Metal-legandaries bleaching compositions

 

The invention relates to macrocyclic metal complex ligands, used as catalysts for the oxidative bleaching. Describes how the discoloration of the chromophores in the wastewater of pulp and paper, which involves the use of a composition consisting of (a) the source of the oxidizing agent in amounts effective for bleaching of the substrate, and (b) resistant to oxidation activator oxidizing agent having the structure (I)

where Y1, Y3and Y4each represent a bridging group having zero, one, two or three carbon link to replace, a Y2is a bridging group having at least one carbon-containing element for substitution, each specified element contains the group C(R) C(R1)(R2) or C(R)2and each substituent R is the same or different from the rest of the substituents R; M denotes a metal of the transition series with oxidation States of I, II, III, IV, V, VI, VII or VIII or selected from groups 3, 4, 5, 6, 7, 8, 9, 10 and 11 of the Periodic system of elements and Q denotes any counterion, which balances the charge of the compound on a stoichiometric basis. The way eak-before:always;">

Statement regarding federally financed research

This work was supported by the National science Foundation, grant SNE, and the National Institute of health, grant GM-44867. The United States government may have certain rights in respect of this application.

BACKGROUND of the INVENTION

This invention relates to the use of macrocyclic metal-ligand complexes as bleaching catalysts, and more specifically to complexes with metals of the transition series of macrocyclic tetraamide ligands as catalysts to enhance the oxidative bleaching.

The United States and Canada are the world's leading producers of wood fiber used in the production of paper and cardboard. In 1994, the United States produced more than 58 million tons of wood fiber. Wood fiber, which is made either mechanically or chemically from wood, contains: 1) cellulose, homopolysaccharides linear polymer of d-glucose of the formula -(C6H10About5)-; 2) lignin, heterogeneous three-dimensional molecule having the following General structure-C9H8,83About2,37(Och3)0,96and 3) gemetzel the eries 397.

Desirable properties of the paper include strength, whiteness and brightness. The strength of the paper is associated with the viscosity of the wood fiber used in its production, which, in turn, related to the condition of the pulp after the cooking operation (transformation into a fibrous mass). Molecular cellulose, as described above, is a linear chain of d-glucose, which natural forms long fibers. The longer a separate chain cellulose polymer, the higher the viscosity of the wood fiber and the higher, in turn, the strength of the paper. Thus, during the processing of the most desirable to avoid splitting cellulose polymers into smaller units.

White is based on the paper for observers, and therefore it is subjective. The brightness (whiteness) is a term used to describe white wood fiber on a scale from 0% (totally black) to 100% (relative to the MLA standard, which has an absolute brightness of approximately 96%) using the reflectance of blue light (457 nm) from the paper produced from this wood fiber. The more incident light is reflected, not absorbed, the brighter the paper.

Brightness is achieved otbelivanie brightness. Bleaching chemicals increase the brightness by removing and bleaching of lignin in wood fiber. Lignin detects color from yellowish to dark brown depending on the type of wood.

The most common bleaching chemicals are oxidizing agents: chlorine, a source of hypochlorite ion and chlorine dioxide. Gaseous oxygen in combination with NaOH can also be used, but it requires expensive equipment and must be used in large quantities. In addition, oxygen leads to loss of strength of wood fibers caused caused by free radicals damage cellulosic polymers, in particular, in cases where the content of lignin in the wood fiber is low.

Chlorine and hypochlorite can lead to loss of strength when used incorrectly, but in General are effective and relatively easy to use oxidants. Hypochlorite is an aggressive oxidizer, which has a tendency to attack (destroy) cellulose, especially in non-optimal use. Chlorine dioxide gives a high brightness level without degradation of wood fibers. However, it is an expensive oxidant and prone to bursts is Vlada dangerous for the environment and for health. In addition, waste water, which contains chlorine in any chemical form, can not be burned in regenerating the boiler of a pulp mill. Chlorine produces corrosion regenerative boiler. In addition, as noted below, the combustion of chlorine-containing particles can lead to the formation of polychlorinated dioxins and dibenzofurans, 17 of which are considered toxic and carcinogenic. In addition, chlorine may, for example, interact strongly with flammable materials. He interacts with H2S, CO and SO2with the formation of toxic and corrosive corrosive gases and liquid causes burns, blisters and tissue destruction. In gaseous form, it causes severe irritation of eyes, nasal passages and respiratory tissue. In high doses it can be fatal. Containing chlorine dioxide bleach breaks down to CL2that is toxic and corrosive.

Polychlorinated aromatic compounds are pollutants to the environment. The most well-known examples are DDT, polychlorinated phenols, dioxins, dibenzofurans and polychlorinated biphenyls (PCB). These types of compounds can be formed during exposure of soutii chlorine in any form can produce dioxin. Even though dioxins and PCBs are no longer manufactured, there are chemical processes that generate these compounds of polychlorinated phenolic precursors. There is a need to prevent the unwanted formation of polychlorinated aromatic compounds and transformation into harmless of such compounds in the case of their presence in the environment.

In the pulp and paper industry chlorinated organic substances (monochloropropane and polychlorinated), called together absorbed or adsorbed organic halogen or Oh, are formed in the bleaching of wood fiber oxidants chlorine-based. One of these compounds is 2,4,6-trichlorophenol (Turkmenistan Helsinki Foundation), which is formed, for example, during the bleaching process with the use of chlorine as a bleaching agent. The Turkmenistan Helsinki Foundation goes in the end in the flow of waste water leaving the plant.

In spite of the danger for the environment oxidising chlorine-based most commonly used for bleaching of wood fiber in the United. States. Commercial equipment for bleaching wood fiber and paper actually uses a combination of several sposabella using NaOH, treatment with chlorine dioxide, another extraction using NaOH and then another treatment with chlorine dioxide. Modification of this sequence adds phase oxidation by hypochlorite between the first NaOH extraction and first treatment with chlorine dioxide. In another sequence, a second extraction using NaOH and the second processing chlorine dioxide is excluded.

November 14, 1997, the office for environmental protection of the United States signed the Rules (Cluster Rule) requiring that the pulp and paper industry has reduced the production of chlorinated organic materials. To meet the requirements of reducing this waste water industry primarily extends the application of bleaching, called "not containing elemental chlorine (ECF) bleaching, and this term is used mainly for bleaching with chlorine dioxide. The important point is that bleaching with chlorine dioxide produces less toxic waste water than it does whitening elemental chlorine (Cl2). However, a number AOH is formed, and an additional drawback is that the waste water whitening equipment cannot be burned in Regener the chlorine-free" (TCF-bleaching). The main oxidants TCF-bleaching are oxygen and hydrogen peroxide, although ozone is also used. Hydrogen peroxide oxidizes and brightens the lignin and produces high outputs of wood pulp. It is easier to use than oxygen, and it does not require expensive equipment, which is one of the biggest drawbacks of bleaching with oxygen. It is generally considered that when using H2About2dissociates with the formation of perhydroxyl ion UN, which discolor the lignin and does not damage the pulp. However, when the destruction of the H2O2produces free radicals, which fragment the lignin, as this is desirable, but also destroy the cellulose. The main aggressive radical is the hydroxyl radical BUT that is extremely selective. Since N-O-bond of water is so strong (approximately 119 kcal·mol-1) radical BUT will extract the atoms N quickly from a wide variety of organic compounds and in fact most sources of atom N. For this reason, the wood fibers are usually treated pestiviruses agent before processing peroxide. In order pestiviruses agent is the removal of metal ions, which razrulit adding additional pestiviruses agent, again to protect peroxidase from exposure of trace amount of metal that can destroy peroksosoedinenii unwanted way and reduce its selectivity. Although hydrogen peroxide is a strong oxidant, which can burn the skin and mucous membranes, it is not seriously dangerous at low concentrations (<8%). Most importantly, its use does not introduce into the environment cell toxicity. Peroxide is an excellent bleaching agent. The main disadvantage of the application of H2O2as the oxidizing agent for bleaching wood fiber and paper is that it is not as selective in the delignification of wood fibres as chlorine dioxide. The process is relatively slow, so that the wood fibre and peroxide should be subjected to heating. Historically peroxide was relatively expensive oxidant. However, rates peroxide fell and plants have freedom of choice in respect of oxidants new generation. Although H2About2would be clearly preferable due to its favorable environmental properties, factors of selectivity and technological costs associated with its use, sposable as increasing the brightness agent for mechanical wood fibers, for example, in newsprint, which do not require long-term color stability, and lignin primarily rather discolored, than essentially removed, or as an aid for chlorination and/or chlorine dioxide bleaching and/or whitening oxygen or oxidation of the resulting wastewater stream.

In the publications WO 98/03625 and WO 98/03626 described bleaching composition consisting of a macrocyclic tetradentate activator bleaching and oxidizing agent. In a recent publication argues that this whitening composition applicable to the bleaching of wood fiber and lignin. In U.S. patent No. 5032286 described method of heating the wastewater pulp factories under pressure to change the chemical composition followed by treatment with acidic solution to remove chromophores from this solution.

The environmental impact of wastewater produced by processing wood fiber and paper, have been the focus of considerable research over the past 30 years. Traditional areas of concern were oxygen demand, suspended solids and acute toxicity. Improvements in control strategies on the plants, the technology is toadie time the focus has shifted to the potential subacute toxicity (e.g., reproductive effects), residual nutrients/eutrophication and stubborn components (recalcitrant), i.e., materials that cannot be processed, in particular pigments and organic chlorine. Reduce load mass pigments and absorbable organic chlorine (chlorinated compounds) after biological treatment can be an average of 10 and 40%, respectively. In some cases, there may occur a significant increase in levels of the coloring matter. Approximately 50% of the demand soluble chemical oxygen bleached wastewater Kraft pulp mill (VCME) remains also after secondary treatment and, apparently, consists of not workable (recalcitrant) high-molecular material (MMOs). Components of higher molecular weight (MW > 1000 daltons) in VCME consist primarily of vysokomehanizirovannyh chlorinated degradation products of lignin with some amount of residual polysaccharide components. In VCME this material may be 40-90% of the total organic material, approximately 80% of the content Oh and 60-100% of contaminants coloring substances from this plant. Little information is available about hiniker, mechanical pulping).

Studies in Scandinavia and North America have demonstrated that this is not workable (recalcitrant), chromophore, and halogenated carbon components are very persistent in the systems raw water and can be detected in tens of kilometers from the source of the drain. Dyed material has a clear effect on the aesthetics of the receiving waste water, and also reduces the depth of light penetration in the water column and, therefore, the available habitat for macrophytes and sources of planktonic and benthic food. Previously believed that MMO is nasionalisme, non-toxic and inert due to its high molecular size and water solubility. More recent studies now show that the bioavailability of part of this material may occur in exposed him organisms, and an assumption was made that the MMO is the primary toxicant, inhibiting the ability of fertilization in some marine species (e.g., echinoderms). MMOs can also absorb low molecular weight lipophilic toxicants, such as chlorphenamine connection. This Association may significantly affect the scattering of the first concerns of the pulp and paper industry is under significant pressure to effectively remove components of wastewater. There are a large number of advanced technologies in various stages of development that have potential application to environmental protection. They include ultrafiltration; flocculation; Electrotechnology, such as ozonolysis, photolysis and wet oxidation; annealing and plasmas. Significant potential exists in respect of the application of a number of different technologies to deliver the desired processing, such as the application of improved processing in combination with biological and/or membrane separation technology.

Advanced oxidation technologies, such as ozone or peroxide, showed specific perspective as a highly effective method of removing organic chlorine or coloring matter from the wastewater of pulp and paper factories. However, high levels of peroxide required in created to date treatments, apparently, make this technology the same prohibitively expensive, as well as other ways.

