CN1384837A - Ligand and complex for catalytically bleaching substrate - Google Patents
Ligand and complex for catalytically bleaching substrate Download PDFInfo
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- CN1384837A CN1384837A CN00814984.4A CN00814984A CN1384837A CN 1384837 A CN1384837 A CN 1384837A CN 00814984 A CN00814984 A CN 00814984A CN 1384837 A CN1384837 A CN 1384837A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/55—Acids; Esters
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3932—Inorganic compounds or complexes
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Abstract
The invention relates to ligands or complexes useful as catalysts for catalytically bleaching substrates with atmospheric oxygen, and as catalysts in the treatment of textiles such as laundry fabrics whereby bleaching by atmospheric oxygen is catalysed after the treatment. The ligand is of general formula (I), wherein R1, R2 and R3 independently represent a group selected from hydrogen, hydroxyl, halogen, -NH-C(NH)NH2, -R and -OR, wherein R= alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group, R being optionally substituted by one or more functional groups, and provided that two of R1, R2 and R3 are coordinating groups and one of R1, R2 and R3 is a non-coordinating group; Q independently represents a group selected from C2-3-alkylene optionally substituted by H, benzyl or C1-8-alkyl; and Q1, Q2 and Q3 independently represent specified linking groups.
Description
Invention field
The present invention relates to useful part of a class or title complex, it can be used as catalyst and bleaches substrate with atmosphericoxygen, and is used as catalyzer makes after processing catalysis with the bleaching of atmosphericoxygen in the processing such as washing cloth fabric.
Background of invention
As everyone knows, peroxide bleaching agent can be removed spot from substrate.In general, with the substrate hydrogen peroxide, maybe can produce for example inorganic or organic peroxide treatment of material of hydroperoxyl radical.Usually, these systems must activate.One of activatory method is to adopt 60 ℃ or higher wash temperature.Yet these high temperature cause the efficient of cleaning not high through regular meeting, also cause the early failure of substrate.
The preferred method that produces peroxide hydroxyl bleaching base is to use and organic precursor compound link coupled inorganic peroxide.Many commercially available washing powder adopt this system exactly.For example, various European systems just are based on tetrem acyl second (support) diamines (TAED) as organic precursor and Sodium peroxoborate or SPC-D coupling, and the laundry bleaching product of the U.S. generally is based on nonanoyl oxygen benzene sulfonic acid sodium salt (SNOBS) as organic precursor and Sodium peroxoborate coupling.
Precursor systems generally is effectively but still demonstrates several shortcomings.For example, organic precursor is the molecule of medium complexity, needs multistep synthetic technological process, thereby the cost of investment height.And precursor systems needs very big prescription space, so that the overwhelming majority of washing powder must be a bleach, only lefts in little space and gives other activeconstituents, and make the exploitation of concentrated detergent powder complicated.Simultaneously, in some country, the user gets used to that consumption is few, scavenging period is short, cleaning temperature is low and with respect to the lacking than scavenging solution of substrate, the precursor systems bleaching is very ineffective.
As selection, or additionally, hydrogen peroxide and mistake oxygen system can activate by bleaching catalyst, and be for example disclosed in WO95/34628, by iron and part N
4The activation of Py (being N, N-two (pyridine-2-base-methyl)-two (pyridine-2-yl) methylamine) title complex is perhaps by disclosed iron in WO97/48787 and the activation of part Tpen (being N, N, N ', N '-four (pyridine-2-base-methyl) quadrol) title complex.According to these publications, molecular oxygen can be used as oxygenant, as the surrogate of superoxide generation structure.Yet in water medium, the effect by the atmosphericoxygen catalytically bleaching yet there are no report.
Think for a long time always and also wish to use the source of atmosphericoxygen (air), so just can avoid the hydroperoxyl radical generation system that needs cost higher as albic material.Unfortunately, present kinetic inertness equally, do not demonstrate whitening capacity for bleaching substrate air.Recently, some progress have been obtained in this field.For example, WO97/38774 has reported in the aqueous solution that contains aldehyde and radical initiator by the method for air bubbling with spot on the atmospheric oxidation fabric fibre.Aldehyde aliphatic, aromatic and that the heterocyclic wide range is interior it is reported it is useful, especially such as the 4-methyl ,-4-ethyl-and the para-orientation aldehyde of 4-isopropyl benzene formaldehyde, and disclosed initiator comprises N-hydroxy-succinamide, various superoxide and transition metal complex.
Yet,, in bleaching process, consumed the aldehyde component and such as the radical initiator of superoxide although this system has adopted airborne molecular oxygen.Therefore these components must be contained in the composition with quite high content, so that bleaching process is not finished not depleted as yet in cycles of washing.And because the component that consumes can not participate in bleaching process again, this just represents a kind of wasting of resources.
Therefore, this just wishes to provide a kind of bleach system based on atmosphericoxygen or air, and it does not mainly depend on hydrogen peroxide or hydroperoxyl radical generation system, does not also need to exist in for example aldehyde of the organic constituent that consumes in the bleaching process.And, also be desirable to provide effective bleach system in water-bearing media.
Should be pointed out that prior art only produces bleaching effect when substrate being bleached processing.Because the necessary albic material of bleach system itself or arbitrary activator can be removed from substrate, consume or inactivation after being assumed to be at and finishing cycles of washing and drying, like this, after can not being desirably in washing and drying, hydrogen peroxide or peroxide bleaching system can continue the generation bleaching action on such as washed fabric at processed substrate.
Therefore also wish to handle fabric like this, make after treating processes is finished, on fabric, observe bleaching effect.And, when the fabric fibre of handling finish dealing with and drying after, also wishing to rely on remaining bleaching action to provide provides the bleaching processing to the fabric cloth such as the washing fabric.
Summary of the invention
We have found part or title complex that a class is novel, and it is shockingly effective in katalysis atmosphericoxygen or air bleaching substrate.
Therefore, in first aspect, the invention provides this general structure:
Wherein,
R
1, R
2And R
3Independent representative is selected from a group of following group: hydrogen, hydroxyl, halogen ,-NH-C (NH) NH
2,-R and-OR, wherein R=alkyl, thiazolinyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl or carbonyl deriveding group, R is optional to be replaced by one or more E of functional group, illustrates further as follows:
Q represents independently and is selected from by H, phenyl or C
1-8The optional C that replaces of-alkyl
2-3-alkylidene group; With
Q
1, Q
2And Q
3Representative links group independently, illustrates further as follows:
Suppose R
1, R
2And R
3In two be coordinating group, R
1, R
2And R
3In one be non-coordinating group; With
Condition is to get rid of following part:
1,4-two (N-methyl-imidazoles-2 ylmethyl)-1,4,7-7-triazacyclononane;
1,4-two (N-methyl-imidazoles-2 ylmethyl)-7-acetoxyl-1,4,7-7-triazacyclononane;
1,4-two (pyridine-2-ylmethyl)-7-ethyl-1,4,7-7-triazacyclononane;
1,4-two (quinoline-2-ylmethyl)-7-ethyl-1,4,7-7-triazacyclononane;
1,4-two (pyrazol-1-yl methyl)-7-ethyl-1,4,7-7-triazacyclononane;
1,4-two (3-1-ylmethyl)-7-ethyl-1,4,7-7-triazacyclononane;
1,4-two (N-Methylimidazole-2-ylmethyl)-7-ethyl-1,4,7-7-triazacyclononane;
1,4-two (N-sec.-propyl kharophen)-7-ethyl-1,4,7-7-triazacyclononane; With
1,4-two (N-methyl kharophen)-7-ethyl-1,4,7-7-triazacyclononane.
In second aspect, the invention provides the title complex of a kind of part and transition metal.
The advantage of this class part of the present invention and title complex is, this title complex can catalysis atmosphericoxygen bleaching substrate, allows it to use in such as the medium of water-bearing media like this and do not use the bleach system of peroxygen bleach or peroxy or generation peroxy substantially.We find that also this class title complex is shockingly effective aspect atmosphericoxygen bleaching substrate in catalysis after substrate is handled.
This class part of the present invention and coordination compound help allowing all or the most of albic material (based on equivalent weight) in medium to be derived from atmosphericoxygen.Like this, producing medium can be fully or do not use peroxide bleaching system or peroxy substantially or produce the bleach system of peroxide.And this title complex is the catalyzer that is used for this bleaching process, and amount remains unchanged and is not consumed, and but can continue to participate in bleaching process.Like this, above-mentioned part or title complex can catalytic activation based on the bleach system of atmosphericoxygen, therefore both cost efficients is again eco-friendly.And, can also be provided at and comprise the bleach system that carries out work under the unfavorable wash conditions that low temperature, duration of contact are short and low used in amounts is wanted.In addition, this catalyzer is effectively in water-bearing media, especially is fit to be applied to the bleaching of laundering of textile fabrics thus.Therefore, though catalyzer of the present invention can be used for any suitable substrate bleaching, preferred bleached woven fabric substrate.By simply substrate being contacted the competent time with medium, bleaching just can be carried out.Yet, the preferred medium that holds substrate that stirs.
