Method for combined synthesis of 1'-alkyl-1'-ethylformyl-(c60-ih)[5,6]fullero[2',3';1,9]cyclopropanes and 1'a-alkyl-1'a-ethylformyl-1'a-carba-1'(2')a-homo(c60-ih)[5,6]fullerenes

FIELD: chemistry.

SUBSTANCE: method involves combined synthesis of 1'-alkyl-1'-ethylformyl-(C60-Ih)[5,6]fullero[2':,3':1,9]cyclopropanes and 1'a-alkyl-1'a ethylformyl-1'a-carba-1'(2')a-homo(C60-Ih)[5,6]fullerenes of general formula

, where Alkyl =Et, i-Pr, i-Bu, Bn, where C60-fullerene reacts with α-alkyldiazoacetic ether of general formula N2C(alkyl)COOEt, where alkyl = Et, i-Pr, i-Bu, Bn, in o-dichlorobenzene in the presence of a three-component catalyst {Pd(acac)2:2PPh3:4Et3Al}, taken in molar ratio C60-fullerene: α-alkyldiazoacetic ether: Pd(acac)2:PPh3:Et3Al=0.01:(0.05-0.15):(0.0015-0.0025):(0.003-0.005):(0.006-0.01), preferably 0.01:0.1:0.002:0.004:0.008, at temperature of 40°C for 0.25-1.0 hours. 1'-alkyl-1'-ethylformyl-(C60-1h)[5,6]fullero[2',3':1,9]cyclopropanes (1) and 1'a-alkyl-1'a ethylformyl-1'a-carba-1'(2')a-homo(C60-Ih)[5,6]fullerenes (2) are obtained in ratio of 1:1 and total output of 55-79%.

EFFECT: high yield.

1 tbl, 10 ex

 

The present invention relates to the field of organic synthesis, namely the way the joint production of 1'-alkyl-1'-ethylpropyl-(C60-Ih)[5,6]fullero[2',3':1,9]cyclopropanes and 1 a-alkyl-1 a-ethylpropyl-1 a-carb-1'(2')a-Homo(C60-Ih)[5,6]fullerenes General formula (1) and (2):

Alkyl=Et, i-Pr, i-Bu, Bn

Functionally substituted fullerenes can be used as complexing agents, sorbents, biologically active compounds, as well as the creation of new materials with tailored electronic, magnetic and optical properties.

The known method (S.R.Wilson, Y.Wu. J.Chem.Soc., Chem.Commun., 1993, 784 [1]) obtain a crown-ether containing fulleroid (5) opening 42% response With60-fullerene (3) with diazacrown-ether (4) at a temperature of 5-10°C for 2-3 hours

The known method does not allow to obtain 1'-alkyl-1'-ethylpropyl-(C60-Ih)[5,6]fullero[2',3':1,9]cyclopropanes and 1 a-alkyl-1 a-ethylpropyl-1 a-carb-1'(2')a-Homo(C60-Ih)[5,6]fullerenes General formula (1) and (2).

The known method (R.Sijbesma, G.Srdanov, F.Wudl, J.A.Castoro, C.Wilkins, S.H.Friedman, D.L.DeCamp, G.L.Kenyon. SoC. 1993, 775, 6510 [2]) get fullarticlenonav (7) with the release of 93% response With60-fullerene (3) with 4,4'-bis(N-acetyl-2-amino-ethyl)diphenyldiazomethane (6) in dry pyridine in the presence of succinic anhydride at on the th temperature within 24 hours

The known method does not allow to obtain 1'-alkyl-1'-ethylpropyl-(C60-Ih)[5,6]fullero[2',3':1,9]cyclopropanes and 1 a-alkyl-1 a-ethylpropyl-1 a-carb-1'(2')a-Homo(C60-Ih)[5,6]fullerenes General formula (1) and (2).

We propose a new way to obtain 1'-alkyl-1'-ethylpropyl-(C60-Ih)[5,6]fullero[2',3':1,9]cyclopropanes (1) and 1 a-alkyl-1 a-ethylpropyl-1 a-carb-1'(2')a-Homo(C60-Ih)[5,6]fullerene (2).