Some chelates of metals of the transition series were subjected to a search for non-related purposes. For example, it is known that complexes of metals of the transition series with a high degree of Oka the matrix, and in recent years there has been widespread interest in understanding the mechanism of action and reactivity of some microsomal catalysts. Sample program described in Collins T. J., "Designing Ligands for Oxidizing Complexes", Accounts of Chemical Research, 279, vol. 27, No. 9 (1994). This article is focused on the design approach for obtaining ligands, which are resistant to oxidative degradation in coordination with the centers containing a metal with a high degree of oxidation. Several diamino-N-diperoxide and diamido-N-alkoxide-acyclic chelating and macrocyclic tetraamido-N-chelate compounds described in this article Collins (Accounts of Chemical Research).

Synthetic path based on the azide to the macrocyclic tetraamido-metal-ligand complexes described Uffelman, E. S., Ph.D. Thesis, California Institute of Technology (1992). In addition, the synthesis of aryl having bridge tetraamido-ligand through the path based on the azide may occur with the use of aromatic diamine as the starting material.

However, in this area is not yet acknowledged that some of the macrocyclic tetraamido-metal-ligand complexes will provide new and extremely effective bleach activators is Udut extremely useful in the fields of bleaching wood fiber and paper.

The INVENTION

The invention includes a method of bleaching of the chromophores in the wastewater of pulp and paper production, involving contacting wastewater with (a) resistant to oxidation activator having the structure

where Y1, Y3and Y4each indicate a bridging group having zero, one, two or three carbon containing nodes for substitution, a Y2is a bridging group having at least one carbon containing node for substitution, each specified node contains the unit of C(R) C(R1)(R2) or C(R)2and each substituent R is the same or different from the rest of the substituents R and (i) selected from the group consisting of alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, quinil, alkylaryl, halogen, alkoxy or phenoxy, CH2CF3, CF3and combinations thereof, or (ii) form a substituted or unsubstituted benzene ring of which two carbon atoms in the ring form nodes in the unit of Y, or (iii) together with dual substituent R, related to the same carbon atom, form cycloalkyl or cycloalkenyl ring, which may include ATO

M denotes a metal of the transition series with oxidation States of I, II, III, IV, V, VI, VII or VIII or selected from groups 3, 4, 5, 6, 7, 8, 9, 10 and 11 of the Periodic system of elements;

Q denotes any counterion, which balances the charge of the compound on a stoichiometric basis, and

(b) the amount of the source of the oxidizing agent effective to oxidize components of wastewater. The oxidation can be conducted with a view whitening substrate, such as fabric or wood fiber, or paper and other cellulose materials, lignin oxidation, bleaching lignin, delignification of wood fibers, discoloration of chromophores, such as lignin chromophores or originating from lignin chromophores, or for oxidation of adsorbed or absorbed organic Halogens and carbon components in the wastewater of industrial operations, such as processing of wood fiber and paper. By-products of the production process of pulp and paper also include absorbable variety of organic halides, such as aromatic compounds. Aromatic compounds include chlorinated phenols, dioxins, dibenzofurans, biphenyls, and combinations thereof.

Can be added passivator, with the Osho known to specialists with expertise in the field of bleaching wood fiber and paper.

Preferred activators oxidants are macrocyclic tetraamido-metal-ligand complexes. Of them, especially preferred are complexes with substituted aromatic Deputy condensed directly in the cyclic structure of the ligand.

For example, the preferred compound has the structure of a

where X and Z can be N, electron-donating or electron-withdrawing groups and R' and R” can be any combination of the substituents H, alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, quinil, alkylaryl, halogen, alkoxy or phenoxy, or be combined with education cycloalkyl or cycloalkenyl ring which may contain at least one atom that is not carbon; M denotes a metal of the transition series with oxidation States of I, II, III, IV, V, VI, VII or VIII or selected from groups 3, 4, 5, 6, 7, 8, 9, 10 and 11 of the Periodic system of elements; Q denotes any counterion, which balances the charge of the compound on a stoichiometric basis.

The rapid development of the pulp and paper industry and increased confidence to chemical bleaching processes to ensure bright, sturdy paper products who need a safe alternative oxidants chlorine-based bleaching. Any such whitening technology will be even more desirable if it performs discoloration of colored wastewater from any process in the plant. This technology will be even more desirable if the oxidizing system will attack and destroy MMOs, Oh, WCMA, and wastewater from any other type of plant.

The compounds used in the method of this invention significantly improves the performance of peroxide for bleaching wood fiber applications with significant reductions needs in chemicals. This connection and this oxidizing composition can be used for the treatment of dye-containing organic chlorine and not workable (recalcitrant) carbon materials in wood fiber (wood pulp).

There is a need for a method of bleaching wood fiber, which significantly reduces the yield of toxic substances in the environment or in the preparation of wood fibers, or in the processing of sewage, or both processes. In addition, there is a great need for non-toxic to the environment the way that is easy to use and which will produce bright, durable Boo is their task. It was shown that the method of the present invention rapidly increases the rate of bleaching of lignin by adding hydrogen peroxide. In addition, it was shown that the compound of this invention is very stable in terms of catalytic oxidation, including the bleaching of wood fibers or the oxidation of wastewaters.

This invention provides a method of oxidative degradation of polychlorinated phenols and discoloration of the chromophores in the wastewater of pulp and paper industry. This method usually involves the stage of contacting wastewater with a source of oxidant, preferably peroxidase and more preferably hydrogen peroxide, and/or the products of its dissociation, and catalytic or substochiometric quantities of activator described above composition. In addition, this method involves adding passivator to protect peroxidase from exposure of trace amounts of metal ions that can undesirable way to destroy it.

The method can be carried out at different temperatures, but preferably in the range from ambient temperature to approximately 130With Ipolzovanie also ranges from ambient temperature to approximately 40C. However, the temperature, apparently, is not decisive. Suitable for a wide range of temperatures. Specialists in this field will be clear that the pressure in the system should increase at higher temperatures.

The preferred pH range is the range of 7-12, and more preferred is a range between 9 and 11.

Although in other applications it has been shown that the activator used in the method of the present invention, is an excellent activator for oxidative reactions in solution, in General and in particular, as an activator for the activation of oxidants transfer oxygen atom, such as hydrogen peroxide, tert-butylhydroperoxide, cumylhydroperoxide, hypochlorite and percolate, the preferred application of the method of the present invention is used as activator peroxidase and most preferred as activators, hydrogen peroxide, oxygen or without oxygen in the bleaching of wood fibers and paper. The method of this invention increases the oxidizing capacity of hydrogen peroxide, thereby increasing the commercial applicability of this environmentally friendly oxidant.

Thousands upon thousands of metacestodes now should no longer be formed. The method of the present invention can substantially reduce, if not replaced, the use of bleaching oxidants chlorine-based and toxic by-products generated by their use. The method of this invention can be used for the treatment of Kraft pulp in the early stages of bleaching followed by the application of chlorine dioxide for additional whitening and lightening and/or using acatalasemia peroxide for additional whitening and lightening. It is reasonable to expect that the method of the present invention can also be used to enhance the oxygen treatment of the pulp by adding the activator and peroxide to the cycles of bleaching with oxygen. In addition, there is reason to expect that the method of this invention can be used for bleaching of pulp at the end of or shortly before the end of the bleaching sequence with multiple treatments.

BRIEF DESCRIPTION of DRAWINGS

Fig.1 is a graph showing long-activating the stability of the preferred compounds of this invention by adding hydrogen peroxide to the sample lignin in comparison with the control using only hydrogen peroxide.

F is the Ust obtain macrocyclic tetraamido-metal-ligand complexes of this invention via azide way.

Fig.4 depicts a synthetic route for obtaining the macrocyclic tetraamido-metal-ligand complexes of this invention via azide path using aromatic diamine as the starting material.

Fig.5 is a graph comparing long-term stability of the catalysts of the preferred variants of the present invention in comparison with the control.

Fig.6 shows the products identified from the oxidation of the Turkmenistan Helsinki Foundation with the help of FePcS and H2O2at pH 7.

Fig.7 is a graph showing the changes that occur with the spectrum of UV/visible light Turkmenistan Helsinki Foundation after adding H2O2. Bold line is the spectrum of unreacted Turkmenistan Helsinki Foundation, and the dotted line is the spectrum of H2O2.

Fig.8 is a graph showing changes in absorbance at three wavelengths shown in Fig.7.

Fig.9 is a graph showing multiple oxidation of the Turkmenistan Helsinki Foundation using [Fe(H2O)DCB*]-/H2O2in the conditions shown in Fig.9. The addition of H2O2shown * and add the Turkmenistan Helsinki Foundation is shown #.

Fig.10 is a series of three graphs showing the oxidation of the Turkmenistan Helsinki Foundation at pH 6.8, pH 7.4 and pH 10 using system [Fe(. The DETAILED DESCRIPTION of the PREFERRED OPTIONS

This invention relates to compositions containing (a) resistant to oxidation activator having the structure

where Y1, Y3and Y4each represent a bridging group having zero, one, two or three carbon containing nodes for substitution, and Y2is a bridging group having at least one carbon containing node for substitution, each specified node contains the unit of C(R) C(R1)(R2) or(R3and each substituent R is the same or different from the rest of the substituents R and is selected from the group consisting of alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, quinil, alkylaryl, halogen, alkoxy or phenoxy, CH2CF3, CF3and combinations thereof, or form a substituted or unsubstituted benzene ring of which two carbon atoms in the ring form nodes in the unit Y or paired with a substituent R, related to the same carbon atom, form cycloalkyl or cycloalkenyl ring which may include an atom other than carbon, for example cyclopropyl, cyclobutyl, cyclopentene or tsiklogeksilnogo K3, 4, 5, 6, 7, 8, 9, 10 and 11 of the Periodic system of elements; Q denotes any counterion, which balances the charge of the compound on a stoichiometric basis, and

(b) the number of the source of the oxidizing agent effective to oxidize the target. The oxidation can be conducted with a view whitening substrate, such as fabric or wood fiber, or paper and other cellulose materials, lignin oxidation, bleaching lignin, delignification of wood fibers, discoloration of chromophores, such as lignin chromophores or originating from lignin chromophores, or for oxidation of adsorbed organic Halogens (Oh) and carbon components in the wastewater of industrial operations, such as processing of wood fiber and paper.

It is shown that the preferred macrocyclic tetraamido-metal-ligand complexes are surprisingly effective in a variety of group performance for activators oxidants.

These ligands are produced in accordance with the procedures shown in Fig.3 or 4, and described in U.S. patent No. 6051704, entitled SYNTHESIS OF MACROCYCLIC TETRAAMIDO-N LIGANDS, incorporated herein by reference, and include, in addition to the compounds described herein, whether the CTL.

1. Macrocyclic tetraamido-metal-ligand complexes

The compounds of this invention have the structure

where Y1, Y3and Y4each represent a bridging group having zero, one, two or three carbon containing nodes for substitution, and Y2is a bridging group having at least one carbon containing node for substitution, each specified node contains the unit of C(R) C(R1)(R2) or (R3and each substituent R is the same or different from the rest of the substituents R and is selected from the group consisting of alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, quinil, alkylaryl, halogen, alkoxy or phenoxy, CH2CF3, CF3and combinations thereof, or form a substituted or unsubstituted benzene ring of which two carbon atoms in the ring form nodes in the unit Y, or paired with a substituent R, related to the same carbon atom, form cycloalkyl or cycloalkenyl ring which may include an atom other than carbon, for example cyclopropyl, cyclobutyl, cyclopentene or tsiklogeksilnogo ring; M represents a metal of the transition series with the s; Q denotes any counterion, which balances the charge of the compound on a stoichiometric basis; L is optional and can be any labile ligand.

