The method of producing arylalkylamines, the transition metal complex

 

(57) Abstract:

Described is a method of obtaining arylalkylamines, which involves the selective oxidation of arylalkylamines having the formula I

where P and Q are alkyl groups and may be the same or different from each other; X is an integer from 1 to 3; and ar is an aromatic hydrocarbon group having a valency of X, the oxygen-containing gas in the presence of a catalyst based on a complex of the transition metal, which contains as a ligand cyclic polyfunctional aminosilane having at least three nitrogen atom in the ring, forming a molecular chain, or a polyfunctional aminosidine with an open circuit, having at least three atoms in the main chain of the molecule, provided the complex of the transition metal is not a complex of porphyrin or phthalocyanine complex. This method allows to obtain arylalkylamine selectively in a high concentration at a high reaction speed without noticeable decomposition of the resulting organic hydroperoxide. Also disclosed are complexes of transition metals such as iron, Nickel, manganese, cobalt, copper, routinel.

This invention relates to a method of obtaining arylalkylamines selective oxidation of arylalkylamines in the corresponding arylalkylamine in high concentration oxygen-containing gases in the presence of transition metal complexes as catalysts, which contain both the ligand cyclic or open-chain polyfunctional organic amino compounds having at least three nitrogen atom in the molecule. This invention further relates to such transition metal complexes.

Arylalkylamines are used as starting materials for the production of several commercial chemicals, for example, for the production of phenol and acetone from monohydroperoxide cumene.

Description of the prior

Already, the number of known methods for the production of arylalkylamines oxidation arylalkylamines in the corresponding arylalkylamine in oxygen-containing gases in the presence of a catalyst.

For example, the method described in the publication of Japanese patent N 50-50020, in which the alkyl benzenes having secondary alkyl groups, such as 3,5-dimethiconol, was oxidized in the presence of the manganese, copper or iron, having polyaminocarboxylic acids such as ethylenediaminetetraacetic acid (EDTA) as the ligand, giving the corresponding arylalkylamine.

In accordance with this method, it is necessary that the alkali was added sequentially in an aqueous solution in which the reaction is carried out in the presence of a catalyst to establish in the solution slightly acidic pH in order to prevent receiving side of oxalic acid or acetic acid, which inactivate the catalyst. Moreover, the method has the additional disadvantage due to the fact that the oxidation reaction does not occur with practical speed at such a relatively low temperature of approximately 80oC, at which thermal decomposition of finite organic hydroperoxides can be neglected.

Summary of the invention

The object of the invention is a method for the production of arylalkylamines selective oxidation of arylalkylamines in the appropriate arylalkylamine in a high concentration, while limiting thermal decomposition of the resulting hydroperoxides oxygen-containing gases using predecessorconditionoperation, which includes the selective oxidation of arylalkylamines having the formula (I):

< / BR>
where P and Q are alkyl and may be the same or different from each other; X is an integer from 1 to 3: and Ar is an aromatic hydrocarbon group having a valency of X, the oxygen-containing gas in the presence of complex transition metal as catalyst, which contains as a ligand cyclic polyfunctional aminosilane having at least three nitrogen atom in the ring, forming a molecular chain, or open-chain polyfunctional aminosilane having at least three nitrogen atom in the main chain of the molecule, provided the complex of the transition metal is not a complex of porphyrin or phthalocyanine.

Description of the preferred embodiments

1. Source arylalkylamine.

Arylalkilether (I), used as a starting material in the method of the invention has the formula (I):

< / BR>
where P and Q are alkyl and may be the same or different from each other; X is an integer from 1 to 3; and Ar is an aromatic hydrocarbon group having a valency of X.

You want arylalkylamine the hydrogen had hydrogen, associated with the tertiary carbon atom. Alkyl is preferably stands. In turn, an aromatic group having a valency of X, such that it is chosen from benzene, naphthalene, biphenyl or diphenyl ether, preferring the first two.

Preferred examples of arylalkylamines include, for example, diisopropylbenzene, such as cumene, zymol, m-diisopropylbenzene or p-diisopropylbenzene, triisopropylbenzene, such as 1,3,5-triisopropylbenzene, ethylbenzene, secondary butylbenzoyl, secondary utilitiesa, isopropylnaphthalene, diisopropylnaphthalene, such as 2,6-diisopropylnaphthalene, isopropylphenyl, diisopropylphenyl, such as 4,4'-diisopropylphenyl. These arylalkylamine only illustrative, and the invention is not necessarily limited to these examples arylalkylamines.

In accordance with the invention, arylalkilether selectively oxidized to the corresponding arylalkylamine oxygen-containing gas in the presence of a catalyst based on a transition metal, which contains as a ligand cyclic polyfunctional aminosilane having at least three nitrogen atom in the ring, forming a molecular chain, and the and molecules.

In the following formulas, which show preferred examples of the transition metal complexes used in the present invention, the formula in the parentheses are the polyfunctional amino compounds, i.e., the ligands.

2. Complex catalysts containing cyclic polyfunctional amino compounds as ligands.

First, the catalyst on the basis of a complex of the transition metal, comprising as a ligand cyclic polyfunctional aminosidine, will be described.

The first catalyst on the basis of a complex of the transition metal used in the invention is an electrically neutral complex has the formula (II):

< / BR>
where A denotes the independent alkylene having 1-6 carbons in the main chain of the group, phenylene, naftilan (naphthalenediol), phenanthrolin (finalrender), pyridinyl, pyrrolidinyl, pyrazinyl, pyrimidinyl or 1,3,5-triazinyl and may contain inert substituents; R is independently hydrogen, alkyl, aryl, alkylaryl or arylalkyl, and alkyl, aryl, alkylaryl or arylalkyl may contain inactive substituents; M is a Central transition metal ion having a valency of +a; X is a counterion, the ima number, n means 1 to 4, n is equal to a/b and m denotes 0 or a positive integer of 1 or greater.

In General, the catalyst on the basis of a complex of the transition metal can change the oxidation state of the Central metal ion during the oxidation of arylalkylamine. For example, the oxidation state of the Central metal ion can be increased. In this case, the anion present in the reaction medium, to form a counterion, corresponding to an increase in the degree of oxidation of the Central metal ion.

In the above formula (II), A is independently alkylene having 1-6 carbons in the main chain of the group, phenylene, naphthalenol, phenanthroline, pyridinium, pirramimma, pyrazinediium, pyrimidinium or 1,3,5-triazinium. An example of alkylene may be ethylene, trimethylene, tetramethylene, pentamethylene or hexamethylene, and ethylene is most preferred.

Group represented by A may contain inert substituents such as alkyl, alkoxyl, aryl, alkylaryl, arylalkyl, ethynylene, ester group, cyano, amino, amido, sulphonamide, carboxyl, carboxylate, hydroxyl or ester group.

R independently denotes hydrogen, alkyl, aryl, alkylaryl or arylalkyl, and and the more.

The alkyl preferably has 1-25 carbons, and may be, for example, stands, ethyl, propylene, bootrom, Pentium, hexyl, actilon, decyl, undecimo, dodecyl or tridecyl. Examples of the aryl can be phenyl or naphthyl. Alkylaryl can be represented, for example, talila, while arylalkyl, for example, benzyl.

Inactive substituents, which R may contain, represent, in particular, hydroxyalkyl, such as hydroxyethyl, hydroxypropyl or hydroxybutyl, alkoxyalkyl, such as methoxyethyl, methoxypropyl, methoxybutyl or methoxyphenyl, ester group containing alkyl, such as carboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl, acetate, propionate or butyrate, cianelli, such as cyanomethyl, cyanoethyl, cyanopropyl or cyanomethyl, aminoalkyl such as aminoethyl, aminopropyl, aminobutyl or aminopentyl, aminogroup containing alkyl, such as acetamidomethyl, acetylamino, acetaminophen, benzoylamino or benzylaminopurine, or sulfa group containing alkyl, such as methylsulfinyl, methylsulfinylpropyl, methylsulfinylbutyl, phenylsulfinyl, phenylsulfinyl, tolilsulfonil or tolilsulfonil has three nitrogen atom in the ring, forming a molecular chain (diazacrown), and which forms a ligand in the first complex of the transition metal, had the formula (II) in which A is an ethylene group.

Preferred examples of such diazacrown are connections from 1-01 to 1-18. (see connections from 1 - 01 to 1 to 18 to the end of the description).

In turn, most preferably, the cyclic polyfunctional aminosidine, which has four nitrogen atom or more in the ring, forming a molecular chain, and which forms a ligand in the first complex of the transition metal, had the formula (II) in which A is ethylene, trimethylene, 2,6 - pyridinediamine, 2,5-Perryville or 2,2'-bipyridyl-6,6'- deeley group, and m is an integer of 1-4.

Preferred examples of such cyclic polyfunctional amino compounds are from 2-01 to 2-16, (see connections from 2 - 01 2 - 16 in the end of the description), where R is alkyl with 1-8 carbons, aryl with 6-14 carbons, such as phenyl, arylalkyl with 7-14 carbons such as benzyl, or alkylaryl with 7-14 carbons, such as tolyl.

The second catalyst on the basis of a complex of the transition metal used in the present invention, has the formula
where Y1and Y2independently are alkylene having 1-6 carbons in the main chain groups, or phenylene, and may contain inactive substituents, R is independently mean hydrogen, alkyl, aryl, alkylaryl or arylalkyl, and alkyl, aryl, alkylaryl or arylalkyl may contain inactive substituents,

M means the Central transition metal ion having a valency of +a; X is a counterion having a valence-b, which is stable under oxidation; a represents an integer of 1-4, b denotes a positive integer, n denotes 1-4, n = a/b.

Particularly preferably, Y1and Y2was ethylene or trimethylene, and R is hydrogen.

Accordingly, preferred examples of the cyclic polyfunctional amino compounds, which form the ligand of the second complex of the transition metal (III) are compounds from 3-01 to 3-08 (see connections from 3-01 to 3-08 at the end of the description).

