry and ironed. 
The brightness value (Y) of the respective test swatches is then determined 
using an ICS SF 500 spectrophotometer. The value Y provides a measure of 
the level of bleach effect achieved. A difference of 1 Y unit is clearly 
detectable visually. 
For reference purposes, the respective Y values are determined for each of 
the washed goods at 25.degree. C. using perborate alone (i.e. using no 
compound of formula 109). 
The results obtained are set out in the following Table. 
TABLE 
______________________________________ 
.DELTA.Y 
15% perborate 15% perborate + 0.2% cpd. 110 
Soil Type 
25.degree. C. 
40.degree. C. 
60.degree. C. 
25.degree. C. 
40.degree. C. 
60.degree. C. 
______________________________________ 
red wine 
Y = 64 +1 +3 +4 +6 +14 
tea Y = 65 0 +5 +4 +10 +22 
coffee Y = 72 +1 +5 +4 +6 +14 
blackberry Y = 60 +2 +7 +7 +10 +23 
______________________________________ 
It is clear from the results in the Table that, at any given temperature, 
the bleaching improvement achieved with a fabric bleaching composition 
according to the invention are 3 to 5 times greater than those achieved 
using perborate alone. Moreover, even at 25.degree. C., a fabric bleaching 
composition according to the invention provides bleaching effects which 
are equivalent to those obtained at 60.degree. C. using perborate alone. 
Similar results are obtained when the compound of formula (111) is replaced 
by a compound of formula (110), (112), (114), (117), (118), (119), (120), 
(121), (122), (123), (124), (125), (126), (128) or (129).