Method of producing enantiomerically pure (s)-amino acids on basis of [(s)-bpb-gly]ni(ii) complex, directly bonded with fullerene core through α-carbon atom in form of chiral (f,ta) and (f,tc) 1,4-adducts of [60]fullerene

FIELD: chemistry.

SUBSTANCE: invention relates to a method for stereoselective synthesis of (S)-α-fullerenylglycine, wherein α-carbon atom of an acid is directly bonded with a fullerene core, in form of complex of Ni(II) of type of Schiff base with an auxiliary [(S)-BPB] ligand in form of chiral (f,tA) and (f,tC) 1,4-adducts of formula (I). Method includes steps A–E. Step A comprises modifying an initial amino acid by its incorporation in form of a Schiff base into coordination sphere of nickel complex with an auxiliary chiral ligand ((S)-2N-(N'-benzylprolyl)aminobenzophenone) [(S)-BPB-Gly]Ni(II). Step B comprises deprotonation of amino acid fragment of obtained complex. Step C comprises stereoselective reaction of anionic (deprotonated) complex with fullerene to form fullerene carbanion. Step D comprises reaction of fullerene carbanion with an electrophile, such as allyl- or benzyl halide, with formation of diastereomeric mixture of target fullerene (f,tA) and (f,tC) 1,4-adducts, containing (S)-α-amino acid fragment, directly bonded with fullerene core through α-carbon atom, in form of Schiff base in coordination sphere of Ni(II). Step E comprises separating and cleaning fullerene-containing adducts by column chromatography on silica gel to obtain a mixture of target fullerene (f,tA) and (f,tC) 1,4-adducts, containing (S)-α-amino acid fragment in coordination sphere of Ni(II). Invention also relates to a mixture of diastereomers, consisting of (f,tA) and (f,tC) 1,4-adducts, and optically pure (f,tA) and (f,tC) adducts.

EFFECT: method enables stereoselective synthesis fullerenylglycine derivative having (S)-configuration of α-amino acid stereocentre.

8 cl, 1 dwg, 6 ex

(I)

 



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to nickel complex of 5,10,15,20-tetrakis [3',5'-di(2"-methylbutyloxy)phenyl]-porphin of formula

EFFECT: invention makes it possible to obtain nickel complex, demonstrating property of stationary phase for gas chromatography.

1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method for enantioselective synthesis of (R)-diethyl(2-nitro-1-phenylethyl)malonate of formula

by enantioselective bonding of diethyl malonate to trans-β-nitrostyrene in the presence of a chiral catalyst. The catalyst is a nickel (II) complex of formula II with (S,S)-N,N'-di(2,4,6-trimethylbenzyl)cyclohexane-1,2-diamine

.

EFFECT: invention enables to obtain a compound of formula I with enantiomeric excess of the (R)-isomer and also simplify the process.

4 cl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to organometallic chemistry and specifically to a method of producing organometallic nickel (III) complexes. The method is realised via oxidative bonding of an olefin to a cationic nickel (I) complex formed by oxidising bis(cyclooctadiene-1,5)nickel with boron trifluoride etherate. Formation of catalytically active organometallic nickel (III) complexes is carried out in molar ratio B:Ni=2:1.

EFFECT: invention considerably simplifies obtaining organometallic nickel (III) complexes which exhibit high catalytic activity with respect to olefins.

2 dwg, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel substituted metal phthalocyanines, which can be used as direct and acid dyes for dyeing cotton and protein fibre. Disclosed are tetra-4-[(4'-carboxy)phenylamino]phthalocyanine metal complexes of formula, where M=Cu, Ni, Zn.

EFFECT: metal phthalocyanines expand the colour gamma of the current light-blue copper tetra-4-carboxyphthalocyanine, which is the closest on structure and application, to a blue-green and green colour.

6 dwg, 5 ex

FIELD: chemistry.

SUBSTANCE: method involves heating, while stirring continuously in a reaction medium, a mixture of ultrafine nickel hydroxide and phthalic anhydride or phthalic acid, taken in molar ratio 3:1, at temperature 85±5°C for 1 hour. Further, a stoichiometric amount of lead oxide and a catalytic amount of an acetate-containing reactant are then added at temperature 97±2°C. The mixture is heated for 8 hours. The obtained reaction product is separated from the mother solution, washed with water heated to 80°C and then filtered.

