Ligand and complex for catalytic whitening substrate

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a whitening composition comprising: (a) monomeric ligand or catalyst with transient metal of ligand of the formula (I): wherein R represents hydrogen atom; R1 and R2 are chosen independently from (C1-C4)-alkyl, pyridine-2-yl-methyl and (C2-C4)-alkylmethyl; X represents -C=O; R3 and R4 are similar and represent -(CH2)nC(O)O-(C1-C4)-alkyl; n = 0-4, and (b) equilibrating carriers and additional components. This composition is useful for catalytic whitening substrates with atmosphere oxygen. Also, invention describes a method for whitening the substrate involving applying step of the whitening composition on substrate in aqueous medium.

EFFECT: valuable properties of substances, improved whitening method.

11 cl, 2 tbl

 

The technical field to which the invention relates.

The present invention relates to the class of ligand or complex, are useful as catalysts for the catalytic bleaching of the substrate by atmospheric oxygen.

The level of technology

In recent years, developing catalysts for bleaching in the case of pathobiochemie. The recent discovery that some catalysts are able to effectively whiten in the absence of additional source of peroxide, aroused great interest, for example: WO 9965905; WO 0012667; WO 0012808 and WO 0029537.

The search continues for new classes of compounds that are suitable as an air bleaching catalyst.

Various [3.3.1] bicyclic compounds and their complexes described in the prior art, see, for example: R. Comba other, J.Chem.Soc. Dalton Trans, 1998, (23) 3997-4001; Borzel and other Chem. Eur. J. 1999, 5, No.6, 1716-1721 and review P. Comba in Coordination Chemistry Reviews 2000, 200-202, 217-245, entitled "Coordination compounds in Entactic State". For these compounds are given their physical properties.

WO 0060045 reveals the whitening system, comprising: from about 1 ppb no weight of transition metal catalyst comprising: i) a transition metal; ii) a ligand having the formula (I):

where each R is independently hydrogen, hydroxyl, C1-C4-alkyl and mixtures thereof; R1 is C1-C4 alkyl is m, C6-C10-aryl and mixtures thereof; R2 is C1-C4-alkyl, C6-C10-aryl and mixtures thereof; R3 and R4 each is independently hydrogen, C1-C8-alkyl, C1-C8-hydroxyalkyl, - (CH2)xCO2R5, where R5 is C1-C4-alkyl, x has a value from 0 to 4, and mixtures thereof; X is carbonyl, -C(R6)2-, where each R6 is independently hydrogen, hydroxyl, C1-C4-alkyl and mixtures thereof; b) optionally a source of an oxide of hydrogen; and (C) equalizing the media and other ingredients. However, the description of WO 0060045 restricts the substituents at Izotov nitrogen (3 and 7 positions) bicycletrailer homoeroticism carbon groups, namely the alkyl and aryl.

The invention

It was found that the presence of a group having a heteroatom by one or more nitrogen atoms of bicycletrailer, provides increased activity. Prepared compounds are surprisingly active catalysts air bleaching. Additionally, it was found that similar compounds are surprisingly active and provide new ligands and their transition metal complexes for use in air bleaching.

Thus, in the first aspect, the present invention relates to bleaching compositions, including:

(a) Monomeric ligand or catalyst ligand with the transition metal, having the formula (I):

where each R is independently selected from: hydrogen, F, Cl, Br, hydroxyl, C1-C4-alkyl-O-, -NH-CO-H, -NH-CO-C1-C4-alkyl, -NH2, -NH-C1-C4-alkyl and C1-C4-alkyl;

R1 and R2 are independently chosen from:

C1-C4-alkyl,

C6-C10-aryl, and

group containing a heteroatom capable of coordinating to the transition metal, where at least one of R1 and R2 is a group containing a heteroatom;

R3 and R4 are independently selected from hydrogen, C1-C8 alkyl, C1-C8-alkyl-O-C1-C8-alkyl, C1-C8-alkyl-O-C6-C10-aryl, C6-C10-aryl, C1-C8-hydroxyalkyl and - (CH2)nC(O)OR5,

where R5 is independently selected from: hydrogen, C1-C4-alkyl, n has a value from 0 to 4, and mixtures thereof; and,

X is selected from C=O, -[C(R6)2]y-where Y has a value from 0 to 3, each R6 is independently selected from hydrogen, hydroxyl, C1-C4-alkoxy and C1-C4-alkyl; and,

(b) equalizing the media and other ingredients.

Preferred groups containing a heteroatom, can be found in heteroseksualci selected from the group consisting of: pyrrolidine; pyrrolidinyl; morpholinyl; piperidinyl; piperazinil; hexamethylenimine; 1,4-piperazinil; tetrahydrothiophene; tetrahydrofuranyl; tetrahydropyranyl and oxazolidinyl where heteroseksualci can be linked to the ligand via any atom in the ring selected geterotsiklicheskie, -C1-C6-alkyl-geterotsiklicheskie where heterocycle lcil-C1-C6-geterotsiklicheskie is selected from the group consisting of: piperidinyl; piperidine; 1,4-piperazine, tetrahydrothiophene, tetrahydrofuran; pyrrolidine and tetrahydropyran where heteroseksualci can be associated with-C1-C6-alkyl via any atom in the ring selected geterotsiklicheskie, -C1-C6-alkylglycerol where heteroaryl-C1-C6-alkylglycerol is selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1,3,5-triazinyl; chinoline; izochinolina; khinoksalinona; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl, oxazolidinyl; pyrrolyl; carbazolyl; indolyl and isoindolyl, where heteroaryl can be associated with-C1-C6-alkyl via any atom in the ring selected heteroaryl and selected heteroaryl is optionally substituted

-C1-C4-alkyl,

-CO-C6-alkyl phenol or thiophenols,

-C2-C4-alkylthio, tieferen or alcohol,

-C2-C4-alkylamino and

-C2-C4-alkylcarboxylic.

In a second aspect the present invention relates to bleaching compositions, including the aquatic environment atmospheric oxygen and bicycleand General formula (I), which forms a complex with the transition metal complex catalytic bleaching of the substrate by using atmospheric oxygen, where the aqueous medium is essentially free from whitening peroxygen or peroxy-whitening system, or peroxy-expressed alyausa whitening system. Preferably, the medium has a pH value in the range from pH 6 to 11 and most preferably from pH 8 to 10.

The present invention also relates to new compounds of General formula (I) provided that the following compounds are excluded:

dimethyl 2,4-di(2-pyridyl)was 3.7-bis-(pyridine-2-ylmethyl)was 3.7-diazabicyclo[3.3.1]nonan-9-one-1,5, in primary forms;

1,5-bis-(hydroxymethyl)-2,4-di-(2-pyridyl)was 3.7-bis-(pyridine-2-ylmethyl)was 3.7-diazabicyclo[3.3.1]nonan-9-ol;

dimethyl 2,4-di(2-pyridyl)was 3.7-bis-(pyridine-2-retil)was 3.7-diazabicyclo[3.3.1]nonan-9-one-1,5, in primary forms;

dimethyl 2,4-di(2-pyridyl)-3-(5-carboxypentyl)-7-methyl-3,7-diazabicyclo[3.3.1]nonan-9-one-1,5, in primary forms;

dimethyl 2,4-di(2-pyridyl)-3-(2-methoxyethyl)-7-methyl-3,7-diazabicyclo[3.3.1]nonan-9-one-1,5, in primary forms;

diethyl-2,4-dipyridyl-7-picolyl-3,7-diazabicyclo-[3.3.1 ]-nonan-9-one-1,5, in primary forms;

diethyl-2,4-dipyridyl-7-benzyl-3-hydroxyethyl-3,7-diazabicyclo-[3.3.1]-nonan-9-one-1,5, in primary forms and,

dimethyl-2,4-dipyridyl-7-benzyl-3-hydroxyethyl-3,7-diazabicyclo-[3.3.1]-nonan-9-one-1,5, in primary forms.