The third catalyst on the basis of a complex of the transition metal used in the invention has the formula (VI):

< / BR>
where A is independently alkylene having 1-6 carbons in the main chain of the group, phenylene, naphthalenol, phenanthroline, pyridinium, pirramimma, pyrazolidine), having 2-10 carbons in the main chain of the group,

< / BR>
and may contain inert substituents; R is independently hydrogen, alkyl, aryl, alkylaryl or arylalkyl, and alkyl, aryl, alkylaryl or arylalkyl may contain inactive substituents; M is a Central transition metal ion having a valency of +a; X is a counterion having a valence-b, which is stable under oxidation; a represents an integer of 1-4, b stands for a positive integer n means 1 to 4, n is equal to a/b and m denotes 0 or a positive integer of 1 or greater.

Preferred examples of the bis(alkylidene) of the group are the following:

< / BR>
The preferred examples, in addition, bis(alkylidene)groups, which contain heteroaromatic ring, are the following:

< / BR>
Accordingly, preferred examples of the cyclic polyfunctional amino compounds represented by the compounds from 5-01 up 5-04 (see connection from 5-01 up 5-04 at the end of the description), where R is alkyl with 1-8 carbons, aryl with 6-14 carbons, such as phenyl, arylalkyl with 7-14 carbons such as benzyl, or alkylaryl with 7-14 carbons, such as tolyl.

The fourth catalyst based on a complex perehodnik the relevant 1-6 carbons in the main chain of the group, the phenylene, naphthalenol, phenanthroline, pyridinium, pirramimma, pyrazinediium, pyrimidinium; B is bis(alkylidene) having 2-10 carbons in the main chain of the group,

< / BR>
and may contain inert substituents; R is independently mean hydrogen, alkyl, aryl, alkylaryl or arylalkyl, and alkyl, aryl, alkylaryl or arylalkyl may contain inactive substituents, M is a Central transition metal ion having a valency of +a; X is a counterion having a valence-b, which is stable under oxidation; a represents an integer of 1-4, b stands for a positive integer n means 1 to 4, n is equal to a/b and m denotes 0 or a positive integer of 1 or greater.

Preferred examples of the bis(alkylidene) groups may be the same as mentioned here in connection with the fourth complex of the transition metal.

Preferred examples of cyclic polyfunctional amino compounds represented by the compounds from 6-01 up 6-04 (see connections from 6-01 up 6-04 at the end of the description), where R is alkyl with 1-8 carbons, aryl with 6-14 carbons, such as phenyl, arylalkyl with 7-14 carbons such as benzyl, or alkylaryl with 7-14 carbons, such as tolyl.

In any of the fo is out, as indicated above, M is a Central transition metal ion having a valency of +a, where a is an integer of 1-4. Preferred examples of the transition metal is iron, Nickel, manganese, cobalt, copper, ruthenium, rhodium, among which iron, Nickel, manganese, cobalt, copper or ruthenium are particularly preferred.

X is a counterion having a valence-b, which is stable under the oxidation, where b is a positive integer.

Preferred examples of the counterion are, for example, halogenation, such as chloride ion or bromide ion, SO4-(sulfate ion), NO3-BF4PF6-, ClO4-, CO3-P2O74-, S2O62-, anions of organic carboxylic acids, such as oxalate ion, acetate ion, triptorelin ion, propionate ion, naphthenate ion, benzoate ion, aftout ion, anions of organic sulfonic acids, such as methanesulfonate ion, triftorbyenzola ion, bansilalpet ion or p-toluensulfonate ion, or peroxidation, such as semiprocessed anion. In addition, the examples include acetylacetonate or squared ion.

In formulas and is an integer of 1-4, b is the integer 1 or more, preferably 0, 1, 2, or 3.

According to the invention the first complex of the transition metal is particularly preferred. Here may be mentioned as preferred examples, in which the ligand or cyclic connection polyfunctional aminosidine are treasureroom, for example, (1,4,7-triazinone)manganese (II) sulfate, (N, N', N"- tributyl-1,4,7-triazinone)manganese (II) sulfate, (N,N',N"- dibenzyl-1,4,7-triazinone)manganese (II) sulfate, (N,N',N"- Tris(3-hydroxypropyl)-1,4,7-triazinone)manganese (II) sulfate or (N, N', N"-Tris(potassium propionate)-1,4,7-triazinone)manganese (II) sulfate.

Here may be mentioned as preferred examples, in which the ligand or cyclic polyfunctional aminosidine has four nitrogen atom or more in the ring, forming a molecular chain, for example,

(1,4,8,11-tetraazacyclotetradecane)manganese (II) sulfate,

(1,4,8,11-tetraazacyclotetradecane)cobalt (III) chloride,

(1,4,8,11-tetraazacyclotetradecane)copper (II) sulfate,

(1,4,8,11-tetraazacyclotetradecane)ruthenium (II) chloride,

(1,4,8,11-tetraazacyclotetradecane)Nickel (II) sulfate,

(1,4,8,11-tetraazacyclotetradecane)manganese (II) benzoate,

(1,4,8,11-tetraazacyclotetradecane)cobalt (II) benzoate,

(1,4, who allamerican)]cobalt (II) sulfate,

(1,4,8,11-tetraazacyclotetradecane)manganese (II) stearate,

(1,4,8,11-tetraazacyclotetradecane)cobalt (II) stearate,

[N, N',N",N"'-Tetra-n-butyl - (1,4,8,11-tetraazacyclotetradecane)] manganese (II) sulfate.

In addition, examples are complexes of copper sulfate, benzoate complexes of copper complexes of cobalt sulfate, cobalt acetate or chloride complexes of ruthenium with one of the cyclic polyfunctional amino compounds 3-01, 3-08, from 4-01 to 4-09, 5-01 to 5-04 and from 6-01 to 6-03.

3. Complex catalysts containing polyfunctional amino compounds with an open circuit as ligands.

Now will be described catalysts based on transition metal complexes that contain as ligand polyfunctional amino compounds with an open circuit.

The first catalyst on the basis of a complex of the transition metal has the formula (II):

< / BR>
where A is independently alkylene having 1-6 carbons in the main chain of the group, o-phenylene, m-phenylene, p-phenylene, 1,8-naphthalenol, 9,10-phenanthroline, 2,6-pyridinium, 3,6 - acridinium, 2,2'-bipyridyl - 6,6'-deylam, 1,10 - phenanthroline-2,9-deylam, 2,6-pyrimidinium, 4,5 - pyrimidinium, 2,6-pyrazinediium, 2-phenyl-1,3,5-triazine-2,6-deylam.

1and R2may contain inactive substituents; K21, K22, K23and K24independently are hydrogen, alkyl, aryl, alkylaryl, arylalkyl, pyridium, pyridylamino or chinaillon, where alkyl, aryl, alkylaryl, arylalkyl, pyridyl, pyridylethyl or chinolin may contain inactive substituents; M is a Central transition metal ion having a valency of +a; X is a counterion having a valence-b, which is stable under oxidation; a denotes an integer of 1-4, b stands for a positive integer n means 1 to 4, n is equal to a/b and m is a positive integer of 2 or more.

In the above formula (II) K21, K22, K23and K24independently are hydrogen, alkyl, aryl, arylalkyl, pyridium, pyridylamino or chinaillon.

The alkyl preferably has 1-25 carbon and can be represented by stands, ethyl, propylene, bootrom, Pentium, hexyl, actilon, decyl, undecimo, dodecyl or tridecyl. Aryl can be represented by a phenyl or naphthyl. Alkylaryl can be represented, for example, talila, while arylalkyl, for example, benzyl.

Alkyl, aryl, alkylaryl, arylalkyl, pyridyl, pyridylethyl or chinolin may contain inert substituents, such as hydroxyl, ether group, ester group, cyano, amino, amido, sulphonamide, carboxyl, or carboxylate.

A2is the above group, and when it means alkylene of 1-6 carbons, it may be ethylene, trimethylene, tetramethylene, pentamethylene or hexamethylene.

A2may also contain inert substituents, such as hydroxyl, ether group, ester group, cyano, amino, amido, sulphonamide, carboxyl or carboxylate.

Preferred examples of the polyfunctional amino compounds with an open circuit, which form the ligand in the first complex of the transition metal (II) are the following compounds from 5-01 to 5-25.

5-01:Diethylenetriamine

5-02:Triethylenetetramine

5-03:Tetraethylenepentamine

5-04:hexamethylenediamine

5-05:heptamethylnonane

5-07:octadecenoamide

5-08:N,N'-bis(2-amino-ethyl)-1,3-propandiamine

5-09:N-(3-aminopropyl)-1,3-propandiamine

5-10:N,N'-bis(2-who:N,N,N',N'-tetramethylethylenediamine

5-14:N,N,N",N"-tetramethylethylenediamine

5-15:N,N,N",N"-tetramethylethylenediamine

5-16:N,N,N",N"-tetrapropylammonium

5-17:N,N,N",N"-tetramethylethylenediamine

5-18:N,N,N",N"-tetramethylethylenediamine

5-19:N,N,N",N"-tetrakis(2-cyanoethyl)Triethylenetetramine

5-20:N,N,N",N"-tetrakis(2-ethoxycarbonylethyl)Triethylenetetramine

5-21:N,N',N",N"'-tetrakis(2-methoxycarbonylethyl)Triethylenetetramine

5-22:N,N',N",N"'-tetrakis(3-hydroxypropyl)Triethylenetetramine

5-23:N,N',N",N"'-tetrakis(3-totalminutes)Triethylenetetramine

5-24:N,N',N",N"'-tetrakis(3-acetylaminophenol)-Triethylenetetramine

5-25:N,N',N",N"'-tetrakis(3-acetoxypropionyl)Triethylenetetramine

In addition to the above compounds from 5-01 to 5-25 here can be mentioned the examples of polyfunctional amino compounds with an open circuit from 5-26 to 5-29 and from 11-01 to 11 - 70 (see connections from 5-26 to 5-29 and from 11-01 to 11-70 at the end of the description).

Among them the most preferred amino compounds which have the formula (II), where A2is ethylene or trimethylene, and m is 2 or 3.