EFFECT: method ensures environmental safety of the process, enables to obtain a product having the required catalytic efficiency, increases efficiency of the apparatus by replacing the basic nickel carbonate reactant with nickel hydroxide.

6 cl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to stable complexes consisting of metal oxides - iron, cobalt or alloys thereof in form of nanoparticles and bifunctional compounds, where the bifunctional compounds are selected from thiols, carboxylic acids, hydroxamic acids, phosphoric esters or salts thereof, having an aliphatic chain containing a second functional group in the terminal position ω, which can be used in certain novel hydrophilic plates and fibres, as well as a method of producing complexes. The method involves reaction of dispersion of said nanoparticles in an organic solvent with a suitable binder. The mixture is stirred for several hours at low temperature and the obtained product is then cooled and separated by centrifuging, and can then be cleaned via repeated dispersion in a suitable solvent and repeated deposition.

EFFECT: novel complexes with improved solubility in water-alcohol medium are obtained.

13 cl, 3 dwg, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing imino-amide π-allyl complexes of nickel. The method involves reaction of Ni(allyl)2 with diimine ligands in molar ratio 1:1. The process is carried out in a solvent medium at temperature between -30°C and 0°C.

EFFECT: invention enables to obtain imino-amide π-allyl complexes of nickel, which can bee used in catalytic conversion of lower olefins.

5 ex

FIELD: chemistry.

SUBSTANCE: disclosed method relates to preparing a catalyst for addition polymerisation of norbornene to polynorbornene. Described is a method of preparing a catalyst for addition polymerisation of norbornene based on complexes of zero-valent nickel and BF3OEt2 involving use of catalyst systems of the composition (L)nNi(PR3)2/BF3OEt2, where n=1, 2; L=PR3 or ethylene; R=Ph, OC6H4CH3-o combined with a controlled amount of water as a modifying component, and the process is carried out in a medium of organic solvent, e.g. toluene in molar ratio of boron to nickel B: Ni=50:1-600:1, ratio H2O/Ni=2-104 and temperature 10-80°C.

EFFECT: high efficiency of the norbornene polymerisation process.

3 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an organonickel sigma-complex of formula ([NiBr(Xy)(bpy)], where Xy=2,6-dimethylphenyl, bry=2,2'-bipyridyl). Said complex exhibits high catalytic activity during oligomerisation of ethylene with retention of good solubility in carbon solvents.

EFFECT: possibility of oligomerisation in completely homogeneous conditions.

2 cl, 7 ex, 1 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to obtaining etyheleneammonium bis(1-hydroxyethane-1,1-diphosphonato(2-))cuprate (+2), etyheleneammonium bis(1-hydroxyethane-1,1-diphosphonato(2-)) zincate(+2) and etyheleneammonium bis(1-hydroxyethane-1,1-diphosphonato(2-)) nickelate(+2) and can be used for processing toxic wastes of obtaining metal coatings - waste electrolytes of galvanic copper, zinc and nickel plating, waste solutions of chemical nickel plating and copper plating. Products, obtained by said method, can be used for preparation of electrolytes, metal corrosion inhibitors, for obtaining various copper, zinc and nickel compounds, including catalysts of organic and inorganic substance synthesis. Claimed method includes using liquid industrial wastes, containing metal(+2), ethyleneammonium and/or anion of 1-hydroxyethane-1,1-diphosphonic acid as reagents. Target products are obtained by crystallisation from reaction water solution with separation of sediment from solution, process is carried out at temperature from (-5) to 105°C and atmospheric pressure. Method allows to obtain pure crystalline products with yield up to 98%, to reduce expenditures on environment protection.

EFFECT: method simplification and increase of its manufacturability.

7 cl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention refers to a method for producing diethyl[3-methyl-(1S)-(nitromethyl)butyl]malonate of formula I by enanthioselective attachment of diethylmalonate to 4-methyl-1-nitropent-1-ene in accordance with the scheme below. A reaction of diethylmalonate and 4-methyl-1-nitropent-1-ene is carried out in the presence of a catalyst system representing a nickel chloride hexahydrate solution, (S,S)-N,N'-dibenzylcyclohexane-1,2-diamine and triethylamine in molar ratio 1:1:1 in methanol. Preferentially, the catalyst system components are used in ratio 0.05-1 mole % in relation to 4-methyl-1-nitropent-1-ene. The method enables producing diethyl[3-methyl-(1S)-(nitromethyl)butyl]malonate with an enanthiomeric excess of 96.6-97.2% with the use of the catalyst system generated from nickel chloride hexahydrate, (S,S)-N,N'-dibenzylcyclohexane-1,2-diamine and triethylamine, avoiding the stage of individual complex recovery.