Especially preferred of these compounds of this invention represented by the structure of the macrocyclic tetraamido-metal-ligand complex

where X and Z can be N, electron-donating or electron-withdrawing groups and R' and R" can be any combination of the substituents H, alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, quinil, alkylaryl, halogen, alkoxy or phenoxy, or be combined with education cycloalkyl or cycloalkenyl ring which may contain at least one atom that is not carbon; M denotes a metal of the transition series with oxidation States of I, II, III, IV, V, VI, VII or VIII or selected from groups 3, 4, 5, 6, 7, 8, 9, 10 and 11 of the Periodic system of elements; Q denotes any counterion, which balances the charge of the compound on a stoichiometric basis; L is optional and can be any labile ligand.

Groups X and Z can be N or either electron-donating or electron-withdrawing groups. Electronicat the diversified groups are SO-3, S-3, OSO3R (where R is defined, without limitation, as H, alkyl, aryl, alkylaryl) and NR-2. Electron-donating groups include alkoxy (without limitation, methoxy, ethoxy, propoxy, butoxy), alkyl (without limitation, methyl, ethyl, propyl, n-butyl and tert-butyl) and hydrogen. These groups alter the electron density of the metal-ligand complex and affect its reactivity.

R' and R", apparently, affect long-term catalytic stability of the macrocyclic tetraamido-ligands of the present invention. Although each of these substituents may be independently selected from the substituents H, alkyl, alkenyl, aryl, quinil, halogen, alkoxy or phenoxy, preferred, apparently, is alkyl short circuit. Particularly preferably, when R' and R" are the same and selected from ethyl and methyl, or when R' and R" together with the formation of cycloalkenes or cycloalkenyl rings, in particular cyclopropenes, cyclobutenes, cyclopentyl or tsiklogeksilnogo rings. Cycloalkyl ring may include at least one atom other than carbon, such as, without limitation, N, O or S. Most preferred and most the C methyl, CF3, hydrogen, halogen and 4-membered ring formed together with the carbon atom to which they are both linked. These latter groups are or directionspanel, form strong bonds with carbon rings are steric (spatial) difficult and/or are conformationally difficult, so that intramolecular oxidative degradation is difficult.

The metal M is a metal of the transition series with oxidation States of I, II, III, IV, V, VI, VII or VIII or may be selected from Group 3 (Sc, Y, lanthanides and actinides), Group 4 (Ti, Zr, Hf), Group 5 (V, Nb, TA), Group 6 (Cr, Mo, W), Group 7 (Mn, TC, Re), Group 8 (Fe, Ru, Os), Group 9 (Co, Rh, Ir)Group 10 (Ni, Pd, Pt) and Group 11 (cu, Ad, AI). Preferably it is selected from the group consisting of Se, Ti, V, Cr, Mn, Fe, Co, Ni, cu, Zn (Group 12), Mo and W.

Q is any counterion which would balance the charge of the compound on a stoichiometric basis. Can be used as negative and positive counterions. Usually positively charged counterion is preferably, but without limitation, selected from the counterions, which are alkaline metals (for example, K, Li, Na), [NR*4]+and [PR*4]+where each R* is individually selected from H, alkyl, aryl, alkylaryl, the aryl ring, which may contain at least one atom other than carbon. Usually negatively charged counterion preferably, but without limitation, selected from [BF4]-1and [PF6]-1.

L is any labile ligand, which can join M These ligands include, preferably, but without limitation, N2O, CL-and CN-.

Due to the complex nature of these compounds, they do not have names in this description, but for convenience they are called by the substituents present in them. For example, the above structure can be named 5,6-(4,5-di-H-benzo)-3,8,11,13-tetraoxo-2,2,9,9-tetramethyl-12,12-diethyl-1,4,7,10-tetraazacyclotridecane (or tetramethyldisilane-X-benzene (TMDE-DXB, where X = Cl, H, Me, OMe)). Thus, for convenience, in the above structure, where there are two methyl groups on each carbonrelative to the amide donor of the ligand, and there are two ethyl groups as R' and R", the compound is called TMDE-DXB. In the case when R' and R" are methyl groups, the compound is called TMDM-DXB. When the groups X and Z both represent chlorine, the compound is called TMDE-DCB or TMDM-DCB. Use additional will corectional, which R' and R" are methyl. The preferred metal of the transition series of the ligand is iron, so that the connection to Fe(III) and the axial ligand N2About may be called the [Fe (H2O)DCB]-.

Conventional methods of bleaching with hydrogen peroxide is practiced at a pH in the range of 11-9 and at a temperature in the range of 30-80And most often when 50-70C. Cm. Charles J. E. et al., 1980, TAPPI Pulping Conference Proceedings, TAPPI Press (1980). When using one of the activators of the present invention, the temperature of this reaction can be reduced to the ambient temperature. Although these activators-catalysts can be used at higher ambient temperature the reaction, they work well also at 35 and 40C. In some applications may be preferred higher the reaction temperature, for example temperatures up to about 130With and preferably in the range from ambient temperature to 90C. it is Known that changes for every ten degrees the reaction rate varies approximately in 2 times. Thus, the reaction rate is much higher when more and oxidation of H2O2that are significantly better than possible hitherto speed can be obtained with temperatures much lower than has been possible up to now, which saves energy and increases the capacity of the plant when other characteristics of this plant make it possible. Thus, the preferred temperature ranges are between ambient temperature and 130With, preferably between ambient temperature and 90C and most preferably between ambient temperature and 60C. For some applications, the preferred range is between about ambient temperature and 90S. whitening System of the present invention will operate effectively even at temperatures below the ambient temperature. A wide range of temperatures over which the activator will function allows you to use the method of the present invention in existing facilities and in combination with other processes of bleaching pulp and paper without the need for special correction rate is e change of temperature reduction.

the pH of the oxidation reaction can also be lowered when using the activator of the present invention. Experiments on bleaching carried out at pH 7 with H2About2and oxidant activator of the present invention, was decolorized lignin at a speed, which is considered an improvement in comparison with normal speed whitening by N2About2but not at the best speed possible for this activator. Much more rapid and satisfactory speed was obtained with the use of pH 10. Thus, there is no need to change the generally accepted pH range 11-9 by adding an activator of the catalyst of this invention, but this may be necessary if you want to avoid decomposition of H2O2which, as you know, takes place at high pH. The decomposition can also be caused by the presence of trace metals in otbelivayushe solution with peroksosoedinenii. Passivator and other known stabilizers are used to reduce the probability of decomposition caused by the presence of trace metals. The experiments below show that passivator can also be used with catalyst-activator of the present invention.

In addition, the car is used in the pulp and paper industry, to show the amount of residual lignin after bleaching. The Kappa number, which should be as low as possible, represents the ratio of the difference between (1) the General equivalent of oxidation required for 100% removal of lignin, and (2) the difference between the actual achievable oxidation and common equivalent oxidation. It is obtained using a test with potassium permanganate in accordance with procedures well known in the pulp and paper industry.

Whitening composition of the present invention can be used for effective removal or substantial reduction of organic chlorine or coloration caused by the lignin chromophores, from the wastewater of pulp and paper production. The combination of oxidant and substance-activator could discolor the chromophores in the effluent of pulp and paper mill to remove the brown color. With the environment in mind, the oxidant in decolorizing wastewater composition is preferably peroksosoedinenii or ozone. Previous attempts to use peroxide processing catalyzed by ferrous iron ion, removal of absorbable organic halogen, were aprigo the use of large quantities of peroxide. It was shown that adding a connection-activator of the present invention to peroxyacetyl significantly reduces the level of peroxide required for oxidation reactions. Thus, the authors believe that the composition of the activator/oxidizer of this invention is quite suitable for handling coloring (coloring matter), organic chlorine and not amenable to processing of carbonaceous materials (recalcitrant) in the effluent of pulp and paper mills. The authors believe that the use of low level effluent stream, or at the place of exit, or in place of re-use is the best. Treatment of combined sewage in areas of the ends of the pipeline has the advantage that a large part degradiruemosti organic material in the waste water is removed, only to not be disposed materials (recalcitrant) that should be targeted composition of the present invention. Treatment at an earlier stage above in the course of the stream from the end of the pipe has the advantage that it can be subjected to a higher concentration of compounds target the action of the compositions of this invention.

Here, we present the experiments that demonstriruuschie connection and pollution, formed during the bleaching process using chlorine as a bleaching agent in pulp and paper production. The inventors believe that the composition of the present invention is effective for oxidation of other polychlorinated aromatic compounds, such as DDT, other polychlorinated phenols, dioxins and polychlorinated biphenyls (PCB).

Because the macrocyclic tetraamido-metal-ligand complexes act as catalysts, their number added to bleaching compositions, is usually substochiometric. However, preferably without limitation to add about 0,0001 approximately 999999 ppm (M. D.), more preferably 0.001 to 100000 M. D., to the compositions of this invention.

In the experimental section below describes selected syntheses preferred macrocyclic tetraamido-metal-ligand complexes. In addition, tests were performed to demonstrate the ability of the bleaching of lignin and long-term catalytic activity of metal complexes of these macrocyclic ligands of the present invention.

2. Connection-oxidants

Connection-oxidants, such as atoms migrate the-peroxide bond. Examples of such compounds include hydrogen peroxide, adducts of hydrogen peroxide, compounds capable of forming hydrogen peroxide in aqueous solution, organic peroxides, persulfates, perphosphate and prsilikat. The adducts of hydrogen peroxide include peroksigidrat carbonate of an alkali metal (e.g. sodium, lithium, potassium) and urea peroxide, which can release hydrogen peroxide in the solution. Compounds capable of forming hydrogen peroxide in an aqueous solution include perborate (mono - and tetrahydrate) alkali metal (sodium, potassium, lithium). Perborate commercially available from sources such as Akzo N. V. and FMC Corporation. Alternative as a source of hydrogen peroxide can be used enzyme alcoholecstasy and suitable alcohol substrate. Organic peroxides include, without limitation, the hydroperoxides benzoyl and cumene. Persulfates include peroxymonosulfate potassium (sold as Oxone®, E. I. duPont de Nemours) and acid Caro.

An effective amount of peroxidase is sufficient to generate at least 0,001 M. D. active oxygen (A. O.). Although this is not a limitation, is preferred is the formation of from approximately 0.01 to approximately 50 m doctor of medicine A. O. Description and explanation of measurement A. O. you can see Sheldon N. Lewis, "Peracid and Peroxide Oxidations", In: Oxidation, 1969, pp. 213-258, which is incorporated herein by reference.

3. Excipients

Macrocyclic tetraamido-metal-ligand complexes of this invention, if desired, can be combined with the auxiliary substance or Foundation that contains the main components of a solution and a surfactant selected from the group consisting of anionic, cationogenic, amphoteric, zwitterionic surfactants and mixtures thereof. There could be other auxiliary materials. These compounds can also be presented in liquid basis, for the bleaching solid surface or another surface. These compounds can be used for bleaching of pulp processing and textiles. Each of these connections and support materials suitable for use here, further discussed below.

a) the Main components of the solution

The main components of the solution are usually alkaline key components of the solution, i.e. those which in aqueous solution will be to give a pH of 7-14, preferably 9-12. Examples of the inorganic basic substances), phosphates (including orthophosphate, tripolyphosphate and tetrapropoxide), aluminosilicate (both natural and synthetic zeolites and mixtures thereof. Carbonates are particularly desirable for use in this invention because of their high alkalinity and efficiency in the removal of hard ions that may be present in hard water, as well as their low cost. Carbonates can be used as the dominant principal component solution. Can also be used silicates (Na2O:SiO2module 4:1-1:1, most preferably about 3:1-1:1). Silicates, due to their solubility in water and ability to form a glassy matrix, can also be advantageously used as a binder.