Another advantage is, continues by make bleaching action after fabric treating, can prolong the bleaching effect on fabric.And owing to can produce bleaching action to fabric after processing, for example, treating processes itself can shorten as the water washing circulation.In addition, owing to produce bleaching action by atmosphericoxygen after handling fabric, handling substrate does not just need hydrogen peroxide or peroxy bleach system.
The present invention also provides the commercial package that comprises bleaching composition, and said composition contains following part and the title complex that defines with its operation instruction.
The present invention also is provided in the bleaching composition production as the part of giving a definition and the application of title complex, and this bleaching composition does not use peroxygen bleach or peroxy or peroxide generation bleach system basically.
Detailed Description Of The Invention
This catalyzer can be with the prefabricated title complex that becomes part and transition metal.As selection, can be by the transition-metal coordination in free ligand and the water Already in, or with substrate on transition-metal coordination and make this catalyzer.Said composition also can be formulated with the metal ligand title complex and the transition metal source of free ligand or available Transition metal substituted, and this title complex just can form in medium on the spot thus.
Part can form title complex with one or several transition metal, and the latter is such as dinuclear complex.For example, suitable transition metal comprises: the manganese of II-V oxidation state, iron II-V, copper I-III, cobalt I-III, titanium II-IV, tungsten IV-VI, vanadium II-V and molybdenum II-VI.
The general structure (A1) of the title complex that part forms is:
[M
aL
kX
n] Y
m(A1) wherein:
M represents to be selected from the metal of Mn (II)-(III)-(IV)-(V), Cu (I)-(II)-(III), Fe (II)-(III)-(IV)-(V), Co (I)-(II)-(III), Ti (II)-(III)-(IV), V (II)-(III)-(IV)-(V), Mo (II)-(III)-(IV)-(V)-(VI) and W (IV)-(V)-(VI), preferred Fe (II)-(III)-(IV)-(V);
The L representative is the part of definition herein, or its analogue protonated or deprotonation;
X representative be selected from any single, double or trivalent negatively charged ion and any can with metal with coordination material single, double, tridentate ligand form coordinate neutral molecule, be preferably selected from O
2-, RBO
2 2-, RCOO
-, RCONR
-, OH
-, NO
3 -, NO, S
2-, RS
-, PO
4 3-, PO
3OR
3-, H
2O, CO
3 2-, HCO
3 -, ROH, N (R)
3, ROO
-, O
2 2-, O
2 -, RCN, Cl
-, Br
-, OCN
-, SCN
-, CN
-, N
3 -, F
-, I
-, RO
-, ClO
4 -And CF
3SO
3 -, more preferably be selected from O
2-, RBO
2 2-, RCOO
-, OH
-, NO
3 -, S
2-, RS
-, PO
3 4-, H
2O, CO
3 2-, HCO
3 -, ROH, N (R)
3, Cl
-, Br
-, OCN
-, SCN
-, RCN, N
3 -, F
-, I
-, RO
-, ClO
4 -And CF
3SO
3 -
Y represents any non-coordinate gegenion, is preferably selected from ClO
4 -, BR
4 -, [MX
4]
-, [MX
4]
2-, PF
6 -, RCOO
-, NO
3 -, RO
-, N
+(R)
4, ROO
-, O
2 2-, O
2 -, Cl
-, Br
-, F
-, I
-, CF
3SO
3 -, S
2O
6 2-, OCN
-, SCN
-, H
2O, RBO
2 2-, BF
4 -And BPh
4 -, more preferably be selected from ClO
4 -, BR
4 -, [FeCl
4]
-, PF
6 -, RCOO
-, NO
3 -, RO
-, N
+(R)
4, Cl
-, Br
-, F
-, I
-, CF
3SO
3 -, S
2O
6 2-, OCN
-, SCN
-, H
2O and BF
4 -
A represents an integer of 1～10, preferred 1～4 integer;
K represents an integer of 1～10;
N represents an integer of 1～10, preferred 1～4 integer;
M represents an integer of 0 or 1～20, preferred 1～8 integer; With
Each R independently represent be selected from hydrogen, hydroxyl ,-R ' and-OR ', wherein R '=alkyl, thiazolinyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl or carbonyl deriveding group, R ' is optional to be replaced by one or more E of functional group, wherein E represent independently be selected from-F ,-Cl ,-Br ,-I ,-OH ,-OR ' ,-NH
2,-NHR ' ,-N (R ')
2,-N (R ')
3 +,-C (O) R ' ,-OC (O) R ' ,-COOH ,-COO
-(Na
+, K
+) ,-COOR ' ,-C (O) NH
2,-C (O) NHR ' ,-C (O) N (R ')
2, heteroaryl ,-R ' ,-SR ' ,-SH ,-P (R ')
2,-P (O) (R ')
2,-P (O) (OH)
2,-P (O) (OR ')
2,-NO
2,-SO
3H ,-SO
3(Na
+, K
+) ,-S (O)
2R ' ,-NHC (O) R ' and-functional group of N (R ') C (O) R ', wherein R ' representation ring alkyl, aryl, aralkyl or optional quilt-F ,-Cl ,-Br ,-I ,-NH
3 +,-SO
3H ,-SO
3(Na
+, K
+) ,-COOH ,-COO
-(Na
+, K
+) ,-P (O) is (OH)
2,-P (O) (O
-(Na
+, K
+))
2The alkyl that replaces, preferably each R independently represents hydrogen, optional substituted alkyl or optional substituted aryl, more preferably hydrogen or optional substituted phenyl, naphthyl or C
1-4-alkyl.
The general formula of ligand L (I) is:
Wherein
R1, R2 and R3 independently represent and are selected from following group: hydrogen, hydroxyl, halogen ,-NH-C (NH) NH
2,-R and-OR, wherein R=alkyl, thiazolinyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl or carbonyl deriveding group, R is optional to be replaced by one or more E of functional group;
Q represents independently and is selected from by H, benzyl or C
1-8The optional C that replaces of-alkyl
2-3-alkylidene group;
Q
1, Q
2And Q
3Represent the group of following general formula independently:
Wherein
5 〉=a+b+c 〉=1; A=0-5; B=0-5; C=0-5; N=1 or 2;
Y represents independently and is selected from-O-,-S-,-SO-,-SO
2-,-C (O)-, arylidene, alkylidene group, heteroarylidene, heterocycle alkylidene group ,-(G) P-,-P (O)-and-(G) group of N-, wherein G is selected from hydrogen, alkyl, aryl, aralkyl, cycloalkyl, outside the dehydrogenation, each group is optional to be replaced by one or more E of functional group; With
R5, R6, R7, R8 represent independently be selected from hydrogen, hydroxyl, halogen ,-R and-group of OR, wherein R represents alkyl, thiazolinyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl or carbonyl deriveding group, R is optional to be replaced by one or more E of functional group;
Or R5 and R6, or R7 and R8, or the both represents oxygen,
Perhaps R5 and R7 and/or R6 and R8 independently, or R5 and R8 and/or R6 and R7 independently, representative is optional by C
1-4-alkyl ,-F ,-Cl ,-Br or-C that I replaces
1-6-alkylidene group,
Suppose R
1, R
2And R
3In two be coordinating group, R
1, R
2And R
3In one be non-coordinating group; With
Condition is to get rid of following part:
1,4-two (N-methyl-imidazoles-2 ylmethyl)-1,4,7-7-triazacyclononane;
1,4-two (N-methyl-imidazoles-2 ylmethyl)-7-acetoxyl-1,4,7-7-triazacyclononane;
1,4-two (pyridine-2-ylmethyl)-7-ethyl-1,4,7-7-triazacyclononane;
1,4-two (quinoline-2-ylmethyl)-7-ethyl-1,4,7-7-triazacyclononane;
1,4-two (pyrazol-1-yl methyl)-7-ethyl-1,4,7-7-triazacyclononane;
1,4-two (3-1-ylmethyl)-7-ethyl-1,4,7-7-triazacyclononane;
1,4-two (N-Methylimidazole-2-ylmethyl)-7-ethyl-1,4,7-7-triazacyclononane;
1,4-two (2 '-(acetyl-N-sec.-propyl kharophen)-7-ethyl-1,4,7-7-triazacyclononane; With
1,4-two (2 '-(acetyl-N-methyl kharophen)-7-ethyl-1,4,7-7-triazacyclononane.