The advantage of this class of ligand and complex in accordance with the present invention is that the complex can catalyze the bleaching of the substrate by using atmospheric oxygen, respectively, allowing it to be applied in the environment, such as water, which is essentially free from bleaching with PE is the other world or peroxy-whitening system, or peroxy-generating whitening system. It was also found that the complexes of this class are surprisingly effective for catalytic bleaching of the substrate by using atmospheric oxygen after processing of the substrate. The composition of the present invention whitens the substrate by at least 10%, preferably by at least 50% and optimally at least 90% more effectively than any bleaching of the substrate by using oxygen from the air.

Specialists in the art it is known that not all peroxyl-activated catalysts can act as oxygen-activated catalyst. However, the converse is not true. There is no evidence indicating that any oxygen-activated catalyst will not act as peroxyl-activated catalyst. In this respect, all oxygen-activated catalysts, as claimed in the present invention, can be used as peroxyl-activated catalyst. The catalysts of the present invention may be combined in a composition together with varieties of peroxyl or their sources. To determine the acceptable types of varieties of peroxyl or their sources, and other adjuvants that may be present, see US 6022490, the contents of which are listed as references

The present invention relates to a method of bleaching a substrate comprising applying a bleaching composition in accordance with the present invention on the substrate in the aquatic environment.

The present invention relates to a commercial package that includes a whitening composition in accordance with the present invention together with instructions for its use.

The present invention also provides a dry cloth with organic matter, which is used as defined above, directly or applied to it, whereby on the fabric is catalyzed by bleaching with the help of atmospheric oxygen.

Due to the fact that the whitening effect is facilitated even after the fabric has already been processed, the benefits of whitening can be extended on the fabric. In addition, because the whitening effect persists after treatment of the fabric, the processing itself, such as the wash cycle may be, for example, reduced. Moreover, since the whitening effect is achieved with the help of atmospheric oxygen after the treatment of tissue, the system bleaching with hydrogen peroxide or peroxy-containing bleaching systems can be excluded from the processing of the substance.

The organic substance may come in contact with the textile fabric in any suitable way. For example, it can realize is taken in dry form, such as in the form of a powder, or in liquid form, which is then dried, for example, as the processing liquid can be water sprayed solution or washing fluid for cleaning fabrics, or non-aqueous liquid for dry cleaning or spray liquid aerosol. Other suitable ways of interaction of organic substances with cloth can be used, as described below.

Can be used with any suitable fabric, which is amenable to bleaching or that you would like be subjected to bleaching. Preferably the fabric is a textile or clothing.

In the preferred embodiment of the method in accordance with the present invention relates to a method for treatment of textile matter, which uses water processing fluid. In particular, the treatment can be effective in the cycle washing for cleaning textile fabrics. More preferably, the processing is carried out in otbelivayushe detergent water solution of detergent.

In the preferred embodiment, the treated fabric is dried, leaving to dry at ambient temperature or at elevated temperatures. Higher temperatures usually provide by using heat convertible environment, as, for example, is carried out in the dryer, which, as you know, accelerates and increases the efficiency of the who is ear whitening.

The whitening method can be carried out by simply contacting the substrate with an organic substance for a sufficient period of time. It is preferable, however, that the organic substance was in the aquatic environment and to the aquatic environment is located on top of the substrate or in contact with the substrate, were mixed.

The organic substance may come in contact with the woven material in any traditional way. For example, it can be applied in a dry form such as a powder, or in liquid form, which is then dried, for example, as the processing liquid can be water sprayed solution or washing fluid for cleaning fabrics, or non-aqueous liquid for dry cleaning or spray liquid aerosol.

In the preferred embodiment, the treated fabric is dried, leaving to dry at ambient temperature or at elevated temperatures.

In a particularly preferred embodiment of the method in accordance with the present invention be carried out on textile cloth, using water processing fluid. In particular, the treatment can be effective for an existing traditional wash cycle for cleaning fabrics or in addition to it. More preferably, the treatment is carried out in the scrubbing liquid aqueous detergent. Organizes what I substance may be injected into the liquid for washing powder, granules, beads, pills, block, plate or other solid form. The solid form may include a carrier, which may be in the form of particles, listopadova or enable a three-dimensional object. The media can be dispersed or dissolved in the scrubbing liquid, or may remain largely intact. In other embodiments, the organic substance may be injected into the washing liquid in the form of a paste, gel or liquid concentrate.

A special advantage is that the organic substance used in the method of the present invention, makes it possible to use atmospheric oxygen for bleaching activity. This eliminates the need to use peroxygen bleach and/or other relatively large quantities of chemically active substances in the process. Therefore, you need to use only a relatively small amount of whitening active ingredients, and this allows us to apply methods of dosage, which could not be used previously. Accordingly, although preferred is the incorporation of organic substance in the composition is usually applied in the washing process, for example, pre-processing, main washing, the composition of the air conditioner or facilitate Ironing, can be provided by other means-ware is also to the organic substance was present in the washing liquid.

For example, it is assumed that the organic substance may be present in a form from which it is slowly released during the whole or part of the Laundry process. This release may occur during a single washing or within a few washings. In the latter case, it is assumed that the organic substance may be released from the carrier substrate used in the washing process, for example from a body placed in the dosing drawer compartment of the washing machine, as well as in the delivery system or in the washing machine drum. When using the washing machine drum, the carrier can move freely or be locked relative to the drum. This fixation can be achieved by mechanical means, for example by means of splines, which are connected with the wall of the drum, or using other forces, such as magnetic force. Modification of the washing machine to enable the retention and storage of such media provides a similar tool known analogues in the prior art for the production of free blocks. Freely moving media, such as shuttles, for dosing of surface-active materials and/or other detergent ingredients for washing can is activated and means for release of organic substances in the wash.

Alternatively, the organic substance may be in the form of a detergent additive, which is preferably soluble. The additive may have any physical form, used for detergent additives, including powder, granule, pill, leaf, tablet, block, tile, or other such solid form or may be in the form of a paste, gel or liquid. The dosage of the additive can be either fixed or in the number defined by the user. Although it is anticipated that such additives can be used in the main washing cycle, does not exclude their use in the cycle of conditioning or drying.

The present invention is not limited to cases that use the washing machine, but can be used when washing is carried out in some alternative capacity. In these cases, it is assumed that the organic substance may be injected by means slow release of the pelvis, buckets or other used containers, or from any used instrument such as a brush, stick or stirrer, or any suitable device.

Appropriate means prior to processing for applying an organic substance to the woven material to the main washing are sprays, pens, roller device, cushioned applicator sticks and impregnated the Kani or tissue containing microcapsules. Such means are well known from counterparts in the prior art for deodorizing application and/or during the processing of spots textiles. A similar tool for use used in such embodiments where the organic substance is injected carried out after the main washing and/or conditioning stage, for example before or after Ironing or drying clothes. For example, the organic substance can be entered with the help of tapes, sheets or adhesive tapes, coated or impregnated with the substance, or containing microcapsules with the substance. The organic substance may, for example, to form a dry leaf so that it is activated or released in the process cycle of drum dryer, or the substance may be impregnated or containing microcapsule sheet to be entered in the fabric when Ironing.

Many complexes with transition metals have high attenuation coefficients in the visible region of the spectrum. In this respect, the use over time can lead to some discoloration on the substrate after repeated washing. Adding a limited number of source peroxyl serves to reduce the discoloration in those cases, when it occurs, allowing air bleaching. In addition, it was found that in certain cases is ach free ligand can be used in the bleaching compositions of the present invention. When using the free ligand whitening composition can be obtained in accordance with the consumer expectation of colors for makeup. In this part metal ion may be provided by the composition or with the help of trace metals found in the paint.