The second used catalyst on the basis of a complex of the transition metal has the formula (III):

[K31=N-A3-N-K32]Ma+(Xb-what nelena, t-phenylene, p-phenylene, 1,8-naphthalenol, 9,10-phenanthroline, 2,6 - pyridinium, 3,6-acridinium, 2,2'-bipyridyl-6,6'-deylam, 1,10-phenanthroline-2,9-deylam, 2,6-pyrimidinium, 4,5 - pyrimidinium, 2,6-pyrazinediium, 2-phenyl-1,3,5-triazine-2,6 - deylam,

< / BR>
where R1is alkylene with 1-8 carbons, and R2is alkyl with 1-8 carbons, aryl with 1 to 8 carbons, arylalkyl with 7-14 carbons or alkylaryl with 7-14 carbons, and may contain inert substituents; K31and K32are 2-aminobenzylidene and may contain inert substituents; M is a Central transition metal ion having a valency of +a; X is a counterion having a valence-b, which is stable under oxidation; a denotes an integer of 1-4, b denotes a positive integer, n denotes 1-4, n = a/b.

Preferred examples of the polyfunctional amino compounds with an open circuit, which forms the ligand of the second complex of the transition metal (III) are compounds from 6-01 up to 6-10 (see connections from 6-01 up to 6-10 in the end of the description).

The third used the catalyst on the basis of a complex of the transition metal has the formula (V):

[K41=N-A4-N=K42]>Ma+(Xb-)n

< / BR>
where R1is alkylene with 1-8 carbons, R2is alkyl with 1-8 carbons, aryl with 1 to 8 carbons, arylalkyl with 7-14 carbons or alkylaryl with 7-14 carbons, and may contain inert substituents; K41and K42are 2-pyridylmethylene or 6-methyl-2-pyridylmethylene and may contain inert substituents; M is a Central transition metal ion having a valency of +a; X is a counterion having a valence-b, which is stable under oxidation; a represents an integer of 1-4, b denotes a positive integer, n denotes 1-4, n = a/b.

Preferred examples of the polyfunctional amino compounds with open circuit: which forms the ligand in the third complex of the transition metal (IV) are compounds from 7-01 to 7-22 (see connections from 7-01 to 7-22 at the end of the description).

The fourth used the catalyst on the basis of a complex of the transition metal has the formula (V):

< / BR>
where A51A53are NASA
for K53are benzylidene, 2-pyridylmethylene or 6-methyl-2-pyridylmethylene and may contain inert substituents; M is a Central transition metal ion having a valency of +a; X is a counterion having a valence-b, which is stable under oxidation; a denotes an integer of 1-4, b stands for a positive integer n means an integer of 1-4, n = a/b.

Preferred examples of the polyfunctional amino compounds with an open circuit, which forms a ligand in the fourth complex of the transition metal (V) are compounds from 8-01 to 8-03 (see connections from 8-01 to 8-03 at the end of the description).

Fifth used the catalyst on the basis of a complex of the transition metal has the formula (VI):

[K61-N=A6=N-K62]Ma+(Xb-)n< / BR>
where A6means

< / BR>
and may contain inert substituents; K61and K62are 2-pyridium, 3-pyridium, 8-chinaillon or aminoalkyl, and alkyl has 2-4 carbon and may contain inert substituents; M is a Central transition metal ion having a valency of +a; X is a counterion having a valence-b, which is stable under oxidation; a denotes an integer which measures polyfunctional amino compounds with an open circuit, which forms a ligand in the fifth complex transition metal (VI) are compounds with 9-01 on 9-18 (see connection 9-01 on 9-18 at the end of the description).

Sixth used catalyst on the basis of a complex of the transition metal has the formula (VII):

< / BR>
where A7means

< / BR>
and may contain inert substituents; K71-K74are 2-pyridium, 3-pyridium, 2-pyridylmethyl or 3-pyridylmethyl and may contain inert substituents; M is a Central transition metal ion having a valency of +a; X is a counterion having a valence-b, which is stable under oxidation; a denotes an integer of 1-4, b stands for a positive integer n means an integer of 1-4, n = a/b.

Preferred examples of the polyfunctional amino compounds with an open circuit, which forms a ligand in the sixth complex transition metal (VII) are compounds with 10-01 10-15 (see connection 10-01 10-15 at the end of the description).

Seventh used catalyst on the basis of a complex of the transition metal has the formula (VIII):

[K81=N-A8-N=K82]Ma+(Xb-)n< / BR>
where A8independently is alkylene having 1-6 carbon in credentials, 2,2'-bipyridyl-6,6'-deylam, 1,10-phenanthroline-2,9-deylam, 2,6-pyrimidinium, 4,5 - pyrimidinium, 2,6-pyrazinediium, 2-phenyl-1,3,5-triazine-2,6 - deylam,

< / BR>
where R1is alkylene of 1-8 carbons, and R is alkyl of 1-8 carbons, aryl of 1 to 8 carbons, arylalkyl of 7-14 carbons or alkylaryl of 7-14 carbons, and may contain inert substituents; K81and K82are a group of the formula:

-T-N=CR81-CR82=

where T is a hydroxyl, amino or General formula:

-NR4R5< / BR>
where R4and R5independently are alkyl with 1-6 carbons and may contain inert substituents; R81and R82independently are hydrogen, alkyl with 1-6 carbons or phenyl, and alkyl or phenyl may contain inactive substituents; M is a Central transition metal ion having a valency of +a; X is a counterion having a valence-b, which is stable under oxidation; a represents an integer of 1-4, b stands for a positive integer n means an integer of 1-4, n = a/b.

The preferred option polyfunctional amino compounds with an open circuit, which forms a ligand in the seventh complex transition metal (VIII) complex of transition metals, containing as a ligand a polyfunctional aminosidine with an open circuit, as described above, M is a Central transition metal ion having a valency of +a, where a is an integer of 1-4. Preferred examples of the transition metal is iron, Nickel, manganese, cobalt, copper, ruthenium, rhodium, among which iron, Nickel, manganese, cobalt, copper or ruthenium are particularly preferred.

X is a counterion having a valence-b, which is stable under the oxidation, where b is a positive integer. Preferred examples of the counterion are, for example, halogenation, such as chloride ion or bromide ion, SO4-(sulfate ion), NO3-BF4-PF6-, ClO4-, CO3-P2O74-, S2O62-, anions of organic carboxylic acids, such as oxalate ion, acetate ion, naphthenate ion, benzoate ion, aftout ion, anions of organic sulfonic acids, such as methanesulfonate ion, triftorbyenzola ion, bansilalpet ion or p-toluensulfonate ion, or peroxidation, such as semiprocessed anion. In addition, the examples include acetylacetonate or squared IO the scrap 1-4, n = a/b and m is a positive integer of 2 or more, preferably 2 or 3.

4. The reaction using the catalysts on the basis of a complex of the transition metal.

According to the invention, the use of a complex of the transition metal in oxidation reactions of arylalkylamines as catalyst, which contains as a polyfunctional ligand aminosidine with cyclic or open-chain, which has a HOMO energy from -10 eV to -3 eV, as calculated by MOPAC VERSION 6.0 PM3 method, gives these arylalkylamine selectively in a high concentration at a high reaction speed without noticeable decomposition of the resulting organic hydroperoxide. It is well known that HOMO energy is the energy that have the highest occupied molecular orbital of the molecule, and the smaller the HOMO energy of the molecules, the less electron-donating molecule.

The catalysts on the basis of a complex of the transition metal used in the invention can be easily prepared in the processing of inorganic salt, a carboxylate or sulfonate transition metal cyclic or open-chain polyfunctional amino compounds so that aminosidine is celata or sulfonate transition metal with aminoguanidinium appropriate solvent, giving a transition metal complex. The resulting complex of the transition metal can be purified, if necessary, for example, recrystallization, extraction or chromatographic separation.

The catalyst on the basis of a complex of the transition metal can be used in solid form or may be dissolved in a reactive substance or in the reaction solvent. You should specify that the catalyst on the basis of a complex of the transition metal can be used in heterogeneous and homogeneous reactions.

The catalyst on the basis of a complex of the transition metal, which contains a cyclic polyfunctional aminosidine as a ligand is used in an amount of 0.000001 to 10 parts by weight, preferably in amounts of 0.00001 to 1 parts by weight, per 100 parts by weight of the original arylalkylamine.

In particular, when the ligand is a polyfunctional aminosidine, which has three nitrogen atom in the ring, forming a molecular chain, the catalyst on the basis of a complex of the transition metal is used preferably in amounts of 0.00001 to 5 parts by weight, more preferably in amounts of 0.0001 to 0.1 parts by weight, per 100 parts by weight of the original arylalkylamine nitrogen atom or more in the ring, forming a molecular chain, the catalyst is used preferably in an amount of 0.000001 to 5 parts by weight, more preferably 0.0001 to 0.1 parts by weight, per 100 parts by weight of the original arylalkylamine.

At the same time, the catalyst on the basis of a complex of the transition metal containing polyfunctional aminosidine open chain as a ligand is used preferably in amounts of 0.00001 to 5 parts by weight, more preferably in amounts of 0.0001 to 0.1 parts by weight, per 100 parts by weight of the original arylalkylamine.

The oxidation source arylalkylamine occurs in the oxygen-containing gas. Usually use air as the oxygen-containing gas, however, the oxygen, carbon dioxide, carbon monoxide or a mixture of oxygen and nitrogen can be used, if necessary. The reaction proceeds usually at normal pressure, however, the reaction can be carried out under increased pressure, if necessary. The reaction temperature may range from 40oC to 130oC, preferably from 50oC to 110oC.

The reaction can be carried out in the presence of solid alkali compounds or aqueous alkaline link is barium or magnesium oxide. The alkaline compound may be used in amounts of 0.0001-10 parts by weight, preferably in amounts of 0.001-5 parts by weight per 100 parts by weight of the original arylalkylamine.

The reaction may start when using a small amount of initiator, usually the end of arylalkylamine, if necessary. For example, monohydroperoxide cumene can be used as the initiator in the oxidation of cumene.

The reaction can be carried out or a periodic or continuous manner. When the reaction is carried out periodically by the way, the catalyst is added to arylalkylamine, if it is a liquid at the temperature at which the oxidation reaction, and the air is blown through the mixture with stirring at elevated temperature.

The reaction may proceed at a transmission source arylalkylamine or its solution together with air over a fixed catalyst bed.

The final arylalkylamine easily stands out from the reaction mixture by standard methods, for example, by distillation.

In accordance with the invention, the use of a complex of a transition metal as a catalyst, which contains as a cyclic ligand floor the Institute of arylalkylamines oxygen-containing gas, such as air, allows you to selectively oxidize the original arylalkylamine in the corresponding arylalkylamine in high concentration at a high response speed without noticeable decomposition of the final organic peroxides.