R1, among R2 and the R3 two independently representative be preferably selected from carboxylate radical, amido ,-NH-C (NH) NH
2, hydroxyphenyl, and be selected from the heterocycle of optional replacement of pyridine, pyrimidine, pyrazine, pyrazoles, imidazoles, benzoglyoxaline, quinoline, quinoxaline, triazole, isoquinoline 99.9, carbazole, indoles, isoindole, azoles and thiazole or the group of the optional hetero-aromatic ring that replaces.Preferably, at R1, among R2 and the R3 two, each all independently representative be selected from the coordinating group of the optional pyridine-2-base that replaces, the optional imidazoles-2-base that replaces, optional substituted imidazole-4-base, the optional pyrazol-1-yl that replaces and the optional quinoline-2-base that replaces.
Work as R1, when R2 and R3 group were represented heterocycle or hetero-aromatic ring, its substituting group was preferably selected from C
1-4-alkyl, aryl, aralkyl, hetero-aromatic ring, methoxyl group, hydroxyl, nitro, amino, carboxyl, halogen and carbonyl.
R5, R6, R7, R8 preferably represent independently and are selected from-H, hydroxyl-C
0-C
20-alkyl, halo-C
0-C
20-alkyl, nitroso-group, formyl radical-C
0-C
20-alkyl, carboxyl-C
0-C
20-alkyl and ester thereof and salt, formamyl-C
0-C
20-alkyl, sulfo group-C
0-C
20-alkyl and ester thereof and salt, sulfamyl-C
0-C
20-alkyl, amino-C
0-C
20-alkyl, aryl-C
0-C
20-alkyl, C
0-C
20-alkyl, alkoxy-C
0-C
8-alkyl, carbonyl-C
0-C
6-alkoxyl group and-C
0-C
20The group of-alkylamidoalkyl.Preferred R6-R8 does not link to each other mutually.
Preferred Q1, Q2, Q3 so defines: a=b=0, c=1,2,3 or 4 and n=1.Preferred Q1, Q2, Q3 represent independently and are selected from-CH
2-and-CH
2CH
2-a group.
Group Q is preferably selected from-CH
2CH
2-and-CH
2CH
2CH
2-group.
In first preferred embodiment, the general formula of ligand L is (II):
R1 wherein, R2, R3 and Q1, Q2, the definition of Q3 is with the definition of front.
According to first embodiment preferred, as the structure of top formula (II) representative, a preferred class part has general formula (II), wherein:
At R1, R2 and R3 among any two each represent independently be preferably selected from carboxylate radical, amido ,-NH-C (NH) NH
2, hydroxyphenyl, and be selected from the heterocycle of optional replacement of pyridine, pyrimidine, pyrazine, pyrazoles, imidazoles, benzoglyoxaline, quinoline, quinoxaline, triazole, isoquinoline 99.9, carbazole, indoles, isoindole, azoles and thiazole or the coordinating group of the optional hetero-aromatic ring that replaces; With
R1, representative is selected from hydrogen, the optional C that replaces one of among R2 and the R3
1-20Alkyl, the optional C that replaces
1-20Aralkyl, aryl and the optional C that replaces
1-20NR
3 +(R=C wherein
1-8-alkyl).
In this case, we are preferred:
At R1, each represents the coordinating group that is selected from the optional pyridine-2-base that replaces, the optional imidazoles-2-base that replaces, optional substituted imidazole-4-base, the optional pyrazol-1-yl that replaces and the optional quinoline-2-base that replaces independently in two of R2 and R3; With
R1, a representative among R2 and the R3 is selected from hydrogen, the optional C that replaces
1-10Alkyl, C
1-5Furyl, the optional C that replaces
1-5Benzyl alkyl, benzyl, the optional C that replaces
1-5Alkoxyl group and the optional C that replaces
1-20N
+Me
3A group.
A kind of particularly preferred part is 1,4-two (5-methyl-pyridine-2-ylmethyl)-7-ethyl-7-triazacyclononane.
Gegenion Y balance in structural formula (A1) the electric charge z on the title complex that becomes by ligand L, metal M and coordination material X-shaped.Like this, if electric charge z for just, Y can be following negatively charged ion: RCOO
-, BPh
4 -, ClO
4 -, BF
4 -, PF
6 -, RSO
3 -, RSO
4 -, SO
4 -, NO
3 -, F
-, Cl
-, Br
-, or I
-, wherein R is a hydrogen, optional alkyl that replaces or the optional aryl that replaces.If electric charge z is for negative, Y can be the common cation as basic metal, alkaline-earth metal or (alkyl) ammonium cation.
Suitable gegenion comprises those ions of the solid formation that promotes stably stored.The preferred counter ion that is used for preferred metal complexes is selected from R
7COO
-, ClO
4 -, BF
4 -, PF
6 -, RSO
3 -(CF especially
3SO
3 -), RSO
4 -, SO
4 -, NO
3 -, F
-, Cl
-, Br
-, and I
-, wherein R represents hydrogen or optional phenyl, naphthyl or the C that replaces
1-C
4Alkyl.
People generate title complex (A1) by any appropriate means with pleasure, comprise on the spot forming, and make this title complex precursor just change into the labile coordination compound of general formula for (A1) thus under storage or working conditions.Preferred title complex forms as the title complex of clearly definition, or in salt that contains metal M and ligand L or produce in the solvent mixture of material of ligand L and form.Another method, catalyzer can form from suitable title complex precursor on the spot, for example in comprising the solution of precursor raw material or in the dispersion liquid.In such embodiment, active catalyst can be in suitable solvent be formed on the spot by salt that contains metal M and ligand L or the mixture that produces the material of ligand L.Like this, if for example M is an iron, just can be with for example FeSO
4Molysite in solution with ligand L or to produce the material of ligand L mixed to generate labile coordination compound.Thus, for example composition just can be from ligand L and metal-salt MX
nMiscellany in form preferred n=1～5 in this metal-salt, more preferably 1～3.In another such embodiment, ligand L or the material that produces ligand L mix with the metal M in being present in substrate or washings and generate active catalyst on the spot.The material of suitable generation part comprises metal-free compound, or contains ligand L and can be formed the metal-complexing title complex of general formula for the labile coordination compound of (A1) by the metal M ionic replacement.
Catalyzer of the present invention can be used to laundry cleaning, hard-surface cleaning (cleaning that comprises toilet, kitchen working face, floor, machinework).As known in the art, bleaching composition also be used for wastewater treatment, at paper-making process bleached pulp, leather manufacturing, suppress bleaching and/or the sterilization of contact lens of dye transfer, food-processing, starch bleaching, sterilization, oral hygienic articles.
In the context of the invention, bleaching is interpreted as relating generally to that spot is attached to or the decolorization of other material on substrate that associates.Yet, can estimate, the present invention can be applied to need by oxidation bleaching reaction remove and/or in and stench or other are attached to or the place of the undesirable composition on substrate that associates.In addition, in the context of the invention, it is to be restricted to anyly not need light to exist or bleaching mechanism or technology by photoactivation that bleaching action is construed as.
In typical cleaning composition, the content of catalyzer is such, and using content is 0.05～50 μ M, and the use content of household laundry washing is preferably 0.5～100 μ M, more preferably 1～10 μ M.High-content more can be applied to the industrial bleaching process, for example bleaching of fabric and paper pulp.
The pH of preferred water-bearing media is 6～13, more preferably 6～11, be more preferably 8～11, and most preferably be 8～10, especially be 9～10.
Bleaching catalyst of the present invention specifically is applied among the detergent formulation, particularly laundry washing.This detergent bleaching composition for example can comprise the surfactant of 10～50 weight %.Surfactant can be a natural derivative, for example soap or be selected from anionic, non-ionic, amphoteric, zwitterionic, the synthetic of cationic activation agent and composition thereof.Many suitable activators are commercially available, introduce fully in the literature, and for example at " tensio-active agent and washing composition ", volume I and volume II, Schwartz, Perry and Berch work.