The method consists in the interaction of fullerene (C60) with α-arcidiocesi ether of General formula N2C(alkyl)COOEt, where alkyl=Et, i-Pr, i-Bu, Bn, in the presence of a three-component catalyst {Pd(acac)2:2PPh3:4Et3Al}, taken in a molar ratio With60:α-arcidiocesi ether:Pd(acac)2:PPh3:Et3Al=0.01:(0.05-0.15):(0.0015-0.0025):(0.003-0.005):(0.006-0.01), preferably 0.01:0.1:0.002:0.004:0.008, in o-dichlorobenzene (o-DHB) as solvent at 40°C for 0.25-1.0 hours Get 1'-alkyl-1'-ethylpropyl-(C60-Ih)[5,6]fullero[2',3':1,9]cyclopropanes (1) and 1 a-alkyl-1 a-ethylpropyl-1 a-carb-1'(2')a-Homo(C60-Ih)[5,6]fullerenes (2) with a total yield 55-79% in the ratio(1):(2)~1:1. The reaction proceeds according to the scheme:

Alkyl=Et, i-Pr, i-Bu, Bn

The conduct of a specified reaction in the presence of a palladium catalyst [Pd] more than 20 mol.% in relation to full erano 60does not lead to a significant increase in the yields of the target products (1) and (2). The use of palladium catalyst [Pd] in the amount of less than 20 mol.% in relation to the fullerene C60reduces the yield of the target product, which is associated with a decrease in reaction centers. The reaction should be carried out at a temperature of 40°C. Carrying out the reaction at a higher temperature (for example 80°C) is associated with increased energy consumption, at a lower temperature (e.g. 20°C) decreases the reaction rate.

Significant differences of the proposed method

The proposed method is based on the use of α-arcidiocesi esters and catalytic amounts of palladium complex, the reaction is available in o-dichlorobenzene.

The proposed method, in contrast to the known, allows to obtain 1'-alkyl-1'-ethylpropyl-(C60-Ih)[5,6]fullero[2',3':1,9]cyclopropanes (1) and 1 a-alkyl-1 a-ethylpropyl-1 a-carb-1'(2')a-Homo(C60-Ih)[5,6]fullerenes (2), the synthesis of which are not described in literature.

The method is illustrated by examples.

To a solution of 0.002 mmol of Pd(acac)2in 0.5 ml of o-DHB in a stream of dry argon at a temperature of -5°C and stirring 0.004 mmol PPh3, 0.008 mmol Et3Al and 0.01 mmol Of60-fullerene in 1 ml of o-DHB. The reaction mass is heated to 40°C and added dropwise 0.1 mmol of α-ethyldiazoacetate ester in 0.5 ml of o-DHB. Through 0.5 the reaction mass is then cooled and passed through a column with a small layer of silica gel. Get 1'-ethyl-1'-ethylpropyl-(C60-Ih)[5,6]fullero[2',3':1,9]cyclopropane (1) and 1 a-ethyl-1 a-ethylpropyl-1 a-carb-1'(2')a-Homo(C60-Ih)[5,6]fullerene (2) in a ratio of ~1:1 with a total yield of 69% (according to HPLC).

Spectral characteristics (1)
An NMR spectrum1N: 1.11 (t, 3H, (6)CH3, J=7 Hz), 1.21 (t, 3H, (8)CH3, J=7 Hz), 3.63 (K, 2N, (7)CH2J=7 Hz), 3.96 (K, 2N, (5)CH2, J=7 Hz).
An NMR spectrum13From: 10.58 (8), 14.34 (6), 24.37 (3), 32.18 (7), 61.40 (5), At 75.03 (1,2), 164.83 (4). The signals of the carbon atoms of fullerene fragment are located in the area of 130-150 ppm
Spectral characteristics (2)
An NMR spectrum1H: 1.28 (t, 3H, (6)CH3, J=7 Hz), 1.34 (t, 3H, (8)CH3, J=7 Hz), 2.70 (K, 2N, (7)CH2, J=7 Hz), 4.27 (K, 2N, (C5)CH2, J=7 Hz).
An NMR spectrum13From: 11.75 (8), 14.60 (6), 51.23 (C3), 23.37 (7), 62.22 (C5), 135.44 (1,2), 168.44 (4). The signals of the carbon atoms of fullerene fragment raspolagayut is in the field of 130-150 ppm

Other examples of the method shown in the table.