Organic basic components are also suitable for use and selected from the group consisting of sulfosuccinates, polyacrylates, polymaleic alkali metals and ammonium, copolymers of acrylic acid and maleic acid or maleic anhydride, citrates and mixtures thereof.

b) Fillers/diluents

Fillers for whitening composition is used to ensure that one application is served exact number or precise on the content of inorganic fillers thinners, such as sugar. In the liquid run as diluents could be used solvents (such as, without limitation, alkanols, glycols, glycol ethers, hydrocarbons, ketones and carboxylic acids), a liquid surfactant and water.

(C) Surfactants

Surfactants are usually added to the bleaching solution to remove specific contaminants targets, for example, nonionic surfactants aimed at oil substrates, and anionic surfactants aimed at consisting of particles substrates. However, generally speaking, oxidative bleaching composition may contain a small amount of surfactant or may not contain surface-active substances.

Particularly effective surfactants, apparently, are anionic surfactants. Examples of such surfactants may include the ammonium salts, substituted ammonium (such as mono-, di - and triethanolamine), alkali metals and alkaline earth metals6-C20fatty acids and rosin acids, alkyl(linear or branched)beta, hydroxyethanesulfonic, sulfates of monoglycerides of fatty acids, sulfates alkylglycerols ethers, acylcarnitines and acyl-N-methyltaurine. Preferred are alkylarylsulfonate surfactants, such as alkylbenzenesulfonate.

Other applicable preferred surfactants include ethoxylated linear alcohols, such as sold by Shell Chemical Company under the trade name NEODOL. Other suitable nonionic surfactants may include other linear ethoxylated alcohols with an average length of 6 to 16 carbon atoms and on average from about 2 to 20 mol of ethylene oxide on 1 mole of alcohol; linear and branched, primary and secondary ethoxylated, propoxycarbonyl alcohols with an average length of approximately 6 to 16 carbon atoms and on average from 0 to 10 mol of ethylene oxide and about 1 to 10 mol of propylene oxide on 1 mole of alcohol; linear and branched, alkylphenoxy(polyatomic)alcohols, also known as ethoxylated ALKYLPHENOLS, with an average chain length of 8-16 carbon atoms and on average from 1.5 to 30 mol of ethylene oxide on 1 mol of the alcohol, and mixtures thereof.

Further suitable nonionic surface-active substances is olamide fatty acids and ethoxylated fatty acids, some block copolymers of propylene oxide and ethylene oxide, and block copolymers of propylene oxide and ethylene oxide with propoxycarbonyl Ethylenediamine. Also included such semipolar nonionic surfactants, as aminoxide, phosphine oxides, sulfoxidov and their ethoxylated derivatives.

Suitable cationogenic surfactants can include Quaternary ammonium compounds in which typically one of the groups linked to the nitrogen atom, is a12-C18-alkyl group, in the other three groups are alkyl groups with short circuits, which may carry substituents as phenyl groups.

Further, suitable amphoteric and zwitterionic surfactants, which contain anionic solubilizer in the water group, a cationic group and a hydrophobic organic group can include aminocarbonyl acids and their salts, aminocarbonyl acids and their salts, alkylbetaine, alkylaminocarbonyl, sulfobetaine, derivatives alkylimidazole, some Quaternary ammonium compounds, some compounds of Quaternary phosphonium and some compounds of tertiary sulfone.

Other examples of anionic, nenene the present invention, presented in Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, Volume 22, pages 347-387, and McCutcheon''s, Detergents and Emulsifiers, North American Edition, 1983, which is incorporated herein by reference.

(d) chelating agents

In some compositions described herein is particularly preferable to include helatoobrazovatel, most preferred in applications for bleaching linen aminophosphonate, and in applications for bleaching of cellulose polycarboxylate. These chelating agents contribute to maintaining stability in the oxidizer solution for optimal performance. Thus they act through the formation of chelates free ions of heavy metals. Helatoobrazovatel selected from a number of well-known agents that are effective in the formation of chelates free ions of heavy metals. Helatoobrazovatel must be resistant to hydrolysis and rapid oxidation by oxidants. Preferably it should have a dissociation constant acid (PKand) 1-9, indicating that he dissociates at low pH to enhance bonding with the metal cations. The most preferred helatoobrazouatelem for applications in bleaching linen is aminophosphonate, which is commercially available under Tova who is also suitable for use. Other chelating agents such as ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), are preferred for use in the bleaching of wood fiber. Other new preferred chelating agents are new propylethylenediamine, such as Hampshire 1,3 the pdta from W. R. Grace and Chel DTPA 100#F from Ciba-Geigy A. G. May be suitable mixture of these chelating agents. The effective amount of chelating agent are in the range of 1 to 1,000, more preferably 5-500, most preferably 10-100 M. D. chelating agent in the washing solution.

E. Other excipients

Standard excipients oxidative bleaching can be included in this invention. Those include enzymes, are particularly preferred support materials are products of oxidative bleaching. However, it may be preferable to activate the enzyme stabilizer.

Especially preferred class of enzymes are proteases. They are chosen from acidic, neutral and alkaline proteases. The terms "acidic", "neutral" and "alkaline" refers to the pH at which the enzyme activity is optimal. Examples of protease available from a wide variety of sources and are typically derived from different microorganisms (for example, Bacillus subtilis). Typical examples of alkaline proteases include MAXATASE and MAXACAL, from International BioSynthetics, ALCALASE, SAVINASE AND ESPERASE, all available from Novo Industri A/S. Cm. also Stanislowski et al., U.S. patent No. 4511490, incorporated herein by reference.

Other suitable enzymes are amylase, which are gidrolizuemye carbohydrates enzymes. It is preferable to include a mixture of amylases and proteases. Suitable amylases include RAPIDASE, from Societe Rapidase, MILEZYME from Miles Laboratory and MAXAMYL from International BioSynthetics.

Other suitable enzymes are lipases such as described in Silver, U.S. patent No. 3950277, and Thom et al., U.S. patent No. 4707291, both incorporated herein by reference.

Other representing interest here is the enzymes are peroxidase, such as horseradish peroxidase and peroxidase, as described in International patent publication WO 93/24628 included here as a reference. Preferred are mixtures of any of the previous hydrolases, in particular a mixture of protease and amylase.

In addition, optional excipients include dyes, such as monastral blue" (phtalocyanine organic pigment) and antrahinonovye dyes (such as described in Zielske, U.S. patent No. 4661293 and U.S. patent No. 4746461).

The pigments that ablauts the see also Chang et al., U.S. patent No. 4708816) and painted aluminosilicates.

Other desirable ancillary substances are fluorescent whitening agents. They include derivatives of stilbene, styrene, and naphthalene, which when illuminated with UV light emit or fluoresce light with a wavelength of visible light.

Additional organic bleach activators, including, but not limited to, esters (see Fong et al., U.S. patent No. 4778618, and Rowland et al., U.S. patent No. 5182045), ketones, imides (see Kaaret, U.S. patent No. 5478569) and NITRILES, all incorporated herein by reference.

These additives may be present in amounts in the range of 0-50%, more preferably 0-30%, and most preferably 0-10%. In certain cases, some of the individual excipients may overlap with other categories. However, this invention considers each of the excipients as providing various beneficial for performance properties in their different categories.

EXPERIMENTAL SECTION

Synthesis of oxidative strong tetraamido-ligands

Materials. All solvents and reagents were required for reagent purity (Aldrich, Aldrich Sure-Seal, spectrometry. Mass spectra using electrospray ionization received on the mass spectrometer FINNIGAN-MAT SSQ700 (San Jose, CA) equipped with an electrospray interface ANALYTICA OF BRANDFORD. Used voltage elektrorazpredelenie 2400-3400 C. the Samples were dissolved in acetonitrile or dichloromethane at concentrations of approximately 10 pmol/ml and was injected into the ESI interface before receiving data by direct infusion at a flow rate of 1 l/min and introduced before receiving data. MS-experiments with ionization by electron impact of positive ions (70 eV) were performed on a quadrupole mass spectrometer FINNIGAN-MAT 4615, United with INCOS data system. The temperature of the electron source was 150With the temperature distribution of the cell was 100C. the Samples were introduced through a gas chromatograph or by direct introduction probe. Mass spectra of positive ions by bombardment with accelerated atoms were obtained using the device with a magnetic sector FINNIGAN MAT 212 in combination with an INCOS data system. Accelerating voltage was 3 kV and the source temperature of the electrons was approximately 70C. Used gun accelerated atoms ION TECH saddle field with xenon at 8 Kev. As MatrixOne ions by electron impact (70 eV) were performed on consecutive quadrupole mass spectrometer FINNIGAN-MAT TSQ/700. Samples were injected using a probe for direct injection. The ion source was maintained at 150And distribution chamber maintained at 70C.-Induced exciton dissociation (CID) was obtained by introduction of argon into the Central octupoles only rf collisions as long as the pressure in the distribution chamber has not reached 0,9-2,510-6Torr. Nominal kinetic energy of ions to product ions CID was <35 eV (laboratory reference). High resolution data were obtained on a mass spectrometer with double focusing JEOL JMS AX-505H in the S-configuration using a resolution of 7500. Samples were injected using a gas chromatograph or probe for direct injection. While obtaining mass spectral data in the ion source was introduced performerin through the heated inlet. Accurate mass spectral correlation has been computed by interpolation from the masses performerin. GC/MS conditions: column 20 m0.25 mm DB-1701 (J & W Scientific); carrier gas, helium with a linear velocity of 40 cm/sec; injector 125C; column temperature 35C for 3 minutes, the cost is 50:1.

Spectroscopic methods.1H-NMR spectra (300 MHz) and13C-NMR spectra (75 MHz) were obtained using the device IBM AF300 using superconducting magnetic system OXFORD, obtaining data managed by the software BRUKER. Infrared spectra were obtained on a spectrophotometer MATTSON GALAXY Series 5000 FTIR, controlled by a MACINTOSH II. Spectra UV/visible light received by the spectrophotometer HEWLETT PACKARD 8452A controlled by a computer ZENITH Z-425/SX. Normal spectra X-band EPR (electron paramagnetic resonance) were recorded on a spectrophotometer BRUKER ER300, equipped with a helium flow cryostat (OXFORD ESR 900. Mössbauer spectra were obtained on devices with constant acceleration and isomer shift is given relative to iron metal standard at 298 K. In order to avoid orientation of polycrystalline samples of the applied magnetic field, these samples are suspended in a frozen nagole (purified paraffin oil).

The syntheses of macrocyclic tetraamido-N-donor ligands

The General scheme of reactions

Below is a diagram of a preferred sequence of reactions for the synthesis of macrocyclic tetraamido-metal-ligand complexes

C. After completion of the reaction selective double bind, 72-144 h, allocate MACRO LINKER (A-L-A). In the second stage, the diamine, preferably o-phenylenediamine, are added to a solution in pyridine this MACRO LINKER in the presence of a coupling agent, preferably l3or pivaloyloxy. Reactions circuit cycle (dual link) allowed to proceed at reflux distilled (under reflux) for 48-110 hours and then target macrocyclic tetraamide produce good output.

The following examples 1-25 presents various parts of these reaction stages. Examples 26-39 demonstrate execution features and advantages of the present invention for oxidative reactions, including discoloration (whitening) of the lignin and the discoloration of the coloring matter.