EFFECT: considerable cost-cutting and simplification of the technological process.

2 cl, 5 ex

FIELD: chemistry.

SUBSTANCE: sesamin or sesamin-containing composition undergoes epimerisation in such a way that a portion of the sesamin converts to episesamin. Episesamin is crystallised through recrystallisation. The device for producing sesamin has an isomerisation unit which has a mixing reservoir for mixing oil or fat containing sesamin or a sesamin-containing composition with an acid catalyst; a crystallisation unit having a crystallisation reservoir for carrying out recrystallisation; a liquid supply line which connects the mixing reservoir with the crystallisation reservoir.

EFFECT: high output of product.

21 cl, 2 dwg, 5 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a stereoselective method of obtaining a fluorinated molecule having a fluorine atom with asymmetrical carbon (R) or (S) configuration in the α position relative an ester or ketone group in which: (i) a fluorosulphite compound of given configuration on C* which carries the fluorosulphite group of formula (III) is put into a reactor, (2i) the fluorosulphite compound is thermally decomposed in the presence of a nucleophilic catalyst which contains a tertiary nitrogen atom, at temperature ranging from 60°C to 180°C, (3i) a fluorinated molecule having reverse configuration of formula (IV) is obtained, provided that: -R1 denotes alkyl, alkenyl, alkynyl, where these groups can be straight or branched, aryl, cycloalkyl, alkylcycloalkyl, CO2R5, - (CH2)n-CO2R5, -COR5, -SOR5, -SO2R5, where n is an integer from 1 to 12, R5 denotes hydrogen or alkyl, alkenyl, alkynyl, where these groups can be straight or branched, cycloalkyl, alkylcycloalkyl, aryl, particularly substituted aryl; R1 can also form an aromatic or not a heterocycle containing, instead of one or more carbon atoms, one or more heteroatoms selected from oxygen, sulphur or nitrogen; -R2 denotes hydrogen or a group corresponding to definition given for R1; - R1 and R2 are different; - R3 denotes hydrogen or a R6 or -OR6 group, where R6 is selected a list given for R5; where R6 and R1 can be identical or different.

EFFECT: use of the present method enables to stereoselectively obtain fluorinated molecules with good output using cheap and reagents which do not lead to large amounts of effluent.

40 cl, 1 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for regiospecific synthesis of isomerically pure 2-(p-isothiocyanatobenzyl)-6-methyldiethylenetriaamino-N,N,N',N'', N''-pentaacetic acid (MX-DTPA) comprising at least 90% of regioisomer of the formula (I): These compounds are used as bifunctional chelating agents in radioimmunotherapy and/or for detection and/or preparing the tumor image. The claimed method provides synthesis of derivatives of DTPA with high yield based on excluding necessity of separation of intermediate compounds by ion-exchange chromatography. Except, method provides preparing a single chelate regioisomer and therefore method provides regiospecific synthesis of desired chelates that can be used as agents labeled with radioactive isotopes.

EFFECT: improved method of synthesis.

24 cl, 11 dwg, 1 ex

FIELD: organic chemistry, medicine, biochemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of pure enantiomers of inhibitors of HMG-CoA-reductase. Invention describes a method for synthesis of compound of the formula (I): or its salt, especially pharmaceutically acceptable salt with a base, or its lactone wherein a member represents -CH2-CH2- or -CH=CH-, and R represents a cyclic residue. Invention provides the enantioselective synthesis of compounds of the formula (I) with high yields, decreasing ecological pollution of environment and possibility for carrying out the large-scale manufacturing.

EFFECT: improved method of synthesis.

6 cl, 1 ex

The invention relates to methods for obtaining optically active ester of Erythro - 3-amino-2-hydroxybutyric acid, which represents an important intermediary product pharmaceutical reagents, in particular inhibitor of HIV protease

FIELD: organic chemistry, medicine, biochemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of pure enantiomers of inhibitors of HMG-CoA-reductase. Invention describes a method for synthesis of compound of the formula (I): or its salt, especially pharmaceutically acceptable salt with a base, or its lactone wherein a member represents -CH2-CH2- or -CH=CH-, and R represents a cyclic residue. Invention provides the enantioselective synthesis of compounds of the formula (I) with high yields, decreasing ecological pollution of environment and possibility for carrying out the large-scale manufacturing.