0.5
№ p/pAlkylThe molar ratio of C60:N2C(alkyl)COOEt: Pd(acac)2:PPh3: Et3Al, mmolReaction time, hoursThe total yield of target products (1) and (2), %
Et
10.01:0.1:0.002:0.004:0.0080.569
20.01:0.15:0.002:0.004:0.0080.572
30.01:0.05:0.002:0.004:0.0080.564
40.01:0.1:0.0025:0.005:0.010.579
50.01:0.1:0.0015:0.003:0.00655
60.01:0.1:0.002:0.004:0.008173
70.01:0.1:0.002:0.004:0.0080.2562
8i-Pr0.01:0.1:0.002:0.004:0.0080.563
9i-Bu0.01:0.1:0.002:0.004:0.0080.560
10Bn0.01:0.1:0.002:0.004:0.0080.566

The reaction was carried out at 40°C in o-dichlorobenzene as a solvent.

The way the joint production of 1'-alkyl-1'-ethylpropyl-(C60-Ih)[5,6]fullero[2',3':1,9]cyclopropanes and 1 a-alkyl-1 a-ethylpropyl-1 a-carb-1'(2')a-Homo(C60-Ih)[5,6]fullerenes General formulas (1) and (2)

where Alkyl - Et, i-Pr, i-Bu, Bn,
characterized by the fact that With60-fullerene interacts with α-arcidiocesi ether of General formula N2C(alkylCOOEt, where alkyl - Et, i-Pr, i-Bu, Bn, o-dichlorobenzene in the presence of a three-component catalyst {Pd(ASAS)2:2PPh3:4Et3Al}, taken in a molar ratio With60; α-arcidiocesi ether: Pd(acac)2:PPh3:Et3Al=0.01:(0.05-0.15):(0.0015-0.0025):(0.003-0.005):(0.006-0.01), preferably 0.01:0.1:0.002:0.004:0.008, at 40°C for 0.25-1.0 hours



 

Same patents:

FIELD: chemistry.

SUBSTANCE: method of producing functionally substituted fullerenes which can be used as complexing agents, sorbents, biologically active compounds, as well as in making new materials with given properties. The method involves combined production of 1'-ethylformyl-(C60-Ih)[5,6]fullero[2',3':1,9]cyclopropane and 1'a-ethylformyl-1'a-carba-1'(2')a-homo(C60-Ih)[5,6]fullerene with general formula 1 and 2

by reacting C60-fullerene with diazoacetic ester (N2CHCOOEt), where the reaction is carried out in o-dichlorobenzene in the presence of a three-component catalyst {Pd(acac)2: 2PPh3: 4Et3Al}, taken in molar ratio C60: diazoacetic ester: : Pd(acac)2: PPh3: Et3Al=0.01:(0.03-0.07):(0.0005-0.0015):(0.001-0.003):(0.002-0.006), preferably 0.01:0.05:0.001:0.002:0.004, at temperature of 80°C for 0.5-1.5 hours. 1'-ethylformyl-(C60-Ih)[5,6]fullero[2',3':1,9]cyclopropane (1) and 1'a-ethylformyl-1'a-carba-1'(2')a-homo(C60-Ih)[5,6]fullerene (2) are obtained with total output of 44-68%.

EFFECT: method is distinguished from known methods by higher output of end products, use of a palladium complex in catalytic amounts, carrying out the reaction in a readily available solvent.

