The whitening composition and methods for its use

 

(57) Abstract:

The invention relates to a bleaching composition for bleaching textiles and suppression of absorption and adsorption stains or dyes for absorbing or adsorbing the substrate. Describes the bleaching composition containing an effective amount of a source of an oxidizing compound and a bleach activator, a stable to oxidation macrocyclic terminoligy formula, where X and Z is a hydrogen atom, electron-donating or electroreceptor group, R1and R11- alkyl and cycloalkyl, M is a transition metal with oxidation States of I, II, III, IV, V, VI, VII, VIII or selected from 3, 4, 5, 6, 7, 8, 9, 10 or 11th group of the Periodic table of elements, the system IU RACES, Q is any counterion which would have balanced the charge of the compound on a stoichiometric basis, L, if present, means labile ligand, and when present in aqueous solution, L represents water. Also describes the method of bleaching textile and method of suppressing the absorption and adsorption of contaminants or dyes for absorbing or adsorbing the substrate. The invention improves the degree of whitening and reduce the degree PE is.p. f-crystals, 3 ill., 5 table.

The invention relates to the use of macrocyclic complexes of metal-ligand as bleaching activators and, more particularly, to a transition metal complexes with macrocyclic tetraamide ligands as catalysts to speed up reactions oxidative bleaching.

A brief description of the prior art

Hydrogen peroxide and other peroxide-forming peroxide in aqueous solutions, have long been used for bleaching materials and surfaces. However, such peroxide compounds, as perborate sodium monohydrate or tetrahydrate), percarbonate sodium, etc., have relatively low efficiency of bleaching at low temperatures (e.g. below 38,8oC/100oF). Organic percolate or nagkalat, such as derbentina acid are stronger oxidants, but in most cases they are unstable if they are not stabilized by expensive and cumbersome methods. In addition, the production of such pretreated perkiset is often costly. The bleaching activators or predecessors of percolat, such as esters, ketones, NITRILES and that the management are usually present in stoichiometric or greater amounts and therefore, their production may not be profitable.

Known application of chelates of transition metals, particularly those containing manganese and iron as catalysts for bleaching with peroxide compounds. They are represented, for example, Favre and others, U.S. patent. 5,246,621, Bragg and others , U.S. patent 5,002,682, Postlethwaite, U.S. patent, 4,119,557 and Ellis, Jr. and others, U.S. patent 4,900,871. These chelates of transition metals can be used, for example, when washing fabrics with appropriate free radical soedinenii, for example, perborate monohydrate sodium.

Despite the available evidence strengthening the oxidizing capacity of peroxide compounds such chelates of transition metals, in some cases, when used as bleaching activators they can contribute immediately paint and even tissue damage.

Studied the application of chelates of transition metals in areas not related to the invention. For example, it is known that complexes of transition metals with high oxidation function as oxidants in numerous biological reactions under the influence of the protein matrix, and in recent years seen a huge interest in understanding the mechanism of action and p is the building of ligands for oxidizing complexes", Accounts of Chemical Research, 279, 27 (9), 1994. In this article, it is planned to create a directional approach to obtaining ligands, which are resistant to oxidative degradation in coordination with metals in high oxidation States. In article Collins in Accounts of Chemical Research described some acyclic, diamino-N-Difenoxin, diamino-N-alkoxide chelate compounds and macrocyclic tetraamide N-chelate compounds.

Synthetic path macrocyclic tetraamide ligands described Uffelman, E. S., Ph.D. Thesis, California Institute of Technology (1992). In addition, the synthesis of tetraamine-ligand with aryl bridge on azide method can be carried out using as starting substances aromatic diamine.

However, until now, remained unknown, which is the basis of some macrocyclic tetraamide ligands, you can get new and extremely effective activators bleaching with peroxide compounds. In addition, it was reported, disclosed in the invention or supposed connection of these types will have extraordinary advantages in the areas associated with the suppression of the process of transfer of ink from one tissue to another, with the suppression of the re-deposition of dirt and adalarami:

a) resistant to oxidation bleaching activator having the structure

< / BR>
where Y1, Y3and Y4individually mean bridging group having 1-3 carbon containing node for substitution, or a single bond,

Y2means bridging group having at least one carbon containing node for substitution, and the above-mentioned node contains a group of CR, CR1R2or C(R)2and each substituent R denotes the same or different from R and is selected from the group consisting of hydrogen atom, alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, quinil, alkylaryl, halogen atom, alkoxyl, fenoxaprop, triptorelin group, triptoreline groups or combinations thereof, or form a substituted or unsubstituted benzene ring, in which two ring carbon atom form a node in the cell Y, or together with a paired substituents R attached to the same carbon atom, forms cycloalkyl ring, for example, cyclopentene or tsiklogeksilnogo, which may include an atom other than carbon atom,

M stands for a transition metal with oxidation States of I, II, III, IV, V or VI or selected from groups 6, 7, 8, 9, 10 and 11 of the Periodic system of elements stored is R>
L is any labile ligand;

b) an effective amount of a source of oxidizing compounds.

The composition can be added surfactants, fillers, binders, amplifiers excretion, antioxidants, enzymes, fluorescent whitening agents, dyes, colouring agents, pigments and other conventional auxiliary substances for cleaning and/or washing.

Preferred bleach activators are macrocyclic tetraaminopyrimidine. Among them are particularly preferred are those containing a substituted aromatic fragment, articulated directly with cyclic ligand.

For example, the preferred compound has the following structure:

< / BR>
where X and Z denote the hydrogen atom, electron-donating or electron-withdrawing group,

R' and R" means any combination of hydrogen atom, alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, quinil, alkylaryl, halogen atom, alkoxyl, fenoxaprop, or when the connection form cycloalkyl or cycloalkenyl ring which may contain at least one atom other than carbon atom,

M stands for a transition metal,

Q is any counterion which would have balanced the charge of the compound on a stoichiometric basis,

L is any labile ligand.

There is a need to create a peroxide bleaching activator with improved ability to suppress the transfer process dye on another fabric. There is a need to create a bleaching activator with improved soil-repellent properties. There is also a need to create a bleaching activator, with a unique stain remover detergents properties. In addition, there is a need to create a bleaching activator with long-lasting catalytic stability in buffered solution. In addition, there is a need to create a bleaching activator, which can be used in substochiometric quantities with respect to oxidizing connection.

Brief description of drawings

Fig. 1 is a synthetic method of obtaining macrocyclic tetraamide ligands according to the invention azide method.

Fig. 2 is a synthetic method of obtaining macrocyclic tetraamide ligands according to the invention azide method using ar is executed with control continuing for a long time catalytic stability in one of the preferred embodiments of the present invention.

Detailed description of preferred embodiments of the invention.

The invention includes a bleaching composition containing:

a) resistant to oxidation bleaching activator having the structure:

< / BR>
where Y1, Y3and Y4individually mean bridging group having 1-3 carbon containing node for substitution, or a single bond,

Y2means bridging group having at least one carbon containing node for substitution, and the above-mentioned node contains a group of CR, CR1R2or(R)2and each substituent R denotes the same or different from R and is selected from the group consisting of hydrogen atom, alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, quinil, alkylaryl, halogen atom, alkoxyl, fenoxaprop, triptorelin group, triptoreline groups or combinations thereof, or form a substituted or unsubstituted benzene ring, in which two ring carbon atom form a node in the cell Y, or together with a paired substituents R attached to the same carbon atom, forms cycloalkyl or cycloalkenyl ring, for example, cyclopentene or tsiklogeksilnogo, which may include atricauda from groups 6, 7, 8, 9, 10 and 11 of the Periodic system of elements,

Q is any counterion which would have balanced the charge of the compound on a stoichiometric basis,

L is any labile ligand;

b) an effective amount of a source of oxidizing compounds.

Preferred macrocyclic tetraamide ligands according to the invention showed extraordinary efficiency in estimation with different operating characteristics for bleaching activators.

These ligands are produced in accordance with the methods described in the simultaneously recorded in the register of the United States the application for the invention Gordon-Wylie, and others, entitled "Synthesis of macrocyclic tetraamido-N-ligands", registration number 08/681,187 and international application 98/03263, Collins and others, entitled "long-Lived homogeneous catalytic oxidation", which are incorporated in this application by reference.

Particularly preferred compounds according to this invention is represented by the structure of the macrocyclic tetraamide derivatives:

< / BR>
where X and Z denote the hydrogen atom, electron-donating or electron-withdrawing group,

R' and R" means any combination of hydrogen atom, alkyl, cycloalkyl, cycloalkene cycloalkyl or cycloalkenyl ring, which may contain at least one atom other than carbon atom,

M stands for a transition metal with oxidation States of I, II, III, IV, V or VI, or is selected from 6, 7, 8, 9, 10 or 11th group of the Periodic table of elements

Q is any counterion which would have balanced the charge of the compound on a stoichiometric basis,

L, if present, refers to a labile ligand.