Detailed description of the invention

The ligand described in this invention can be dynamic inversion. The ability of the ligand to helatirovat TM depends on the stereochemistry of the substituents. Preferably the substituents are in position endo-endo, but preferably stereochemical conversion is effected through the conversion of retro manniche. Conversion of retro manniche can be prevented by replacing groups, so that the reaction retro manniche become the least preferred. However, likely that the endo-Exo and Exo-Exo ligands, as described in the present invention, the coordinate (interact through coordination with transition metal ions in many cases and can function as catalysts for air bleaching.

As for the ligands and their complexes, as well as bleaching compositions obtained according to the formula (I), preferably, each R is the same; and R3=R4, and more preferable that R3 and R4 are the same and are -(CH2)nC(O)O-C1-C4-alkilani preferably, that R3 and R4 are selected from the group consisting of-CH2HE, -C(O)O-C1-C6-alkyl and phenyl.

As for X, it is preferable that Y=1 and most preferably, when X is=O.

It is preferable that at least one of R1 and R2 is 3-CO-C6-alkyl-pyridine-2-yl-CO-C6-alkyl. It is most preferable that at least one of R1 and R2 is selected from the group consisting of: 3-ethylpyridine-2-ylmethyl, pyridine-2-ylmethyl, 3-methylpyridin-2-ylmethyl and 6-lepirudin-2-ylmethyl, of which pyridine-2-ylmethyl is preferred. More preferably, both R1 and R2 are selected from this group.

The catalyst can be used as a preformed complex of the ligand and the transition metal. Alternatively, the catalyst may be formed from the free ligand that complexes with a transition metal already present in the water or complexes with transition metal present in the substrate. The composition can also be formed as a composition of a free ligand or a complex of a transition metal - alternative metal - ligand and source of transition metal, whereby the complex is formed in situ in the environment.

The ligand forms a complex with one or more transition metals, in the latter case, for example, as a dual complex. Suitable transition metals include, for example: organic with oxidation States II-V, iron II-V, copper I-III, cobalt I-III, Titan II-IV, tungsten IV-VI, vanadium II-V and molybdenum II-VI.

The ligand forms a complex with the General formula (A1):

where:

M represents a metal selected from Mn(II)-(III) (IV) (V), Cu(I)-(II)-(III), Fe(II)-(III) (IV) (V), Co(I)-(II)-(III), Ti(II)-(III)-(IV), V(II) (III) (IV) (V), Mo(II)(III) (IV) (V) (VI) and W(IV) (V) (VI). preferably selected from Fe(II)-(III) (IV) (V);

L is a ligand as defined in the present invention, or its protonated or deprotonirovannym analogue;

X represents the focal points selected from any mono -, bi-or three charged anions and any neutral molecules, capable of binding metal mono -, bi-or triple bonds, preferably selected from O2-, RBO22-, RCOO-, RCONR-HE-, NO3-NO, S2-RS-, PO43-, PO3OR3-H2O CO32-HCO3-, ROH, N(R)3, ROO-About22-About2-, RCN, Cl-, Br-, OCN-, SCN-CN-N3-, F-I-, RO-, ClO4-and CF3SO3-and more preferably, is selected from Oh2-, RBO22-, RCOO-HE-, NO3-S2-RS-, RHO34-H2O CO3 HCO3-, ROH, N(R)3, Cl-, Br-, OCN-, SCN-, RCN, N3-, F-I-, RO-, ClO4-and CF3SO3-;

Y represents any coordinational cautery-ion, preferably selected from ClO4-, BR4-, [MH4]-, [MH4]2-PF6-, RCOO-, NO3-, RO-N+(R)4, ROO-O22-O2-, Cl-, Br-, F-I-, CF3SO3-, S2O62-, OCN-, SCN-H2O RBO22-BF4-and BPh4-and more preferably selected from ClO4-, BR4-, [FeCl4]-PF6-, RCOO-, NO3-, RO-N+(R)4, Cl-, Br-, F-I-, CF3SO3-, S2O62-, OCN-, SCN-H2O and BF4-;

a represents an integer from 1 to 10, preferably from 1 to 4;

k represents an integer from 1 to 10;

n represents an integer from 1 to 10, preferably from 1 to 4;

m represents 0 or an integer from 1 to 20, preferably from 1 to 8; and

each R independently is a small town in the place group, selected from hydrogen, hydroxyl, -R' and-OR', where R' = alkyl, alkenyl, cycloalkyl, heteroseksualci, aryl, heteroaryl or group carbonyl derivative, R' is optionally substituted one or more functional groups E, where E is independently represents a functional group selected from-F, -Cl, -Br, -I, -OH, -OR', -NH2-The other', -N(R')2, -N(R')3+, -C(O)R', -OC(O)R', -COOH, -COO-(Na+, K+), -COOR', -C(O)NH2, -C(O)other', -C(O)N(R')2, heteroaryl, -R', -SR', -SH, -P(R')2, -P(O)(R')2, -P(O)(OH)2, -P(O)(OR')2, -NO2, -SO3H, -SO3-(Na+, K+), -S(O)2R', -NHC(O)R', and-N(R')C(O)R', where R' represents cycloalkyl, aryl, arylalkyl or alkyl, optionally substituted with-F, -Cl, -Br, -I, -NH3+-SO3H, -SO3-(Na+To+), -COOH, -COO-(Na+, K+), -P(O)(OH)2or-P(O)(O-(Na+, K+))2and preferably each R independently represents hydrogen, optionally substituted alkyl or optionally substituted aryl, more preferably hydrogen or optionally substituted phenyl, naphthyl or C1-4-alkyl.

Cautery-ions Y in the formula (A1) balance the charge z of the complex formed with the ligand L, metal M and the coordinating center X. Accordingly, if the charge z is positive, Y may be an anion, such as RCOO-,BPh 4-, ClO4-BF4-PF6-, RSO3-, RSO4-, SO42-, NO3-, F-, Cl-, Br-or I-with R being hydrogen, optionally substituted alkyl or optionally substituted aryl. If z is negative, Y may be a common cation, such as alkali metal, alkaline earth metal or (alkyl)ammonium cation.

Appropriate cautery-ions Y include those that cause the formation of stable storage of solid particles. Preferred cautery-ions for the preferred metal complexes are selected from R7COO-, ClO4-BF4-PF6-, RSO3-(in particular, CF3SO3-), RSO4-, SO42-, NO3-, F-, Cl-, Br-and I-where R represents hydrogen or optionally substituted phenyl, naphthyl or1-C4alkyl.

The new compounds of Formula (I)as provided in accordance with the present invention, also apply to their various complexes with transition metal as described above in reference (A1).

It is expected that the complex (A1) can be formed by any appropriate method, including in situ formation through h the th predecessor of the complex is converted into an active complex of General formula (A1) after storage or use. Preferably, the complex form as clear a complex or in a mixture solvent including a salt of the metal M and the ligand L or type L-generating ligand. Alternatively, the catalyst can be formed in situ from suitable precursors for complex, for example in solution or dispersion containing materials predecessor. In one such example, an active catalyst can be formed in situ in the mixture comprising the salt of the metal M and the ligand L or a variant of L-generating ligand, in an appropriate solvent. Thus, for example, if M represents iron, iron salt, such as FeSO4it can be mixed in solution with the ligand L, or a variant L-generating ligand, forming an active complex. Thus, for example, the composition may be formed from a mixture of the ligand L and a metal salt MXnin which preferably n=1-5, more preferably 1-3. In another such example, the ligand L or type L-generating ligand can interact with metal ions M present in the substrate or wash liquid, forming an active catalyst in situ. Suitable varieties L-generating ligand include compounds without metal or metal coordination complexes, the ligand L may be replaced by ions of the metal M, forming the active is complex, providing the formula (A1).

The catalysts according to the present invention can be used in the process of cleaning clothes, cleaning hard surfaces (including cleaning toilets, kitchen work surfaces, floors, wash mechanical products etc). It is known that the bleaching compositions are also used in wastewater treatment, bleaching of pulp in paper production, sebum production, inhibition of colour reproduction, food handling, bleaching starch, sterilization, bleaching in the prepared media oral hygiene and/or disinfecting contact lenses.