1 tbl, 7 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: method of producing functionally substituted fullerenes which can be used as complexing agents, sorbents, biologically active compounds, as well as in making new materials with given properties. The method involves combined production of 1'-ethylformyl-(C60-Ih)[5,6]fullero[2',3':1,9]cyclopropane and 1'a-ethylformyl-1'a-carba-1'(2')a-homo(C60-Ih)[5,6]fullerene with general formula 1 and 2

by reacting C60-fullerene with diazoacetic ester (N2CHCOOEt), where the reaction is carried out in o-dichlorobenzene in the presence of a three-component catalyst {Pd(acac)2: 2PPh3: 4Et3Al}, taken in molar ratio C60: diazoacetic ester: : Pd(acac)2: PPh3: Et3Al=0.01:(0.03-0.07):(0.0005-0.0015):(0.001-0.003):(0.002-0.006), preferably 0.01:0.05:0.001:0.002:0.004, at temperature of 80°C for 0.5-1.5 hours. 1'-ethylformyl-(C60-Ih)[5,6]fullero[2',3':1,9]cyclopropane (1) and 1'a-ethylformyl-1'a-carba-1'(2')a-homo(C60-Ih)[5,6]fullerene (2) are obtained with total output of 44-68%.

EFFECT: method is distinguished from known methods by higher output of end products, use of a palladium complex in catalytic amounts, carrying out the reaction in a readily available solvent.

1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to new compounds with formula , in which R represents H, (C1-C12)-alkyl or (C1-C4)-alkyl-(C6-C12)-aryl. In the alkyl, one or more CH2-groups can be substituted with -O-. The invention also relates to the method of obtaining these compounds. The method involves reacting dimethylbenzoic acid ester with formula where R assumes values given above, with a chlorinating agent in an inert solvent or without a solvent at temperature above 40°C, and then cleaning, if necessary. Formula (I) compounds are essential intermediate products during synthesis of PPAR agonists with formula , in which R represents H, (C1-C12)-alkyl or (C1-C4)-alkyl-(C6-C12)-aryl. In the alkyl, one or more CH2-groups can be substituted with -O-; Y represents -(CH2)3-, 1,3-phenylene, 1,3-cyclohexanediyl; R' represents H, F, Br, CF3, (C1-C6)-alkyl, O-(C1-C6)-alkyl, phenyl; CF3; obtained from reaction of compounds with formula with formula (I) compounds in toluene, N-methylpyrrolidone or other aprotic solvents, in the presence of a suitable base, at temperature lying in the -78°C - +50°C interval, with subsequent extractive processing and, if necessary, crystallisation of the end product.

EFFECT: obtaining new compounds.

8 cl, 5 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to chemistry of adamantane derivatives, namely, to a novel method for synthesis of 3-halogen-1-(ethoxycarbonyl)-alkyladamantanes of the general formula: wherein Hal means bromine atom (Br); R means hydrogen atom (H), -CH3, -C2H5, -C3H7; Hal means Br; R means -CH3; R1 means -CH3; Hal means chlorine atom (Cl); R means Cl; R1 means Cl that can be used as intermediate compounds used for synthesis of some biologically active substances. Method involves interaction of 1,3-dehydroadamantane with α-halogenalkane carboxylic acids ethyl esters chosen from the following group: ethyl-2-bromoacetate, ethyl-2-bromopropionate, ethyl-2-bromobutyrate, ethyl-2-bromovalerate, ethyl-2-bromo-2-methylpropionate and ethyl-2,2,2-trichloroacetate taken in the mole ratio = 1:(3-5), respectively, in the parent α-halogenalkane carboxylic acid ethyl esters medium, at temperature 50-60°C for 4-6 h. Invention provides expanding assortment of chemical compounds, in particular, synthesis of novel 3-halogen-1-(ethoxycarbonyl)-alkyladamantanes with the high yield.

EFFECT: improved method of synthesis.

6 ex

FIELD: chemical industry; method of production of the fluorine-containing compounds.

SUBSTANCE: the invention is pertaining to the chemical industry, in particular, to the improved method of production of fluorine-containing compounds from the halogen-containing, compounds, preferably, from chlorine-containing compounds due to an exchange of halogen for fluorine at presence of the HF-additional compound of the mono- or bicyclic amine with at least two atoms of nitrogen. At that at least one atom of nitrogen is built in the cyclic system as the fluorating agent; or at presence of anhydrous hydrogen fluoride - as the fluorating agent and the indicated HF-additional compound of the mono- or bicyclic amine as the catalyst. At usage of the applicable solvents the reaction mixtures can be divided into two phases and thus to simplify the reprocessing of the products. The invention also is pertaining to the HF-additional compounds of 1.5-diazabicyclo[4.3.0]non-5-en and N,N-dialkylaminopiridin, where alkyl represents C1-C4alkyl and where the molar ratio of HF to amine makes 1:1, and to HF- additional compounds 1.8- diazabicyclo[5.4.0]undecyl-7-ene, where the molar ratio of HF to amine compounds more than 1:1.