5. Examples.

The invention is described in detail in the following examples. However, the invention is not limited to these examples. As follows, the concentration of monohydroperoxide hydroperoxide in the reaction mixture after the reaction was measured by iodometry and gas chromatography, whereas the selectivity of cumene hydroperoxide was measured by gas chromatography.

The results of the reactions in the following examples and comparative examples, namely, the concentration of the final monohydroperoxide hydroperoxide in the reaction mixture after the reaction, the rate of formation of monohydroperoxide cumene during the reaction and the selectivity of monohydroperoxide cumene shown in the table. 1 and 2.

HOMO energy cyclic polyfunctional amines used as ligands in the preparation of catalysts on the basis of a complex of the transition metal, also shown in the table. 1 and 2, which was calculated using MOPAC VERSION 6.0 RMZ method.

Kie polyfunctional amines as ligands

Getting arylalkylamines when using the first catalyst on the basis of a complex of the transition metal, where the cyclic polyfunctional aminosilane are diazacrown connection.

Example 1.

20 mg [1,4,7-triazacyclononane] manganese (II) sulfate was added to a mixture of 90 g of cumene and 10 g of nonoperated cumene. The resulting mixture was heated to 80oC, and cumene oxidized for 8 hours with stirring, while air was supplied to the mixture at a speed of 60 ml per minute.

Example 2.

The air oxidation of cumene was performed in the same manner as in example 1, in 10 hours using 20 mg [N,N',N"- Tris(3-hydroxypropyl)-1,4,7-triazacyclononane] manganese (II) sulfate instead of [1,4,7-triazacyclononane]manganese (II) sulfate.

Example 3.

The air oxidation of cumene was performed in the same manner as in example 1, for 9 hours when using 2 mg (N,N',N"- Tris(3-hydroxypropyl)-1,4,7-triazacyclononane] manganese (II) sulfate instead of [1,4,7-triazacyclononane]manganese (II) sulfate.

Example 4.

The air oxidation of cumene was performed in the same manner as in example 2, except that 10 ml of distilled water Bild pressure of 6 kg/cm2air in the autoclave for 6 hours and then in the same way as in example 3.

Example 6.

The air oxidation of cumene was carried out for 7 hours in the same manner as in example 5, using 5 mg of the complex catalyst.

Comparative example 1.

10 ml of an aqueous solution containing 20 mg of manganese sulfate was added to a mixture of 90 g of cumene and 10 g of monohydroperoxide cumene. The resulting mixture was heated to 80oC, and cumene were oxidized for 6 hours under stirring, and the air was applied to the mixture at a speed of 60 ml per minute.

Getting arylhydroxamic when using the first catalyst on the basis of a complex of the transition metal, in which the cyclic polyfunctional aminosilane are amines having four or more nitrogen atoms in the molecule.

Example 7.

10 mg [1,4,8,11-tetraazacyclotetradecane]manganese (II) sulfate was added to a mixture of 90 g of cumene and 10 g of nonoperated cumene. The resulting mixture was heated to 80oC, and cumene were oxidized for 8 hours under stirring, and the air was applied to the mixture at a speed of 60 ml per minute.

Example 8.

The reaction was carried out using 20 is of that, and then in the same way as in example 7.

Example 9.

The reaction was carried out using 20 mg [1,4,8,11 - tetraazacyclotetradecane]copper (II) sulfate instead of (1,4,8,11 - tetraazacyclotetradecane]manganese (II) sulfate, and then in the same way as in example 7.

Example 10.

The reaction was carried out using 2 mg (1,4,8,11-tetraazacyclotetradecane] ruthenium (II) sulfate instead of [1,4,8,11-tetraazacyclotetradecane]manganese (II) sulfate, and then in the same way as in example 7.

Example 11.

The reaction was carried out using 20 mg [1,4,8,11 - tetraazacyclotetradecane] Nickel (II) sulfate instead of [1,4,8,11 - tetraazacyclotetradecane]manganese (II) sulfate, and then in the same way as in example 7.

Example 12.

The reaction was carried out using 2 mg [1,4,8,11 - tetraazacyclotetradecane] manganese (II) benzoate instead of [1,4,8,11 - tetraazacyclotetradecane)manganese (II) sulfate, and then in the same way as in example 7.

Example 13.

The reaction was carried out using 20 mg [1,4,8,11 - tetraazacyclotetradecane)cobalt (II) benzoate instead of [1,4,8,11 - tetraazacyclotetradecane] manganese (II) sulfate, and then in the same way as in example 7.

Premierwest (1,4,8,11 - tetraazacyclotetradecane] manganese (II) sulfate, and then in the same way as in example 7.

Example 15.

The reaction was carried out using 20 mg [1,4,7,10,13,16 - hexasaccharides] manganese (II) sulfate instead of [1,4,8,11 - tetraazacyclotetradecane]manganese (II) sulfate, and then in the same way as in example 7.

Example 16.

The reaction was carried out using 20 mg [N,N', N",N"'- tetrakis(2-ethoxycarbonylethyl)-1,4,8,11 - tetraazacyclotetradecane] cobalt (II) sulfate instead of (1,4,8,11 - tetraazacyclotetradecane] manganese (II) sulfate, and then in the same way as in example 7.

Example 17.

The reaction was carried out using 2 mg [1,4,8,11 - tetraazacyclotetradecane] manganese (II) stearate instead of [1,4,8,11 - tetraazacyclotetradecane] manganese (II) sulfate, and then in the same way as in example 7.

Example 18.

The reaction was carried out using 2 mg (1,4,8,11 - tetraazacyclotetradecane] cobalt (II) stearate instead of (1,4,8,11 - tetraazacyclotetradecane)manganese (II) sulfate, and then in the same way as in example 7.

Example 19.

The reaction was carried out using 2 mg (N,N',N",N"'-Tetra-n-butyl-1,4,8,11-tetraazacyclotetradecane)manganese (II) sulfate instead of [1,4,8,11-tetraazacyclotetradecane)manganese (II)complex of the transition metal.

Example 20.

The reaction was carried out in the presence of 2 mg of the complex of the transition metal obtained when using bromide cobalt (III) and compounds (6-02) instead of (1,4,8,11-tetraazacyclotetradecane]manganese (II) sulfate, and then in the same way as in example 7.

The use of the third catalyst on the basis of a complex of the transition metal.

Example 21.

To a mixture of 80 g of cumene, 20 g of monohydroperoxide hydroperoxide and 50 g of 0.02% by weight aqueous solution of sodium carbonate was added 2 mg of the complex of the transition metal obtained when using sulfate heptahydrate cobalt and compounds (4-02). The resulting mixture was heated to 90oC and cumene were oxidized for 4 hours under stirring, and the air was applied to the mixture at 180 ml / min.

The use of the fourth catalyst based on a transition metal.

Example 22.

The reaction was carried out in the presence of 2 mg of the complex of the transition metal obtained by using a pentahydrate of copper sulfate (II) and compound (5-02, where R is associated with a nitrogen is a hydrogen, and R, associated with carbon, is stands) instead of the complex obtained when using sulfate heptahydrate kobal on the basis of a complex of the transition metal.

Example 23.

The reaction was carried out in the presence of 2 mg of the complex of the transition metal obtained by using a pentahydrate of copper sulfate (II) and compound (3-01) instead of the complex obtained when using sulfate heptahydrate cobalt and compounds (4-02), and then in the same way as in example 21.

Using the fifth catalyst on the basis of a complex of the transition metal.

Example 24.

The reaction was carried out in the presence of 2 mg of the complex of the transition metal obtained by using a pentahydrate of copper sulfate (II) and compound (6-03) instead of the complex obtained when using sulfate heptahydrate cobalt and compounds (4-02), and then in the same way as in example 21.

Comparative example 2.

The reaction was carried out in the presence of 2 mg (phthalocyanine)cobalt (II) instead of [1,4,8,11-tetraazacyclotetradecane] manganese (II) sulfate, and then in the same way as in example 7.

Comparative example 3.

The air oxidation of cumene was performed in the same manner as in example 7, for 10 hours using 2 mg (tetraphenylporphyrin)cobalt (II) instead of [1,4,8,11 - tetraazacyclotetradecane]manganese (II) sulfate.

Pilnie amines with an open circuit as ligands

The first use of catalysts on the basis of a complex of the transition metal.

Example 1.

20 mg [N,N'-bis(2-amino-ethyl)-1,3-propandiamine)manganese (II) sulfate was added to a mixture of 90 g of cumene and 10 g of monohydroperoxide cumene. The resulting mixture was heated to 80oC, and cumene were oxidized for 8 hours under stirring, and the air was applied to the mixture at a speed of 60 ml per minute.

After the reaction, the concentration of the obtained monohydroperoxide cumene was 29.6 per cent by weight. Accordingly, the rate of accumulation of monohydroperoxide cumene was found, is 2,42% by weight per hour. The selectivity obtained monohydroperoxide cumene was found, is 77% despite the fact that monohydroperoxide cumene was accumulated in the reaction mixture in the amount of 29.6% by weight.

Comparative example 1.

20 mg pentahydrate sulfate manganese (II) was added to a mixture of 90 g of cumene and 10 g of monohydroperoxide cumene. The resulting mixture was heated up to 80oC and cumene were oxidized for 8 hours with stirring, and water was applied to the mixture at a speed of 60 ml per minute.

After the reaction, the concentration of the final monohydroperoxide cumene was 15.8% by weight. Rela is C.

Comparative example 2.

20 mg (Ethylenediamine)cobalt (II) sulfate was added to a mixture of 90 g of cumene and 10 g of monohydroperoxide cumene. The resulting mixture was heated up to 80oC and cumene were oxidized for 8 hours with stirring, and water was applied to the mixture at a speed of 60 ml per minute.

After the reaction, the concentration of the final monohydroperoxide cumene was 17.3% by weight. Accordingly, the rate of accumulation of monohydroperoxide cumene was found, is only 0.91% by weight per hour.

The first study of catalysts based on transition metal complexes.

Example 2.

The reaction was carried out using 20 mg (Tetraethylenepentamine)manganese (II) sulfate instead of [N, N'-bis(2 - amino-ethyl)-1,3-propandiamine]manganese (II) sulfate, and then in the same manner as in example 1. Accumulation rate monohydroperoxide cumene was found, is 1.96% by weight per hour, and the selectivity of monohydroperoxide cumene was found, is 75%.