X and Z can be hydrogen atoms or electron-donating or electron-withdrawing groups. Electron-withdrawing group include a halogen atom such as bromine atom, iodine atom and preferably a chlorine atom. In addition, suitable groups are SO3-, S3-, OSO3R (and R without limitation means a hydrogen atom, alkyl, aryl, alkylaryl) and a group of NO2-. Electron-donating groups include alkoxygroup without limitation, methoxy, ethoxy, propoxy, butoxy), alkyl (without limitation methyl, ethyl, propyl, n-butyl and tert. -butyl) and a hydrogen atom. These groups alter the electron density of the complex metal-ligand and affect its reactivity.

R' and R", apparently, have an impact on the duration of preservation of catalytic stable which may be selected from the group consisting of hydrogen atom, alkyl, alkenyl, aryl, quinil, halogen atom, alkoxyl or fenoxaprop, preferred is an alkyl with a short chain. Particularly preferably, when R' and R" are the same and are selected from ethyl or methyl, or when R' and R" are joined, forming cycloalkyl or cycloalkenyl ring, especially cyclopentenone or tsiklogeksilnogo. Cycloalkyl ring may include at least one atom other than carbon atom, without restrictions such as nitrogen atom, oxygen atom or sulfur atom.

The metal M stands for a transition metal with oxidation States of I, II, III, IV, V or VI or is selected from 6, 7, 8, 9, 10 or 11th group of the Periodic table of elements. Preferably it is selected from the group consisting of iron, manganese, chromium, copper, cobalt, Nickel, molybdenum, zinc, or tungsten. Possible mixtures thereof.

Q is any counterion which would have balanced the connection charge (usually negative, preferably -1) on a stoichiometric basis. Thus, preferred is usually positively charged counterion, but not limited to the counter-ions of alkaline-earth metals (for example, potassium ions, lithium, sodium), Jonah is, alkenyl, or they can be connected, forming cycloalkyl, cycloalkenyl or aryl ring which may contain at least one atom other than carbon atom.

L is any labile ligand, which can connect with the metal M These ligands preferably, but without limitation, include water molecule, the chlorine atom and a group C=n

Due to the complexity of the structure of these compounds with the description of the invention for the convenience of their names replaced with the names of those present in their structure deputies. For example, the structure described above 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 tetramethyl-diately-X-benzene (TMDE-DXB, where X denotes a chlorine atom, a hydrogen atom, methyl, methoxyl). Thus, for convenience, in the case of the above-mentioned structure, where the two methyl groups are located each at the amino group of the ligand and two ethyl groups play the role of the substituents R' and R", the compound is designated as TMDE. When both substituent X and Z indicate the chlorine atoms, the compound is designated as DCB. Preferred transition metal ligand is iron, so the connection can be marked as FeDCB.

Below, in the experimental part, the individual syntheses preferred macrocyclic tetraaminopyrimidine. In addition, tests were conducted that demonstrates the ability to suppress the transfer process dye, the duration of preservation of catalytic activity and stain remover detergents properties of macrocyclic ligands according to the invention.

Oxidizing compounds

Oxidizing compounds may be organic and inorganic. Preferred are peroxide compounds containing the peroxide bond-o-O-. Given as examples of the 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 perrykaty carbonates of alkali metals (e.g. sodium, lithium, potassium and urea peroxide. Compounds capable of forming hydrogen peroxide in an aqueous solution, include mono - changes and manufactured by such companies, as Akzo N. V. and FMC Corporation. As an alternative source of hydrogen peroxide may be the enzyme alcohol oxidase and its substrate corresponding alcohol. Organic peroxides include, without limitation gidroperekisi benzoyl and cumene. Persulfates include monopersulfate potassium (trade name Oxonethe company E. I. du Pont de Nemours) and acid Caro (monandrous acid).

An effective amount of peroxide is sufficient to generate at least 0,001 M. D. active oxygen (AO). Without restrictions and at the same time, it is preferable to obtain from 0.001 memorial plaques to 1000 M. D. AO. When the bleaching of fabrics is preferred amount of from 0.01 to 50 meters D. AO. Description and method of measurement JSC are presented in the publication Sheldon N. Lewis "Oxidation using nakilat and peroxides" in the book "Oxidation", 1969, pp. 213-258, included in this invention by reference.

Cleaning and/or washing excipients

Macrocyclic tetraamide ligands according to the invention can be mixed with an oxidizing bleaching or washing base, and said base includes a binder, and optionally a surfactant, select the substances and their mixtures. There could be other excipients. These compounds can be in the liquid base for use on hard surfaces to remove stains or other procedures cleaning/bleaching. These compounds can also be used in the process of obtaining technical pulp and bleaching of textiles. Each of these compounds and excipients suitable for use according to the invention, are discussed below.

A. binder

Binders are usually substances with alkaline properties, i.e. those which in aqueous solution have a pH of 7-14, preferably 9-12. Examples of the inorganic bonding agents include alkali metal and ammonium carbonates (including sesquicarbonate and bicarbonate), phosphates (including orthophosphate, politifact and tetrapropoxide), aluminosilicates (both natural and synthetic zeolites and mixtures thereof. For use in this invention are particularly suitable carbonates because of their high alkalinity and efficiency in the removal of ions present in hard water, but also because of their low cost. Carbonates can be used as the predominant binder. Can also ikats, due to their solubility in water and ability to form a glassy matrix, may also be preferred when used as a binder for detergent.

Organic binding substances are also suitable for use and can be selected from the group consisting of sulfosuccinates alkali metal and ammonium polyacrylate, polymaleic, copolymers of acrylic and maleic acid or maleic anhydride, citrates and mixtures thereof.

B. Fillers/Diluents

Fillers for bleaching or washing composition used for directed delivery of the appropriate amount or dose of the washing or cleaning agent. Preferred are salts such as sodium chloride, sodium sulfate and borax. You can use organic solvents, such as carbohydrates. Liquid performance as a diluents may be used solvents (without restrictions such as alcamovia alcohols, glycols, glycol ethers, hydrocarbons, ketones and carboxylic acids), a liquid surfactant and water.

Century Surfactants

Surfactants are usually added to otbelivanie additives for oil stains and anionic surfactants for solid impurities. However, as a rule, oxidative bleaching compositions contain small amounts or not at all contain surface-active substances.

Especially effective surface-active additives are anionic surfactants. Examples of such surfactants include compounds of ammonium, substituted ammonium (such as mono-, di - and triethanolammonium), salts of fatty acids WITH6-C20and resin acids with alkali and alkaline earth metals, linear and branched alkylbenzenesulfonate, alkyl sulphates, alkalemia ether sulfates, alkanesulfonyl, reincorporate, hydroxyethanesulfonic, monoglycerides fatty acids, alkylglycerol ether sulfates, acylcarnitines and acyl-N-methyltaurine. Preferred are surface-active alkylarylsulfonate, such as alkylbenzenesulfonate.

Other preferred surfactants include ethoxylated linear alcohols, such as manufactured by Shell Chemical Company under the trade name Neodol. Other suitable surfactants can include other linear ethoxylated alcohols with a chain length from 6 to 16 atoms of plastics technology: turning & cnie ethoxylated, propoxycarbonyl alcohols with conventional chain length from 6 to 16 carbon atoms containing 0-10 moles of ethylene oxide and 1-10 moles of propylene oxide per mole of alcohol; linear and branched alkylphenoxy (polyethoxysiloxane), known as ethoxylated ALKYLPHENOLS, with the usual chain length from 8 to 16 carbon atoms, containing 1.5 to 30 moles of ethylene oxide per mole of alcohol, and mixtures thereof.

In addition, suitable nonionic surfactants may include esters polyoxyethylenesorbitan acids, glycerol esters of fatty acids, alkanolamine fatty acids and ethoxylated fatty acids, certain block copolymers of propylene oxide and of ethylene oxide, block polymers of propylene oxide and ethylene oxide with propoxycarbonyl Ethylenediamine. In addition, they may include such semipolar non-ionic surfactants, as aminoxide, phosphineoxide, sulfoxidov and their ethoxycarbonyl derivatives.

Suitable cationic surfactants may include the ammonium derivatives, in which typically one of the groups linked to the nitrogen atom is an alkyl group 12-C18and other groups are alkyl groups with rooted and zwitterionic surfactants, containing anionic group, contributing to the solubility of compounds in water, a cationic group and a hydrophobic organic group can include carboxylic acids and their salts, dicarboxylic amino acids and their salts, alkylbetaine, alkylaminocarbonyl, sulfobetaine, derivatives alkylimidazole, some Quaternary ammonium compounds, some Quaternary postname compounds and certain tertiary sulfonamide connection. Other examples of potentially suitable zwitterionic surfactants can be found in compiled Jones U.S. patent 4,005,029, columns 11-15, included in this invention by reference.

In addition, examples of anionic, nonionic, cationic and amphoteric surfactants that can be used in this invention are described in the monographs Kirk-Othmer "encyclopedia of chemical technology", third edition, volume 22, pages 347-387 and "Detergents and emulsifiers of Maccutcheon", North American edition, 1983, which are incorporated into this invention by reference.