In a typical detergent compositions the level of organic substance is such that the level of use has a value of from 1 μm to 50 mm, with preferred levels of use in a home washing operation, is reduced in the range of 10-100 μm. The upper levels can be desirable and applied in industrial bleaching processes, such as bleaching paper pulp and textiles. These levels reflect the amount of catalyst which may be present in the detergent dose of the detergent composition. Whitening composition includes at least 1 ppb ligand or complex.

In the context of the present invention whitening is generally understood as the bleaching of stains or other materials applied or is provided with the substrate. However, it is envisaged that the present invention can be used where the requirement is the removal and/or neutralization of oxidative reaction whitening odors or other undesirable components, relating to or otherwise associated with the substrate. In addition, in the context of the present invention whitening should be understood as referring to any mechanism of bleaching or process, which does not require the presence of light or activated by the light.

Synthesis

In addition to the usefulness of the ligands and complexes of the present invention as catalysts, another advantage is that the ligands are in General relatively easy to synthesize in comparison with other ligands. The following is one example of a strategic approach to their synthesis; for professionals in the field of chemistry organic synthesis it is obvious that many approaches can be used to obtain ligands and complexes of the present invention. The ease of synthesis of the ligand of Formula (I) depends on the nature of the substituents in the structure. The ligands of Formula (I) is most preferably symmetrical. The synthesis of these types of molecules are described in U.Hoizgrabe and other Arch. Pharm. (Weinheim, Ger.) 1992, 325, 657 and A.Samhammer and other Arch. Pharm. (Weinheim, Ger.) 1984, 322, 557. Below is a schematic example illustrating the ease of synthesis. The synthesis is shown in two stages si is thesis, Scheme 1 and Scheme 2, but in some cases may be conducted as a synthesis of "one-stage" depending on the nature of the substituents. However, where the substituents R7=R8 are different from R3=R4, the preferred two-step synthesis. The product of the reaction depicted in Scheme 1, is referred to as dimethyl 2,6-di-(2-pyridyl)-1-methylpiperid-4-one-3,5-in primary forms (NPy2), which can easily take the tautomeric enol form. The synthesis is illustrated in R.Haller, .W.Merz, Pharm. Acta Helv., 1963, 442.

Scheme 1

Scheme 2

Get another important intermediate compound that can be produced according to the General Scheme 1, in which methylamine (CH3NH2), substituted at the 2-aminomethylpyridine so that the manufactured product is dimethyl 2,6-di-(2-pyridyl)-1-(pyridine-2-ylmethyl)-piperid-4-one-3,5-in primary forms (NPy3), the structure of which is given below.

The average specialist clear that while AC[-CO(O)Me] is the electron-acceptor group and an electron-acceptor group is generally preferred for ease of synthesis, other groups will contribute to the reaction. Examples of suitable electron-acceptor groups presented above and will be apparent to a qualified specialist in this field of technology. The reaction also Prov is car Ried out by precipitation of the product from solution.

In the examples, depending on the nature of the substituents, for example, a phenolic group, the necessary protection of certain functional groups. The choice of protective groups in the synthesis process to prevent unwanted reactions is evident to any person skilled in the art. For the choice of protective groups in organic synthesis, see .W.Green and .G.M.Wuts, Protective Groups In Organic Synthesis 3nd Ed.; J.Wiley and Sons, 1999.

Obviously, if the diamine is substituted for methylamine in the reaction presented in Scheme 2, the two structures can be linked together through 7 position, as shown in the structure below.

In addition, if the diamine is substituted for methylamine in the reaction presented in Scheme 1, is formed NPy2 structure associated in 3 positions. Obviously, this dimer can be in the form of a precursor to other structures of dimeric and polymeric type. The present invention relates to "Monomeric" ligands, and not to dimeric and polymeric units associated with the covalent bond as described above. The term "monomer"as used in the present invention, is used to exclude those products that receive type structure covalently linked Pollyanna.

The composition of the detergent

Air bleaching catalyst can be used in detergent compositions, especially suitable for the OTB is the air traffic management paint, and this is the second aspect of the invention. In this case, the composition includes a surfactant and optionally other conventional detergent ingredients. The invention in its second aspect relates to an enzymatic detergent composition which comprises from 0.1 to 50% by weight of the total weight of the detergent composition, one or more surfactants. This system surfactants may on the other hand enable 0-95% by weight of one or more anionic surfactants and from 5 to 100% by weight of one or more nonionic surfactants. System surfactants may optionally contain amphoteric or zwitterionic detergent compounds, but it is usually not required due to their relatively high prices. Enzymatic detergent composition in accordance with the invention, generally used in the form of 0.05-2% aqueous solution.

In General, non-ionic and anionic surfactants in the system of surfactants can be chosen from the surfactants described in "Surface Active Agents" Vol.1, Schwartz &Perry, Interscience 1949, Vol.2 Schwartz, Perry &Berch, Interscience 1958, the current edition of McCutcheon''s Emulsifiers and Detergents"published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H.Stache, 2nd Edn., Carl Hauser Verlag, 1981.

Suitable nonionic d is terentia connection which can be used include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic; alcohol, acids, amides or alkyl phenols with acceleratedly, especially ethylenoxide, separately or with propylenoxide. Specific nejnymi detergent compounds are6-C22the alkyl phenol-ethylene oxide condensates, generally 5 to 25 EO, i.e., from 5 to 25 units of ethylene oxide per molecule and the condensation products of aliphatic C8-C18primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.

Suitable anionic detergent compounds which can be used are usually water-soluble alkali metal salt of organic sulfates and sulfonates having alkyl radicals containing from about 8 to about 22 carbon atoms, where used, the term alkyl includes alkyl group higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are the alkyl sulphates of sodium and potassium, especially obtained by sulfation of higher C8-C18alcohols obtained, for example, from tallow or coconut oil, alkyl With9-C20benzosulfimide sodium and potassium, especially line is tricky alkyl With 10-C15benzosulfimide sodium; and alkyl glycerol ether sulfates of sodium, especially the esters derived from higher fatty alcohols or coconut oil and synthetic alcohols derived from petroleum. The preferred anionic detergent compounds are sodium C11-C15alkyl benzosulfimide and sodium C12-C18alkyl sulfates. Also applicable are surface-active substances, such as described in EP-A-328177 (Unilever), which are resistant to leaching of salts, alkyl polyglycoside surfactants described in EP-A-070074, and alkyl monoglycoside.

Preferred systems surfactants are mixtures of anionic and nonionic detergent active materials, in particular groups and examples of anionic and nonionic surfactants mentioned in EP-A-346995 (Unilever). Especially preferred is a system of surface-active agents, that is, a mixture of salts of alkaline metal C16-C18primary alcohol sulfate with C12-C15the primary alcohol 3-7 SW-ethoxylate.

Non-ionic detergent is preferably present in amounts greater than 10%, for example 25-90% by weight of the system surface-active substances. Anionic surfactants may be present, for example, in the range from OK is lo 5% to about 40% by weight of the system surface-active substances.

Detergent composition may be in any suitable physical form, such as powder, granular composition, tablets, pastes or anhydrous gel.

Enzymes

Detergent compositions of the present invention can additionally include one or more enzymes which provide cleaning quality, safety matter and/or sanitation.

These enzymes include oxidoreductase, transferases, hydrolases, LiAZ, isomerase, and ligase. Suitable members of these classes of enzymes are described in Enzyme nomenclature 1992: recommendations of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology on nomenclature and classification of enzymes, 1992, ISBN 0-12-227165-3, Academic Press.