Example 3.

The reaction was carried out using 20 mg (pentamethylenebis)manganese (II) sulfate instead of [N, N'-bis(2 - amino-ethyl)-1,3-propandiamine]manganese (II) sulfate, and then the same SP is yet 1.81% by weight per hour, and selectivity of monohydroperoxide cumene was found, is 73%.

Example 4.

The reaction was carried out using 20 mg (Diethylenetriamine)manganese (II) sulfate instead of [N,N'-bis(2 - amino-ethyl)-1,3-propandiamine]manganese (II) sulfate, and then in the same manner as in example 1.

Accumulation rate monohydroperoxide cumene, it has been found that amounts to 1.64% by weight per hour, and the selectivity of monohydroperoxide cumene was found, is 81%.

Example 5.

The reaction was carried out using 20 mg [N,N'-bis(2-amino-ethyl)-1,3-propandiamine] cobalt (II) sulfate instead of [N,N'- bis(2-amino-ethyl)-1,3-propandiamine)manganese (II) sulfate, and then in the same manner as in example 1.

Accumulation rate monohydroperoxide cumene was found, is 2.19% by weight per hour, and the selectivity of monohydroperoxide cumene, it has been found that 79%.

Example 6.

The reaction was carried out using 20 mg [N,N'-bis(2 - amino-ethyl)-1,3-propandiamine] copper (II) sulfate instead of [N,N'- bis(2-amino-ethyl)-1,3-propandiamine]manganese (II) sulfate, and then in the same manner as in example 1.

Accumulation rate monohydroperoxide cumene, as Bilet 82%.

Example 7.

The reaction was carried out using 20 mg [N,N'-bis(2 - amino-ethyl)-1,3-propandiamine] iron (II) sulfate instead of [N,N'- bis(2-amino-ethyl)-1,3-propandiamine] manganese (II) sulfate, and then in the same manner as in example 1.

Accumulation rate monohydroperoxide cumene was found, is 1.79% by weight per hour, and the selectivity of monohydroperoxide cumene, it has been found that 72%).

Example 8.

The reaction was carried out using 20 mg [N,N'-bis(2-amino-ethyl)-1,3-propandiamine] Nickel (II) sulfate instead of [N,N'- bis(2-amino-ethyl)-1,3-propandiamine] manganese (II) sulfate, and then in the same manner as in example 1.

Accumulation rate monohydroperoxide cumene, it has been found that amounts to 1.80% by weight per hour, and the selectivity of monohydroperoxide cumene was found, is 71%.

Example 9.

To a mixture of 90 g of cumene and 10 g of monohydroperoxide of cumene was added 2 mg of the complex of the transition metal obtained by treatment of compound (11-20) sulfate cobalt, and then added to a mixture of 50 g of 0.02% by weight aqueous solution of sodium carbonate.

The resulting mixture was heated to 90oC, and cumene were oxidized for 8 hours at peremeshivaniem in example 10 used the first catalyst on the basis of a complex of the transition metal; in examples 11 to 16 were used third catalyst on the basis of a complex of the transition metal; in examples 17 and 18 used a fourth catalyst on the basis of a complex of the transition metal; in examples 19 to 23 used fifth catalyst on the basis of a complex of the transition metal; and in examples 24 to 27 used a sixth-based catalyst complex of the transition metal.

Examples 10-27.

The air oxidation of cumene was performed in the same manner as in example 9 using 100 g of a mixture of cumene and monohydroperoxide having different ratios of monohydroperoxide cumene and cumene in the mixture, in the presence of a catalyst at a temperature within a period of time, as shown in the table. 2.

Comparative example 3.

The reaction was carried out using 2 mg (ftalian)cobalt (II) instead of (Ethylenediamine)cobalt (II) sulfate, and then in the same manner as in comparative example 2. The results are presented in table. 2.

Comparative example 4.

The reaction was carried out using 2 mg (tetraphenylporphyrin)cobalt (II) instead of (Ethylenediamine)cobalt (II) sulfate, and then in the same manner as in comparative example 2. The results are presented in Tagomago specified number of imagereference, 50 g of a 0.02% aqueous solution of salts of sodium carbonate and catalyst (complex transition metal) was placed in a separate flask a volume of 200 ml equipped with a condenser, Dimroth, the input gas pipe, a heat tank and agitator. The flask was heated in an oil bath while simultaneously the air in the flask at atmospheric pressure in the amount of 210 ml/min through the meter the feed stream, so that the reaction was carried out at a given temperature. During the reaction were taken the sample of the aqueous phase to test the pH value of the aqueous phase, whether it is alkaline, and added 1% aqueous salt solution sodium carbonate, when it was necessary to maintain the aqueous alkaline phase. During the second part of the reaction the aqueous phase formed a buffer zone, so that the pH value of the aqueous phase was set at a value of 7.5.

After half an hour and one hour after start of the reaction, respectively, were analyzed phase of the reaction mixture through iodometry and 0.5 g of the organic phase were analyzed by liquid chromatography with precise characteristics.

A small amount of sodium hydroxide was added to the aqueous phase, in order to make this phase is alkaline, and analyzed by liquid chromatographic centrifuge, to remove the aqueous phase and the concentration of imagereference (CyHP) in the organic phase was determined by iodometry by use of a potentiometer. The concentration of imagereference (CyHP) can be calculated using the following equation, if the weight of the sample x(g) and its volume - y(ml).

CyHP (% by weight) + [y(ml)(1/200)KZT 166.2]x(g). Then about 0.5 g of the organic phase were also analyzed by liquid chromatography with precise characteristics. The results of the analysis are shown in table 3.

Used in the table. 3 abbreviations indicate the following:

< / BR>
Notes to the table. 3:

1) calculated as metal with respect to the organic phase.

2) calculated by subtracting the initial concentration of T - CyHP(3oCyHP+1oCyHP) one hour after the starting of reaction.

3) is defined as kumanova acid by analysis of the aqueous phase by reversing the column (Bond-DDS, aq/H3PO4/CH3CN=1/1).

4) 3o/1othe ratio CyHP = (3oCyHP/T-CyHP) 100(%).

5) 3o/1othe ratio in cimoli = [product of the oxidation of the tertiary hydrogen/(product of the oxidation of the tertiary hydrogen + oxidation product of a primary hydrogen)]100(%).

Wow sodium and catalyst (complex transition metal) was placed in a separate flask a volume of 200 ml, equipped with a condenser, Dimroth, the input gas pipe, a heat tank and agitator. The flask was heated in an oil bath while filing into the flask gas containing 80% oxygen at atmospheric pressure in the amount of 210 ml/min through the meter the feed stream, so that the reaction was carried out at a given temperature. During the reaction were taken the sample of the aqueous phase to test the pH value of the aqueous phase, whether it is alkaline and added, 1% aqueous salt solution sodium carbonate, when it was necessary to maintain the aqueous alkaline phase. During the entire period of the reaction, which lasted almost 20 hours, there was added the total number of 40 ml.

Because the original connection and the product, i.e. diisopropylethylamine were in the solid state at room temperature, the organic phase was slowly heated with a heating gun to melt the organic phase prior to analysis of the reaction mixture. A sample of the organic phase of the reaction mixture was analyzed by iodometry and 0.5 g of the organic phase by liquid chromatography with precise characteristics.

The concentration of hydroperoxide in the organic phase, analizirana) can be calculated using the following equation, if the weight of the sample x(g) and the volume of titration - y(ml):

T-HPO (% by weight) = [y(ml)(1/200)244,3]/x(g).

Then about 0.5 g of the organic phase was accurately weighed and heated and melted. Was added 50 mg of 4,4'- dihydroxydiphenylmethane to the organic phase as the usual norm and the mixture was dissolved in 10 ml of methanol and analyzed by liquid chromatography with precise characteristics. The results are shown in table. 4.

Used in the table. 2 the abbreviations mean the following:

T-HPO: concentration of total hydroperoxide

DIPN: 2,6-diisopropylnaphthalene

MHP: 2-isopropyl-6-(2-hydroperoxy-2-propyl)naphthalene

DND: 2,6-diisopropylnaphthalene dihydroperoxide

HHP: 2-(2-hydroxy-2-propyl)-6-(2-hydroperoxy-2-propyl)- naphthalene

JS: 2,6-bis(2-hydroxy-2-propyl)naphthalene

Notes to the table. 4:

1) the reaction was carried out at a temperature of 90oC in organic/aqueous phase ratio 1/2 (W/W), using a feed gas containing 80% of oxygen at a rate of 210 ml/min at atmospheric pressure;

2) calculated as the metal;

3) the total number of hydroperoxide provided MHP.

Appendix B

Preparation of transition metal complexes

1. Manganese complex soedinenie 2-03).

In nitrogen atmosphere were placed 2.00 g (50 mmol) of a 60% dispersion of sodium hydride in a flask with a volume of 300 ml and washed with hexane by decantation. After drying under vacuum was added sodium hydride to 10 ml of N-methylpyrrolidone to obtain a slurry of sodium hydride in N-organic.

The solution was cooled on ice and 40 ml 2,04 g (10 mmol) 1,4,8,11-tetraazacyclotetradecane in N-organic was added in drops to a solution of sodium hydride, and then formed hydrogen and the mixture was formed into a slurry. The suspension was warmed to room temperature and then 6.85 g (50 mmol) of n-butyl bromide was added in drops to a suspension, followed by stirring at room temperature for 5 days.

Insoluble substances were filtered, the final filtrate was concentrated by distillation of the solution. The final concentrate was fraktsionirovanija by chromatography in neutral column of alumina using methylene chloride as eluent. The fractions obtained were evaporated to dryness and dried in vacuum to obtain 1.25 g (30% yield) 1,4,8,11-Tetra-n-butyl - tetraazacyclotetradecane in the form of a white solid mass.

FD-MS: 424

1H-NMR(CDCl3):1,00(t; 12H,CH45H2O at room temperature. The mixture was then stirred at a temperature of 60oC for two hours. The solid mass was filtered and dried to obtain 0,29 g (36% yield) of the desired complex metal in the form of a milk-white solid mass.