As mentioned above, other known detergent auxiliary substances may be added if necessary to bleaching or cleaning bleaching Orada - 0.5 to 50.0% of

The activator is 0.0001-10000 memorial plaques

Surfactant - 1.0 to 50.0% of

Binder - 1.0 to 50.0% of

Filler, stabilizers, dyes, perfumes, optical brighteners, etc. to 5.0 to 99.9%

G. Gelatinous agents

In some compounds according to the invention particularly preferred is the inclusion of a chelating agent, most preferably aminophosphonate. These chelating agents help to maintain the stability of the oxidant in the solution to achieve the optimal effect. Their action is reduced to the formation of complexes (chelates) with free ions of heavy metals. Chelating agent selected from a large number of well-known agents that are effective in the formation of complexes with the free ions of heavy metals. Chelating agent must be stable to hydrolysis and rapid oxidation under the influence of an oxidant. Preferably it should have an acid dissociation constant (PKandin the range of 1-9, indicating its dissociation at low pH values, which increases its binding to metal cations. The most preferred chelating agent is aminophosphonate, which is commercially available under the Bossu, U.S. patent, 4,473,594, column 12, line 63 to column 13, line 22, are included in this invention in the form of links). You can also use this polyphosphonate as Dequest 2010. Other chelating agents, such as ethylenediaminetetra-acetic acid (EDTA), nitrilotriacetic acid (NTA) can also be used. In addition, the new preferred chelating agents are propylethylenediamine, such as Hampshire 1,3 the pdta from W. R. Geace and Chel DTPA 100# F from companies Ciba-Geigy A. G. Apply the mixture mentioned chelating agents. The effective amount of chelating agent are in the range 1-1000 memorial plaques , more preferably 5-500 memorial plaques, most preferably 10-100 M. D. chelating agent in the scrubbing liquid.

D. Other excipients

Standard detergent auxiliary or oxidative bleaching excipients can be included in the present invention.

These include enzymes, the presence of which in detergents and oxidizing bleaching compositions the most desirable. However, it may be preferable to inclusion and enzyme stabilizer.

Proteases are particularly preferred class of enzymes. They are chosen from the group consisting of the value of pH, at which enzyme activity is optimal. Examples of neutral proteases include milsim (from the firm of Miles Laboratory) and trypsin, which is the natural protease. Alkaline protease available from a variety of sources, usually get them from a variety of microorganisms (for example, Bacillis subtilisis). Typical examples of alkaline proteases include maksataju and maxical from the firm's International BioSynthetics, alcalase, savinase and esperase, all from the firm Novo Industri A/S. Cm. also Stanislowski and others, U.S. patent 4,511,490 included in this invention by reference.

In addition, suitable enzymes are amylase, which represents a carbohydrate-gidrolizuemye enzymes. Preferred also is the inclusion of mixtures of amylases and proteases. Acceptable amylase include rapidash from the firm Societe Rapidase, milazim Miles from the company Laboratory and maxamyl from the firm's International BioSynthetics.

Other acceptable enzymes include cellulase, such as described Tai, U.S. patent 4,479,881, Murata and others, U.S. patent 4,443,355, Barbesgaard and others , U.S. patent 4,435,307 and Ohya and others, U.S. patent 3,983,082 included in this invention in the form of links.

Another group of acceptable enzymes are lipases such as those described Silver, U.S. patent 3,950,277 and Thom, U.S. patent 4,707,291, including the mu invention are peroxidase, such as horseradish peroxidase and the enzymes disclosed in the international application WO 93/24628, which is incorporated into this invention by reference.

The enzyme may be present in amounts of 0-5%, more preferably 0.01 to 3%, most preferably 0.1 to 2% by weight from the washing/bleaching/cleaning basics. It is desirable to use mixtures of any of the above-mentioned hydrolases, particularly a mixture of protease/amylase.

In addition, optional excipients include dyes such as dye Monastral blue and antrahinonovye dyes (as described Zielske, U.S. patent 4,661,293 and U.S. patent 4,746,461).

Pigments, which are also acceptable coloring agents, can be selected without limitation from titanium dioxide, ultramarine blue (see, for example, Chang and others, U.S. patent 4,708,816) and non-ferrous silicates.

Fluorescent whitening agents are another group acceptable auxiliary substances. They include derivatives of stilbene, styrene and naphthalene, which upon irradiation with UV light emit or absorb light in the visible region of the spectrum. To improve the appearance of textiles, which faded from repeated pollution or washings, ispolzue Phorwite RKH from the company Mobay Chemicals. Examples of acceptable FWA can be found in U.S. patents 1,298,577, 2,076,011, 2,026,054, 2.026.566. 1,393.042, as well as in U.S. patent 3,951,960, 4,298,290, 3,993,659, 3,980.713 and 3,627.758, included in this invention in the form of links.

Agents that prevent the re-deposition of impurities, such as carboxymethylcellulose, are potentially suitable for use according to the invention. In addition, it can be included foam enhancers, such as appropriate surfactants. In addition, if excess foam arising from the use of certain surface-active substances, it is desirable to use antifoaming agents, such as alkylated polysiloxane, for example, dimethylpolysiloxane. Odorants are also desirable excipients in these formulations.

Additional organic bleach activators can be incorporated, including, but not limited to, esters (see Fong and others, U.S. patent 4,778,618 and Rowland and others, U.S. patent 5,182,045), ketones, imides (see Kaaret, U.S. patent 5,478,569) and NITRILES.

Additives can be present in an amount of 0-50%, more preferably 0-30%, most preferably 0-10%. In some cases, a separate auxiliary substances mo is substances as providing concrete benefits to various categories.

Experimental part

Synthesis of stable to oxidation tetraamine ligands

Materials. All solvents and reagents were of chemically pure (firms Aldrich, Aldrich Sure-Seal, Fisher) and were used without purification. The analyses were conducted company Midwest Microlabs, Indianapolis, Indiana, USA.

Mass-spectrometry. Mass spectra (MS) when ionization electrospray received on the device Finnigan-MAT SSQ700 (San Jose, California, USA), equipped with a device for electrospray company Analytica of Brandford. Electrospray conducted at a voltage 2400-3400 C. the Samples were dissolved in acetonitrile or dichloromethane at a concentration of approximately 10 pmol/l and introduced into the ESI device before the accumulation of data by direct input at a flow rate of 1 l/min and was introduced to the accumulation of data. Mass spectra under electron impact ionization (770 eV) were obtained on a quadrupole mass spectrometer Finnigan-MAT 4615 connected to the data processing system INCOS. The temperature of the ion source was 150oTemperatures cumulative camera 100oC. the Samples were injected using a gas chromatograph or probe direct input. Mass spectra in the regime of fast atom bombardment (FAB) were obtained using the device Finnigan MAT 212 magnetic sector connected the 70oC. Used sedatory injector fast atoms firms Ion Tech with xenon at 8 Kev. Diglycerin used as matrix FAB. Experiments MS/MS with electron impact ionization (70 kV) was performed on a tandem quadrupole mass spectrometer Finnigan-MAT TSQ/700. The sample was injected using a probe direct input. Maintained the temperature of the ion source at 150oSince, in the accumulation chamber at 70oC. Induced by a collision dissociation (ID) was achieved by introducing argon into the center collusional of octupole up until the accumulator pressure is not reached 0.9-2,5x10-6Torr (120-130 µpa). The nominal ion kinetic energy for ions obtained ID, was less than 35 eV (laboratory standard). High resolution data were obtained on a mass spectrometer Jeol JMS AX-505H with a dual focus in configuration S, using a resolution of 7500. The sample was injected using a gas chromatograph or probe direct input. When the accumulation in the ion source was introduced performerin using the heated input. Accurate inclusion mass has been computed by interpolating mass performerin. Conditions of gas chromatography-mass spectrometry (GC/MS): column DB-1701 20 m x 0.25 mm (J&W Scientific), media - helium with LineIn increasing at a rate of 10oC/min to 100oWith, split about 50:1.

Spectroscopic methods. Spectra1H-NMR operating frequency of 300 MHz and13C-NMR operating frequency of 75 MHz were obtained using the device IBM AF300 equipped superprotgame magnetic Oxford, the data accumulation was controlled by software (Bruker). Infrared spectra were obtained on a spectrometer (Mattson Galaxy 5000 FTIR under the control of a Macintosh II. Spectra UV/visible region was filmed spectrophotometer Hewlett Packard 8452A with computer Zenith Z-425/SX. EPR spectra were recorded on Bruker spectrometer ER300, equipped with a helium cryostat Oxford ESR 900. Mössbauer spectra were obtained using the instrument constant acceleration, the isomer shifts are expressed relative to iron standard at 298K. In order to avoid orientation of polycrystalline samples with imposed magnetic field, the samples suspended in a frozen Noyola.

The syntheses of macrocyclic tetraamido-N-donor ligands

The General scheme

Listed at the end of the description scheme is preferred sequence of reactions to obtain macrocyclic tetraamide ligands according to the invention.