Examples of hydrolases are carboxylic ether hydrolase, tilefona hydrolase, phosphoric monoamina hydrolase and phosphoric diperna hydrolase that act on the ester linkage; glycosidase, which operates on O-glucosamine connection; glycosylase, gidrolizutaya N-glucosamine connection; the thioester hydrolase, which acts on the ester linkage and ectopeptidases and endopeptidase that act on the peptide bond. Of them, preferred are carboxylic ether hydrolase, glycosidase and Exo - and endopeptidase. Specific examples of suitable hydrolases include (1) ectopeptidases, such as aminopeptidase and CT is exopeptidase a and b and endopeptidase, such as pepsin, pepsin, chymosin, trypsin, chymotrypsin, elastase, enteropeptidase, cathepsin, papain, chymopapain, ficin, thrombin, plasmin, renin, subtilisin, aspergillosis, collagenase, closepin, kallickrein, gastritis, cathepsin D, bromelain, chymotrypsin, urokinase, cusomizing, origin, proteinase K, thermometry, thermitase, lactocidin, thermolysin, bacillales. Preferred of them is subtilisin; (2) glycosidase, such as α-amylase, β-amylase, glucoamylase, isoamylase, cellulase, endo-1,3(4)-β-glucanase (β-glucanase, xylanase, dextranase, polygalacturonase (pectinase, lysozyme, invertase, hyaluronidase, pullulanase, neopolitans, chitinase, arabinosidases, ectocervical, hexosaminidase, Icodextrin, endo-1,4-β-mannanase (hemicellulase), xyloglucans, endo-β-galactosidase (keratanase), mannanase and other sacharine enzymes, collapsing when chewing, described in WO-A-99/09127. Preferred of them are α-amylase and cellulase; (3) carboxylic ether hydrolase, including carboxylesterase, lipase, phospholipase, pectinesterase, cholesterylester, chlorofresh, tannase and wax ester hydrolase. Preferred of them is lipase.

Examples of transferring enzyme and ligase are glutathione S-transferase and acid-tylna ligase, as described in the WO-A-98/59028 and xyloglucan endotransglucosylase, as described in WO-A-98/38288.

Examples LiAZ are gialuronatnye lease, peccata lease, chondroitinase, pectin lease, arginase II. Especially preferred is pectolyase, which is a mixture of pectinase and pectin LiAZ.

Examples of oxidoreductases are oxidases, such as glucoseoxidase, metaloxides, bilirubinaemia, catecholamines, laccase, peroxidase, such as ligninase and those described in WO-A-97/31090, monooxygenase, dioxygenase, such as lipoxygenase and other oxygenase described in WO-A-99/02632, WO-A-99/02638, WO-A-99/02639 and systems enzymatic bleaching, based on cytochrome described in WO-A-99/02641.

The activity of oxidoreductases, particularly the phenol oxidizing enzymes in the process of bleaching stains on fabrics and/or color in the solution and/or antimicrobial treatment can be increased by adding certain organic compounds, called amplifiers. Examples of amplifiers are 2,2'-azo-bis-(3-ethylbenzo-thiazoline-6-sulfonate (ABTS) and phenothiazines-10-propionate (RTR). Other amplifiers are described in WO-A-94/12619, WO-A-94/12620, WO-A-94/12621, WO-A-97/11217, WO-A-99/23887. Amplifiers generally added in an amount of from 0.01% to 5% by weight of detergent composition.

Components, polymers and other enzymes as selective ingredients may also be present in accordance with WO 0060045.

Suitable components of the detergent as election ingredients may also be present in accordance with WO 0034427.

The present invention is further illustrated by the following, non-limiting examples.

Examples

[(MeN4Py)FeCl]Cl

The ligand N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-1-aminoethane (MeN4py) are obtained as described in EP 0909809 A2.

Ligand MeN4Py (33,7 g; and 88.5 mmol) is dissolved in 500 ml of dry methanol. Then add small portions FeCl2.4H2O of (0.95 equiv.; 16.7 g; 84,0 mmol), which in turn yields the solution of a light red colour. After addition the solution is stirred for 30 minutes at room temperature, after which the methanol is removed (rotary evaporator). The dry solid is precipitated and 150 ml of ethyl acetate and the mixture is stirred until then, until you get the powder is bright red in color. This powder is washed twice with ethyl acetate, air-dried and further dried under vacuum at reduced pressure at a temperature of 40°C. Elemental analysis calculated: [Fe(MeN4py)Cl]Cl·2H2O: 53,03; H 5,16; N 12,89; Cl 13,07;

Fe of 10.01%. Found 52,29/52,03; N. Of 5.05/5,03; N 12,55/12,61; Cl: Of 12.73/12,69; Fe: 10,06/10,01%.

Dimethyl 2,6-di-(2-pyridyl)-1-methyl-piperid-4-one-3,5-in primary forms (NPy2) (MW; 383,4 g/mol)

Picalilly (83.1 mmol; 8 ml) is added dropwise to the cooled using an ice bath a solution of dimethyl who Fira acetonylacetone acid (41,55 mmol, 6 ml) in methanol (30 ml), then added an aqueous solution (40%) of methylamine (41,55 ml, 4.8 ml), which in turn yields a solution of red-orange color. The solution is stirred for 5 minutes at a temperature of 0°S, and then cooled to 18°C. After approximately two days of storage at a temperature of 18°in the reaction mixture formed large crystals. The crystals are removed by filtration and washed with cold ethanol and recrystallized from ethanol. Then the concentration of the filtrate gives the output an additional 10% of the product. The total yield of these compounds 12,43 g (78%).

1H-NMR (CD2Cl2) (mainly enol): 1.70 (s, 3H, -NMe); 3,60; to 3.67 (2s, 6N, -OMe); 4,19 (d, J=10 Hz, 1H, pipn); to 4.46 (d, J=10 Hz, 1H, pipn); to 4.81 (s, 1H, pipn); 7,10-at 8.60 (m, 10H, pyHs)

Dimethyl 2,6-di-(2-pyridine)-1-(pyridine-2-ylmethyl)-piperid-4-one-3,5-in primary forms (NPy3) (MW: 460,5 g/mol)

The process of synthesis NPy3 in General the same as NPy2 except that used the following precursors: dimethyl ether aacondicionado acid (0.05 mol; 7,2 ml); 2-pyridinylmethyl (0.1 mol; 9,56 ml); and picolylamine (0.05 ml; 5,1 ml to get 19,31 g (84%).

1H-NMR: (DCCl3) (mainly enol): 3,55; 3,81 (s, 6N, -OMe); a 3.83 (s, 2H, CH2-PY); the 4.29 (d, J=12 Hz, 1H, pipn); to 4.81 (d, J=12 Hz, 1H, pipn); 4,89 (s, 1H, pipn); 7,05 for 7.78 (m, N, pyHs); 8,42-8,48 (m, 2H, run, run); at 8.62 (d, J=8 Hz), 1H, UN)

Dimethyl 2,4-di(2-pyridyl)was 3.7-dimethyl-3,7-diaza-bicyclo[3.3.1]nonan-9He-1,5, in primary forms (N2Py2) (MW; 438,5 g/mol)

To a suspension NPy2 (26,1 mmol; 10 g) in 80 ml of ethanol is added an aqueous solution (37%) formaldehyde (62,66 mmol, 5,64 ml), then aqueous 40% solution of methylamine (31,33 ml; 3.6 ml). Then the reaction mixture is heated to boiling point under reflux for 5 minutes, after which the reaction mixture is cooled to ambient temperature. After scraping the inside of the vessel containing the reaction mixture, the formed white crystals. After filtration of the crystalline product washed with ethanol and the crystalline product is dried under produced pressure to get 8.61 g (75,3%) of these connections.

1H-NMR (CD2Cl2): 2.00 (s, 3H, 7-Me); 2,22 (s, 3H, N3-Me); of 2.45 (d, J=12 Hz, 2H, bisno, bisno); of 2.93 (d, J=12 Hz, 2H, 6q, 8q); of 3.75 (s, 6N, -OMe); of 4.67 (s, 2H, bin, bin); of 7.23 (m, 2H, run); 7,80 (t, J=8 Hz, 2H, run); 8,07 (d, J=8 Hz, 2H, run); 8,49 (d, J=5 Hz, 2H, run).