EFFECT: the invention ensures at usage of the applicable solvents to divide the reaction mixture into two phases and thus to simplify reprocessing of the products.

17 cl, 13 ex

FIELD: organic chemistry, in particular polymers.

SUBSTANCE: invention relates to new method for production of vic-dichlorofluoroanhydride useful as intermediate of starting monomer for fluorinated polymers with good yield from available raw material. Claimed method includes fluorination of starting material (I): (RH1-EH1-)CRH2RH3CH2-0CORHB in liquid phase to form compound of formula (II): (CF2ClCFCl-EF1-)CRF2RF3CF2-OCORFB; ester bond splitting of formula (II) in gaseous phase under solvent absence to form compound of formula (III): (CF2ClCFCl-EF1-)CRF2RF3COF or compound of formula (III) and compound of formula (IV): FCORFB, wherein RH1 is CX1X2ClCX3Cl- or CClX4=CCl, wherein each X1-X4 independently is hydrogen; RH2 and RH3 independently are hydrogen or linear or branched alkyl, optionally substituted with one or more oxygen; EH1 is alkylene, optionally substituted with one or more oxygen; EF1 = EH1 wherein perfluoroalkylene group is optionally substituted with one or more oxygen; RHB = RFB and are linear or branched perfluoroalkyl group, optionally substituted with chlorine one or more oxygen; RF2 is fluorinated RH2; RF3 is fluorinated RH3; with the proviso, that RF2 is fluorinated RH2; RF3 is fluorinated RH3, i.e. RF2 and RF3 represent RH2 or RH3 with at least one fluorinated hydrogen. Also disclosed are new compounds, represented in claims of invention.

EFFECT: new intermediates useful in polymer fluorination.

11 cl, 7 ex

The invention relates to an improved process for the preparation of ethyl ester of 10-(2,3,4-trimetoksi-6-were) decanoas acid, which is an intermediate product, suitable for the synthesis of idebenone - drug nootropic action

The invention relates to an improved process for the preparation of ester 2-alkylidene-4-bromocatechol acid of the formula (3), where R1and R2each independently from each other represent a lower alkyl group with 1-5 carbon atoms, which is used as an intermediate connection upon receipt of the substances for pharmaceutical purposes, such as antibiotics

The invention relates to new alicyclic compounds of General formula (I) where the connection between C2and C3and/or between C4and C5are unsaturated; X represents COOH, H, F, Br, I, СООR", R represents alkyl, arylalkyl, arylalkyl group, protected or unsubstituted aryl group, provided that each of these groups must have 6-30 carbon atoms, and R is not a group of formula (II); aryl means phenyl, naphthyl or until, and if R is a substituted group, it substituents can be C1-12-alkyloxy, C2-12-alkenylamine, C3-12-cycloalkyl, C1-12-hydroxyalkyl or substituted; R' represents H or C1-16-alkyl; R" represents H, C1-6-alkyl

FIELD: organic chemistry, in particular polymers.

SUBSTANCE: invention relates to new method for production of vic-dichlorofluoroanhydride useful as intermediate of starting monomer for fluorinated polymers with good yield from available raw material. Claimed method includes fluorination of starting material (I): (RH1-EH1-)CRH2RH3CH2-0CORHB in liquid phase to form compound of formula (II): (CF2ClCFCl-EF1-)CRF2RF3CF2-OCORFB; ester bond splitting of formula (II) in gaseous phase under solvent absence to form compound of formula (III): (CF2ClCFCl-EF1-)CRF2RF3COF or compound of formula (III) and compound of formula (IV): FCORFB, wherein RH1 is CX1X2ClCX3Cl- or CClX4=CCl, wherein each X1-X4 independently is hydrogen; RH2 and RH3 independently are hydrogen or linear or branched alkyl, optionally substituted with one or more oxygen; EH1 is alkylene, optionally substituted with one or more oxygen; EF1 = EH1 wherein perfluoroalkylene group is optionally substituted with one or more oxygen; RHB = RFB and are linear or branched perfluoroalkyl group, optionally substituted with chlorine one or more oxygen; RF2 is fluorinated RH2; RF3 is fluorinated RH3; with the proviso, that RF2 is fluorinated RH2; RF3 is fluorinated RH3, i.e. RF2 and RF3 represent RH2 or RH3 with at least one fluorinated hydrogen. Also disclosed are new compounds, represented in claims of invention.