Carboxylic-amino acid is th selective condensation (72-144 hours), allocated metroliner (A-L-A). In the second stage diamine, preferably o-phenylenediamine was added to a solution of microlender in pyridine in the presence of a condensing agent, preferably phosphorus trichloride or pivaloyloxy. The reaction of the double circuit (double-condensing) proceeded at boiling within 48-110 hours, after which the target macrocyclic tetraamide was isolated in good yield.

In the following examples 1-25 describes the different stages of the scheme. Examples 26-32 illustrate the characteristic features of the invention and its advantages.

Example 1

Synthesis microlensing intermediate (A-L-A)- methylalanine and diethyltoluenediamine (TETRAMETHYLBUTYL substituted intermediate connection)

In a two-neck flask of 1 l, equipped with addition funnel (250 ml) with pereekhala for pressure equalization and a septum, was placed in the stream of nitrogen-aminoadamantane acid (i.e., methylalanine) (vs. 20.62 g, 0.2 mol) and anhydrous pyridine (250 ml, dried over molecular sieve 0.4 nm/4 (a), the mixture was stirred under heating to 60-70oSince, then, using a dropping funnel was added a solution of diethylmalonate (23,23 ml, is 0.135 mol) in anhydrous pyridine (100 ml, Ei 60-70oWith in a stream of nitrogen or protected from moisture in the air using a tube with desiccant. The reaction was stopped by adding water (30 ml) and stirred 24 hours at 60-70oC. the Solvent was evaporated on a rotary evaporator, receiving the oil, then added concentrated hydrochloric acid (about 25 ml) to pH 2-3. The solution was cooled in the refrigerator (4oWith 15 hours) obtained yellowish-brown product was collected by filtration on a porous glass filter, thoroughly washed with acetonitrile (CH ml). The air-dried product (16,5-19,8 g, yield 50-60%) should be stored in a desiccator. This product is pure enough to be used in the reaction circuit cycle, but in some cases you may need to crystallization. Feature: range 1H-NMR (DataRepeater), , M. D.: 8.9 (s, 2H, NH amide), 2.2 (q. 4H), 1.8 (s. 12H), 1.2 (t, 6H). IR-spectrum (nujol), cm-1: 3310 (NH amide), 1721 (FROM carboxyl), 1623 (CO amide). Analysis. Calculated for C19H21N2ABOUT9: 54,53; N, 7.93; N, 8.48. Found: 54.48; N, 7.88; N, 8.47.

Example 2

Large-scale synthesis microlensing intermediate (A-L-A)- methylalanine and diethyltoluenediamine (D-substituted intermediate connection)< the partition, placed in a stream of nitrogen, -aminoadamantane acid (i.e., methylalanine) (90,3 g, 0.9 mol), then Coulibaly in the flask anhydrous pyridine (1.4 l, securely sealed), the reaction mixture was heated at 45-55oWith under stirring. Consistently Coulibaly in an addition funnel pyridine (100 ml, securely sealed and diethylmalonate (104,4 ml, 0.61 mol), the content funnel was added dropwise to the reaction mixture (3-4 hours), after which the funnel was removed and continued reaction when heated to 55-65o(120-130 hours in a stream of nitrogen. Upon completion of the acylation reaction was stopped by adding water (100 ml) and was stirred for 24-36 hours at 60-70oC. the Solvent was evaporated on a rotary evaporator, receiving the oil, then added concentrated hydrochloric acid (about 110 ml) to a final pH of 2-3. The hot solution was placed in a refrigerator (4oWith 15 hours) obtained yellowish-brown product was collected by filtration on a porous glass filter, thoroughly washed with acetonitrile (700 ml, 150 ml) while stirring in an Erlenmeyer flask. Air-dried colorless product (87,9 g, yield 60%) were crushed with a pestle in a mortar and stored in a desiccator. Amide intermediate compound, polucen the Chania cycle.

Example 3

Recrystallization of the above TMDE-substituted intermediate compounds

Untreated TMDE intermediate compound from example 2 (of 50.4 g, 0,153 mol) was dissolved in water (500 ml deionized), adding sodium carbonate (16.2 g, 0,153 mol) in three portions, to prevent excessive foaming, with stirring and slight heating. The solution was brought to boiling, filtered and acidified with concentrated hydrochloric acid (30 ml, 0.36 mol). The solution was chilled (overnight, 4oC) a white precipitate was separated by filtration 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

Hexamethylene (NM) of the intermediate compound (A-L-A)

Synthesis of NM-intermediate compounds identical to the synthesis of TMDE intermediate compounds of example 2, with some exceptions: diethylmalonate replaced diethylaluminiumchloride (17,8 ml, is 0.135 mol), the reaction temperature was lowered to 55-65oWith because of the lower boiling point Alliluyeva agent. Output hexamethylene derived 45-60%. Feature: range1H-NMR (DataRepeater), , M. D.: 9.2-9.8 (br, s, 2H, HE carboxyla), 8,23 (s, 2H, amide), 1 amide). Analysis (sample dried at 100oC). Calculated for C13H22N2ABOUT6: 51.63; N, 7.34; N, 9.27. Found: 51.64; N, 7.35; N, 9.33.

Example 5

Recrystallization NM-intermediate

Untreated hexamethylene (NM) intermediate compound was recrystallized as TMDE-amide intermediate compound. Due to better solubility in water NM-amide intermediate connections, use less water.

Example 6

Dicyclohexylmethane intermediate connection (DiCyHexDE intermediate connection)

In a round bottom flask (500 ml) were placed 1-amino-1-cyclohexanecarbonyl acid (15 g, 0.1 mol), was then inserted a drip funnel (40 ml) with pereekhala for pressure equalization, closed the septum and purged with nitrogen. Anhydrous pyridine (300 ml) was Coulibaly into the reaction flask through the addition funnel and 20 ml inside a dropping funnel. Started heating system to establish a temperature of 60oC. once the temperature has reached this value, the funnel was added with a syringe one-third of the total number of diethyltoluenediamine, which was intended to be used in this reaction (i.e., 6 ml, 0,033 mol). A mixture of the e 12 hours. The second portion (6 ml, 0,033 mol) and the third portion (6 ml, 0,033 mol) were added at intervals of 12 hours. Upon completion of addition, Alliluyeva agent and continuing the reaction (total reaction time 48-56 hours) was added dropwise 20 ml of water. The reaction mixture was additionally heated for 24 hours for disclosure ring mono - and bisoxazolines intermediate compounds with the formation of diamide dicarboxylic acid. The pyridine was removed on a rotary evaporator, receiving light yellowish-brown oil, which was acidified to pH 2 with concentrated hydrochloric acid. The crude product was collected by filtration, washed with acetonitrile and dried in the air, getting transparent DiCyHexDE-amide derivative (16 g, 74%). Feature: range1H-NMR (DataRepeater), , M. D.: 8,30 (s, 2H, NH amide), 2,60 (m, 4H, cyclohexane in), 2.25 (q, 4H, CH2ethyl), of 2.15 (m, 4H, cyclohexane), 1,8-1,5 (m, 10H, cyclohexane), 1,25 (m, 2H, cyclohexane), of 1.20 (t, 6H, CH3ethyl).13C-NMR (broadband decaborane, DataRepeater), , M. D.: 178,0 (FROM carboxyl), 174,3 (CO amide), 60,5 (cyclohexane Thu.), 59,4 (malonyl Thursday. ), 33.0 (CH2cyclohexane), 30,3 (CH2ethyl), 26,0 (CH2cyclohexane), 22,3 (CH2cyclohexane), 9,9 (CH3ethyl). IR-spectrum (nujol-NaCl) cm-1<, 621 (s, str, CO amide). Analysis. Calculated for C21H24N2ABOUT6: 61,44; N 8,35; N 6,82. Found: 61,41; N Scored 8.38; N 6,90.

Example 7

DiCyHex-determinisation

Unsuccessful attempt to stop the reaction DiCyHexDE-ethyl intermediate compounds (with the help of heat and water, see above) when using 1,35 EQ. diethyltoluenediamine; 2 EQ. Sunah-amino acids lead to a mixture DiCyHexDE-amide intermediate and monooxygenase product. Because DiCyHexDE-monoaxially the product is moderately soluble in boiling cyclohexane and cyclohexylamine intermediate compound is insoluble, there is a possibility of a simple separation of mixtures of these products, namely: about 10 g of the mixture in 400-500 ml of cyclohexane containing residual amounts of methylene chloride, was heated at boiling and vigorous stirring. Insoluble DiCyHexDE-amide intermediate product was collected by hot gravity filtration, cooling of the filtrate, and the process of evaporation slowly crystallized manookian. The output of the amide intermediate

connections approximately 6 g, the output of monoaxially about 4, the Characteristic of monoaxially. Range1H-NMR (DataRepeater), , M. D.: a 9.7 (s, 1H, NH amide is IDA), 3229 (s, str, amide linked NH/OH carboxyl), 3166 (s, str, amide linked NH/OH carboxyl), 3083 (s, str, amide linked NH/OH carboxyl), 1834 (s, str, C= O oxazolone), 1809 (s, m, associated With=About oxazolone), 1743 (s, str, CO carboxyl), 1663 (s, str, C=N oxazolone), 1639 (s, br, str, CO amide). Analysis. Calculated for C122H22N2ABOUT5x0,25 C6H12: 65,35; N 8,53 N 6,77. Found: 65,07; N 8,67; N 6,68. The presence of cyclohexane solvate confirmed13C-NMR.