Dimethyl 2,4-di(2-pyridyl)-3-methyl-7-(pyridine-2-ylmethyl)was 3.7-diaza-bicyclo[3.3.1]nonan-9-one-1,5, in primary forms (N2Py3) (MW: 515,22 g/mol)

2-Aminomethyl-pyridine (4.3 g, and 39.7 mmol) and formaldehyde (37% in water) (6,5 ml, 79,4 mmol) are added to the suspension NPy2 (12,71 g, up 33.1 mmol) in 200 ml of ethanol. The suspension is stirred at the boil under reflux for 30 minutes, obtaining a solution of a light-brown C the ETA. The solvent is removed under reduced pressure and the remaining solid is recrystallized from ethanol to obtain the titled compound in the form of a solid white (or 4.2 g, 25%).

1H-NMR (300 MHz, CDCl3): of 1.94 (s, 3H, N-Me), 2,68 (d, 2H, J=12 Hz, bisno, bisno-); 3,14 (d, 2H, J=12 Hz, 6q, 6H8eq): only 3.57 (s, 2H, CH2-PY), 3,76 (s, 6N, OMe), of 4.66 (s, 2H, bin, bin), to 7.09 (t, 2H, J=1.5 Hz, PY-H), 7,21 (t, 1H, J=6.0 Hz, PY-H), 7,33 (d, 1H, J=7.6 Hz, PY-H), to 7.50 (t, 2H, J=I,7 Hz, PY-H), 7,66 (t, 1H. J=7.5 Hz, PY-H), 7,92 (d, 2H, J=7.8 Hz, PY-H), to 8.45 (d, 2H, J=4.0 Hz, PY-H), 8,62 (D. 1H, J=4,8 Hz, PY-H).

Dimethyl 2,4-di(2-pyridyl)-3-(pyrid-2-ylmethyl)-7-methyl-3,7-diaza-bicyclo[3.3.1]nonan-9-one-1,5, in primary forms (N2Py3u) (MW: 515,22 g/mol)

To a suspension NPy3 (21,79 g of 47.3 mmol) in 250 ml of ethanol is added an aqueous solution (40%) of methylamine (4.8 ml, of 56.7 mmol) and aqueous solution (37%) formaldehyde (9,2 ml, to 113.4 mmol). The suspension is stirred at the boil under reflux for 3 hours, the resulting solution is dark brown. The solvent is removed under reduced pressure and the resulting greenish-brown solid is recrystallized from ethanol, to obtain the return of 6.58 g (27%) of the named compound in a solid white color.

1H-NMR (300 MHz, CDCl3): of 2.20 (s, 3H, N-Me), of 2.56 (d, 2H, J=12 Hz, bisno, bisno), 2,98 (d, 2H, JNN=12 Hz, 6q, 6H8eq), and 3.72 (s, 8H, OMe, CH2-PY), 5,42 (C. 2H, bin,bin), 6,76 (d, 1H, J=7.7 Hz, PY-H), 6,97 (t, 1H, J=5.7 Hz, PY-H), 7,13 (t, 2H, J=6.0 Hz, PY-H), 7,38 (t, 2H. J=7,6 Hz, PY-H), 7,68 (t, 2H, J=7,6 Hz, PY-H), 8.06 (d, 1H, J=7,6 Hz, PY-H), 8,43 (d, 1H, J=4,6 Hz, PY-H), of 8.47 (d, 2H, J=4.4 Hz, PY-H).

Analytically calculated for C28H29N5O5: 65,23, N 5,67, N of 13.58; found: 64,86, N the ceiling of 5.60, N 13,41.

Dimethyl 2,4-di(2-pyridyl)was 3.7-bis-(pyridine-2-ylmethyl)was 3.7-diaza-bicyclo[3.3.1]nonan-9-one-1,5, in primary forms (N2Py4) (MW: 594,7 g/mol)

The hot solution NPy3 (32,61 mmol; 15 g) in 25 ml THF, is added dropwise an aqueous solution (40%) formaldehyde (to 78.3 mmol; 7,0 ml), then added dropwise 2-aminomethyl-pyridine (39,1 mmol; 4 ml), which in turn yields the solution a dark color. Then the mixture is heated for one hour at a temperature of 85°C. After cooling, the reaction mixture get greenish precipitate. The precipitate is then washed with cold ethanol and crystallized from ethanol to obtain the titled compound, and 4.75 g (25%). In some cases, the precipitate is not formed, and when it is desirable to remove the THF under reduced pressure to obtain oil of black color, and add 5 ml of EtOH. After adding EtOH named compound is recrystallized within 3 to 4 hours.

1H-NMR (CDCl3): 2,87 (d, J=12 Hz, 2H, bisno, bisno); of 3.46 (d, J 12 Hz, 2H, H6eq, 8q), 3,66-3,71 (m, 10H, -ome, -CH2-PY); to 5.35 (s, 2H, bin, bin); 6.73 x-8,63 (m S, 20H, pyHs).

Table 1 illustrates the structures of ligands this is part II of the invention, which is used in bleaching experiments.

Table 1
The ligand
R3=R4=-C(O)OMeN2Py4
R1 = R2 = pyridine-2-ylmethyl
R3=R4=-C(O)OMeN2Py2
R1=R2=-CH3
R3=R4=-C(O)OMeN2Py3u
R1=Me
R2 = pyridine-2-ylmethyl
R3=R4=-C(O)OMeN2Py3o
R1 = pyridin-2-ylmethyl
R2=Me

Total synthesis of the complex of the ligand

A solution of 2 mmol of metal salt (FeSO4, FeCl2, CuCl2, Fe(ClO4)2etc) in 1 ml of methanol are added to a solution of 2 mmol of the ligand in 1 ml of acetonitrile. Pure dark (usually brown for Fe complex and blue for Cu complex) solution is placed in a diffusion bath with titilation. After a few hours dyed crystals are precipitated from the solution.

(Dimethyl 2,4-di(2-pyridyl)-3-methyl-7-(pyridine-2-ylmethyl)was 3.7-diaza-bicyclo[3.3.1]nonan-9-one-1,5, in primary forms) sulfate iron (II) [C28H29FeN5 9S M=667,13 g/mol]

Analytically calculated for C28H29FeN5O9S: 47,80, N 4,73, N 9,96; found +2H2O: 47,16, N, N 9,84. FAB+MS (nitrobenzyl alcohol): 686,1 (MH++H2O)

((Dimethyl-2,4-di-(2-pyridyl)-3-(pyridine-2-ylmethyl)-7-methyl-3,7-diazabicyclo[3.3.1]nonan-9-one-1,5, in primary forms)sulfate iron(II) (M=667,13 g/mol)

Analytically calculated for C28H29FeN5O9S: 46,61, N 4,89, N 9,71; found +3H2O: 47,27, N TO 4.81, N 9,88. FAB+MS (nitrobenzyl alcohol): 686,1 (MH++H2O)

Chloro(dimethyl 2,4-di(2-pyridyl)-3-methyl-7-(pyridine-2-ylmethyl)was 3.7-diaza-bicyclo[3.3.1]nonan-9-one-1,5, in primary forms)iron(II)hydrochloride

Analytically calculated for C28H29Cl2FeN5O5: C 49,58, N 4,90, N 10,45; found +2H2ABOUT: 49,45, N 4,79, N 10,00. FAB+MS (nitrobenzyl alcohol): 624,1 [FeCl(N2Py3o)·H2O]

(Dimethyl-2,4-di-(2-pyridyl)was 3.7-bis-(pyridine-2-ylmethyl)was 3.7-diazabicyclo [33.1]nonan-9-one-1,5, in primary forms)iron(II)-dichlorhydrate [C33H38Cl2FeN6About6M=741,44 g/mol]

Analytically calculated for C33H38Cl2FeN6About6: 53,75, N 4,65, N 11,40; found: 53,20, N 4,74, N 11,22. FAB+MS(nitrobenzyl alcohol): 683,1 [Fe(N2Py4)·H2O]

The following reaction is carried out in anhydrous conditions in an argon atmosphere using standard Schlenck/tubular technology.