Typical normally water miscible organic sulfuric acid and the sulfonic acid alkali metal salts that contains the alkyl of 8～22 carbon atoms of synthetic anion surface active agent, term " alkyl " is used to comprise the more moieties of high-grade aryl.The example of suitable synthetic anionic washing composition is sodium alkyl sulfate and ammonium, especially passes through more high-grade alcohol (C of sulfation
8～C
18) vitriol that obtains, for example alcohol that makes from Tallow, beef or Oleum Cocois; Alkyl (C
9～C
20) Phenylsulfonic acid sodium salt and ammonium salt, especially linear secondary alkyl (C
10～C
15) the Phenylsulfonic acid sodium salt; Alkyl glycerol ether sodium sulfate, the especially ether of the higher alcohols that makes from the single sulfuric ester of glycerol of Tallow, beef or fatty acid distribution of coconut oil and sulphonate; High fatty alcohol (C
9～C
18) the epoxy alkane especially sodium salt and the ammonium salt of the sulfuric ester of oxirane reaction product; Lipid acid such as fatty acid distribution of coconut oil is also used sodium hydroxide neutral reaction product with the isethionic acid esterification; The sodium salt of the fatty acid amide of N-methyltaurine and ammonium salt; Such as by alpha-olefin (C
8～C
20) with the sodium bisulfite reaction with by paraffin and SO
2And Cl
2Reaction and obtain the alkane list sulphonate that any sulfonate radical obtains with basic hydrolysis; Sulfosuccinic acid dialkyl (C
7～C
12) sodium and the ammonium salt of ester; With the alkene sulfonic acid ester, this term is used for describing with alkene, particularly (C
10～C
20) alpha-olefin, with SO
3Neutralization and the material that makes of hydrolysis reaction product again after the reaction.The preferred anionic detergent compound is alkyl (C
10～C
15) benzene sulfonic acid sodium salt and alkyl (C
16～C
18) ether sodium sulfate.
The example of the non-ionic surfactant compound that is suitable for specifically comprises epoxy alkane normally oxyethane and alkyl (C
6～C
22) reaction product of phenol, be generally 5～25EO, promptly per molecule has the oxyethane of 5～25 units; And aliphatics (C
8～C
18) condensation product of uncle or secondary straight or branched alcohol and oxyethane, be generally 2～30EO; Preferred its uses with anion surfactant.Other so-called ionic surfactant pack is drawn together alkyl polyglycoside, sugar ester, long chain tertiary amine oxide compound, long chain tertiary phosphine oxide and dialkyl sulfoxide.
Because its cost is higher relatively, though both sexes or zwitterionics can use general and unwilling use.If use any both sexes or zwitterionic detergent, in composition, generally also be a small amount of use based on the synthetic anionic of more common use and nonionogenic tenside.
Detergent bleaching composition preferably contains the anion surfactant of 1～15 weight % and the nonionogenic tenside of 10～40 weight %.In preferred embodiment, the washing activation system does not contain C
12～C
16Fatty acid soaps.
Bleaching composition also can contain detergent builder compound, and for example consumption is 5～80 weight %, preferred 10～60 weight %.
Builder material can be selected from 1) calcium sequestrant 2) material of precipitation usefulness, 3) calcium ion-exchange material and 4) their mixture.
The example of calcium sequestrant builder material comprises alkali metal polysilicate phosphoric acid salt, for example tripoly phosphate sodium STPP; Nitrilotriacetic acid(NTA) and its water-soluble salt; An alkali metal salt of carboxy methoxy-succinic acid, ethylenediamine tetraacetic acid (EDTA), oxygen di-succsinic acid, mellitic acid, benzene polycarboxylic acid, citric acid and polymeric acetal carboxylate is as disclosing in US-A-4 144 226 and US-A-4 146 495.
Precipitation comprises sodium orthophosphate and yellow soda ash with the example of builder material.
The example of calcium ion-exchange auxiliary material comprises various types of water-fast crystal or unbodied aluminosilicate, wherein, zeolite is the most known representatives, for example the P-class zeolite of zeolite A, zeolite B (also being zeolite P), zeolite C, X zeolite, zeolite Y and introduction in EP-A-0 384 070.
Particularly, composition can comprise any class in organic and the inorganic builders material, however, for the consideration to environment, does not preferably use phosphate builders or only uses minute quantity.For example, available typical case washing assistant has yellow soda ash, calcite/carbonate, sodium nitrilo triacetate salt, Trisodium Citrate, carboxymethyloxymalo,ates, carboxy methoxy-succinic acid salt and water-insoluble crystal or unbodied aluminosilicate builder material among the present invention, wherein each can both be used as main washing assistant, both can use separately, also can use with a spot of other washing assistant or as the mixed with polymers of auxiliary washing assistant.
If composition pH is the weak base district less than 10, preferably contain the carbonate builders that is no more than 5 weight %, be expressed as yellow soda ash, more preferably be 0 to being no more than 2.5 weight % substantially.
Except the component of having mentioned, bleaching composition can contain any conventional additive, and the consumption of these additives is for being used in the consumption in the fabric cloth detergent composition usually.The example of these additives comprises the buffer reagent such as carbonate; Such as the suds booster of alkanolamide, particularly from palm kernel fatty acid and fatty acid distribution of coconut oil deutero-single ethanol amide; Defoamer such as alkylphosphonic and siloxanes; Anti-redeposition agent such as Xylo-Mucine and alkyl or substituted alkyl ether of cellulose; Stablizer such as phosphoric acid derivatives (being Dequest class); Fabric softener; Inorganic salt and ealkaline buffer such as sodium sulfate and water glass; Common consumption fluorescent agent seldom; Spices; Such as proteolytic enzyme, cellulase, lipase, amylase and oxidasic enzyme; Sterilant; And tinting material.
Except part to list, also can comprise such as the EDTA transition metal chelator with such as the phosphoric acid derivatives of EDTMP (four (methyne phosphoric acid) quadrol), for example in order to improving stability, and keep composition bleaching usefulness such as the sensitive ingredients of enzyme, fluorescent agent and essence.Yet preferred composition does not use transition metal chelator (except part) basically and more preferably fully.
Though the present invention is based on catalysis and bleaches substrate with atmosphericoxygen or air, if desired, containing a small amount of hydrogen peroxide or peroxy or peroxide generation system effect in the composition will be better.Therefore, " do not use peroxygen bleach or peroxy or peroxide generation system basically " and mean that composition contains 0～50 molal weight %, preferred 0～10 molal weight %, more preferably 0～5 molal weight %, peroxygen bleach or peroxy or the peroxide generation system of best 0～2 molal weight % (calculating) based on oxygen.Yet preferred composition does not use peroxygen bleach or peroxy or peroxide generation bleach system fully.
Like this, at least 10% of any bleaching action of substrate, preferably from lacking 50%, best at least 90% is worked by the oxygen that is derived from air.