Reaction macrocyclization

Some examples of synthetic methods to obtain macrocyclic tetraamide ligands are listed below.

Condensation in the presence of phosphorus trichloride

The method of condensation of the amide intermediate (A-L-A) with an aromatic 1,2-diamines in the presence of phosphorus trichloride is safe, affordable and allows you to get macrocyclic amides in high yields. Use two different versions of condensation in the presence of phosphorus trichloride, the differences associated with the order of addition and the choice of reagents. The method is applicable to a large variety of macrocycles with different electronic properties of the substituents in the bridge diamine or otlichajushegosja parallel use of amide intermediates microlensing type in all syntheses.

Example 8

A. Synthesis of macrocycle by condensation in the presence of phosphorus trichloride

In dinagalu flask (250 ml) was loaded amide intermediate compound (10 mmol) described in examples 2-7, stop stirring and the flask was heated at 80-100oC for 30-45 minutes. In hot flask was blowing nitrogen, were added erillinen (10 mmol) and Coulibaly anhydrous pyridine (50 ml, with protection from moisture in the air). The flask was heated (50-60oC) was added by syringe phosphorus trichloride (d=l,574 g/ml, 1,72 ml, 20 mmol) with such speed, to prevent violent boiling. The reaction is exothermic, so be careful. Then raised the temperature to boiling or slightly below (100-115oC) the reaction was carried out in nitrogen atmosphere for 48 hours. Upon completion of the acylation of the contents of the flask was acidified with hydrochloric acid (1 EQ. approximately 60 ml) to a final pH of 2. The mixture was transferred into an Erlenmeyer flask (use water to rinse the flask and stirred with methylene chloride (300 ml, 2-3 hours), then was extracted with additional methylene chloride (CH ml). The combined organic layers were washed with diluted hydrochloric acid (0.1 M, h ml), then diluted with water rest the hydrated product (30%). Usually the weight of the crude product equal to the weight of the original diamine.

B. Synthesis of macrocycle by condensation in the presence of phosphorus trichloride

In dinagalu flask (250 ml) was loaded magnesium sulfate (5 g), stop stirring, were added erillinen (10 mmol) and pyridine (50 ml, dried over molecular sieve 0.4 nm/4A), then let the nitrogen and a syringe was added phosphorus trichloride (d= l,574 g/ml, 1,72 ml, 20 mmol), the mixture was heated at boiling for 30 minutes, forming an orange-yellow precipitate. The mixture was cooled, was added amide intermediate compound (10 mmol), after which the mixture was heated at the boil under nitrogen atmosphere (115oC, 48 hours). Upon completion of the acylation of the contents of the flask was acidified with hydrochloric acid (1 EQ. approximately 60 ml) to a final pH of 2. The mixture was transferred into an Erlenmeyer flask and stirred with methylene chloride (CH ml). The combined organic layers were washed with diluted hydrochloric acid (0.1 M, h ml), then diluted aqueous solution of sodium carbonate (2x5 g/100 ml). Organic solvents were removed on a rotary evaporator, obtaining the crude product (30%). Usually the weight of the crude product equal to the weight of the original diamine.

Note: the greater part of pyridine before acidification removed on a rotary evaporator.

Example 9

Getting TMDE-DCB from D-intermediate and DCB-diamine

Used 1,2-diamino-4,5-dichlorobenzene (1.77 g, 10 mmol) as ariginine in the reaction of macrocyclization with TMDE-amide intermediate compound (3.3 g, 10 mmol) in the presence of phosphorus trichloride according to method a or B. the Crude macrocyclic product (2.7 g) was recrystallized from the minimum amount of hot 95% ethanol by evaporation, received net TMDE-DCB (1.5 g, 32%). Feature: range 1H-NMR (CD2C12), , M. D.: the 7.65 (s, 1H, AGN), 7,35 (s, 2H, NH amide), of 6.45 (s, 2H, NH amide), 1,90 (q, 4H, CH2ethyl), of 1.57 (s, 12H, R3) to 0.85 (t, 6H, CH3ethyl). IR-spectrum (nujol-NaCl) cm-1: 3454 (traces ROH), 3346 (br, amide NH), 1706, 1688, 1645 (amide). Analysis. Calculated for C22H28Cl2N4O4: 53.51; N, 5.99; N, 11.89. Found: 53.58; H 6.09; N, 11.89.

Example 10

Getting TMDE-B of TMDE intermediate compounds and diamine

Used 1,2-diaminobenzene (i.e., o-phenylenediamine) (1.08 g, 10 mmol) as ariginine in the reaction of macrocyclization with TMDE-amide intermediate compound (3.3 g, 10 mmol) in the presence of phosphorus trichloride according to method a or B. the Crude macrocyclic product (1.5 g) was recrystallized from the AC: range 1H-NMR (CDCl3), , M. D.: of 7.55 (m, 2H, AGN), of 7.48 (s, br, 2H, NH arylamide), 7,17 (m, 2H, AGN), 6,46 (s, br, 2H, NH alkylamide), 2.07 (m, br, 4H, CH2ethyl), to 1.60 (s, 12H, R3), to 0.89 (t, 6H, CH3ethyl). IR-spectrum (nujol-NaCl) cm-1: 3395, 3363 (NH amide), 1702, 1680, 1652, 1635 (WITH amide). Analysis. Calculated for C21H10N4ABOUT4xH2O: 59,98; N TO 7.67; N 13,32. Found: 60,18; N 7,20; N Of 13.18.

Example 11

Getting TMDE-DMB from TMDE-intermediate and DMB-diamine

Used 1,2-diamino-4,5-xylene (about 1.36 g, 10 mmol) as ariginine in the reaction of macrocyclization with TMDE-amide intermediate compound (3.3 g, 10 mmol) in the presence of phosphorus trichloride according to method a or B. the Crude macrocyclic product (1.6 g) was recrystallized from the minimum amount of hot 95% ethanol by evaporation, received net TMDE-DMB (25% diamine). Feature: range1H-NMR (d6-DMSO), , M. D. : 8,00 (s, 2H, NH amide), to 7.67 (s, 2H, NH amide), 7,28 (s, 2H, AGN), 2,17 (s, 6H, CH3aryl), 1,99 (q, 4H, CH2ethyl), a 1.46 (s, 12H, RCH3in ), 0.75 (t, 6H, CH3ethyl). IR-spectrum (nujol-NaCl) cm-1: 3446 (s, m, traces ROH), 3362 (s, str, amide NH), 3348 (sh, m, amide NH), 3332 (s, str, associated NH), 1696 (CO amide), 1679 (CO amide), 1641 (CO amide), 1584 (s, m/w, overlapping rings of the aryl and amide). Analysis.>/P>Example 12

Getting TMDE-DMOB of D-amide intermediate and D-diamine

Used dihydrobromide 1,2-diamino-4,5-dimethoxybenzene (5.0 g, 15 mmol), obtained as described above, as ariginine in scaled 1.5 times the reaction of macrocyclization with TMDE-amide intermediate compound (5.0 g, 15 mmol) in the presence of phosphorus trichloride according to method a or B. the Crude macrocyclic product (3.57 g) was recrystallized from the minimum amount of hot 80-85% ethanol (1 g/40 ml) by evaporation, received net TMDE-DMOB (30% diamine). Feature: range1H-NMR (CD2Cl2), , M. D.: 7,26 (s, 2H, NH amide), 7,01 (s, 2H, AGN), 6.41 (s, 2H, NH amide), of 3.80 (s, 6H, och3aryl), 2.07 (q, br, 4H, CH3ethyl), and 1.54 (s, 12H, R3), of 0.90 (t, 6H, CH3ethyl). IR-spectrum (nujol-NaCl) cm-1: 3451 (s, m, associated H2O), 3391, 3347 (NH amide), 1695, 1670, 1655 (amide). Analysis. Calculated for C23H34N4ABOUT6x0,22 H2O: 58,96; N 7,46; N 11,96. Found: 58,90; N 7,26; N 11,76. The presence of solvate water confirmed1H-NMR and IR spectrum.

Example 13

Getting TMDE-Nap from D-intermediate and Nap-diamine

Used 4,5-diamino naphthalene (1.68 g, 10 mmol) as Arild is East of phosphorus by the method a or B. Unoptimized output amounted to 15-20%, based on the diamine. Range1H-NMR (CDCl3), , M. D.: 8,05 (s, 2H, ring AGN), of 7.75 (m, 2H, ring AGN), 7,55 (s, 2H, NH arylamide), 7,35 (m, 2H, ring AGN), of 6.45 (s, 2H, NH alkylamide), of 2.15 (m, br, 4H, CH2ethyl), of 1.65 (s, 12H, R3), of 0.90 (t, 6H, CH3ethyl).