Example 1

Synthesis of intermediate product macrocentra (A-L-A)-methylalanine and diethyltoluenediamine (tetramethyldisiloxane intermediate product)

Two-neck flask (1 l) equipped with drip surge hopper (to equalize pressure) (250 ml) and the separation membrane is placed under the N2. In this flask, add-aminoadamantane acid (i.e.) and heated at 60-70With stirring, then in a separating funnel, add diethylmalonate (23,23 ml; is 0.135 mol), dissolved in dry pyridine (100 ml, dried over molecular sieves 4). The contents of the dropping funnel add (dropwise, 1 h) to the reaction and the acylation give leaking (60-70With, 30-36 h) under N2or using a drying tube, which supply the flask. Upon completion of the acylation reaction quenched by adding a2O (30 ml) and stirring (60-70C, 24 h). The volume of solvent is reduced on a rotary evaporator to obtain the oil, then add Hcl (concentrated, with approximately 25 ml) to a final pH of 2-3. The hot solution is put in the refrigerator (4C, 15 h) and the resulting reddish-brown product is collected by filtration through a Frit and washed thoroughly with acetonitrile (2100 ml). Air-dried white product (16,5-19,8 g, yield 50-60%) should be stored in a desiccator. This product is usually pure enough for the reaction ring closure, but sometimes may require recrystallization.

1H-NMR-spectrum (d5-p is 310 (amide NH); 1721 (carboxylic CO); 1623 (amide CO). Anal., the expect. for C15H21N2O6, %; 54,53; N. OF 7.93; N 8,48. Found, %: C 54,48; N 7,88; N Of 8.47.

Example 2

Large scale synthesis of intermediate product macrocentra (A-L-A)-methylalanine and diethyltoluenediamine (TMDE-substituted intermediate product)

Two-neck flask (2 l, RB + bulb Clausena), equipped with a drip surge hopper (to equalize pressure) (250 ml) and the membrane is placed under the N2. In this flask, add-aminoadamantane acid (i.e.methylalanine) (90,3 g, 0.9 mol), kanyoro anhydrous pyridine (1.4 l, Aldrich Sure seal) and this reaction mixture is heated to 45-55With and mix. Pyridine (100 ml, Aldrich Sure seal) and then diethylmalonate (104,4 ml, 0.61 mol) kanyoro into a separating funnel. The contents of the separating funnel add (dropwise, 3-4 h) to the reaction, and then separating funnel and remove the acylation give leaking (55-65With, 120-130 h) under N2. Upon completion of the acylation reaction quenched by the addition of N2O (100 ml) and stirring (60-70With, 24-36 h). The volume of solvent is reduced on the rotary evaporator is t in a refrigerator (4C, 15 h) and the resulting reddish-brown product is collected by filtration through a Frit and washed thoroughly with acetonitrile (700 ml, 150 ml) with stirring in an Erlenmeyer flask. Air-dried white product (87,9 g, yield 60%) crushed with the pestle in a mortar and stored in a desiccator. This intermediate amide reaction product of a large scale, more likely, require recrystallization before use it in the reaction ring closure.

Example 3

Recrystallization TMDE-substituted intermediate product

Untreated TMDE intermediate product from example 2 (of 50.4 g, 0,153 mol) is dissolved in N2About (500 ml deionized water) by adding PA2CO3(16.2 g, 0,153 mol) in three aliquot slowly and carefully to avoid excessive foaming, with good stirring and slight heating. This solution is brought to a boil, filtered and acidified with Hcl (conc., 30 ml, 0.36 mol). The solution is allowed to cool (overnight, 4C) and the white precipitate is filtered and washed with acetonitrile (250 ml). The air-dried product (38,8 of 45.4 g, recrystallized, the output 77-90%) should be stored in a desiccator.

Example 4

TMDM-substituted intermediate product (A-L-A)

Synthesis TMDM-zalegowski exceptions: diethylmalonate replace dimethylmethyleneammonium (17,8 ml, is 0.135 mol) and the reaction temperature should be reduced to 55-65With because of the lower boiling point of this Alliluyeva agent. Output TMDM-intermediate product is equal to 45-60%.

1H-NMR-spectrum (d5-pyridine)[M. D.]: 9,2-9,8 (CL, 2H, carboxyl HE), 8,23 (s, 2H, amide), to 1.87 (s, N, CH3), 1,74 (s, 6N, CH3). IR (nujol/NaCl)[cm-1]: 3317,0 (amide NH); 1717,9 (carboxylic CO); 1625,7 (amide CO). Anal. (dried at 100(C) the expect. for C13H22N2O6, %: 51,63, N 7,34, N 9,27. Found, %: C To 51.64, N 7,35, N Was 9.33.

Example 5

Recrystallization TMDM-substituted intermediate product

Untreated TMDM-intermediate product was recrystallized in the same way that TMDE-substituted intermediate product. Due to a slightly higher solubility in water for TMDM-substituted intermediate product you should use a slightly lower number of H2O.

Example 6

Di CyHex Di Ethyl (DiCyHexDE)-substituted intermediate product

A round bottom flask (500 ml) download 1-amino-1-cyclohexanecarboxylic acid (15 g, 0.1 mol), then connect a surge addition funnel (40 ml), a closed separation memco and 20 ml addition funnel. Begin heating system and stabilize the temperature at 60C. Upon reaching 60With one third of the entire diethylmalonate that should be used in this reaction (i.e., 6 ml, 0,033 mol), is added through a syringe into an addition funnel. A mixture of pyridine/diethylmalonate added dropwise to the reaction and the acylation allowed to proceed for 12 hours. A second aliquot (6 ml, 0,033 mol) and the third aliquot (6 ml, 0,033 mol) are added at intervals of 12 hours. After adding the total number Alliluyeva agent and reaction (total reaction time 48-56 h) to the reaction is added dropwise 20 ml of water. The reaction is heated for an additional 24 hours for the disclosure of the ring intermediate products of mono - and bis-oxazoline and get dimidiochromis acid. Remove pyridine on a rotary evaporator gives a pale yellowish-reddish precipitate (sludge), which is acidified to pH 2 Hcl (concentrated). The crude product is collected by filtration, washed with acetonitrile and air-dried to obtain white DiCyHexDE-substituted intermediate product (16 g, 74%).

1H-NMR-spectrum (d5-pyridine)[M. D.]: 8,30 (s, 2H, amide NH), 2,60 (m, 4H, cyhex), 2,25 (K, 4 isolated wide bandwidth (d5-pyridine)[M. D.]: 178,0 (FROM carboxyl), 174,3 (CO amide), 60,5 (cyhex Quat), 59,4 (malonyl Quat), 33,0 (CH2cyhex a) 30,3 (CH2ethyl), 26,0 (CH2cyhex g) 22,3 (CH2cyhex b), 9,9 (CH3ethyl). IR (nujol/NaCl)[cm-1]: 3307 (amide NH); 3150 (sh shoulder), FB, amide NH/carboxylic OH), 3057 (C, str (strong), N-linked amide NH/carboxylic OH), 1717 (s, str, carboxyl); 1621 (s, str, amide CO). Anal. the expect. for C21H34N2O6, %: C, 61,44; N 8,35; N 6,82. Found, %: C 61,41, N. Scored 8.38; N 6,90%.

Example 7

Di CyHex Diethyl monoaxial

The inability to repay the reaction of Di CyHex Diethyl-intermediate ( heating and water, see above) with stoichiometry 1.35 diethylmalonate : 2 Sunah-amino acid leads to a mixture of Di CyHex Diethyl-substituted intermediate product monoaxially. Di CyHex Diethyl-monoaxially product is moderately soluble in boiling cyclohexane, whereas cyclohexylamine intermediate product is insoluble, allowing easy separation of the mixture of products. Approximately 10 g of a mixture of amide intermediate product and monoaxially containing a small amount of residual CH2Cl2, boiled and when is birali hot gravity filtration, while monoaxially product crystallized gradually cooling and evaporation of a solution of cyclohexane. The output of the amide derivative is equal to approximately 6 g, yield monoaxially equal to approximately 4, the Characteristic monoaxially:1H-NMR-spectrum (d5-pyridine)[M. D.]: 9,7 (s, 1H, amide NH), 2,7-1,6 (undivided group yHes), of 1.05 (t, 6N, CH3ethyl). IR (nujol/NaCl)[cm-1]: 3309 (sh, w, amide NH), 3229 (s, str, H associated amide NH/carboxylic OH), 3166 (s, str, N-linked amide NH/carboxylic OH), 3083 (s, str, H associated amide NH/carboxylic OH), 1834 (s, str, C=O oxaz), 1809 (C, m, H associated With=O oxaz), 1743 (s, str, carboxyl), 1663 (s, str, C=N oxaz), 1639 (C, width, str, amide CO). Anal. the expect. for C21H32N2O5(C6H12), %: 0,25; 65,35; H 8,53; N 6,77. Found, %: C 65,07; H 8,67; N 6.68 Percent. The presence of solvated cyclohexane was confirmed by13C-NMR.

Reaction macrocyclization

Here are examples of several synthetic routes to obtain macrocyclic tetraamido-metal-ligand complexes.

Linking through trichloride phosphorus

Linking through trichloride phosphorus amiodaronesee tetraamide. Apply two different ways l3binding, the differences between them relate to the order of addition and the choice of reagents used. These methods are applicable to a large variety of different macrocycles with different electronic substituents present at diamino the bridge, or steric substituents present in the amide intermediate product, primarily due to the parallel connection microlensing type amide intermediates in these syntheses.

Example 8

A. Synthesis of macrocycles via l3binding

Dinagalu flask (250 ml) download amide intermediate product of examples 2-7 (10 mmol), rod-mixer and then calcined in the kiln (80-100C, 30-45 minutes). Hot flask under N2add erillinen (10 mmol) and injected through the cannula anhydrous pyridine (50 ml, Aldrich Sure seal). The flask is heated (50-60C) and injected through a syringe l3(d=1,574 g/ml, 1,72 ml, 20 mmol) as fast as possible without excessive reflux distilled. The reaction is exothermic, so be careful. The temperature was then increased to the temperature of reflux distilled or almost complete acylation of the contents of the flask acidified with Hcl (1 EQ., approximately 60 ml) to a final pH of 2. The mixture is transferred into an Erlenmeyer flask (for rinsing the flask using water) and stirred with CH2Cl2(300 ml, 2-3 h), then extracted with additional CH2Cl2(2150 ml). The combined organic layers are washed with dilute Hcl (0.1 M, 2100 ml), then diluted with water PA2CO3(25 g/100 ml). Organic solvents are removed on a rotary evaporator to obtain the crude product (30%). The weight of the crude product is generally equivalent to the initial weight of the diamine.

C. Synthesis of macrocycles via l3binding

Dinagalu flask (250 ml) download gSO4(5 g), a core-stirrer, araldimines (10 mmol) and pyridine (50 ml, dried over molecular sieves 4), then placed under the N2. l3(d=1,754 g/ml, 1,72 ml, 20 mmol) is added via syringe and the mixture is brought to reflux distilled for 30 minutes, forming an orange-yellow precipitate. The mixture is slightly cooled, add amide intermediate product (10 mmol), then the contents of the flask are heated under reflux with reflux distilled under N2(115150 ml). The combined organic layers are washed with dilute Hcl (0.1 M, 2100 ml), then diluted with water PA2CO3(25 g/100 ml). Organic solvents are removed on a rotary evaporator to obtain the crude product (30%). The weight of the crude product is generally equivalent to the initial weight of the diamine.

Note. For reactions macrocyclization large scale periods of time for ring closure increased to 4-5 days at reflux distilled and most of the pyridine present in the end of the reaction, is removed on a rotary evaporator before acidification.