In all descriptions and claim, used the generic attribute group, for example alkyl, alkoxyl group, aryl.Unless spell out, the generic attribute group that is applied in the compound disclosed herein is preferably limited in the following group:
Alkyl: straight chain and side chain C1～C8-alkyl,
Thiazolinyl: C2～C6-thiazolinyl,
Cycloalkyl: C3～C8-cycloalkyl,
Alkoxyl group: C1～C6-alkoxyl group,
Alkylidene group: be selected from methylene radical, 1,1-ethylidene, ethylene, 1,1-propylidene, propylene, trimethylene, 2,2-propylidene, fourth-2-alcohol-1,4-two bases, propan-2-ol-1,3-two bases, 1,4-butylidene, hexanaphthene-1,1-two bases, hexanaphthene-1,2-two bases, hexanaphthene-1,3-two bases, hexanaphthene-1,4-two bases, suberane-1,1-two bases, suberane-1,2-two base and suberane-1,3-two bases
Aryl: be selected from molecular weight and be lower than 300 homoaromaticity compound,
Arylidene: be selected from 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,2-naphthylidene, 1,3-naphthylidene, 1,4-naphthylidene, 2,3-naphthylidene, 1-hydroxyl-2,3-phenylene, 1-hydroxyl-2,4-phenylene, 1-hydroxyl-2,5-phenylene and 1-hydroxyl-2,6-phenylene
Heteroaryl: be selected from pyridyl, pyrimidyl, pyrazinyl, triazolyl, pyridazinyl, 1,3,5-triazolyl, quinolyl, isoquinolyl, quinoxalinyl, imidazolyl, pyrazolyl, benzimidazolyl-, thiazolyl, oxazolidinyl, pyrryl, carbazyl, indyl and pseudoindoyl, wherein hetero-aromatic ring can compound be continuous therewith by any atom on the selected hetero-aromatic ring ring
Heteroarylidene: be selected from pyridine two bases, quinoline two bases, pyrazoles two bases, triazole two bases, pyrazine two base and imidazoles two bases, wherein assorted inferior aromatic ring can through any atom on the selected assorted inferior aromatic ring ring in compound as bridge, more special being preferably: pyridine-2,3-two bases, pyridine-2,4-two bases, pyridine-2,5-two bases, pyridine-2,6-two bases, pyridine-3,4-two bases, pyridine-3,5-two bases, quinoline-2,3-two bases, quinoline-2,4-two bases, quinoline-2,8-two bases, isoquinoline 99.9-1,3-two bases, isoquinoline 99.9-1,4-two bases, pyrazoles-1,3-two bases, pyrazoles-3,5-two bases, triazole-3,5-two bases, triazole-1,3-two bases, pyrazine-2,5-two base and imidazoles-2,4-two bases
Heterocyclylalkyl: be selected from pyrrolinyl, pyrrolidyl, morpholinyl, piperidyl, piperazinyl, the hexamethylene imine base, 1, the 4-piperazinyl, the tetrahydrochysene thiophene phenyl, tetrahydrofuran base, 1,4,7-7-triazacyclononane base, 1,4,8,11-tetraazacyclododecane tetradecane base, 1,4,7,10,13-five-nitrogen heterocyclic pentadecyl, 1,4-diaza-7-thia-cyclononane base, 1,4-diaza-7-oxa--cyclononane base, 1,4,7,10-tetraazacyclododecanand base, 1,4-dioxane base, 1,4,7-three thias-cyclononane base, THP trtrahydropyranyl is with oxazolidinyl, wherein Heterocyclylalkyl can compound be continuous therewith by any atom on the selected heterocycloalkyl ring
Heterocycle alkylene: be selected from piperidines-1, the 2-support, piperidines-2, the 6-support, piperidines-4, the 4-support, 1,4-piperazine-1,4-support, 1,4-piperazine-2, the 3-support, 1,4-piperazine-2, the 5-support, 1,4-piperazine-2,6-support, 1,4-piperazine-1, the 2-support, 1,4-piperazine-1, the 3-support, 1,4-piperazine-1,4-support, tetrahydrochysene thiophenol-2, the 5-support, tetrahydrochysene thiophenol-3, the 4-support, tetrahydrochysene thiophenol-2, the 3-support, tetrahydrofuran (THF)-2, the 5-support, tetrahydrofuran (THF)-3, the 4-support, tetrahydrofuran (THF)-2, the 3-support, tetramethyleneimine-2, the 5-support, tetramethyleneimine-3, the 4-support, tetramethyleneimine-2, the 3-support, tetramethyleneimine-1, the 2-support, tetramethyleneimine-1, the 3-support, tetramethyleneimine-2, the 2-support, 1,4,7-7-triazacyclononane-1,4-support, 1,4,7-7-triazacyclononane-2,3-support, 1,4,7-7-triazacyclononane-2,9-support, 1,4,7-7-triazacyclononane-3,8-support, 1,4,7-7-triazacyclononane-2,2-support, 1,4,8,11-tetraazacyclododecane tetradecane-1, the 4-support, 1,4,8,11-tetraazacyclododecane tetradecane-1, the 8-support, 1,4,8,11-tetraazacyclododecane tetradecane-2,3-support, 1,4,8,11-tetraazacyclododecane tetradecane-2, the 5-support, 1,4,8,11-tetraazacyclododecane tetradecane-1, the 2-support, 1,4,8,11-tetraazacyclododecane tetradecane-2,2-support, 1,4,7,10-tetraazacyclododecanand-1, the 4-support, 1,4,7,10-tetraazacyclododecanand-1, the 7-support, 1,4,7,10-tetraazacyclododecanand-1,2-support, 1,4,7,10-tetraazacyclododecanand-2, the 3-support, 1,4,7,10-tetraazacyclododecanand-2, the 2-support, 1,4,7,10,13-five-nitrogen heterocyclic pentadecane-1, the 4-support, 1,4,7,10,13-five-nitrogen heterocyclic pentadecane-1,7-support, 1,4,7,10,13-five-nitrogen heterocyclic pentadecane-2, the 3-support, 1,4,7,10,13-five-nitrogen heterocyclic pentadecane-1, the 2-support, 1,4,7,10,13-five-nitrogen heterocyclic pentadecane-2,2-support, 1,4-diaza-7-thia-cyclononane-1, the 4-support, 1,4-diaza-7-thia-cyclononane-1,2-support, 1,4-diaza-7-thia-cyclononane-2, the 3-support, 1,4-diaza-7-thia-cyclononane-6,8-support, 1,4-diaza-7-thia-cyclononane-2, the 2-support, 1,4-diaza-7-oxa--cyclononane-1,4-support, 1,4-diaza-7-oxa--cyclononane-1, the 2-support, 1,4-diaza-7-oxa--cyclononane-2,3-support, 1,4-diaza-7-oxa--cyclononane-6, the 8-support, 1,4-diaza-7-oxa--cyclononane-2,2-support, 1,4-dioxane-2, the 3-support, 1,4-dioxane-2,6-support, 1,4-dioxane-2, the 2-support, tetrahydropyrans-2, the 3-support, tetrahydropyrans-2, the 6-support, tetrahydropyrans-2, the 5-support, tetrahydropyrans-2, the 2-support, 1,4,7-three thias-cyclononane-2, the 3-support, 1,4,7-three thias-cyclononane-2,9-support and 1,4,7-three thias-cyclononane-2, the 2-support
Amido: group-N (R)
2In each R be independently selected from: hydrogen, C1～C6-alkyl, C1～C6-alkyl-C6H5 and phenyl, wherein when two R were C1～C6-alkyl, two R can form one-NC
3To-NC
5Heterocycle, remain alkyl chain simultaneously and form alkyl substituent on the heterocycle.
Halogen: be selected from F, Cl, Br and I,
Sulphonate (salt): group-S (O)
2R is selected from hydrogen, C1～C6-alkyl, phenyl, C1～C6-alkyl-C6H5, Li, Na, K, Cs, Mg and Ca among the OR,
Sulfuric ester (or salt): group-OS (O)
2R is selected among the OR: hydrogen, C1～C6-alkyl, phenyl, C1～C6-alkyl-C6H5, Li, Na, K, Cs, Mg and Ca,
Sulfone: group-S (O)
2R is selected among the R: hydrogen, C1～C6-alkyl, phenyl, C1～C6-alkyl-C6H5 and amido (obtaining sulphonamide), wherein amido all is selected from-NR '
2, each R ' is independently selected from hydrogen, C1～C6-alkyl, C1～C6-alkyl-C6H5 and phenyl, and wherein when two R ' are C1～C6-alkyl, two R ' can form-and NC3 is to the heterocycle of-NC5, and remaining alkyl chain forms this heterocyclic alkyl substituent,
R is selected from hydrogen, C1～C6-alkyl, phenyl, C1～C6-alkyl-C6H5, Li, Na, K, Cs, Mg and Ca among carboxylicesters (salt) derivative: group-C (O) OR,
R is selected among carbonyl derivative: group-C (O) R: hydrogen, C1～C6-alkyl, phenyl, C1～C6-alkyl-C6H5 and amido (obtaining acid amides), wherein amido all is selected from-NR '
2, each R ' is independently selected from hydrogen, C1～C6-alkyl, C1～C6-alkyl-C6H5 and phenyl, and wherein when two R ' are C1～C6-alkyl, two R ' can form-and NC3 is to the heterocycle of-NC5, and remaining alkyl chain forms this heterocyclic alkyl substituent,
Phosphonic acid ester (salt): group-P (O) (OR)
2In each R be independently selected from hydrogen, C1～C6-alkyl, phenyl, C1～C6-alkyl-C6H5, Li, Na, K, Cs, Mg and Ca,
Phosphoric acid ester (salt): group-OP (O) (OR)
2In each R be independently selected from hydrogen, C1～C6-alkyl, phenyl, C1～C6-alkyl-C6H5, Li, Na, K, Cs, Mg and Ca,
Phosphino-: group-P (R)
2In each R be independently selected from hydrogen, C1～C6-alkyl, phenyl and C1～C6-alkyl-C6H5,
Oxidation phosphino-: group-P (O) (R)
2In each R be independently selected from hydrogen, C1～C6-alkyl, phenyl, C1～C6-alkyl-C6H5 and amido (obtaining the phosphono aminate), wherein amido all is selected from-NR '
2, each R ' is independently selected from hydrogen, C1～C6-alkyl, C1～C6-alkyl-C6H5 and phenyl, and wherein when two R ' are C1～C6-alkyl, two R ' can form-and NC3 is to the heterocycle of-NC5, and the residue alkyl chain forms this heterocyclic alkyl substituent.