Example 14

Getting HM-DCB from NM-intermediate and DCB-diamine

Used 1,2-diamino-4,5-dichlorobenzene (1.77 g, 10 mmol) as the diamine in the reaction of macrocyclization with hexamethylene-intermediate connection (to 3.02 g, 10 mmol) in the presence of phosphorus trichloride according to method a or B. the Crude macrocyclic product (1,33 g, 30%) was recrystallized from the minimum amount of hot propanol by evaporation, received the first portion of the crystals with a yield of 60%. Feature: range1H-NMR, , M. D. : of 7.69 (s, 2H, AGN), 7.39 (s, 2H, amide NH), 6.44 (s, 2H, NH amide), was 1.58 (s, 12H, CH3shoulder), of 1.53 (s, 6H, CH3malonate), indicated by the small peaks propanol. IR-spectrum (nujol-NaCl) cm-1: 3503 (s, br, m-w, HE propanol), 3381 (sh, m, amide NH), 3338 (s, str, amide NH), 1689 (s, str, CO amide), 1643 (s, str, CO amide). Analysis. Calculated for C17H24N4ABOUT4Cl2x0.2C3H8ABOUT: 51,70; N TO 5.57; N 12,30. Found: 51,69; N, 5.63; N Of 12.33.

Example 15

the e connection for the synthesis of NM and NM-DMOB the same method and with the results shown in example 14 for chlorinated. Range1H-NMR for HM-DMOB (D13), , M. D.: the 7.65 (s, 2H, NH amide), 7,21 (s, 2H, aryl), 6,72 (s, 2H, NH amide), of 4.00 (s, 6H, CH3methoxy), to 1.76 (s, 12H, CH3shoulder), was 1.58 (s, 6H, CH3malonate).1H-NMR for NM-(DataRepeater), , M. D. : 8,55 (s, 2H, NH amide), 8,40 (s, 2H, NH amide), 7,81 (m, 2H, aa'bb' AGN), 7,10 (m, 2H, aa'bb' AGN), or 1.77 (s, 12H, CH3), is 1.73 (s, 6H, CH3malonate). The signal of the amide proton shifts for a few tenths of memorial plaques in the presence of such impurities as water, acids, etc.

Example 16

Getting DiCyHexDE of DiCyHexDE-intermediate and DC-diamine

Used 1,2-diamino-4,5-dichlorobenzene (1.77 g, 10 mmol) as ariginine in the reaction of macrocyclization with DiD intermediate compound (3.3 g, 10 mmol) in the presence of phosphorus trichloride according to method a or B. In connection with sterically strained it is recommended to increase the response time of the circuit cycle (3-4 days compared to the usual 48 hours). Sunah-oxazolone formed as a by-product of the reaction is not removed by acid treatment of the reaction mixture, so to remove them you need a dedicated original product, soluble in methylene chloride, treat/wash intercrystallite by dissolving in methylene chloride or chloroform with the addition of cyclohexane to the light, turbidity, after evaporation of the solvent in air (1-2 days) received DiCyHexDE-DCB in the form of a colorless microcrystalline product, which was collected by filtration (1,38 g, 25% per diamine). Recrystallization from hot toluene by evaporation seems also promising. Feature: range1H-NMR (CDCl3), , M. D.: of 7.70 (s, 2H, AGN), was 7.45 (s, 2H, NH amide). of 6.45 (s, 2H, NH amide), 2,35 (m, br, 4H, cyclohexane), 2,00 (m, br, 8H, CH3cyclohexane/ethyl), to 1.70 (m, br. 8H, cyclohexane), of 1.30 (m, br, 4H, cyclohexane), of 0.90 (t, 6H, CH3ethyl). Analysis (substance dried at 100oC). Calculated for C37H34CL2N4ABOUT4x0.2C6H12: 59,60; N FOR 6.81; N 9,86. Found: 59,60; N 6,77; N 9,77. The presence of cyclohexane confirmed1The h and13C-NMR.

Example 17

Getting DiCyHexDE-B from DiCyHexDE-intermediate and In-diamine

Used 1,2-diaminobenzene (o-phenylenediamine) (1.08 g, 10 mmol) as ariginine in the synthesis described for DiCyHexDE-DCB, got DiCyHexDE-B (1.25 g, 26% (based on diamine). Feature: range1H-NMR (CD3CN), , M. D.: a 7.62 (s, 2H, NH arylamide), 7.51 (m, 2H, AGN), 7,18 (m, 2H, AGN), 6.71 (s, 2H, NH alkylamide), 2,12 (m, 6H, cyclohexane), 1,85 (q&m, CH2cyclohexane/ethyl), of 1.62 (m, cyclohexane), to 1.37 (m, cyclone amide), 3314 (s, str, amide NH), 3258 (s, m, br, linked amide NH), 1694 (s, str, CO amide), 1651 (s, str, CO amide), 1594 (s, m, aryl ring/ amide).

Example 18

Getting DiCyHexDE-bisoxazoline

This product was obtained as a side connection in response to macrocyclization DiCyHexDE-amide intermediate with o-phenylenediamine in the presence of phosphorus trichloride. Bisoxazole was not removed by acid and alkaline processing of the reaction mixture (it is a neutral molecule, soluble in organic solvents). When washing the crude mixture of macrocyclic product and oxazolone most oxazolone goes into pentane. After evaporation of the pentane in air pure bisoxazole in the form of large (HH,5 cm) transparent prisms. Due to the presence of bulky hydrophobic Sunah groups this oxazolone much more resistant to hydrolysis than the corresponding methyl derivatives. Characteristics of bisoxazoline: range1H-NMR (CD3SP), , M. D.: 2,05 (q, 4H, CH3ethyl), 1,8-1,4 (unresolved signal cyclohexanone groups) to 0.88 (t, t N, CH3ethyl). Range13C-NMR (broadband decaborane, CD3SP), , M. D.: 181,0 (C=O of oxazolone), 162,7 (C=N oxazolone), 69,0 (kV, cyclohexane of oxazolone), 49,0 (clohexane), 8,3 (CH3ethyl). IR-spectrum (nujol-NaCl) cm-1: 1822 (s, str, br, C=O oxazolone), 1662 (s, str, C=N oxazolone). Analysis. Calculated for C22H10N2ABOUT4: 67,36; N 8,07; N OF 7.48. Found: 67,26; N 8,15; N Of 7.64.

Synthesis of chelate complexes

Example 19

Synthesis of [Et4N]2 and [E4N]3 [tetraethylammonium salts of iron(III)D-D-monoanion and iron(III)D-D-monoanion, respectively].

Source macrocyclic tetraamide (525 mg, 1.1 mmol) described in any of the above examples 10-18, was dissolved in tetrahydrofuran (Aldrich, 40 ml) in a stream of nitrogen. To the solution was added tert.-utility (2,6 ml, 4.4 mmol, 1.7 M 2.4-dimethylpentane, the firm Aldrich) in a stream of nitrogen at -108oWith using the device Slanka. Then were added ferric chloride (anhydrous, 155 mg, 1.2 mmol, Alfa), to the solution under stirring was allowed to warm to room temperature (16 hours) were sensitive to air moisture complex of FeII. The air is admitted through the tube with desiccant (2 hours), solid orange substance was collected and washed with methylene chloride (2x10 ml). The obtained orange powder was dried under reduced pressure. The output of 595 mg (93%). In connection with changing solvation and limited solubility ü (595 mg) in methanol (50 ml) was applied to the ion-exchange column (Dowex h-100, 25 g, 2x12,5 cm), which was pre-saturated cation [Et4N]+the orange band was suirable methanol (100 ml). The solvent was removed under reduced pressure. The residue is suspended in methylene chloride (20 ml), the mixture was filtered. The solvent was removed from the filtrate under reduced pressure, getting orange hygroscopic glassy residue [Et4N]22, which was used for final purification. IR-spectrum (nujol-NaCl) cm-1: 1619 (CO amide), 1575 (CO amide), 1534 (CO amide). A thorough treatment of the source material (iron(III) was more easily achieved in the case of axial aquatuning complex and not this axial hardening complex. Dissolved [Et4N]22 (550 mg, 0.7 mmol) in acetonitrile (50 ml). Tetrafluoroborate silver (140 mg, 0.7 mmol) was dissolved in acetonitrile (2 ml) and was added to the solution under stirring (1 hour). The precipitate of silver chloride was separated, the solvent was removed under reduced pressure. Received [Et4N]23 was purified column chromatography on silica gel (8% methanol in methylene chloride). The solvent was removed under reduced pressure, the product was recrystallized from water. Yield 360 mg (77% unstable solvate with water on the 35 (CO amide). Analysis. Calculated for C29H46C12FN5ABOUT5(H2O): 50,52; N 7,02; C1 10,28; N 10,16. Found: 50,24; N 6,84; C1 10,32; N 9,82. Mass spectrum (electrospray, negative ion), m/z: 522,2 [3-N2O]1-, (100%); 269,7 [3-N]2-, (18%).