Elementary analysis: Mn; 9,5(8,7), (C; 50,2(49,6), H; 9,6(9,9), N; 8,9(8,9). Values in parentheses are calculated values of three-hydrate.

Thanks to the use of compounds of cyclic polyfunctional amine having different sizes of rings instead of 1,4,8,11-Tetra-n-butyl-tetraazacyclotetradecane it was possible to obtain a cyclic compound 2-01 to 2-15 in the same way. Through the use of allylbromide instead of n-butylbromide could be obtained cyclic compounds 2-01 to 2-15, alkyl having instead butyl, in the same way.

2. The connection of the complex copper polyfunctional amine with an open circuit 7-08.

(preparation 7-08).

A solution of 6.1 g (42 mmol) of 3,3'-diamino-N-methyldiphenylamine in 10 ml of ethanol was added in drops to a solution of 9.0 g (84 mmol) of 2 - pyridinecarboxamide in 15 ml of anhydrous ethanol under stirring at room temperature and the mixture was stirred for another four hours. The mixture was kontsentrirovannykh to a total volume of 400 ml and then cooled in the refrigerator overnight, after that, the extract was separated reddish-orange oil. The oil was separated and dried in vacuum to obtain 8.5 g (71% yield) of the desired amine compound 7-08.

FD-MS: 286

1H-NMR(CDCl3):1,8-2,4(m; 4H, CH2), A 2.45 (S: 3H, CH3), 2,90 (t; 4H), 3,85 (t; 4H), and 7.1 to 7.4 (m; 2H), 7,5-7,9 (m; 2H), 7,9-8,05 (m; 2H), and 8.4 (s; 2H), 8.6 out of 8.7(m; 2H).

(preparation of the complex).

1.0 g (3.5 mmol) of the amine compounds were dissolved in 15 ml of anhydrous methanol under nitrogen atmosphere, to obtain a reddish - orange solution. 0.75 g (3.0 mmol) CuSO45H2O covered in mortar in the mortar and added in this form in the solution at room temperature, to obtain a blackish-blue solution. The solution was mixed for one hour at room temperature and was heated to a temperature of 60oC, followed by stirring for a further three hours. The solution is then cooled to room temperature and was extracted three times with 30 ml of hexane. Methanol was removed from the extract by distillation. The residue was dissolved in 5 ml of methylene chloride and then added 20 ml of hexane to the solution precipitated viscous black solid mass. The solution is then removed by decantation. The precipitate was washed with a small amount hexane at room temperature, was filtered and dried in vacuum to obtain 1.0 g (62% yield) of the desired amine compounds in the form of a black-brown powder.

Elementary analysis: Cu; 11,3(11,8), C: 42,3(42,5), H; 6,1(5,8), N; 13,1(13,0), S; 6,3(6,0). The values in parentheses are calculated values of three-hydrate.

In use, respectively electrovanne of dialdehydes and di - or triamino can be obtained polyfunctional compound with an open chain 7-01 to 7-22 in the same way.

3. The connection of the complex copper polyfunctional amine with an open circuit 9-08.

1.35 g (10 mmol) of 2,6-pyridinedicarboxylate and 1.88 g (20 mmol) of 2-aminopyridine were dissolved in 100 ml of ethanol in a nitrogen atmosphere. 2.50 g (10 mmol) CuSO45H2O covered in mortar in the mortar and added in small portions to the solution at room temperature under stirring, to obtain a blue solution. The solution is further stirred for five hours at room temperature, after which the blue and white solid mass was deposited in the form of sludge. After that, the slurry was mixed at a temperature of 50oC for six hours, then filtered. The solid mass was converted into a slurry in acetone, rinsed ate the powder. Elementary analysis: Cu; 11,9(14,2), (C; 42,5(45,7), H; 4,3(2,9), N; 13,2(15,7), S, 6,0(7,2). The values in parentheses are calculated values monohydrate.

IR(KBr): 3000-3500, 1620, 1540, 1480, 1420, 1335, 1120, 1070, 1040, 770 cm-1.

UV-vis: 670 gr (shifted to 750 PM after aging in water for three hours).

Through the use of respectively electrovanne of dialdehydes and amines can be obtained polyfunctional compound with an open chain 9-01 to 9-18 in the same way.

4. The connection of the complex copper polyfunctional amine with an open circuit 8-02.

(preparation 8-02).

A solution of 1.41 g (7.5 mmol) of Tris(2-amino-ethyl)-amine in 20 ml of atenol was added in drops to a chilled on ice the solution to 3.09 g (25 mmol) of 6-methyl-2-pyridine-carboxaldehyde in 10 ml of anhydrous ethanol under stirring and the mixture is stirred at room temperature for eight hours. The mixture was concentrated by distillation of the solution and the precipitate was extracted with 500 ml of warm hexane. The extract was cooled in the refrigerator overnight, then stood reddish-brown oil as an extract. The oil was separated and dried in vacuum to obtain 3.1 g (82% yield) of the desired coedine was dissolved in 20 ml of anhydrous methanol under nitrogen atmosphere, to get the red - orange solution. 1,9 g (7.6 mmol) CuSO45H2O was filled in the mortar in the mortar and added to the solution at room temperature, to obtain black-and-blue solution. After stirring the solution for 12 hours at room temperature, it was extracted three times with 20 ml of hexane. The methanol was removed by distillation from the extract. The precipitate was mixed in 10 ml of acetonitrile at a temperature of 160oC and then filtered. Solid mass in the form of slurry was poured into 10 ml of methylene chloride at room temperature and filtered. The solid mass was washed with hexane and dried in vacuum to obtain 2.85 g (53% yield) of the desired complex as a reddish-brown powder.

Elementary analysis: Cu; 11,3(9,0), (C; 40,0(46,0), H; 6,0(6,1), N; 13,1(13,9), S; 4,8(4,5). The values in parentheses are calculated values pentahydrate.

In use, respectively electrovanne aldehydes and amines can be obtained polyfunctional compound with an open chain 8-01 to 8-03 in the same way.

5. The connection of the complex copper polyfunctional amine with an open circuit 12-02.

(preparation 12-02).

Solution 4,P>-diamino-n-methyldibromo-amine in 20 ml of ethanol at room temperature under stirring. The mixture was watered by heating for six hours. After cooling, the mixture was concentrated by distillation of the solution to produce oil, and added 6 ml of methylene chloride to the oil to dissolve the oil in it. The mixture was stirred with 6 ml of hexane, followed by separation of the solution into two phases. Thus, the solution was extracted three times. Were allocated small phase and concentrated by distillation of the solution to get 6,67 (quantitative) of the desired amine compounds in the form of a dark red oil - syrup.

FM DS:311.

(preparation of the complex).

0.9 g (2.9 mmol) of the compound amine was dissolved in 20 ml of anhydrous methanol under nitrogen atmosphere, to obtain a yellow solution. of 0.62 g (2.5 mmol) CuSO45H2O was filled in the mortar in the mortar and added to the solution at room temperature under stirring, to obtain a greenish-black solution. The solution is stirred for 12 hours at room temperature and then was heated to a temperature of 60oC for four hours. The solution is then cooled to room temperature and extra in 3 ml of methanol, and 20 ml of acetonitrile was added to the solution to get to precipitate a solid mass. The solid mass was poured in the form of a slurry in 10 ml of acetonitrile and then was rinsed with hexane, followed by drying in vacuum, to obtain 0.9 g (64% yield) of the desired complex in the form of greenish-black powder.

Elementary analysis: Cu; 13,0(12,5), (C; 30,5(32,1), H; 6,7(7,0) N; 12,3(12,5) S; 7,8(5,7). The values in parentheses are calculated values pentahydrate.

Through the use of respectively electrovanne Akimov and diamines can be obtained polyfunctional compound with an open chain 12-01 up to 12-13 in the same way.

1. A method of obtaining a series of arylalkylamines, which involves the selective oxidation of a series of arylalkylamines having the formula I

< / BR>
where P and Q are alkyl groups and may be the same or different from each other;

x is an integer from 1 to 3;

Ar is an aromatic hydrocarbon group having a valency X,

oxygen-containing gas in the presence of a catalyst based on a complex of the transition metal, wherein the complex of the transition metal comprises a ligand cyclic Polish is, or polyfunctional aminosidine with an open circuit, having at least three atoms in the main chain of the molecule, provided that the complex of the transition metal is not a complex of porphyrin or phthalocyanine complex.

2. The method according to p. 1, characterized in that the complex of the transition metal has the formula II

< / BR>
where A denotes the independent alkylene having 1 to 6 carbons in the main chain of the group, phenylene, naftilan (naphthalenediol), phenanthrolin (finalrender), pyridinyl, pyrrolidinyl, pyrazinyl, pyrimidinyl or 1,3,5-triazinyl and may contain inert substituents;

R is independently hydrogen, alkyl, aryl, alkylaryl or arylalkyl, and alkyl, aryl, alkylaryl or arylalkyl may contain inactive substituents;

M means the Central transition metal ion having a valency of +a;

X is a counterion having a valence-b, which is stable under oxidation;

a denotes an integer of 1 to 4;

b indicates a positive integer;

n means an integer of 1 to 4, n = a/b;

m denotes 0 or a positive integer of 1 or greater.

3. The method according to p. 1, characterized in that the complex of the transition metal has the formula III

< / BR>
where B is isimo are alkylene, having 1 to 6 carbons in the main chain groups, or phenylene, and may contain inert substituents;

R independently denotes hydrogen, alkyl, aryl, alkylaryl or arylalkyl, and alkyl, aryl, alkylaryl or arylalkyl may contain inactive substituents;

M means the Central transition metal ion having a valency of +a;

X is a counterion having a valence-b, which is stable under oxidation;

a denotes an integer of 1 to 4;

b indicates a positive integer;

n means an integer of 1 to 4, n is equal to a/b.

4. The method according to p. 1, characterized in that the complex of the transition metal has the formula VI

< / BR>
where A is independently alkylene having 1 to 6 carbons in the main chain of the group, phenylene, naphthalenol, phenanthroline, pyridinium, pirramimma, pyrazinediium, pyrimidinium or 1,3,5-triazinium, and may contain inert substituents;

B is bis(alkylidene) having 2 to 10 carbons in the main chain groups

< / BR>
< / BR>
and may contain inert substituents;

R is independently hydrogen, alkyl, aryl, alkylaryl or arylalkyl, and alkyl, aryl, alkylaryl or arylalkyl may contain inactive substituents;

M OSN ntest-b, which is stable under oxidation;

a denotes an integer of 1 to 4;

b indicates a positive integer;

n means an integer of 1 to 4, n = a/b;

m denotes 0 or a positive integer of 1 or more.