Unless offer some clarification on, the generic attribute group that is applied in the compound of the present disclosure is preferably limited in the following group:
Alkyl: straight chain and side chain C1～C6-alkyl,
Thiazolinyl: C3～C6-thiazolinyl,
Cycloalkyl: C6～C8-cycloalkyl,
Alkoxyl group: C1～C4-alkoxyl group,
Alkylidene group: be selected from methylene radical, ethylene, trimethylene, fourth-2-alcohol-1,4-two bases, tetramethylene, hexanaphthene-1,1-two bases, hexanaphthene-1,2-two bases, hexanaphthene-1,4-two bases, pentamethylene-1,1-two base and pentamethylene-1,2-two bases,
Aryl: be selected from phenyl, xenyl, naphthyl, anthryl and phenanthryl,
Arylidene: be selected from 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,2-naphthylidene, 1,4-naphthylidene, 2,3-naphthylidene and 1-hydroxyl-2, the 6-phenylene,
Heteroaryl: be selected from pyridyl, pyrimidyl, quinolyl, pyrazolyl, triazolyl, isoquinolyl, imidazolyl and oxazolidinyl, wherein hetero-aromatic ring can compound be continuous therewith by any atom on the selected hetero-aromatic ring ring,
Heteroarylidene: be selected from pyridine-2,3-two bases, pyridine-2,4-two bases, pyridine-2,6-two bases, pyridine-3,5-two bases, quinoline-2,3-two bases, quinoline-2,4-two bases, isoquinoline 99.9-1,3-two bases, isoquinoline 99.9-1,4-two bases, pyrazoles-3,5-two base and imidazoles-2,4-two bases
Heterocyclylalkyl: be selected from pyrrolidyl, morpholinyl, piperidyl, piperidyl, 1,4-piperazinyl, THP trtrahydropyranyl, 1,4,7-7-triazacyclononane base, 1,4,8,11-tetraazacyclododecane tetradecane base, 1,4,7,10,13-five-nitrogen heterocyclic pentadecyl, 1,4,7,10-tetraazacyclododecanand base and piperazinyl, wherein Heterocyclylalkyl can compound be continuous therewith by any atom on the selected heterocycloalkyl ring
Heterocycle alkylene: be selected from piperidines-2, the 6-support, piperidines-4, the 4-support, 1,4-piperazine-1, the 4-support, 1,4-piperazine-2,3-support, 1,4-piperazine-2, the 6-support, tetrahydrochysene thiophenol-2, the 5-support, tetrahydrochysene thiophenol-3, the 4-support, tetrahydrofuran (THF)-2, the 5-support, tetrahydrofuran (THF)-3, the 4-support, tetramethyleneimine-2, the 5-support, tetramethyleneimine-2, the 2-support, 1,4,7-7-triazacyclononane-1, the 4-support, 1,4,7-7-triazacyclononane-2, the 3-support, 1,4,7-7-triazacyclononane-2,2-support, 1,4,8,11-tetraazacyclododecane tetradecane-1,4-support, 1,4,8,11-tetraazacyclododecane tetradecane-1,8-support, 1,4,8,11-tetraazacyclododecane tetradecane-2, the 3-support, 1,4,8,11-tetraazacyclododecane tetradecane-2, the 2-support, 1,4,7,10-tetraazacyclododecanand-1,4-support, 1,4,7,10-tetraazacyclododecanand-1, the 7-support, 1,4,7,10-tetraazacyclododecanand-2, the 3-support, 1,4,7,10-tetraazacyclododecanand-2,2-support, 1,4,7,10,13-five-nitrogen heterocyclic pentadecane-1, the 4-support, 1,4,7,10,13-five-nitrogen heterocyclic pentadecane-1, the 7-support, 1,4-diaza-7-thia-cyclononane-1,4-support, 1,4-diaza-7-thia-cyclononane-2, the 3-support, 1,4-diaza-7-thia-cyclononane-2, the 2-support, 1,4-diaza-7-oxa--cyclononane-1,4-support, 1,4-diaza-7-oxa--cyclononane-2, the 3-support, 1,4-diaza-7-oxa--cyclononane-2, the 2-support, 1,4-dioxane-2,6-support, 1,4-dioxane-2, the 2-support, tetrahydropyrans-2, the 6-support, tetrahydropyrans-2,5-support and tetrahydropyrans-2, the 2-support
Amido: group-N (R)
2In each R be independently selected from hydrogen, C1～C6-alkyl and benzyl,
Halogen: be selected from F and C1,
Sulphonate (salt): group-S (O)
2R is selected from hydrogen, C1～C6-alkyl, Na, K, Mg and Ca among the OR,
Sulfuric ester (salt): group-OS (O)
2R is selected from hydrogen, C1～C6-alkyl, Na, K, Mg and Ca among the OR,
Sulfone: group-S (O)
2R is selected from hydrogen, C1～C6-alkyl, benzyl and amido among the R, and wherein amido is selected from-NR '
2, each R ' is independently selected from hydrogen, C1～C6-alkyl and benzyl,
R is selected from hydrogen, Na, K, Mg, Ca, C1～C6-alkyl and benzyl among carboxylicesters (salt) derivative: group-C (O) OR,
R is selected from hydrogen, C1～C6-alkyl, benzyl and amido among carbonyl derivative: group-C (O) R, and wherein amido is selected from-NR '
2, each R ' is independently selected from hydrogen, C1～C6-alkyl and benzyl,
Phosphonic acid ester (salt): group-P (O) (OR)
2In each R be independently selected from hydrogen, C1～C6-alkyl, benzyl, Na, K, Mg and Ca,
Phosphoric acid ester (salt): group-OP (O) (OR)
2In each R be independently selected from hydrogen, C1～C6-alkyl, benzyl, Na, K, Mg and Ca,
Phosphino-: group-P (R)
2In each R be independently selected from hydrogen, C1～C6-alkyl and benzyl,
Oxidation phosphino-: group-P (O) (R)
2In each R be independently selected from hydrogen, C1～C6-alkyl, benzyl and amido, wherein amido is selected from-NR '
2, each R ' is independently selected from hydrogen, C1～C6-alkyl and benzyl.
The present invention will further illustrate by following indefiniteness embodiment now:
Embodiment prepares following compounds: compound 1:[FeL
4C1] (C1O
4)
2L
1=1,4-two (5-methyl-pyridine-2-ylmethyl)-7-ethyl-1,4,7-7-triazacyclononane ligand L
1Synthetic: 1,4-two (5-methyl-pyridyl-2-methyl)-7-ethyl-1,4,7-7-triazacyclononane 1,4,7-7-triazacyclononane
Ligand 1,4, the 7-7-triazacyclononane is the preparation of using according to Wieghardt professor research group of improving one's methods.In this method, 1,4,7-three-right-toluenesulphonic acids base-1,4,7-three nitrogen heterocyclic pelargonamides carry out 5 minutes piptonychia Phenylsulfonic acid radical reaction in 180 ℃ hot sulfuric acid.After solution cools down, under violent stirring, change in the ether.The top layer of solution other container of impouring lightly, residuum dissolves in boiling water.When boiling, drip several concentrated hydrochloric acids.Drain sedimentary brown crystal, earlier with cold hydrochloric acid flushing, again with ethanol and ether washing.Just obtain 1,4, the 7-7-triazacyclononane.The trihydrochloride of making like this is then as like that further handling that (K.Wieghardt etc., Chem Ber., 112,2200 (1979)) such as Wieghardt are introduced.1,4,7-three aza-tricycle [5.2.1.0
410] decane (former acid amides)
With 0.5mol 1,4, the 7-7-triazacyclononane, 64.3g, the 0.54mol triethyl orthoformate, 74.8g and 20mmol be right-toluenesulphonic acids, 4g is heated to 150 ℃.Distill out ethanol and some esters of generation.According to document (T.J.Atkins, J.Am.Chem.Soc., 102,6365 (1980)), after reaction is finished, under less than the pressure of 80mbar, can steam former acid amides with the form of glassy yellow ethereal oil (b.p.350K under 133Pa).1-ethyl-1,4,7-7-triazacyclononane (Et-tacn)
The former acid amides 13.92g of 0.1mol is dissolved among the anhydrous THF, in this miscellany, slowly drips 0.1mol monobromethane 10.9g.Suspension stirred 2 days under room temperature in the flask of sealing.Drain the microcrystal powder, and wash with anhydrous THF.The bromine salt of gained is that water absorbability is very strong.Salt is dissolved in the 80ml water boiling reflux 4h.Add the 16g sodium hydroxide that is dissolved in the 20ml water then, this obtains the 4mol reaction mixture.Isolate glassy yellow oil very soon.For finishing reaction, continue to boil 20h.The cooling back adds 300ml toluene, steams water by water trap.Filter reaction mixture, and steam toluene with rotatory evaporator, resultant product is a glassy yellow oil.Productive rate: 13.8g (89%)
1H-NMR (CDCl
3-270MHz; 300K): 2.59-2.39 (m; 14H); 1.83 (s, 2H); 0.90ppm (t; 3H);
13C-NMR:52.1; 50.7; 46.5; 46.4; 12.4ppm.2-methylol-5-picoline
2-acetyl-o-methyl-5-picoline (30g, 182mmol) be dissolved in hydrochloric acid (100ml, 4N) in.This mixture heating up is refluxed, up to TLC (silica gel; Triethylamine: ethyl acetate: sherwood oil 40～60=1: 9: 19) show that acetate has not had (being generally 1h) fully.Cooling mixture is regulated PH＞11, and (3 * 50ml) extractions remove in a vacuum and desolvate with methylene dichloride.Obtain pure 2-methylol-5-picoline (18.80g, 152mmol, 84%) by the Kugelrohr distillation, be light yellow oil.