Example 20

Synthesis of [Et4N] 4 [tetraethylammonium salt of iron(IV)D-D-monoanion]

Dissolved [Et4N]22 (500 mg, about 0.6 mmol) in methylene chloride (30 ml). To the solution was added ammoniate(IV)nitrate (10.3 g, and 18.3 mmol), the mixture was stirred for 2 hours. The precipitate salts of cerium was removed by filtration. After removal of the solvent under reduced pressure and dry the residue in vacuum received a purple product. 400 mg (95%). Purple crystals were obtained by recrystallization from a mixture of methylene chloride-ether. IR-spectrum (nujol-NaCl) cm-1: 1688 (CO amide), 1611 (CO amide), 1582 (CO amide). Mass spectrum (electrospray, negative ion), m/z: 557 [4]1-, (100%); 522 [4-C1]1-. (65%).

Example 21

Synthesis of [Ph4P] 5 [tetraphenylphosphonium salt of iron(IV)D-D-monoanion] from [E4N]4 [tetraethylammonium salt of iron(IV)D-D-monoanion] and sodium cyanide

Suspended [Et4N] 4 [tetraethylammonium salt iron is ribasso with suspension, the mixture was irradiated with ultrasound (device mark Branson 1200, 0.5 hours). Suspension changed color from purple to dark blue, almost all of the solid had dissolved. The mixture was filtered, the product is blue besieged, adding PPh4Cl (chloride tetraphenylporphine) dissolved in water (600 mg, 1.6 mmol, 10 ml, Aldrich company). Gathered blue precipitate and washed with water (2x10 ml). Yield 250 mg (0.28 mmol, 85%). This substance (120 mg) was then purified by thin-layer chromatography (TLC) (plate with silica gel GF, 20x20 cm, methylene chloride-acetonitrile, 10:1). The blue substance was extracted from silica gel with a mixture of acetonitrile-methylene chloride (1: 1, 60 ml). The solvent was removed under reduced pressure, the residue was dissolved in methylene chloride (3 ml), the solution was filtered. Adding pentane (150 ml) was awarded a blue precipitate (90 mg, 0.10 mmol). The yield after purification 75%. IR-spectrum (nujol-NaCl) cm-1: 2129 (CN), 1659 (CO amide), 1598 (CO amide), 1571 (CO amide). Analysis. Calculated for C46H44CL2FeN5PR: WITH 62,18; N 4,99; C1 7,98; N 7,88. Found: 61,96; N 5,04; C1 Of 8.06; N 7,84. Mass spectrum (electrospray, negative ion), m/z: 548,2[5]1-, (100%); 522,1 [5-CN]1-, (20%). For13C-labeled cyanide m/z: 549,2[5]1-, (100%); 522,1[5-13CN]1-. (8%).

Example 22

SIA

[Ph4P] 5 [tetraphenylphosphonium salt of iron(IV)D-D-monoanion] can be obtained in the presence and in the absence of base. In the absence of base blue color by removal of the solvent in the processing goes to yellow-orange. Therefore, in order to get the blue precipitate, there should be a selection in the presence of added base at pH in the range of 9-10. In the following reaction 5 is formed using any of nitrilotri solvents (acetonitrile, deuterocanonical, propionitrile, isobutyronitrile). In the case described catalytic reactions base is not added. It was shown that the blue connection is an effective catalyst precursor: adding selected [RH4R]5 to a solution of TNR (tert. -butylhydroperoxide) in acetonitrile as a solvent and oxidant were used, suggesting that, although [RH4R]5 is the final product of the process of catalytic oxidation, it is not deactivated form of the catalyst.

Example 23

Synthesis of [Ph4P]5 in the presence of base

Dissolved [Et4N]4 (160 mg, of 0.23 mmole) in selected matrilateral solvent, was added tetradium the peroxide (90%, 0,605 mm, 5.4 mmol) with stirring for 20 minutes, forming a blue solution. The reaction mixture was evaporated under reduced pressure, the remaining oily residue (15 ml) was filtered. The blue substance was besieged from aqueous solution PPh4Cl (800 mg, 2.1 mmol, Aldrich company), collected and washed with water (2x10 ml). The output of 130%. Further purification was performed as described for [Ph4P]5.

Example 24

These x-ray analysis and cleanup [Et4N]3H2ABOUT

C29H48Cl2FeN5ABOUT6M 689,47, triclinic space group P-1, a= 9,899(2); b=11,771(2); C=1,4991(4) nm/14.991(4) =95,33(2), =100,09(2); = 92,31(2)oV=1,7096(6) nm3/1709,6(6) DOBS.=l,33 Pol-3Dthe calc.(Z=2)=1,339 fuel-3T=293 K, =0,071069 nm/(0,71069 =0.64 mm-1TRANS-coefficient. of 0.87 to 1.00. These diffraction were obtained at room temperature on the diffractometer Enraff-Nonius CAD-4 using graphite monochromatic radiation Mo-K. during data collection was controlled by three reflection, and watched only the random fluctuations of intensity. The structure was solved using direct methods. Hydrogen atoms associated with carbon included in the calculation of provisions with a bond length of carbon-hydrogen 0,096 nm/0,96 , purification was performed using the stroke is spilogale on the differential electron density maps, their coordinates were allowed to clean thermal parameter fixed at 20% higher than that of oxygen. All other atoms were cleaned with anisotropic thermal parameters. The final differential maps were deprived of the characteristic features. Cleaning conversional to R=0,053, wR2= 0,112 with a multiplier of 1.0/[2(F02)+{0,0652(F2+ 2F2)/3}2] for 2262 received reflections.

Example 25

These x-ray analysis and cleanup [Et4N]4

The single crystals [Et4N] 4 201oTo represent the monoclinic spatial P2l/c-c52h(No. 14) with a=0,9958(2) nm/(9,958(2) b=1,4956(3) nm/14,956(3)=2,2688(5) nm/(22,688(5) =90,00, =93,83(2), =90,00, V= 3,372(1) nm3/(3372(l) Z= 4 (dthe calc.=l,Pol 357-3:1(CuK)=6,17 mm-1). From 4626 independent reflections with corrected absorption, with 2(SiC), were selected 115,0 using 2 scan and radiation SiC with Ni-filter. The structure was solved using Direct methods, software Nicolet SHELXTL modification Crystalytics Company. The obtained structural parameters are restricted convergence R1(unweighted average value, based on F)= 0,037 for 2680 independent reflections with 2(SiC)<115,0 and >3(I). Ten methyl groups were refined group was determined by the difference of the provisions of the Fourier series for hydrogen atoms. The final orientation of the metal group was determined using the parameters of free rotation. Peeled provisions for rigid rotating methyl groups had the angles C-C-H, which varies 103-118. The remaining hydrogen atoms were included in calculations of structural factors such as idealized atoms (assuming sp2or SP3-hybridization of carbon atoms and the bond length of C-H 0,096 nm/0,96 located at the respective carbon atoms. The isotropic thermal parameter of each hydrogen atom was set to 1.2 equivalent isotropic thermal parameter of the carbon atom to which it is covalently bonded.

Example 26

Increased duration catalytic stability

Compared catalytic durability in two variants of the embodiment of the present invention (Fig. 3). In compound 1, each of the substituents R' and R" means a metal group, whereas in compound 2, each of the substituents R' and R" means ethyl group. In the control did not add any catalyst.

Conditions: pH 9, room temperature (21,1oC) a buffer containing bicarbonate and sodium carbonate, as the developer used 4 mm (30%) hydrogen peroxide. Each asterisk means PR is Ribalta dye almost immediately led to discoloration. In the case of compound 2 discoloration occurred gradually. In the control discoloration occurred even slower.

It follows from the above that the compounds according to the invention, particularly compound 1, are effective in the oxidation and discoloration of extraneous dyes and dyes coming from dyed textiles in the washing process. Coming dyes may be absorbed or adsorbed on the adsorbent or absorbent, such as other textile product. Thus, macrocyclic tetraamide compounds according to the invention provide a unique advantage oxidative system, namely, give it the property trap dye, thereby preventing the unauthorized transfer, and therefore undesirable, dyes in the washing liquid from one textile to another.

The following examples 27-30 illustrate the unique ability of bleach activators according to the invention to oxidize the absorbed or adsorbed substances, such as dyes in the solution at a rate sufficient to suppress the absorption or adsorption them on a substrate such as a textile product. The ability to rapidly oxidize in solution gives macrocyclic tetraamine absorption depending on the time recorded on a Shimadzu spectrophotometer. The samples were scanned in the range of 350-700 nm before adding peroxide or catalyst in order to determine the wavelength of maximum absorption of the dyes. Then the spectrophotometer was set at a specific wavelength and added peroxide and/or a catalyst. After 2 minutes was determined changes of maximum absorption.

In the case of the dye Acid Blue 25 was measured at 600 nm. The samples were measured at 25oWith a cuvette of 1 cm, containing 2 ml of solution.