Example 9

TMDE-DCB from TMDE-intermediate + DCB-diamine

1,2-Diamino-4,5-dichlorobenzene (1.77 g, 10 mmol) was used as ariginine with TMDE-amide intermediate (3.3 g, 10 mmol) in the reaction of macrocyclization or l3-how. The crude macrocyclic product (2.7 g) was recrystallized from the minimum amount of hot 95% EtOH by evaporation to obtain pure TMDE-DCB (1.5 g, 32%).

1H-NMR (CD2Cl2)[M. D.]: the 7.65 (s, 1H, AGN), 7,35 (s, 2H, l)[cm-1]: 3454 (traces ROH), 3346 (Shir, amide NH), 1706 and 1688 and 1645 (amide CO). Anal. the expect. for C21H28Cl2N4O4, %: 53,51; N. OF 5.99; N 11,89. Found, %: C 53,58; N 6,09; N 11,89.

Example 10

TMDE-B of TMDE-intermediate + -diamine

1,2-diaminobenzene (i.e., o-phenylenediamine) (1.08 g, 10 mmol) was used as ariginine with TMDE-amide intermediate (3.3 g, 10 mmol) in the reaction of macrocyclization and l3-how. The crude macrocyclic product (1.5 g) was recrystallized from the minimum amount of hot 95% EtOH by evaporation to obtain pure TMDE-B (25% per diamine).

1H-NMR (CDCl3)[M. D.]: at 7.55 (m, 2H, AGN), of 7.48 (s, W, 2N, kilmeny NH), 7,17 (m, 2H, AGN), 6,46 (s, W, 2N, alkylamines NH), 2,07 (m, Shire, 4H, CH2ethyl), 1,60 (s, N, R3), to 0.89 (t, 6N, CH3ethyl). IR (nujol/NaCl)[cm-1]: 3395, 3363 (amide NH), 1702, 1680, 1652, 1635 (amide CO). Anal. the expect. for C21H10N4O4·H2O %: 59,98; N TO 7.67; N 13,32. Found, %: C 60,18; N 7,20; N Of 13.18.

Example 11

TMDE-DMB from TMDE-intermediate + DMB-diamine

1,2-Diamino-4,5-xylene (about 1.36 g, 10 mmol) was used as ariginine with TMDE intermediate product (3.3 grams,kristalizovati minimum number of hot 95% EtOH by evaporation to obtain pure TMDE-DMB (25% per diamine).

1H-NMR (DMSO-d6)[M. D.]: 8,00 (s, 2H, amide NH), to 7.67 (s, 2H, amide NH), 7,28 (s, 2H, AGN), 2,17 (s, 6N, CH3aryl), 1,99 (K, 4H, CH2ethyl), a 1.46 (s, N, R3in ), 0.75 (t, 6N, CH3ethyl). IR (nujol/NaCl)[cm-1]: 3446 (s, m, traces ROH), 3362 (s, str, amide NH), 3348 (sh, m, amide NH), 3332 (s, str, H, amide NH), 1696 (CO amide), 1679 (CO amide), 1651 (CO amide), 1641 (CO amide), 1584 (s, m/w (medium-weak), aryl ring/amide). Anal. the expect. for C23H34N4O4, %: 64,16; N. OF 7.96; N 13,01. Found, %: C 64,09, 64,28; N 8,04, A 7.92; N 12,86, 13,04.

Example 12

TMDE-DMOB of TMDE-intermediate + DMOB-diamine

1,2-Diamino-4,5-dimethoxybenzoyl·2 HBr (5.0 g, 15 mmol), obtained as described above was used as ariginine directly with TMDE intermediate product (5.0 g, 15 mmol) in the reaction of macrocyclization or 1.5 large-scale l3-how. The crude macrocyclic product (3.57 g) was recrystallized from the minimum amount of hot 80-85% EtOH (1 g/40 ml) by evaporation to obtain pure TMDE-DMOB (30% per diamine).

1H-NMR (CD2Cl2)[M. D.]: 7,26 (s, 2H, amide NH), 7,01 (s, 2H, AGN), 6,41 (s, 2H, amide NH), 3,80 (s, 6N, co3aryl), 2,07 (SHK, 4H, CH3ethyl), 1 the data N2O), 3391, 3347 (amide NH), 1695, 1670, 1655 (amide CO). Anal. the expect. for C23H34N4O6·(H2O)0,33, %: 58,96; N 7,46; N 11,96. Found (ESU), %: 58,90; N 7,26; N 11,76. The presence of solvated H2About confirmed1H-NMR and IR.

Example 13

TMDE-naphthalene of TMDE-intermediate + naphthaleneamine

4,5-Diaminonaphthalene (1.68 g, 10 mmol) was used as ariginine with TMDE intermediate product (3.3 g, 10 mmol) in the reaction of macrocyclization or l3-how. Unoptimized yield was 15-20% (based on the diamine.1H-NMR (Dl3)[M. D.]: with 8.05 (s, 2H, ring AGN), of 7.75 (m, 2H, ring AGN b) of 7.55 (s, 2H, amide NH AG), 7,35 (m, 2H, ring AGN b) of 6.45 (s, 2H, NH alkylamide), 2,15 (BL, 4H, CH2ethyl), of 1.65 (s, N, R3), 0,90 (e, 6N, CH3ethyl).

Example 14

TMDM-DCB from TMDM-intermediate + DCB-diamine

1,2-Diamino-4,5-dichlorobenzene (1.77 g, 10 mmol) was used as the diamine intermediate product TMDM-amidon (to 3.02 g, 10 mmol) in the reaction of macrocyclization or l3-how. The crude macrocycle (1,33 g, 30%) was recrystallized from the minimum amount of hot n-propanol by evaporation, the output of the first recrystallization was 60%.

1H-NMR< THE, mately of malonate), observed small peaks of n-propanol. IR (nujol/NaCl)[cm-1]: 3503 (s, W, m-w, HE n-propanol), 3381 (sh, m, amide NH), 3338 s, str, amide NH), 1689 (s, str, amide CO), (s, str, amide CO). Anal. the expect. for C19H24N4O4Cl2·(C3H8O)of 0.2, %: 51,70; N TO 5.57; N 12,30. Found, %: C 51,69; N 5,63; N Of 12.33.

Example 15

TMDM-DMOB and TMDM-B from TMDM-intermediate + DMOB or In-diamine

TMDM-intermediate used for the synthesis of TMDM-B and TMDM-DMOB in accordance with the same manner and with like results obtained in example 14 for dichloropropanol. Data1H-NMR for TMDM-DMOB in CDCl3,[M. D.]: the 7.65 (s, 2H, amide NH), 7,21 (s, 2H, CH aryl), 6,72 (s, 2H, amide NH), 4,00 (s, 6N, CH3methoxy), to 1.76 (s, N, shoulders. mately), was 1.58 (s, 6N, metely of malonate). Data1H-NMR for TMDM-B-d5-pyridine,[M. D.]: 8,55 (s, 2H, amide NH), 8,40 (s, 2H, amide NH), 7,81 (m, 2H, ArH aa'bb'), 7,10 (m, 2H, ArH aa'bb'), or 1.77 (s, N, shoulders. mately), 1,73 (s, 6N, metely of malonate). Amide peaks tend to shift a few tenths of memorial plaques in the presence of contaminants, such as water, acids, etc.

Example 16

DiCyHexDE-DCB from DiCyHexDE-intermediate + DCB-diamine

1,2-Diamino the ol) in the reaction of macrocyclization or l3-how. Due to the increased spatial difficulties it is recommended that increased reaction time circuit ring (3-4 days versus the usual 48 hours). Su Hex Oxazalone formed as a by-product during the reaction are not removed the main acid treatment, so you need to RUB/rinse originally allocated CH2CL2-soluble product with pentane to remove these oxazalone. Evaporation pentanoic leaching makes it possible to reuse oxazolones. The crude insoluble in pentane, the product was recrystallized by dissolving in CH2CL2or l3with the addition of cyclohexane to the light, turbidity and subsequent evaporation in air (1-2 days) to give a white microcrystalline DiCyHexDE-DCB-product, which was collected by filtration (1,38 g, 25% per diamine). Recrystallization from hot toluene by evaporation also seems promising.

1H-NMR (CDCl3)[M. D.]: of 7.70 (s, 2H, AGN), was 7.45 (s, 2H, amide NH), of 6.45 (s, 2H, amide NH), 2,35 (BL, 4H, cyhex), 2,00 (BL, >>8H, cyhex/CH2ethyl), 1,70 (BL, >>8H, cyhex), 1,30 (BL, >> 4H, cyhex), of 0.90 (t, 6N, CH3ethyl). Anal. (dried at 1001H and13C-NMR.

Example 17

DiCyHexDE-B from DiCyHexDE-intermediate + -diamine

1,2-Diaminobenzene (ortho-phenylenediamine, 1.08 g, 10 mmol) was used as ariginine in obtaining similar to getting DiCyHexDE-DCB with getting DiCyHexDE-B (1.25 g, 26% (based on diamine).

1H-NMR (DC3CN)[M. D.]: a 7.62 (s, 2H, kilmeny NH), 7,51 (m, 2H, AGN), 7,18 (m, 2H, AGN), of 6.71 (s, 2H, alkylamines NH), 2,12 (m, 6N, Cyhex), 1,85 (K + m, CH2ethyl + cyhex), of 1.62 (m, cyhex), to 1.37 (m, cyhex), of 0.90 (t, 6N, CH3ethyl) to 0.85 (m, cyhex). IR (nujol/NaCl)[cm-1]: 3750 (C, m, H2O), 3385 (s, str, amide NH), 314 (s, str, amide NH), 3258 (s, m, W, N associated amide NH), 1694 (s, str, amide CO), 1651 (s, str, amide CO), 1594 (s, m, aryl ring/amide).

Example 18

DiCyHexDE-bis-oxazole

This product was obtained as a side product of the reaction of macrocyclization l3-how DiCyHexDE-amide intermediate with o-phenylenediamine. Bis-oxazole not removed by acid-base treatment (it is a neutral molecule and is very well soluble in organic solvents). Washing the crude macrocyclic/oxazalone the CSOs layer gives pure bis-oxazole in the form of large (1 cm1 cm0.5 cm) transparent prisms. Due to the volume of hydrophobic Sunah groups this oxazolone is much more resistant to hydrolysis than the corresponding methylesterase derived. Characterization of bis-oxazoline:1H-NMR (DS3SP)[M. D.]: 2,05 (K, 4H, CH2ethyl), 1,8-1,4 (undivided su Hex group) to 0.88 (t, t, CH3ethyl).13C-NMR the spin decoupling broad band (CD3SP)[M. D.]: 181,0 (C=O Oxus.), 162,7 (C=N Oxus.), 69,0 (Sneh Oxus. Quat), 49,0 (malonate Quat), 34,3 (methylene cyhex), 25.5 methylene cyhex g) 24,9 (methylene of malonate), 21,8 (methylene cyhex b) of 8.3 (CH3ethyl). IR (nujol/NaCl)[cm-1]: 1822 (C, str, width,=O Oxus.), 1662 (C, str, C=N Oxus.). Anal. (dried at 50(C) calculated for C21H30N2O4, %: 67,36; N 8,07; N OF 7.48. Found, %: C 67,26; N 8,15; N 7, 64.

Synthesis of chelate complexes

Example 19

[Et4N]2 and [Et4N]3, [tetraethylammonium salt dianion iron(III)-chloro-TMDE-DCB [Fe(Cl)DCB]2-and monoanion iron(III)-akvo-TMDE-DCB [Fe(H2O)DCB]-respectively].