1H NMR: δ 8.39 (s, 1H), 7.50 (dd, J=7.8, J=1.8,1H), 7.15 (d, J=8.1,1H), 4.73 (s, 2H), 3.83 (br s, 1H), 2.34 (s, 3H);
13C NMR: δ 156.67,148.66,137.32,131.62,120.24,64.12,17.98.1,4-two (5-methyl-pyridyl-2-methyl)-7-ethyl-1,4,7-7-triazacyclononane
(2.70g 21.9mmol) is dissolved in the methylene dichloride (25ml) with 2-methylol-5-picoline.Under the cooling ice bath, dropwise splash into thionyl chloride (25ml).The mixture of gained is stirred 1h, and remove in a vacuum and desolvate (rotary evaporation, up to P=20mmHg, T=± 35 ℃).Because as can be known, free chlorinated picoline less stable is very strong lacrymator from document, so remaining oil directly uses in part synthetic.In product mixture, add methylene dichloride (25ml) and 1.55g Et-tacn (10mmol).Under with ice-cooled condition, be lower than 9 and temperature is no more than 0 ℃ mode according to pH value, adding 8.0g NaOH in proportion surpassing in 5 days time.Solution becomes brown by red stain gradually.Solution is put into refrigerator 1 day, isolate the organic phase of any formation.Water is with chloroform oscillation extraction repeatedly.Merge organic phase and use the CaO drying.Rotary evaporation falls chloroform, remaining a kind of dense thick, almost be oil russet.This oil still has the picolyl chlorination thing and the alkaline hydrolysis by product (about 5%) thereof of trace.
Claims (12)
1. the part of a following general formula (I):
Wherein
R
1, R
2And R
3Representative is selected from a group of following group independently: hydrogen, hydroxyl, halogen ,-NH-C (NH) NH
2,-R and-OR, wherein R=alkyl, thiazolinyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl or carbonyl deriveding group, R is optional to be replaced by one or more E of functional group;
Q represents independently and is selected from by H, benzyl or C
1-8The optional C that replaces of-alkyl
2-3-alkylidene group;
Q
1, Q
2And Q
3Represent the group of following general formula independently:
Wherein
5 〉=a+b+c 〉=1; A=0-5; B=0-5; C=0-5; N=1 or 2;
Y represents independently and is selected from-O-,-S-,-SO-,-SO
2-,-C (O)-, arylidene, alkylidene group, heteroarylidene, heterocycle alkylidene group ,-(G) P-,-P (O)-and-(G) group of N-, wherein G is selected from hydrogen, alkyl, aryl, aralkyl, cycloalkyl, outside the dehydrogenation, each group is optional to be replaced by one or more E of functional group;
R5, R6, R7, R8 represent independently be selected from hydrogen, hydroxyl, halogen ,-R and-group of OR, wherein R=alkyl, thiazolinyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl or carbonyl deriveding group, R is optional to be replaced by one or more E of functional group;
Or R5 is with R6, or R7 is with R8, or the both represents oxygen,
Or R5 is with R7 and/or R6 is with R8 independently, or R5 is with R8 and/or R6 is with R7 independently, and representative is optional by C
1-4-alkyl ,-F ,-Cl ,-Br or-C that I replaces
1-6-alkylidene group; With
Wherein E represent independently the functional group that is selected from following group :-F ,-Cl ,-Br ,-I ,-OH ,-OR ' ,-NH
2,-NHR ' ,-N (R ')
2,-N (R ')
3 +,-C (O) R ' ,-OC (O) R ' ,-COOH ,-COO
-(Na
+, K
+) ,-COOR ' ,-C (O) NH
2,-C (O) NHR ' ,-C (O) N (R ')
2, heteroaryl ,-R ' ,-SR ' ,-SH ,-P (R ')
2,-P (O) (R ')
2,-P (O) (OH)
2,-P (O) (OR ')
2,-NO
2,-SO
3H ,-SO
3 -(Na
+, K
+) ,-S (O)
2R ' ,-NHC (O) R ' and-N (R ') C (O) R ', wherein R ' represent cycloalkyl group, aryl, aralkyl or optional quilt-F ,-Cl ,-Br ,-I ,-NH
3 +,-SO3H ,-SO
3 -(Na
+, K
+) ,-COOH ,-COO
-(Na
+, K
+) ,-P (O) is (OH)
2Or-P (O) (O
-(Na
+, K
+))
2The alkyl that replaces,
Suppose R
1, R
2And R
3In two be coordinating group, R
1, R
2And R
3In one be non-coordinating group; With
Condition is to get rid of following part:
1,4-two (N-methyl-imidazoles-2 ylmethyl)-1,4,7-7-triazacyclononane;
1,4-two (N-methyl-imidazoles-2 ylmethyl)-7-acetoxyl-1,4,7-7-triazacyclononane;
1,4-two (pyridine-2-ylmethyl)-7-ethyl-1,4,7-7-triazacyclononane;
1,4-two (quinoline-2-ylmethyl)-7-ethyl-1,4,7-7-triazacyclononane;
1,4-two (pyrazol-1-yl methyl)-7-ethyl-1,4,7-7-triazacyclononane;
1,4-two (3-1-ylmethyl)-7-ethyl-1,4,7-7-triazacyclononane;
1,4-two (N-Methylimidazole-2-ylmethyl)-7-ethyl-1,4,7-7-triazacyclononane;
1,4-two (N-sec.-propyl kharophen)-7-ethyl-1,4,7-7-triazacyclononane; With
1,4-two (N-methyl kharophen)-7-ethyl-1,4,7-7-triazacyclononane.
2. the part of claim 1, R1 wherein, among R2 and the R3 two independently representative be selected from following coordinating group: carboxylate radical, amido ,-NH-C (NH) NH
2, hydroxyphenyl, and be selected from the heterocycle of optional replacement of pyridine, pyrimidine, pyrazine, pyrazoles, imidazoles, benzoglyoxaline, quinoline, quinoxaline, triazole, isoquinoline 99.9, carbazole, indoles, isoindole, azoles and thiazole or the group of the optional hetero-aromatic ring that replaces.
3. the part in above-mentioned any one claim, R1 wherein, in two of R2 and R3 each all independently representative be selected from the coordinating group of the optional pyridine-2-base that replaces, the optional imidazoles-2-base that replaces, the optional imidazol-4 yl that replaces, the optional pyrazol-1-yl that replaces and the optional quinoline-2-base that replaces.
4. the part in above-mentioned any one claim, R5 wherein, R6, R7, R8 represent independently and are selected from-H, hydroxyl-C
0-C
20-alkyl, halo-C
0-C
20-alkyl, nitroso-group, formyl radical-C
0-C
20-alkyl, carboxyl-C
0-C
20-alkyl and ester thereof and salt, formamyl-C
0-C
20-alkyl, sulfo group-C
0-C
20-alkyl and ester thereof and salt, sulfamyl-C
0-C
20-alkyl, amino-C
0-C
20-alkyl, aryl-C
0-C
20-alkyl, C
0-C
20-alkyl, alkoxy-C
0-C
8-alkyl, carbonyl-C
0-C
6-alkyl and-C
0-C
20The group of-alkylamidoalkyl.
5. the part in above-mentioned any one claim, Q1 wherein, Q2, Q3 so defines, and makes a=b=0, c=1,2,3 or 4, and n=1.
6. the part in above-mentioned any one claim, Q1 wherein, Q2, Q3 represent independently and are selected from-CH
2-and-CH
2CH
2-group.