Example 27

Bleaching of the dye Acid Blue 25 in solution

To a solution of Acid Blue 25 (120 mg/l, the content of the colorant 45%, the initial absorption at 600 nm was 1.2) added; (a) 20 M. D. A. O. H2ABOUT2; (b) 20 M. D. A. O. H2ABOUT21 M. D. compounds according to the invention, where Z and Y each denote a hydrogen atom ("FeB"); (C) 20 M. D. A. O. H2ABOUT21 M. D. compounds according to the invention, where Z and Y each denote a chlorine atom (hereinafter "FeDCB"). As shown below, only with systems containing catalyst obtained any whitening effect (controlled for the observed change in absorption at 600 nm after two minutes). For comparison has detected a loss absorption caused by sodium hypochlorite (5.25% of the solution, the average value of the bleaching of the dye. The above data show that when using the catalysts according to the invention there is effective suppression of the migration of the dye. When compared to the number of added dye (initial absorption 1,2) loss of dye was more than 90% (1,15:1,h=95,83%).

Example 28

Bleaching of the dye Acid Orange 8 in solution

The experiments were conducted as in example 27, except that he used a solution of dye Acid Orange 8 (210 mg/l, the content of the colorant 65%, the initial absorption at 490 nm was 1.2). Bleaching was measured by the change in absorption at 490 nm (see tab.2).

And again when compared to the number of added dye (initial absorption 1.2) loss of dye was more than 90% (1,15: 1,h= 95,83%). The transfer of dye (E) was calculated in accordance with the methodology described in U.S. patent 5,698,476 of 16 December 1997 authors Johnson and others, entitled "Washing composition for preventing migration of the dye and its indicator. The value of E reflects the average of the observed changes of the articles of fabrics before and after washing in accordance with the above equation. The increase in the calculated values of E for the test items, washed in with what the product has absorbed the dye. All dyes were obtained from the firm Aldrich Chemicals.

The following examples 29 and 30 were used in the following conditions: 0.95 g of detergent Ultra Tide(Procter & Gamble) was made in the washtub Terg-O-Tometer with 1.5 liters of warm water, two examinees products made from cotton size 20,h,32 cm/8 x 8 inches (large sample) and the product which was isolated dye in solution. The purpose of the test items was to serve as a receptor for any extraneous dye that has not been bleached or oxidized. The samples were stirred for 12 minutes after addition of catching paint system (hydrogen peroxide and catalyst), using a Terg-O-Tometer, then for two minutes, rinsed with water and ambient temperature and within 20 minutes was dried in an automatic dryer.

Example 29

The transfer of ink from one fabric to another by use of the dye Direct Red 79

In order to demonstrate that the phenomena observed in the above experiments carried out in solutions, influence present in solution, the fabric, conducted an experiment of pure samples of cotton fabric were immersed in the model washing liquid containing the product, which was released in races is ilenia E. The intensity of the suppression of the migration of the dye was compared with the effect of polyvinylpyrrolidone (PVP), a standard inhibitor of the transfer process dye. In the data the smaller the score, the better the suppression (see tab.3).

The above data show that the macrocyclic tetraamide ligands according to the invention not only exhibit high inhibitory effect on the transfer process dye, but far superior in efficiency polyvinylpyrrolidone, known and effective inhibitor of the transfer process dye.

Example 30

The transfer of dye from the fabric on the fabric using dye Acid Red 151

The experiments were conducted in accordance with example 29, using a product that was released 0.1 g of the dye Acid Red 151 (see tab.4).

In the following example, the action FeDCB on mustard and natural alumina were compared with those for systems containing only hydrogen peroxide. Compounds according to the invention are excellent in specific relation dye effect on the mustard, which is charged cationic dye.

Example 31

Remove mustard stains and soil

This example demonstrates the removal of stains when similaralcohol detergent Alland oxidant system (either hydrogen peroxide or the hydrogen peroxide with the catalyst according to the invention FeDCB). Washing conditions: the average level of warm water, rinse with cold water using a Terg-O-Tometer. Measured the removal of stains and calculated % of spot removal (%SRE). Thus, the preferred are the higher scores.

The results are given in table. 5.

In the following example, the action of the compounds according to the invention against the re-deposition of contamination were compared with those in the control (no activator compounds) and in the presence of commercially available organic bleaching activator - tetraacetylethylenediamine (TAED).

Example 32

A comparative study of the actions against the re-deposition is shown below.

The system is Re-deposition

Control - 0

Control and FeDCB - 1,3

Control and TAED - 0,7

Re-deposition of contamination was evaluated after the washing process of the product, using the method of calculation whitening Stensby. This study shows that random dyes, collapsing in an aqueous washing liquid, prevent the re-deposition of dirt on the products; and that the effect according to the invention is superior to the source of an oxidizing compound and a bleach activator, characterized in that the bleach activator it contains resistant to oxidation macrocyclic terminoligy formula

< / BR>
where X and Z denote the hydrogen atom, electron-donating or electron-withdrawing group;

R' and R" denote alkyl and cycloalkyl;

M stands for a transition metal with oxidation States of I, II, III, IV, V or VI, VII or VIII or selected from 3, 4, 5, 6, 7, 8, 9, 10 or 11th group of the Periodic table of elements, the system IU;

Q is any counterion which would have balanced the charge of the compound on a stoichiometric basis;

L, if present, means labile ligand, and when present in aqueous solution, L represents water.

2. The bleaching composition containing an effective amount of a source of an oxidizing compound and a bleach activator, characterized in that the bleach activator it contains resistant to oxidation macrocyclic terminoligy formula

< / BR>
where X and Z denote the hydrogen atom, electron-donating or electron-withdrawing group;

R, R' and R" means any combination of alkyl and cycloalkyl;

M stands for a transition metal with oxidation States of I, II, III, IV, V, VI, VII or VIII or selected from 3, 4 is which balances the charge of the compound on a stoichiometric basis;

L, if present, means labile ligand, and, when present in aqueous solution, L represents water.

3. The whitening composition under item 1 or 2, characterized in that the said oxidizing compound is a peroxide compound selected from the group consisting of hydrogen peroxide, adducts of hydrogen peroxide, compounds capable of forming hydrogen peroxide in aqueous solutions, organic peroxides, persulfates, perphosphate and perserikatan.

4. The whitening composition under item 1 or 2, characterized in that X and Z independently are selected from the group consisting of hydrogen atom, halogen atom, group of SO3-group OSO3-group S3R, in which R means a hydrogen atom, alkyl, aryl or alkylaryl, and group NO2-.

5. The whitening composition under item 1 or 2, wherein R' and R" are selected from alkyl (C1-6.

6. The whitening composition under item 1 or 2, characterized in that it further comprises an excipient selected from the group consisting of surfactants, fillers, bonding agents, insulating substances, antioxidants, enzymes, fluorescent whitening agents, krasivi composition p. 1 or 2, wherein M stands for an atom of iron or manganese atom.

8. The bleaching composition according to p. 5, wherein R' and R" are selected from alkyl (C1-6or connected to form cycloalkyl.

9. The method of bleaching textile comprising contacting the surface or products with bleaching composition, wherein the whitening composition is a composition under item 1.

10. The method of suppressing the absorption and adsorption of contaminants or dyes on at least one absorbent or absorbent substrate, representing a textile product, water and washing up liquid, using a bleaching composition, characterized in that use an aqueous solution of a bleaching composition according to p. 2.

11. The method according to p. 10, wherein the oxidizing compound is a peroxide compound.

12. The method according to p. 11, characterized in that the said peroxide compound selected from the group consisting of hydrogen peroxide, adducts of hydrogen peroxide, compounds capable of forming hydrogen peroxide in aqueous solutions, organic peroxides, persulfates, perphosphate and perserikatan.

13. The method according to p. 10, the same time, what solvent is water.

15. The method according to p. 10, wherein M stands for an atom of iron or manganese atom.

 

Same patents:

The invention relates to macrocyclic metal complexes of ligands, used as bleach activators

The invention relates to the field of pulp and paper production and concerning the technology of bleaching of sulphate pulp from deciduous or coniferous wood, or a mixture thereof

The invention relates to the pulp and paper industry and can be used in the manufacture of bleached sulfite cellulose magnesium base for the production of paper with the increased demand for white

The invention relates to the pulp and paper industry and relates to a technology of bleaching wood pulp from deciduous or coniferous wood

The invention relates to the pulp and paper industry, in particular to methods of producing bleached chemi-thermomechanical pulp for making paper of various kinds

The invention relates to the field of pulp and can be used to produce bleached pulp without using chlorine-containing reagents, molecular chlorine, and chlorine dioxide (TCF - cellulose)

The invention relates to macrocyclic metal complexes of ligands, used as bleach activators

The invention relates to percarbonate sodium-containing detergent compositions

The invention relates to household chemicals, in particular to a composition for bleaching textile materials

Powdered detergent // 2177986
The invention relates to the production of synthetic detergent designed for washing textiles

The invention relates to synthetic detergents used for washing textiles

The invention relates to pre-treatment of contaminated tissues, to compositions suitable for use in pre-processing and pre-processing

The invention relates to pre-treatment of contaminated tissues, to compositions suitable for use in pre-processing and pre-processing

The invention relates to detergent compositions for soaking

The invention relates to methods of pre-treatment of fabrics to improve their safety and/or color using a peroxide bleaching compositions

The invention relates to macrocyclic metal complexes of ligands, used as bleach activators
Up!