EFFECT: new intermediates useful in polymer fluorination.

11 cl, 7 ex

FIELD: chemical industry; method of production of the fluorine-containing compounds.

SUBSTANCE: the invention is pertaining to the chemical industry, in particular, to the improved method of production of fluorine-containing compounds from the halogen-containing, compounds, preferably, from chlorine-containing compounds due to an exchange of halogen for fluorine at presence of the HF-additional compound of the mono- or bicyclic amine with at least two atoms of nitrogen. At that at least one atom of nitrogen is built in the cyclic system as the fluorating agent; or at presence of anhydrous hydrogen fluoride - as the fluorating agent and the indicated HF-additional compound of the mono- or bicyclic amine as the catalyst. At usage of the applicable solvents the reaction mixtures can be divided into two phases and thus to simplify the reprocessing of the products. The invention also is pertaining to the HF-additional compounds of 1.5-diazabicyclo[4.3.0]non-5-en and N,N-dialkylaminopiridin, where alkyl represents C1-C4alkyl and where the molar ratio of HF to amine makes 1:1, and to HF- additional compounds 1.8- diazabicyclo[5.4.0]undecyl-7-ene, where the molar ratio of HF to amine compounds more than 1:1.

EFFECT: the invention ensures at usage of the applicable solvents to divide the reaction mixture into two phases and thus to simplify reprocessing of the products.

17 cl, 13 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to chemistry of adamantane derivatives, namely, to a novel method for synthesis of 3-halogen-1-(ethoxycarbonyl)-alkyladamantanes of the general formula: wherein Hal means bromine atom (Br); R means hydrogen atom (H), -CH3, -C2H5, -C3H7; Hal means Br; R means -CH3; R1 means -CH3; Hal means chlorine atom (Cl); R means Cl; R1 means Cl that can be used as intermediate compounds used for synthesis of some biologically active substances. Method involves interaction of 1,3-dehydroadamantane with α-halogenalkane carboxylic acids ethyl esters chosen from the following group: ethyl-2-bromoacetate, ethyl-2-bromopropionate, ethyl-2-bromobutyrate, ethyl-2-bromovalerate, ethyl-2-bromo-2-methylpropionate and ethyl-2,2,2-trichloroacetate taken in the mole ratio = 1:(3-5), respectively, in the parent α-halogenalkane carboxylic acid ethyl esters medium, at temperature 50-60°C for 4-6 h. Invention provides expanding assortment of chemical compounds, in particular, synthesis of novel 3-halogen-1-(ethoxycarbonyl)-alkyladamantanes with the high yield.

EFFECT: improved method of synthesis.

6 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to new compounds with formula , in which R represents H, (C1-C12)-alkyl or (C1-C4)-alkyl-(C6-C12)-aryl. In the alkyl, one or more CH2-groups can be substituted with -O-. The invention also relates to the method of obtaining these compounds. The method involves reacting dimethylbenzoic acid ester with formula where R assumes values given above, with a chlorinating agent in an inert solvent or without a solvent at temperature above 40°C, and then cleaning, if necessary. Formula (I) compounds are essential intermediate products during synthesis of PPAR agonists with formula , in which R represents H, (C1-C12)-alkyl or (C1-C4)-alkyl-(C6-C12)-aryl. In the alkyl, one or more CH2-groups can be substituted with -O-; Y represents -(CH2)3-, 1,3-phenylene, 1,3-cyclohexanediyl; R' represents H, F, Br, CF3, (C1-C6)-alkyl, O-(C1-C6)-alkyl, phenyl; CF3; obtained from reaction of compounds with formula with formula (I) compounds in toluene, N-methylpyrrolidone or other aprotic solvents, in the presence of a suitable base, at temperature lying in the -78°C - +50°C interval, with subsequent extractive processing and, if necessary, crystallisation of the end product.