7. the part in above-mentioned any one claim, wherein the Q representative is selected from-CH
2CH
2-and-CH
2CH
2CH
2-group.
8. the part in above-mentioned any one claim, wherein the general formula of ligand L is (II):
9. the part of claim 8, wherein
R1, two among R2 and the R3 each all independently representative be selected from the coordinating group of following group: carboxylate radical, amido ,-NH-C (NH) NH
2, hydroxyphenyl, and the heterocycle or the optional hetero-aromatic ring that replaces that are selected from the optional replacement of pyridine, pyrimidine, pyrazine, pyrazoles, imidazoles, benzoglyoxaline, quinoline, quinoxaline, triazole, isoquinoline 99.9, carbazole, indoles, isoindole, azoles and thiazole; With
R1, a representative among R2 and the R3 is selected from hydrogen, the optional C that replaces
1-20Alkyl, the optional C that replaces
1-20Aralkyl, aryl and the optional C that replaces
1-20NR
3 +(R=C wherein
1-8-alkyl) group.
10. the part of claim 9, R1 wherein, two among R2 and the R3 each all independently representative be selected from the coordinating group of the optional pyridine-2-base that replaces, the optional imidazoles-2-base that replaces, optional substituted imidazole-4-base, the optional pyrazol-1-yl that replaces and the optional quinoline-2-base that replaces; With
R1, a representative among R2 and the R3 is selected from hydrogen, the optional C that replaces
1-10Alkyl, C
1-5Furyl, the optional C that replaces
1-5Benzyl alkyl, benzyl, the optional C that replaces
1-5Alkoxyl group and the optional C that replaces
1-20N
+Me
3Group.
11. the title complex of part and transition metal, wherein the general formula of this title complex (A1) is:
[M
aL
kX
n] Y
m(A1) wherein:
M represents to be selected from the metal of Mn (II)-(III)-(IV)-(V), Cu (I)-(II)-(III), Fe (II)-(III)-(IV)-(V), Co (I)-(II)-(III), Ti (II)-(III)-(IV), V (II)-(III)-(IV)-(V), Mo (II)-(III)-(IV)-(V)-(VI) and W (IV)-(V)-(VI);
X representative be selected from any single, two or the trivalent negatively charged ion and any can with metal with coordination material single, double, tridentate ligand mode coordinate neutral molecule;
Y represents any non-coordinate counter ion;
A represents an integer of 1～10;
K represents an integer of 1～10;
N represents an integer of 1～10;
M represents an integer of 0 or 1～20; With
The part of any as described above claim definition of L representative, or its protonated or deprotonation analogue.
12. the title complex of claim 11, wherein:
M represents Fe (II)-(III)-(IV)-(V);
The X representative is selected from O
2-, RBO
2 2-, RCOO
-, OH
-, NO
3 -, S
2-, RS
-, PO
3 4-, H
2O, CO
3 2-, HCO
3 -, ROH, N (R)
3, Cl
-, Br
-, OCN
-, SCN
-, RCN, N
3 -, F
-, I
-, RO
-, ClO
4 -And CF
3SO
3 -The coordination material;
Y represents any non-coordinate gegenion, and it is selected from ClO
4 -, BR
4 -, [FeCl
4]
-, PF
6 -, RCOO
-, NO
3 -, RO
-, N
+(R)
4, Cl
-, Br
-, F
-, I
-, CF
3SO
3 -, S
2O
6 2-, OCN
-, SCN
-, H
2O and BF
4 -
A represents an integer of 1～4;
K represents an integer of 1～10;
N represents one 1～4 integer;
M represents 0 or one 1～8 integer; With
Each R independently represents the group that is selected from hydrogen, the optional alkyl that replaces and the optional aryl that replaces.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/GB1999/002876 WO2000012667A1 (en) | 1998-09-01 | 1999-09-01 | Composition and method for bleaching a substrate |
| WOPCT/GB99/02876 | 1999-09-01 | ||
| GBGB0004854.6A GB0004854D0 (en) | 2000-02-29 | 2000-02-29 | Ligand and complex for catalytically bleaching a substrate |
| GB0004854.6 | 2000-02-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1384837A true CN1384837A (en) | 2002-12-11 |
Family
ID=26243765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00814984.4A Pending CN1384837A (en) | 1999-09-01 | 2000-08-17 | Ligand and complex for catalytically bleaching substrate |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1208107A2 (en) |
| CN (1) | CN1384837A (en) |
| AU (1) | AU7903300A (en) |
| CA (1) | CA2383695A1 (en) |
| TR (1) | TR200201278T2 (en) |
| WO (1) | WO2001016272A2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103180302A (en) * | 2010-07-06 | 2013-06-26 | 卡特克塞尔有限公司 | 1,2-bis-(4,7-dimethyl-1,4,7-triazacyclonon-1-yl)-ethane and intermediate thereof |
| CN108948050A (en) * | 2018-06-29 | 2018-12-07 | 浙江理工大学 | A kind of metal complex and preparation method thereof and a kind of bleaching working solution |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4045626A4 (en) * | 2019-10-17 | 2023-10-25 | Specialty Operations France | Metal complex and use thereof |
| WO2021097601A1 (en) * | 2019-11-18 | 2021-05-27 | Solvay Sa | Solid bleach particles |
| CN113321624A (en) * | 2021-06-15 | 2021-08-31 | 仪征市海帆化工有限公司 | Synthesis method of 1,4, 7-triazacyclononane |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE133165T1 (en) * | 1989-02-10 | 1996-02-15 | Celltech Therapeutics Ltd | AZA MACROCYCLES AND METHOD FOR THE PRODUCTION THEREOF |
| US5364613A (en) * | 1989-04-07 | 1994-11-15 | Sieving Paul F | Polychelants containing macrocyclic chelant moieties |
| MX9305039A (en) * | 1992-08-19 | 1994-05-31 | Mallinckrodt Medical Inc | LINKED TO GA-68 FOR TEP CARDIAC APPLICATIONS. |
| JPH06256512A (en) * | 1993-03-05 | 1994-09-13 | Rikagaku Kenkyusho | Laminated macrocyclic polyamine derivative and its production |
| US5554749A (en) * | 1994-01-14 | 1996-09-10 | Mallinckrodt Medical, Inc. | Functionalized macrocyclic ligands for imaging applications |
| BR9709798A (en) * | 1996-06-19 | 1999-08-10 | Unilever Nv | Bleaching and oxidation catalyst catalytic oxidation system and bleaching composition |
| JPH10279411A (en) * | 1997-03-31 | 1998-10-20 | Lion Corp | Mildew-removing agent composition |
| DE19756361A1 (en) * | 1997-12-18 | 1999-06-24 | Philips Patentverwaltung | Organic light emitting diode with terbium complex |
-
2000
- 2000-08-17 EP EP00969243A patent/EP1208107A2/en not_active Ceased
- 2000-08-17 TR TR2002/01278T patent/TR200201278T2/en unknown
- 2000-08-17 AU AU79033/00A patent/AU7903300A/en not_active Abandoned
- 2000-08-17 CA CA002383695A patent/CA2383695A1/en not_active Abandoned
- 2000-08-17 CN CN00814984.4A patent/CN1384837A/en active Pending
- 2000-08-17 WO PCT/EP2000/008144 patent/WO2001016272A2/en not_active Application Discontinuation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103180302A (en) * | 2010-07-06 | 2013-06-26 | 卡特克塞尔有限公司 | 1,2-bis-(4,7-dimethyl-1,4,7-triazacyclonon-1-yl)-ethane and intermediate thereof |
| CN103180302B (en) * | 2010-07-06 | 2016-08-03 | 卡特克塞尔有限公司 | 1,2-bis-(4,7-dimethyl-1,4,7-three azacyclo-nonyl-1-yl)-ethane and intermediate thereof |
| CN108948050A (en) * | 2018-06-29 | 2018-12-07 | 浙江理工大学 | A kind of metal complex and preparation method thereof and a kind of bleaching working solution |
| CN108948050B (en) * | 2018-06-29 | 2020-11-03 | 浙江理工大学 | Metal complex, preparation method thereof and bleaching working solution |
Also Published As
| Publication number | Publication date |
|---|---|
| AU7903300A (en) | 2001-03-26 |
| EP1208107A2 (en) | 2002-05-29 |
| TR200201278T2 (en) | 2002-08-21 |
| WO2001016272A2 (en) | 2001-03-08 |
| WO2001016272A3 (en) | 2001-08-30 |
| CA2383695A1 (en) | 2001-03-08 |
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