To a cooled stirred mixture of iron powder (5.6 g, 0.1 mol) in acetonitrile (60 ml) add triftormetilfullerenov (0.2 mol of 17.7 ml). After the addition the reaction mixture is heated for 45 minutes at a temperature of 90°C. Then the reaction mixture is cooled, after which the remaining solid is filtered off. To the remaining solution is added slowly to 40 ml of diethyl ether, which in turn yields a residue of white. Specified sucked off in an argon atmosphere and washed with 20 ml of ether. Hygroscopic material remain. The output of 31.7% (13.8 g).

[Fe(N2Py2)(triplet)2] (MW: 792,46 g/mol)

In the anhydrous system add 0.23 mmol (100 mg), [Fe(CH3CN)2(triplet)2] and the ligand (0.23 mmol; 100 mg) in dry acetonitrile. With slow diffusion of ether into this solution to obtain crystals of the iron complex. The output for this procedure is usually 50%. Analytically calculated for FeC25H29N4O11S2F6calculated: 38,91, N 3,51, N 8,40; found: 38,86, N 3,41, N 8,32.

Experiments on bleaching

The results of the whitening get tomato stains for different complexes (10 μm) or formed in advance types of ligand/iron (from what omashu pre-mixing 2 mm ligand/1 mm of iron perchlorate in ethanol/water (1/1). Tomato stains washed LAS/buffer system (0.6 g/l NaLAS in 10 mm carbonate buffer) for 30 minutes at a temperature of 30°in a vessel containing 25 ml of washing solution. After washing, the tissue was washed with water and dried in the dryer, turning to drying.

Measurements reflect the benefits of using Minolta™ 3700d spectrophotometer at 460 nm. Differences in the reflection before and after washing define as ΔR460 value. Shows the results of the whitening obtained immediately after drying (t=0). All values are expressed in ΔΔR 460 units (pale, LAS only basis); typical errors are in the order of 2 points. Higher values mean better results implementation of bleaching.

Table 2. The results of bleaching (ΔΔR 460) on tomato oil with complexes formed in advance and mixtures of salt ligand/iron (the active ingredient).

Table 2
the active ingredientt=0
N2Py4+Fe(II)10
[Fe(N2py3o)Cl]Cl24
[Fe(N2py3u)SO4]22
N2py3u+Fe(II)11
N2py3o+Fe(II)20
[Fe(N2py2)Cl2]7
N2py2+Fe(II)1

the results in Table 2 indicate the following.

Good whitening activity received spots on tomato oil, especially with the help of iron complexes containing N2Py3 ligands (u and o), and to a lesser extent with N2py4 mixture of the ligand/iron air bleaching. In all cases, the results of teeth whitening are much better than those of systems containing N2py2 (or Fe complex or mixture of salt ligand/iron). It is noteworthy that the ligand in combination with a salt of iron is effective in air bleaching.

1. Whitening composition, including

(a) Monomeric ligand or catalyst with a transition metal ligand having the formula (I)

where R represents hydrogen;

R1 and R2 are independently selected from C1-C4-alkyl, pyridine-2-yl-methyl, and C2-C4-alkyl-amine;

X represents-C=O;

R3 and R4 are the same and represent -(CH2)nC(O)O-C1-C4-alkyl;

n has a value from 0 to 4, and

b) balancing carriers and other ingredients.

2. Whitening composition according to claim 1, in which at least one of R1 and R2 is pyridin-2-Iletisim.

3. Whitening composition according to any one of claims 1 or 2, in which both R1 and R2 are pyridine-2-Iletisim.

4. Whitening composition according to any of the preceding paragraphs, in which bleach is the one composition includes the free ligand.

5. Whitening composition according to any one of claims 1 to 4, in which the complex is defined by the General formula (A1)

where M is a metal selected from Mn(II)-(III) (IV) (V), Cu(I)-(II)-(III), Fe(II)-(III) (IV) (V), Co(I)-(II)-(III), Ti(II)-(III)-(IV), V(II) (III) (IV) (V), Mo(II)-(III) (IV) (V) (VI) and W(IV) (V) (VI);

X is the focal point selected from any mono -, bi-or three charged anions and any neutral molecules, capable of binding metal mono -, bi-or three ties;

Y is any disorderly cautery ion;

and is an integer from 1 to 10;

k is an integer from 1 to 10;

n is an integer from 1 to 10;

m is 0 or an integer from 1 to 20

and L is a ligand as defined in claims 1 to 4, or its protonated or deprotonirovannym equivalent.

6. Whitening composition according to claim 5, where M is a metal selected from Fe(II)-(III) (IV) (V).

7. Whitening composition according to claim 6, where M is a metal selected from Fe(II) and Fe(III).

8. The ligand of formula (I) according to claim 1 or catalyst ligand with the transition metal, having the formula (I)

where R represents hydrogen;

R1 and R2 are independently selected from C1-C4-alkyl, pyridine-2-yl-methyl, and C2-C4-alkyl-amine;

X represents-C=O;

R3 and R4 are the same and represent -(CH2)nC(O)O-C1-C4-alkyl;

n has a value from 0 to 4.

9. The ligand of formula (I) of claim 8 or a catalyst with a transition metal ligand in which at least one of R1 or R2 is pyridin-2-elmetron, and the other is selected from-CH3, -CN, -CN and-C4H9.

10. The ligand of formula (I) of claim 8 or a catalyst with a transition metal ligand, which ligand is selected from the formula consisting of dimethyl 2,4-di(2-pyridyl)-3-methyl-7-(pyridine-2-ylmethyl)was 3.7-diaza-bicyclo[3.3.1]nonan-9-one-1,5-in primary forms (N2Py3o); dimethyl 2,4-di(2-pyridyl)-3-(pyrid-2-ylmethyl)-7-methyl-3,7-diaza-bicyclo[3.3.1]nonan-9-one-1,5-in primary forms (N2Py3u) and dimethyl 2,4-di(2-pyridyl)was 3.7-bis-(pyridine-2-ylmethyl)was 3.7-diaza-bicyclo[3.3.1]nonan-9-one-1,5-in primary forms (N2Py4).

11. Method of bleaching a substrate comprising the step of applying to the substrate in the aquatic environment bleaching composition according to any one of claims 1 to 7.



 

Same patents:

FIELD: process for treatment of textile materials, in particular, whitening of flax fiber for producing of hygroscopic wool used for medicine purposes.

SUBSTANCE: method involves subjecting flax fiber to oxidizing cooking followed by whitening with the use of hydrogen peroxide in the presence of stabilizing preparation based on oxyethylidene diphosphonic acid; after final rinsing, providing brightening processing, preferably with the use of solution containing higher fatty acid based softener used in an amount of 0.5-1.0 g/l. Method is realized in industrial plants with the use of proper equipment and chemical substances available and produced on industrial scale by home enterprises. Said method does not require substantial alterations in chemical processes.

EFFECT: increased whitening extent, capillarity and moisture absorbing capacity of wool produced.

2 tbl, 5 ex

FIELD: light industry, in particular, raw material dyeing processes used, for example, in whitening of mink skin fur hair.

SUBSTANCE: method involves providing additional tinning of skin with aqueous composition containing sodium chloride, composition based on low-molecular alcohol polyacetals, mixture of non-ionogen surfactants and cyclic terpenes; whitening for 2.0-4.5 hours with the use of aqueous composition containing sodium chloride, potassium persulfate, composition based on mineral and organic acids as pH stabilizers, mixture of primary fatty alcohols as protective admixture and 30%-hydrogen peroxide; providing reduction with the use of aqueous composition comprising sodium chloride, oxalic acid and mixture of non-ionogen surfactants with cyclic terpenes.

EFFECT: improved consumer properties of fur skins.