5. The method according to p. 1, characterized in that the complex of the transition metal has the formula VII

< / BR>
where A is independently alkylene having 1 to 6 carbons in the main chain of the group, phenylene, naphthalenol, phenanthroline, pyridinium, pirramimma, pyrazinediium, pyrimidinium or 1,3,5-triazinium, and may contain inert substituents;

B is bis(alkylidene) having 2 to 10 carbons in the main chain groups

< / BR>
< / BR>
and may contain inert substituents;

R independently denotes hydrogen, alkyl, aryl, alkylaryl or arylalkyl, and alkyl, aryl, alkylaryl or arylalkyl may contain inactive substituents;

M means the Central transition metal ion having a valency of +a;

X is a counterion having a valence-b, which is stable under oxidation;

a denotes an integer of 1 to 4;

b indicates a positive integer;

n means an integer of 1 to 4, n = a/b;

m denotes 0 or a positive integer of 1 or more.

independently is alkylene having 1 to 6 carbons in the main chain of the group, o-phenylene, m-phenylene, p-phenylene, 1,8-naphthalenol, 9,10-phenanthroline, 2,6-pyridinium, 3,6-acridinium, 2,2'-bipyridyl - 6,6'-deylam, 1,10-phenanthroline - 2,9-deylam, 2,6-pyrimidinium, 4,5-pyrimidinium, 2,6-pyrazinediium, 2-phenyl-1,3,5 - triazine-2,6-deylam,

< / BR>
< / BR>
where R1is alkylene with 1 to 8 carbons, and R2is alkyl with 1 to 8 carbons, aryl with 1 to 8 carbons, arylalkyl from 7 to 14 carbons or alkylaryl from 7 to 14 carbons, and R1and R2may contain inactive substituents;

K21, K22, K23and K24independently are hydrogen, alkyl, aryl, alkylaryl, arylalkyl, pyridium, pyridylamino or chinaillon, where alkyl, aryl, alkylaryl, arylalkyl, pyridyl, pyridylethyl or chinolin may contain inactive substituents;

M means the Central transition metal ion having a valency of +a;

X is a counterion having a valence-b, which is stable under oxidation;

a denotes an integer of 1 to 4;

b indicates a positive integer;

n means an integer of 1 to 4, n = a/b;

m is a positive integer of 2 or more.

- N = K32] Ma+(Xb-)n,

where A3independently is alkylene having 1 to 6 carbons in the main chain of the group, o-phenylene, m-phenylene, p-phenylene, 1,8-naphthalenol, 9,10-phenanthroline, 2,6-pyridinium, 3,6-acridinium, 2,2'-bipyridyl-6,6'-deylam, 1,10-phenanthroline-2,9-deylam, 2,6-pyrimidinium, 4,5-pyrimidinium, 2,6-pyrazinediium, 2-phenyl-1,3,5-triazine-2,6-deylam,

< / BR>
< / BR>
where R is alkylene with 1 to 8 carbons, and R is alkyl with 1 to 8 carbons, aryl with 1 to 8 carbons, arylalkyl from 7 to 14 carbons or alkylaryl from 7 to 14 carbons, and may contain inert substituents;

K31and K32are 2-aminobenzylidene and may contain inert substituents; M is a Central transition metal ion having a valency of +a;

X is a counterion having a valence-b, which is stable under oxidation;

a denotes an integer of 1 to 4;

b indicates a positive integer;

n means an integer of 1 to 4, n is equal to a/b.

8. The method according to p. 1, characterized in that the complex of the transition metal has the formula IV

[K41= N - A4- N = K42]Ma+(Xb-)n,

where A4independently is alkylene having 1 to 6 is ndira, 3,6-acridinium, 2,2'-bipyridyl - 6,6'-deylam, 1,10-phenanthroline-2,9-deylam, 2,6-pyrimidinium, 4,5-pyrimidinium, 2,6-pyrazinediium, 2-phenyl-1,3,5-triazine-2,6-deylam,

< / BR>
< / BR>
where R1is alkylene with 1 to 8 carbons, and R is alkyl with 1 to 8 carbons, aryl with 1 to 8 carbons, arylalkyl from 7 to 14 carbons or alkylaryl from 7 to 14 carbons, and may contain inert substituents;

K41and K42are 2-pyridylmethylene or 6-methyl-2-pyridylmethylene and may contain inert substituents;

M means the Central transition metal ion having a valency of +a;

X is protivoiona having a valence-b, which is stable under oxidation;

a denotes an integer of 1 to 4;

b indicates a positive integer;

n means an integer of 1 to 4, n is equal to a/b.

9. The method according to p. 1, characterized in that the complex of the transition metal has the formula V

< / BR>
where A51A53are independent alkylene having 1 to 6 carbons in the main chain group and may contain inert substituents;

with K51for K53are benzylidene, 2-pyridylmethylene or 6-methyl-2-pyridylmethylene and may contain inert substituents; M means the CC-b, which is stable under oxidation;

a denotes an integer of 1 to 4;

b indicates a positive integer;

n means an integer of 1 to 4, n is equal to a/b.

10. The method according to p. 1, characterized in that the complex of the transition metal has the formula VI

[K61- N = A6= N - K62]Ma+(Xb-)n,

where A6means

< / BR>
< / BR>
< / BR>
< / BR>
and may contain inert substituents;

K61and K62are 2-pyridium, 3-pyridium, 8-chinaillon or aminoalkyl, and alkyl has 2 to 4 carbon and may contain inert substituents;

M means the Central transition metal ion having a valency of +a;

X is a counterion having a valence-b, which is stable under oxidation;

a denotes an integer of 1 to 4;

b indicates a positive integer;

n means an integer of 1 to 4, n is equal to a/b.

11. The method according to p. 1, characterized in that the complex of the transition metal has the formula VII

< / BR>
where A7means

< / BR>
< / BR>
and may contain inert substituents;

K71- K74are 2-pyridium, 3-pyridium, 2-pyridylmethyl or 3-pyridylmethyl and may contain inert substituents;

M Osnach the ness-b, which is stable under oxidation;

a denotes an integer of 1 to 4;

b indicates a positive integer;

n means an integer of 1 to 4, n is equal to a/b.

12. The method according to p. 1, characterized in that the complex of the transition metal has the formula VIII

[K81= N - A8- N = K82]Ma+(Xb-)n,

where A8independently is alkylene, keysym 1 to 6 carbons in the main chain of the group, o-phenylene, m-phenylene, p-phenylene, 1,8-naphthalenol, 9,10-phenantroline, 2,6-pyridinium, 3,6-acridinium, 2,2'-bipyridyl - 6,6'-deylam, 1,10-phenanthroline-2,9-deylam, 2,6-pyrimidinium, 4,5-pyrimidinium, 2,6-pyrazinediium, 2-phenyl-1,3,5-triazine-2,6-deylam,

< / BR>
< / BR>
where R1is alkylene from 1 to 8 carbons, and R2is alkyl of 1 to 8 carbons, aryl of 1 to 8 carbons, arylalkyl from 7 to 14 carbons or alkylaryl from 7 to 14 carbons, and may contain inert substituents;

K81and K82are a group of the formula

-T - N = CR81- CR82=,

where T is a hydroxyl, amino or General formula

-NR4R5,

where R4and R5independently are alkyl with 1 to 6 carbons, and may contain inert substituents;

R81and R82aktivnye deputies;

M means the Central transition metal ion having a valency of +a;

X is a counterion having a valence-b, which is stable under oxidation;

a denotes an integer of 1 to 4;

b indicates a positive integer;

n means an integer of 1 to 4, n is equal to a/b.

13. The method according to p. 1, wherein the cyclic or open-chain polyfunctional aminosidine used in the preparation of the complex of the transition metal as the ligand has a HOMO energy from -10 eV to -3 eV, as calculated by MOPAC VERSION 6.0 PM3 method.

14. The method according to any of paragraphs.1 - 13, characterized in that the transition metal is iron, Nickel, manganese, cobalt, copper, ruthenium or rhodium.

15. The complex of the transition metal, which includes cyclic polyfunctional aminosilane having at least three nitrogen atom in the ring, forming a molecular chain, or a polyfunctional aminosidine with an open circuit, having at least three nitrogen atom in the main chain of the molecule as a ligand, where the transition metal is iron, Nickel, manganese, cobalt, copper, ruthenium or rhodium, provided that the complex of the transition metal is not a complex porfiri is the complex as the ligand has a HOMO energy from -10 eV to -3 eV, as calculated by MOPAC VERSION 6.0 PM3 method.

16. The complex of the transition metal under item 15, which has the formula II

< / BR>
where A denotes the independent alkylene having 1 to 6 carbons in the main chain of the group, phenylene, naftilan (naphthalenediol), phenanthrolin (finalrender), pyridinyl, pyrrolidinyl, pyrazinyl, pyrimidinyl or 1,3,5-triazinyl and may contain inert substituents;

R is independently hydrogen, alkyl, aryl, alkylaryl or arylalkyl, and alkyl, aryl, alkylaryl or arylalkyl may contain inactive substituents;

M means the Central transition metal ion having a valency of +a;

X is a counterion having a valence-b, which is stable under oxidation;

a denotes an integer of 1 to 4;

b indicates a positive integer;

n means an integer of 1 to 4, n = a/b;

m denotes 0 or a positive integer of 1 or greater.

17. The complex of the transition metal under item 15, which has the formula III

< / BR>
where B is divalent organic group having formula IV

< / BR>
or

< / BR>
where Y1and Y2independently are alkylene having 1 to 6 carbons in the main cemalcilar or arylalkyl, and alkyl, aryl, alkylaryl or arylalkyl may contain inactive substituents, M is a Central transition metal ion having a valency of +a;

X is a counterion having a valence-b, which is stable under oxidation;

a denotes an integer of 1 to 4;

b indicates a positive integer;

n means an integer of 1 to 4, n is equal to a/b.