Source macrocyclic tetraamide any of examples 10-18 above (525 mg, 1.1 mmol), dissolved in tetlichi (2,6 ml, 4.4 mmol, 1.7 M 2.4-dimethylpentane, Aldrich) in nitrogen atmosphere at -108C. Then was added iron chloride(II) (anhydrous, 155 mg, 1.2 mmol, Alfa) and the solution was heated to room temperature with stirring (16 h) to give the olive-green precipitate, sensitive to air complex of Fe(II). The air is admitted through shitennou tube (2 h) and the orange solid was collected and washed with CH2CL2(210 ml). The obtained orange powder was dried under reduced pressure. The output of 595 mg (>>93%). Due to the variable solvation in the limited solubility of this salt is lithium made and tetraethylammonium salt for later use. The lithium salt (595 mg) in CH3HE (50 ml) was applied to the ion-exchange column (Dowex® H-100, 25 g, 2 cm12.5 cm), which was pre-saturated with cations [Et4N]+and the orange band was suirable CH3HE (100 ml). The solvent was removed under reduced pressure.

The residue is suspended in CH2Cl2(20 ml) and the mixture was filtered. The solvent was removed from the mother liquor under reduced pressure to obtain an orange hygroscopic glassy residue [Et4N]2, which apolized> CO amide), 1575 (WITH amide), 1534 (CO amide). A more convenient approach to thoroughly clean source of iron(III)-material was the use of axial Aqua monoanionic complex than the axial chlorine-dianionic complex. [Et4N]2 (550 mg, about 0.7 mmol) was dissolved in CH3JV (50 ml). Tetrafluoroborate silver (140 mg, 0.7 mmol) was dissolved in CH3SP (2 ml) was added to this solution with stirring (1 h). AgCl-precipitate was filtered and the solvent was removed under reduced pressure. Received [Et4N]3 was further purified by elution through a column of silica gel (8% Meon in CH3CL2). The solvent was removed under reduced pressure and the product recrystallized from N2O. the Yield 360 mg (>>77% variable solvation with water was detected in a variety of microcrystalline samples). IR (nujol/NaCl) [cm-1]: 1590 (WITH amide), 1565 (CO amide), 1535 (n amide). Anal. the expect. for C29H46N5FeO5Cl2·(H2O), %: 50,52; N 7,02; N 10,16; Cl 10,28. Found, %: C 50,24; N 6,84; N 9,82; Cl 10,32. ESIMS (negative ion): m/z 552/2, [3-N2On]1-(100%); m/z 269,7, [3-N+]2-(18%).

Example 20

mmol) was dissolved in CH2Cl2(30 ml). To the solution was added nitrate ammonium cerium(IV) (10.3 g, and 18.3 mmol) and the mixture was stirred (2 h). Solid cerium salt was removed by filtration. The purple product was obtained by removal of solvent under reduced pressure and drying under vacuum. 400 mg (>>95%). Purple crystals were obtained by recrystallization from a mixture of CH2Cl2/Et2O. IR (nujol/NaCl) [cm-1]: 1688 (WITH amide), 1611 (WITH amide), 1582 (CO amide). ESIMS (negative ion): m/z 557 [4]-1(100%); m/z 522 [4-CL]1-(65%).

Example 21

Synthesis of [Ph4P]5 [tetraphenylphosphonium salt monoanion iron(IV)-cyano-TMDE-DCB] [Et4N]4 [tetraethylammonium salt monoanion iron(IV)-chloro-TMDE-DCB] and NaCN

[Et4N]4 [tetraethylammonium salt monoanion iron(IV)-chloro-TMDE-DCB] (225 mg, 0.33 mmol) suspended in N2O (10 ml). Sodium cyanide (140 mg, 2,85 mmol) was dissolved in N2O (10 ml), was added to this suspension and the mixture was treated with ultrasound (Branson 1200, 0.5 h). Purple suspension was changed, turning into a dark blue solution, and almost all the solid material had dissolved. The mixture was filtered and the blue product was besieged by the addition of PPh4Cl [tetraphenylphosphonium], Rast is mg>10 ml). Yield 250 mg (0.28 mmol, >>85%). This material (120 mg) was further purified by thin-layer chromatography (TLC) (plate silica gel GF, 20 cm20 cm1000 mm, 10:1 CH2CL2: CH3JV). The blue material was extracted from the silica gel with a mixture of CH3SP :CH2CL2(1:1, 60 ml). The solvent was removed under reduced pressure and the residue was dissolved in CH2CL2(3 ml) and filtered. Addition of pentane (150 ml) to give a blue powder (90 mg, 0.10 mmol). The yield after purification 75%. IR (nujol/NaCl) [cm-1]: 2119 (CN), 1659 (WITH amide), 1598 (WITH amide), 1571 (WITH amide). Anal., the expect. for C46H44N5FeOCl2P, %: 62,18; N 4,99; N 7,88; Cl 7,98. Found, %: C 61,96; N 5,04; N 7,84; Cl 8,06. ESIMS (negative ion): m/z 548,2, [5]1-(100%); m/z 522,1, [5-CN]1-(20%). For13C-labeled cyanide: m/z 549,2, [5]1-(100%); m/z 522,1, [5-13CN]1-(8%).

Example 22

Synthesis of [Ph4P]5 [tetraphenylphosphonium salt monoanion iron(IV)-cyano-TMDE-DCB] from sources NITRILES (cyanides)

[Ph4P]5 [tetraphenylphosphonium salt monoanion iron(IV)-cyano-TMDE-DCB] can be formed in the presence or Amorites in processing procedures. Thus, the selection of the product to obtain a blue solid best carried out in the presence of added base in the range of pH 9-10. Subsequent reaction network [Ph4P]5 with each of CH3JV, CD3CN, CH3CH2JV and (CH3)2N as the substrate-solvent. The base is not added to the described catalytic reactions. It was determined that the blue connection is an effective catalyst precursor, adding a dedicated [Ph4P]5 to a solution in acetonitrile TNR (tert-butylhydroperoxide) as a solvent and an oxidant was consumed, indicating that, although [Ph4P]5is formed as the end product of the catalytic oxidation process, it is not deactivated form of the catalyst.

Example 23

Synthesis of [Ph4P]5 in the presence of base

[Et4N]3 (160 mg, 0.23 mmol) was dissolved in the selected nitrile solvent (6 ml), see example 19. The base is a hydroxide of tetraethylammonium was added (20 wt.%, 0,370 ml, 0.52 mmol, Aldrich) was then added dropwise with stirring (20 min) tert-butylhydroperoxide (90%, 0,605 ml, 5.4 mmol, Aldrich) to give a blue solution. Residual nitrile was removed with a poly. The blue material was besieged from the filtrate by addition of an aqueous solution of PPh4Cl (800 mg, 2.1 mmol, Aldrich, 10 ml). The blue precipitate was collected and washed with H2O (210 ml). The output 130 g, 0.15 mmol (65%). Additional purification was performed as described in [PH4P]5, in example 25.

Example 24

X-ray data (crystalline) structure and refinement for [Et4N]3-H2O

C29H48Cl2FeN5O6M = 689,47, triclinic, space group P-1, a = 9,899(2); b = 11,771(2); C = 14,991(4)= 95,33(2); = 100,09(2); g = 92,31(2)V = 1709,6(6)3DOBS= 1,33 g·cm-3DRasch(Z = 2) = 1,339 g·cm-3T = 293 K, 1 = 0,71069m=0.64 mm-1the transport coefficient of 0.87 to 1.00. Data diraction processes were collected at room temperature on diffractometer Enraff-Nonius CAD-4 using monochromatizing graphite Mo-Ka radiation. Three reflections were monitored during the entire data collection, and was only observed random fluctuations in intensity. The structure was determined by direct methods. Hydrogen atoms associated with carbon included in calculated positions with bond length C/s 0,96

Example 25

X-ray data (crystalline) structure and refinement for [Et4N]4

Single crystals [Et4N]4 at 20±1With are monoclinic, space group P21/c-c52h(No. 14) with a = 9,958(2)b = 14,956(3)with = 22,688(5)and= 90,00, _ = 93,83(2), g = 90,00, V= 3372(1)3and Z = 4 (dRasch= 1,357 g·cm-3: ma(CuKa)collected using a Q-2Q scans and Ni-filtered cu-Ka radiation. The structure was determined using the "Direct methods" with the software package NICOLET SHELXTL modified in Crystalytics Company. The obtained structural parameters were agaricales convergence R1(unweighted, based on F) = 0,037 for 2680 independent reflections having 2Q(CuKa) < 115,0and I > 3s (I). Ten methyl groups were refined as rigid rotating parts with SP3-hybridizing geometry and bond length of C - H 0,96. The initial orientation of each methyl group was determined from the difference of the provisions of the Fourier series for hydrogen atoms. The final orientation of each methyl group has identified three rotational parameters. Amended provisions for rigid rotating methyl groups are C-C-H angles, which have a range from 103to 118. The remaining hydrogen atoms were included in the calculation of the index structure as idealized atoms (assuming sp2or SP3-hybridization of carbon atoms and the bond length of C - H 0,96) carried on their respective carbon atoms. From valenty isotropic thermal parameter of the carbon with which it is covalently bonded.

Example 26

Bleaching of lignin with hydrogen peroxide and [Fe (H2O)DCB*]-at pH 10

In a quartz cuvette with a path length of light 1 cm, containing 3.0 ml of a mixture of 0.1 M Panso3/PA2CO3(pH 10), thermostatted at 25C, was added 60 μl of a saturated solution of alkali lignin and 300 ál of a solution of catalyst (1,2410-4M [Fe (H2O) DCB* ]-(where R' and R" are methyl, what is meant by an asterisk *, and the counterion is a cation of tetraethylammonium), all in water. This solution was mixed and added to 3.8 μl of 30% H2O2. Changes in absorbance at 350, 376, 400, 426, 450, 476 nm was measured using spectrophotometer Hewlett-Packard UV/Vis operating mode of the kinetics of a single cell. Adding H2O2absorption rapidly increases at all wavelengths and then rapidly decreased. After 15 minutes the absorbance at each wavelength was below the original value, indicating that there was discoloration of lignin. Produced the second addition of 60 μl of lignin, which has caused a rapid increase in acquisitions, as before, and then the following reduction of the initial increase going the extra μl of 3.8 H2O2. The behavior was similar to the behavior observed previously. A rapid increase absorption should decrease.

Example 27

Bleaching of lignin without [Fe(H2O)DCB*]-at pH 10

Stage of example 26 was repeated with the exception of the catalyst. In a quartz cuvette with a path length of light 1 cm, containing 3.0 ml of a mixture of 0.1 M NaHCO3/Na2CO3(pH 10), thermostatted at 25C, was added 60 μl of a saturated solution of alkali lignin and the mixture was stirred. After a short period of time after the start of data added to 3.8 μl of 30% H2About2.

Measurements of absorption produced using the same parameters that described in example 26.

Adding N2About2all six wavelengths discovered increased absorption. This increase was not rapid and was not as sharp as in the catalyzed reaction. The absorption gradually began to descend, but it was very slow. Bubbles were not observed in the mixture within the first 15 minutes. At the end of the hour began to appear bubbles.

Comparison of preliminary experiments in examples 26 and 27 shows that the addition of the activator of the present invention increases the speed with the om hydrogen, passivation and without [Fe(H2O)DCB*]-at pH 10

Stage of example 27 was repeated with the addition of passivator DEQUEST 2066, 2 ál, chelating agent for the ions to the free metal. The addition of H2O2was given a picture of a gradual increase and decrease, similar to what one observes in example 27.