EFFECT: improved method of synthesis.

6 cl, 1 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for regiospecific synthesis of isomerically pure 2-(p-isothiocyanatobenzyl)-6-methyldiethylenetriaamino-N,N,N',N'', N''-pentaacetic acid (MX-DTPA) comprising at least 90% of regioisomer of the formula (I): These compounds are used as bifunctional chelating agents in radioimmunotherapy and/or for detection and/or preparing the tumor image. The claimed method provides synthesis of derivatives of DTPA with high yield based on excluding necessity of separation of intermediate compounds by ion-exchange chromatography. Except, method provides preparing a single chelate regioisomer and therefore method provides regiospecific synthesis of desired chelates that can be used as agents labeled with radioactive isotopes.

EFFECT: improved method of synthesis.

24 cl, 11 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a stereoselective method of obtaining a fluorinated molecule having a fluorine atom with asymmetrical carbon (R) or (S) configuration in the α position relative an ester or ketone group in which: (i) a fluorosulphite compound of given configuration on C* which carries the fluorosulphite group of formula (III) is put into a reactor, (2i) the fluorosulphite compound is thermally decomposed in the presence of a nucleophilic catalyst which contains a tertiary nitrogen atom, at temperature ranging from 60°C to 180°C, (3i) a fluorinated molecule having reverse configuration of formula (IV) is obtained, provided that: -R1 denotes alkyl, alkenyl, alkynyl, where these groups can be straight or branched, aryl, cycloalkyl, alkylcycloalkyl, CO2R5, - (CH2)n-CO2R5, -COR5, -SOR5, -SO2R5, where n is an integer from 1 to 12, R5 denotes hydrogen or alkyl, alkenyl, alkynyl, where these groups can be straight or branched, cycloalkyl, alkylcycloalkyl, aryl, particularly substituted aryl; R1 can also form an aromatic or not a heterocycle containing, instead of one or more carbon atoms, one or more heteroatoms selected from oxygen, sulphur or nitrogen; -R2 denotes hydrogen or a group corresponding to definition given for R1; - R1 and R2 are different; - R3 denotes hydrogen or a R6 or -OR6 group, where R6 is selected a list given for R5; where R6 and R1 can be identical or different.

EFFECT: use of the present method enables to stereoselectively obtain fluorinated molecules with good output using cheap and reagents which do not lead to large amounts of effluent.

40 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: sesamin or sesamin-containing composition undergoes epimerisation in such a way that a portion of the sesamin converts to episesamin. Episesamin is crystallised through recrystallisation. The device for producing sesamin has an isomerisation unit which has a mixing reservoir for mixing oil or fat containing sesamin or a sesamin-containing composition with an acid catalyst; a crystallisation unit having a crystallisation reservoir for carrying out recrystallisation; a liquid supply line which connects the mixing reservoir with the crystallisation reservoir.

EFFECT: high output of product.

21 cl, 2 dwg, 5 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention refers to a method for producing diethyl[3-methyl-(1S)-(nitromethyl)butyl]malonate of formula I by enanthioselective attachment of diethylmalonate to 4-methyl-1-nitropent-1-ene in accordance with the scheme below. A reaction of diethylmalonate and 4-methyl-1-nitropent-1-ene is carried out in the presence of a catalyst system representing a nickel chloride hexahydrate solution, (S,S)-N,N'-dibenzylcyclohexane-1,2-diamine and triethylamine in molar ratio 1:1:1 in methanol. Preferentially, the catalyst system components are used in ratio 0.05-1 mole % in relation to 4-methyl-1-nitropent-1-ene. The method enables producing diethyl[3-methyl-(1S)-(nitromethyl)butyl]malonate with an enanthiomeric excess of 96.6-97.2% with the use of the catalyst system generated from nickel chloride hexahydrate, (S,S)-N,N'-dibenzylcyclohexane-1,2-diamine and triethylamine, avoiding the stage of individual complex recovery.

EFFECT: considerable cost-cutting and simplification of the technological process.

2 cl, 5 ex

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