2 tbl

FIELD: light industry, in particular, raw material dyeing processes used, for example, in whitening of mink skin fur hair.

SUBSTANCE: method involves providing additional tinning of skin with aqueous composition containing sodium chloride, composition based on low-molecular alcohol polyacetals, mixture of non-ionogen surfactants and cyclic terpenes; whitening for 2.0-4.5 hours with the use of aqueous composition containing sodium chloride, potassium persulfate, composition based on mineral and organic acids as pH stabilizers, mixture of primary fatty alcohols as protective admixture and 30%-hydrogen peroxide; providing reduction with the use of aqueous composition comprising sodium chloride, oxalic acid and mixture of non-ionogen surfactants with cyclic terpenes.

EFFECT: improved consumer properties of fur skins.

2 tbl

FIELD: fur industry.

SUBSTANCE: composition used for restoration of fell scalps after oxidative bleaching contains sodium dithionite, sodium chloride, sodium pyrophosphate, isopropyl alcohol, composition based on nonionic surfactants and cyclic terpenes ("Gamma" preparation), and water.

EFFECT: enhanced brightness of bleached scalp and improved plastic properties of skin tissue of fell.

2 tbl, 5 ex

FIELD: light and fur industry.

SUBSTANCE: invention relates to a composition used for whitening hair cover of fur hides. The composition comprises sodium chloride, hydrogen peroxide, potassium persulfate, the composition based on mineral and organic acid salts - "Antikolor 1" or "Antikolor-2" as an agent for stabilizing pH value, and a mixture of primary saturated alcohols - "Antikolor-3" as a protective additive. The composition provides reducing the negative effect of leather and hair cover of hide. The composition can be used in raw-dye manufacture in treatment of hides with pigmented hair cover, for example, hides of karakul group.

EFFECT: valuable properties of composition.

2 tbl

FIELD: light and fur industry.

SUBSTANCE: invention relates to a composition used for whitening hair cover of fur hides. The composition comprises sodium chloride, hydrogen peroxide, potassium persulfate, the composition based on mineral and organic acid salts - "Antikolor 1" or "Antikolor-2" as an agent for stabilizing pH value, and a mixture of primary saturated alcohols - "Antikolor-3" as a protective additive. The composition provides reducing the negative effect of leather and hair cover of hide. The composition can be used in raw-dye manufacture in treatment of hides with pigmented hair cover, for example, hides of karakul group.

EFFECT: valuable properties of composition.

2 tbl

FIELD: light and fur industry.

SUBSTANCE: invention relates to a composition used for whitening hair cover of fur hides. The composition comprises sodium chloride, hydrogen peroxide, potassium persulfate, the composition based on mineral and organic acid salts - "Antikolor 1" or "Antikolor-2" as an agent for stabilizing pH value, and a mixture of primary saturated alcohols - "Antikolor-3" as a protective additive. The composition provides reducing the negative effect of leather and hair cover of hide. The composition can be used in raw-dye manufacture in treatment of hides with pigmented hair cover, for example, hides of karakul group.

EFFECT: valuable properties of composition.

2 tbl

FIELD: organic chemistry, paper industry.

SUBSTANCE: invention relates to compositions used for coating paper covers. Invention describes a composition for coating paper cover comprising whitening pigment comprising: (a) product of melamine formaldehyde or phenol-formaldehyde polycondensation, and (b) water-soluble fluorescent whitening agent of the formula:

wherein R1 and R2 represent independently of one another -OH, -Cl, -NH2, -O-(C1-C4)-alkyl, -O-aryl, -NH-(C1-C4)-alkyl, -N-(C1-C4-alkyl)2, -N-(C1-C4)-alkyl-(C1-C4-hydroxyalkyl)- -N-(C1-C4-hydroxyalkyl)2 or -NH-aryl, for example, anilino-, anilinemono- or disulfonic acid or aniline sulfone amide, morpholino-, -S-(C1-C4)-alkyl(aryl) or radical of amino acid, for example, aspartic acid or iminoacetic acid that is replaced with radical in amino-group; M means hydrogen, sodium, potassium, calcium, magnesium atom or ammonium, mono-, di-, tri- or tetra-(C1-C4)-alkylammonium, mono-, di- or tri-(C1-C4)-hydroxyalkylammonium, or ammonium di- or tri-substituted with a mixture of (C1-C4)-alkyl and (C1-C4)-hydroxyalkyl groups. Covers prepared on coating paper elicit high photostability and enhanced whiteness degree.

EFFECT: improved method for preparing, improved properties of covers.

7 cl, 1 tbl, 3 ex

FIELD: textile industry.

SUBSTANCE: composition contains hydrogen peroxide, aqueous ammonia, silicate-containing hydrogen peroxide stabilizer, nonionic or anionic surfactant, and water, said stabilizer being, in particular, taken separately or in various proportions to each other substances selected from group including kaolin, talc, bentonite, zeolite sorbent, and diatomite.

EFFECT: reduced loss in strength, felting tendency, and rigidity of textiles.

2 tbl, 6 ex

FIELD: manufacture of washing machines.

SUBSTANCE: proposed washing machine consists of radical generating system 300 combining bubble and ozone generating units 302,304 and 308 and radical replacement units in housing 310. Bubble generating unit 302 includes air pump 312 and working compartment. Air contained in working compartment is compressed and expanded under action of diaphragm 312a of air pump 312 made from elastic material forming mixture of air and air bubbles which is admitted to gas mixing chamber 306. First check valve 311 excludes return flow of mixture from gas mixing chamber 306 to bubble generating unit 302. High voltage is formed in ozone generating unit 304 for forming ozone from mixture contained in chamber 306. Second check valve 313 located between gas mixing chamber 306 and radical replacement unit 308 lets mixture pass selectively preventing it from return flow. Radical replacement unit 308 contains catalyst 308a in form of main, auxiliary and carrier catalysts. Main catalyst is TiO2, MnO2 or CuO2, auxiliary is catalyst Pt or Pd and carrier catalyst is Al2O3, SiO2 or MgO. Under action of catalyst 308a, ozone is decomposed into active oxygen radicals of first raw which react with water forming active oxygen radical of second raw containing OH group. Left-hand side wall 308c of unit 308 has ozone inlet hole 308d. Right-hand wall 308e has hole 308f for outlet of active oxygen radical of second row.

EFFECT: improved quality of washing; reduced amount of ozone.

7 cl, 4 dwg

The invention relates to catalytic bleaching of substrates, for example, subjected to washing fabrics, atmospheric oxygen or air

The invention relates to the technical detergents for cleaning food processing equipment, glass, plastic, metal containers, pipelines and other equipment for the dairy, meat and canning industry

The invention relates to the food industry and can be used for cleaning apparatus used in the manufacture of food products, particularly when filtering

The invention relates to a method of pre-treatment of the contaminated fabrics with a liquid composition containing a peroxide bleaching agent and an agent that removes impurities selected from the group comprising ethoxylated monoamine, ethoxylated diamine, ethoxylated polyamine and polymeric ethoxylated amine and mixtures thereof

The invention relates to a liquid bleaching gipohloridom composition containing pH-supports buffer component in an amount of 0.5 to 9 wt

The invention relates to bleaching, detergent and disinfectants, in particular to the preparation and storage of solutions of sodium hypochlorite

The invention relates to methods for alkaline bleaching compounds - products designed for cleaning hard surfaces, bleaching, and disinfecting

The invention relates to catalytic bleaching of substrates, for example, subjected to washing fabrics, atmospheric oxygen or air

The invention relates to a method of stabilizing insoluble colorant containing hypochlorite compositions intended for bleaching fabrics and hard surfaces

The invention relates to an improved method for producing a detergent in the form of a gel and can be used for cleaning sanitary products, boiler equipment, household and industrial premises

The invention relates to detergent-disinfectants and can be used for sanitization underground maintenance, cleaning and disinfection of milking machines with a long pipeline
Up!