Example 29

Bleaching of lignin with hydrogen peroxide, passivation and without [Fe(H2O)DCB*]-at pH 7

Stage of example 27 was repeated at pH 7 using buffer 0,0087 Moralny KN2RHO4/0,030 Moralny Na2HPO4. In the cuvette were added 2 μl of chelating agent DEQUEST 2066. Did not observe measurable whitening within time 1 hour this experiment. Minimal activity was observed in the traces of the absorption at 350 nm, but it was attributed to noise.

Example 30

Bleaching of lignin with hydrogen peroxide, [Fe(H2O)DCB*]-and passivation at pH 10

In the cell, equipped with a mixing shaft, mixing 1 equivalent of the catalyst of example 26 (300 ál solution of [Fe(H2O)DCB*]-, 60 μl of a saturated solution of alkali lignin, buffered, as described above, and 2 μl of chelating agent DEQUEST 2066. Absorption was measured with the use of those parameters that are described in the rapid increase in the uptake followed by rapid decrease, as described in example 26.

After 20 minutes an additional 60 μl of lignin was added to the cuvette. The absorption at all wavelengths increased more slowly and then declined more slowly than after addition of H2O2.

30 minutes later added an additional equivalent (300 µl) of the catalyst [Fe(H2O)DCB*]-. Did not observe significant changes.

After 40 more minutes of 3.8 μl of H2O2was added to the cuvette. This caused a significant reduction in the absorption at all wavelengths, indicating that again was the bleaching of lignin.

Example 31

Bleaching of lignin with hydrogen peroxide, [Fe(H2O)DCB*]- and passivation at pH 7

Example 29 was repeated, but with the addition of 300 μl of the catalyst. 3,8 ál of 30% H2About2added after a few cycles. Adding H2O2absorption was increased in each of the six wavelengths used in example 26, but not dramatic. Acquisitions continued to slowly rise during the first 15 minutes, they were on a plateau and then began to fall for all six wavelengths. One hour later, the absorption was higher than the initial absorption.

Example 32

Long-term activity of the catalyst

In quercuum at 25C, was added 60 μl of a saturated solution of alkali lignin, 300 ál (of 12.4 μm) initial solution of the catalyst (1,2410-4M [Fe(H2O)DCB*]-) and 2 μl of DEQUEST 2066, all in water. The mixture was stirred, the acquisition of data started out as in example 26, and then was added to 19 μl (5000 equivalents) of 30% H2O2. After the first rapid increase uptake followed by rapid decline, every 15 minutes was added to aliquots of 60 μl of a saturated solution of alkali lignin and 19 μl (5000 equivalents) of 30% H2O2.

The results obtained when subjected to monitoring the wavelength of 476 nm, shown by the solid line in the graph of Fig.1. The same results were obtained when other exposed monitoring wavelengths. Adding lignin and N2About2indicated by asterisks.

For comparison was prepared cuvette saturated solution of lignin, chelating agent and N2O2without catalyst and measured absorption. These results are shown by the dashed line in Fig.1.

Example 33

Long-term stability of the catalyst

In Fig.5 shows a comparison of the catalytic "longevity" of the two variants of the present invention in the test with the dye. Connection 1 has the substituents R' and R", each ostavlaet a-CH2CH3. The control catalyst was added.

The conditions were: pH 9, room temperature (21,1C) a buffer system Panso3/PA2CO3. Oxidant was 4 mm (30%) H2O2. In each of the asterisks were added to 12 μm binationally dye.

As you can see from the graph in Fig.5, each adding a dye in the form, which was attended by compound 1 resulted in almost immediate discoloration. Compound 2, diethylsilane, showed a more gradual discoloration. The control showed only a very gradual rate of discoloration.

Example 34

Oxidation of 2,4,6-trichlorophenol (Turkmenistan Helsinki Foundation)

The Turkmenistan Helsinki Foundation could quickly be oxidized under various conditions in the water by H2O2using the iron complex [Fe(H2O)DCB*]-shown on Fig.1, an activator of H2O2. Recent work on the oxidation of the Turkmenistan Helsinki Foundation was carried out using either H2About2or KHSO5as the oxidizing agent and water-soluble iron complex 2,9,16,23-tetrachloroaniline (FePcS) as activator oxidant. Cm. Sorokin A., Seris J.-L., Meunier, C., Science, vol. 268, PP. 1163-1166 (1995). In these studies it was found that the Turkmenistan Helsinki Foundation of more effective is a practical standpoint, it is desirable to use as the oxidizer H2O2due to its easy availability at low cost. In article Sorokin et al., Science, cited above, reported that compounds called "related products" in Fig.6, give a purple solution. These related products are not oxidized further system FePcS/H2O2. Cm. Sorokin, A., De Suzzoni-Dezard S.; Poullain, D., Noel J.-P., Meunier B. J. Am. Chem. Soc., vol. 118, pp. 7410-7411 (1996). Because these related products are also polychlorinated aromatic compounds, there is a probability that they are undesirable from the point of view of environmental protection. Here is provided the evidence that [Fe (H2O)DCB*]-oxidizes some of the related products of oxidation of the Turkmenistan Helsinki Foundation or all of these related products.

In Fig.7, shows the changes in the spectrum of the ultraviolet/visible light (UV/vis), which take place in the oxidation of the Turkmenistan Helsinki Foundation in phosphate buffer with pH 7.4 1 mm [Fe(H2O) DCB*]-in the presence of 5.4 mm H2About2. In this experiment, [Fe(H2O)DCB*]-and the Turkmenistan Helsinki Foundation unite in a buffer with pH 7.4, add H2O2and then subjected to monitoring the spectral changes. The absorption maxima observed at the Turkmenistan Helsinki Foundation 220, 256, and 316 nm. The wavelengths selected for kinetic analysis of the oxidation process, dormancy is I three wavelengths). In the absence of [Fe(H2O)DCB*]-no reductions in the values of the absorption bands arising from the Turkmenistan Helsinki Foundation.

It is evident from Fig.8 shows that the absorption for the bands at 316 nm decreases, there is a new absorption at 516 nm, which increases in intensity for about 100 seconds, but then again reduced to its initial value. In experiments where conducted visual monitoring of this reaction, the rapid formation of a purple solution occurred after addition of N2About2and then this solution was gradually bleached, giving in the end a colorless solution. The purple color was attributed to related products, similar products in Fig.6. The fact that this solution becomes colorless, indicates that the system [Fe(H2O)DCB*]-/H2O2able to oxidize these related products.

System [Fe(H2O)DCB*]-/N2About2able to perform multiple oxidation of the Turkmenistan Helsinki Foundation, as shown in Fig.9. Experimental procedures were the same as used in Fig.8 (note, however at a higher temperature for Fig.9), but after the first cycle of oxidation of the Turkmenistan Helsinki Foundation has added an additional portion 45 μm Turkmenistan Helsinki Foundation, award # when will the Kund, while the fifth portion requires more than 400 seconds for its oxidation. The reduction of the oxidation process occurs, perhaps from a combination of decomposition of [Fe(H2O)DCB*]-and additional oxidation of some part of the oxidation products through the Turkmenistan Helsinki Foundation [Fe(H2O)DCB*]-.

System [Fe(H2O)DCB*]-/H2O2oxidizes the Turkmenistan Helsinki Foundation at different pH. In Fig.10 shows the kinetic line for oxidation of the Turkmenistan Helsinki Foundation under the conditions listed in Fig.10. These data show that the oxidation of the Turkmenistan Helsinki Foundation is most rapid at pH 10. However, in contrast to the results shown in Fig.9, multiple cycles of oxidation of the Turkmenistan Helsinki Foundation not attained one loading [Fe(H2O)DCB*]-. In addition, changes in absorbance at 300 and 316 nm are more complex at pH 10, indicating increased complexity of this oxidation process. Thus, of the three pH values tested in this experiment, the optimal values under the conditions of this experiment in terms of time and durability of the activator, are, apparently, values at pH 7.4. This is a very important result, since the release of sewage into lakes and rivers should be at pH 7.

Example 35

Bleaching wastewater

Two samples of 25 ml of sewage enterprises in Tasmania, New Zealand, prepared in a solution of pH 11. One of these solutions was added 25 mg of N2O2and 12.5 µg activator, [Fe(H2O)DCB*]-. Four hours later the amount of absorption of this sample was measured at 465 nm using a spectrophotometer visible light. Added substances are shown in the table.

The sample containing the activator, was a weak yellow color after processing. Visual inspection of the solution containing the activator, showed that the transformation of the black/brown solution in pale yellow was actually completed within the first hour of treatment, with approximately 30-60 minutes. Comparable changes were not observed for the solution containing only H2O2.

Claims

1. Method of bleaching of the chromophores in the wastewater process of manufacturing pulp and paper, involving contacting wastewater with (a) resistant to oxidation bleaching activator having the structure

where Y1, Y3and Y4each represent a bridging group having zero, one, two or three carbon containing nodes for substitution;

Y2is the bridge contains the group C(R), C(R1)(R2) or C(R)2and where R, R1, R2are the same or different and is (i) selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkylaryl, halogen, alkoxy or phenoxy, CH2CF3, CF3or (ii) form a substituted or unsubstituted benzene ring of which two carbon atoms in the ring form nodes bridging group Y, or (iii) together with the substituent R, related to the same carbon atom, form cycloalkyl or cycloalkenyl ring which may include an atom other than carbon;

M denotes a metal of the transition series with oxidation States of I, II, III, IV, V, VI, VII or VIII or selected from groups 3, 4, 5, 6, 7, 8, 9, 10 and 11 of the Periodic table of elements (system IOPAC);

Q denotes any counterion, which balances the charge of the compound on a stoichiometric basis,

and (b) with a source of oxidant in an amount effective to whiten substrate.

2. The method according to p. 1, characterized in that it is carried out at a temperature in the range from ambient temperature to approximately 130C.

3. The method according to p. 1, characterized in that as the oxidant used peroksosoedinenii.

C.

6. The method according to p. 1, characterized in that it is carried out at a temperature in the range from ambient temperature to approximately 60C.

7. The method according to p. 1, characterized in that it is carried out at a pH in the range of 7-12.

8. The method of oxidation of carbonaceous substances wastewater, where these carbon materials contain chromophores, absorbable type of organic halogen and combinations thereof, providing for the contacting of the effluent with (a) resistant to oxidation bleaching activator having the structure

where Y1, Y3and Y4each represent a bridging group having zero, one, two or three carbon containing nodes for substitution;

Y2is a bridging group having at least one carbon containing node for substitution, each specified node contains the group C (R) C(R1)(R2) or C(R)2and where R, R1, R2are the same or different and is (i) selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkylaryl, ginee ring, with the two carbon atoms in the ring form nodes bridging group Y, or (iii) together with the substituent R, related to the same carbon atom, form cycloalkyl or cycloalkenyl ring which may include an atom other than carbon;

M denotes a metal of the transition series with oxidation States of I, II, III, IV, V, VI, VII or VIII or selected from groups 3, 4, 5, 6, 7, 8, 9, 10 and 11 of the Periodic table of elements (system IOPAC);

Q denotes any counterion, which balances the charge of the compound on a stoichiometric basis,

and (b) with a source of oxidant in an amount effective to oxidize these carbon emissions.

9. The method according to p. 8, characterized in that the said absorbable types of organic halogen represent a chlorinated aromatic compound.

10. The method according to p. 9, characterized in that the chlorinated aromatic compound selected from the group consisting of chlorinated phenols, dioxins, dibenzofurans, biphenyls and their combinations.

11. The method according to p. 8, characterized in that the chromophores are lignin chromophores.

 

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