18. The complex of the transition metal under item 15, which has the formula VI

< / BR>
where A is independently alkylene having 1 to 6 carbons in the main chain of the group, phenylene, naphthalenol, phenanthroline, pyridinium, pirramimma, pyrazinediium, pyrimidinium or 1,3,5-triazinium, and may contain inert substituents;

B is bis(alkylidene) having 2 to 10 carbons in the main chain groups

< / BR>
< / BR>
and may contain inert substituents;

R is independently hydrogen, alkyl, aryl, alkylaryl or arylalkyl, and alkyl, aryl, alkylaryl or arylalkyl may contain inactive substituents;

M means the Central transition metal ion having a valency of +a;

X is a counterion having a valence-b, which is stable under oxidation;

a denotes an integer of 1 to 4;

b oznaczanie number of 1 or more.

19. The complex of the transition metal under item 15, which has the formula VII

< / BR>
where A is independently alkylene having 1 to 6 carbons in the main chain of the group, phenylene, naphthalenol, phenanthroline, pyridinium, pirramimma, pyrazinediium, pyrimidinium or 1,3,5-triazinium, and may contain inert substituents;

B is bis(alkylidene) having 2 to 10 carbons in the main chain groups

< / BR>
< / BR>
and may contain inert substituents;

R independently denotes hydrogen, alkyl, aryl, alkylaryl or arylalkyl, and alkyl, aryl, alkylaryl or arylalkyl may contain inactive substituents;

M means the Central transition metal ion having a valency of +a;

X is a counterion having a valence-b, which is stable under oxidation;

a denotes an integer of 1 to 4;

b indicates a positive integer;

n means an integer of 1 to 4, n = a/b; m indicates 0 or a positive integer of 1 or more.

20. The complex of the transition metal under item 15, which has the formula II

< / BR>
where A2independently is alkylene having 1 to 6 carbons in the main chain of the group, o-phenylene, m-phenylene, p-phenylene, 1,8-naphthalenol, 9,10-phenanthroline, 2,6-Piri is eilam, 2,6-pyrazinediium, 2-phenyl-1,3,5-triazine-2,6-deylam.

< / BR>
< / BR>
where R1is alkylene with 1 to 8 carbons, and R2is alkyl with 1 to 8 carbons, aryl with 1 to 8 carbons, arylalkyl from 7 to 14 carbons or alkylaryl from 7 to 14 carbons, and R1and R2may contain inactive substituents;

K21, K22, K23and K24independently are hydrogen, alkyl, aryl, alkylaryl, arylalkyl, pyridium, pyridylamino or chinaillon, where alkyl, aryl, alkylaryl, arylalkyl, pyridyl, pyridylethyl or chinolin may contain inactive substituents;

M means the Central transition metal ion having a valency of +a;

X is a counterion having a valence-b, which is stable under oxidation;

a denotes an integer of 1 to 4;

b indicates a positive integer;

n means an integer of 1 to 4, n = a/b;

m is a positive integer of 2 or more.

21. The complex of the transition metal under item 15, which has the formula III

[K31= N - A3- N = K32] Ma+(Xb-)n,

where A3independently is alkylene having 1 to 6 carbons in the main chain of the group, o-phenylene, m-phenylene, p-phenylene, 1,8 the sludge, 2,6-pyrimidinium, 4,5-pyrimidinium, 2,6-pyrazinediium, 2-phenyl-1,3,5-triazine-2,6-deylam,

< / BR>
< / BR>
where R1is alkylene with 1 to 8 carbons, and R2is alkyl with 1 to 8 carbons, aryl with 1 to 8 carbons, arylalkyl from 7 to 14 carbons or alkylaryl from 7 to 14 carbons, and may contain inert substituents;

K31and K32are 2-aminobenzylidene and may contain inert substituents;

M means the Central transition metal ion having a valency of +a;

X is a counterion having a valence-b, which is stable under oxidation;

a denotes an integer of 1 to 4;

b indicates a positive integer;

n means an integer of 1 to 4, n is equal to a/b.

22. The complex of the transition metal under item 15, which has the formula IV

[K41= N - A4- N = K42]Ma+(Xb-)n,

where A4independently is alkylene having 1 to 6 carbons in the main chain of the group, o-phenylene, m-phenylene, p-phenylene, 1,8-naphthalenol, 9,10-phenanthroline, 2,6-pyridinium, 3,6-acridinium, 2,2'-bipyridyl-6,6'-deylam, 1,10-phenanthroline-2,9-deylam, 2,6-pyrimidinium, 4,5-pyrimidinium, 2,6-pyrazinediium, 2-phenyl-1,3,5-triazine-2,6-deylam,

< / BR>
< / BR>
gerdami, arylalkyl from 7 to 14 carbons or alkylaryl from 7 to 14 carbons, and may contain inert substituents;

K41and K42are 2-pyridylmethylene or 6-methyl-2-pyridylmethylene and may contain inert substituents;

M means the Central transition metal ion having a valency of +a;

X is a counterion having a valence-b, which is stable under oxidation;

a denotes an integer of 1 to 4;

b indicates a positive integer;

n means an integer of 1 to 4, n is equal to a/b.

23. The complex of the transition metal under item 15, which has the formula V

< / BR>
where A51A53are independent alkylene having 1 to 6 carbons in the main chain group and may contain inert substituents;

K51for K53are benzylidene, 2-pyridylmethylene or 6-methyl-2-pyridylmethylene and may contain inert substituents;

M means the Central transition metal ion having a valency of +a;

X is a counterion having a valence-b, which is stable under oxidation;

a denotes an integer of 1 to 4;

b indicates a positive integer;

n means an integer of 1 to 4, n is equal to a/b.

24. The complex transition is ,

where A6means

< / BR>
< / BR>
< / BR>
< / BR>
and may contain inert substituents;

K61and K62are 2-pyridium, 3-pyridium, 8-chinaillon or aminoalkyl, and alkyl has 2 to 4 carbon and may contain inert substituents;

M means the Central transition metal ion having a valency of +a;

X is a counterion having a valence-b, which is stable under oxidation;

a denotes an integer of 1 to 4;

b indicates a positive integer;

n means an integer of 1 to 4, n is equal to a/b.

25. The complex of the transition metal under item 15, which has the formula VII

< / BR>
where A denotes the

< / BR>
< / BR>
and may contain inert substituents;

K71- K74are 2-pyridium, 3-pyridium, 2-pyridylmethyl or 3-pyridylmethyl and may contain inert substituents;

M means the Central transition metal ion having a valency of +a;

X is a counterion having a valence-b, which is stable under oxidation;

a denotes an integer of 1 to 4;

b indicates a positive integer;

n means an integer of 1 to 4, n is equal to a/b.

Priority points and features:

14.03.95 under item 1, where complete and p. 2, where m = 0;

28.02.95 under item 1, where the complex of the transition metal comprises a ligand cyclic polyfunctional aminosidine having four or more nitrogen atoms in the molecule; p. 2, where m > 1 and p. 15;

24.05.95 under item 1, where the complex of the transition metal comprises a polyfunctional ligand aminosidine with an open circuit, having three or more nitrogen atoms in the molecule; partially under item 8.

 

Same patents:

The invention relates to new trehlitrovy complexes, processes for their preparation and their use as pharmaceuticals, in particular for the treatment of cancer

The invention relates to a method for Organoelement compounds, which can be used as additives to lubricating oils

The invention relates to a method of obtaining new compounds - 6,8,10-trinitro-1,4-dioxaspiro[4,5] DECA-6,9-dianatal cations p-, d-, and f - elements of the formula I (anioniccomplexes of Meisenheimer), which can be used for metal-complex catalysis

The invention relates to platinum complexes with antitumor activity, to processes for their preparation and to pharmaceutical compositions containing said complexes

The invention relates to new chemical compounds, complexes of 1-vinyl - 1-ethylimidazole with zinc and cobalt salts of organic and inorganic acids with the General formula given in the description text

The invention relates to biologically active agents with antiproliferative and cytotoxic activity and can be used in pharmaceutical, chemical industries and medicine

The invention relates to new chemical compounds, specifically to derived TRANS-sodium dichloro(bromo)-bis{ gamma-1,2,5-trimethyl-4-(3,4-dimethyl-3,4 - dihydroxy-1-pentenyl)-4-piperidin this, N}Pt (II), General formula

< / BR>
where

X is Cl or Br;

- the remainder of the ligand-gamma 1,2,5-trimethyl-4-(3,4-dimethyl-3,4-dihydroxy-1-pentenyl)-4-piperidone,

showing antihelminthic activity

The invention relates to the derivatives of alkylpyridine, in particular, to the monohydrate complex of cobalt chloride N-oxide 2-methylpyridine gross formulaYou have received a new chemical compound in ethanol at 25 - 78oWith

The invention relates to methods of obtaining Tris-beta-diketonates rare platinum metals General formula (R'-CO-CH-CO-R)3M, where M Rh(III), Ir(III), Ru(III), Os(III); R', R" -CH3, -CF3, -CF3, -C6H5, -C(CH3)3, -C3F7in various combinations, relates to the field of inorganic chemistry synthesis of volatile kislorodnykh complexes with organic ligands

The invention relates to the synthesis of ORGANOMETALLIC compounds, namely, to obtain cyclopentanetetracarboxylic manganese, which can be used as antiknock motor fuels

The invention relates to a derivative of pyridine, namely the coordination compound of manganese (2) gross f-ly Mn
The invention relates to inorganic chemistry, namely to receive tocomplex elements of the seventh group, in particular to a method for tetrathionate of tetraethylammonium

The invention relates to the synthesis of new macrocyclic complex compounds of some Tetra-2,3-Hino - clinophobia manganese, which can be used as a thermo stabilizer of polyvinyl chloride in the production of plastics, artificial leather, film materials

The invention relates to radiopharmaceutical products

The invention relates to the production of unbalanced porphyrazines, combining in the molecule two diphenylpyraline or two isoindoline fragment

The invention relates to a method of obtaining new compounds - 6,8,10-trinitro-1,4-dioxaspiro[4,5] DECA-6,9-dianatal cations p-, d-, and f - elements of the formula I (anioniccomplexes of Meisenheimer), which can be used for metal-complex catalysis

The invention relates to magnetic materials that can be used in electronics, nanotechnology, magneto-optics, etc
Up!