EFFECT: obtaining new compounds.

8 cl, 5 ex

FIELD: chemistry.

SUBSTANCE: method of producing functionally substituted fullerenes which can be used as complexing agents, sorbents, biologically active compounds, as well as in making new materials with given properties. The method involves combined production of 1'-ethylformyl-(C60-Ih)[5,6]fullero[2',3':1,9]cyclopropane and 1'a-ethylformyl-1'a-carba-1'(2')a-homo(C60-Ih)[5,6]fullerene with general formula 1 and 2

by reacting C60-fullerene with diazoacetic ester (N2CHCOOEt), where the reaction is carried out in o-dichlorobenzene in the presence of a three-component catalyst {Pd(acac)2: 2PPh3: 4Et3Al}, taken in molar ratio C60: diazoacetic ester: : Pd(acac)2: PPh3: Et3Al=0.01:(0.03-0.07):(0.0005-0.0015):(0.001-0.003):(0.002-0.006), preferably 0.01:0.05:0.001:0.002:0.004, at temperature of 80°C for 0.5-1.5 hours. 1'-ethylformyl-(C60-Ih)[5,6]fullero[2',3':1,9]cyclopropane (1) and 1'a-ethylformyl-1'a-carba-1'(2')a-homo(C60-Ih)[5,6]fullerene (2) are obtained with total output of 44-68%.

EFFECT: method is distinguished from known methods by higher output of end products, use of a palladium complex in catalytic amounts, carrying out the reaction in a readily available solvent.

1 tbl, 7 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: method involves combined synthesis of 1'-alkyl-1'-ethylformyl-(C60-Ih)[5,6]fullero[2':,3':1,9]cyclopropanes and 1'a-alkyl-1'a ethylformyl-1'a-carba-1'(2')a-homo(C60-Ih)[5,6]fullerenes of general formula

, where Alkyl =Et, i-Pr, i-Bu, Bn, where C60-fullerene reacts with α-alkyldiazoacetic ether of general formula N2C(alkyl)COOEt, where alkyl = Et, i-Pr, i-Bu, Bn, in o-dichlorobenzene in the presence of a three-component catalyst {Pd(acac)2:2PPh3:4Et3Al}, taken in molar ratio C60-fullerene: α-alkyldiazoacetic ether: Pd(acac)2:PPh3:Et3Al=0.01:(0.05-0.15):(0.0015-0.0025):(0.003-0.005):(0.006-0.01), preferably 0.01:0.1:0.002:0.004:0.008, at temperature of 40°C for 0.25-1.0 hours. 1'-alkyl-1'-ethylformyl-(C60-1h)[5,6]fullero[2',3':1,9]cyclopropanes (1) and 1'a-alkyl-1'a ethylformyl-1'a-carba-1'(2')a-homo(C60-Ih)[5,6]fullerenes (2) are obtained in ratio of 1:1 and total output of 55-79%.

EFFECT: high yield.

1 tbl, 10 ex

FIELD: process engineering.

SUBSTANCE: invention relates to catalysis. Proposed catalyst contains alcoholate of alkaline metal in solution of monohydroxy alcohol. Note here that said monohydroxy alcohol represents isobutyl alcohol, while alcoholate of alkaline metal represents potassium isobutyl with the following ratio of components in wt %: potassium isobutyl - 10-25; isobutyl alcohol - 75-90.

EFFECT: production of biodiesel from various vegetable oils, simplified process.

18 ex, 4 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to versions of a method of producing a phenylpropionic acid derivative of general formula: or salt thereof, where R2a is a methoxy group or ethoxy group; R3b is a cyclopentyl group and R5 is a methyl group which can be substituted with one or more phenyl groups, or an oxygen-containing heterocyclic group used as an intermediate compound during synthesis of 3-{5-[4-(cyclpentyloxy)-2-hydroxybenzoyl]-2-[(3-hydroxy-1,2-benzisoxazol-6-yl)methoxy]phenyl}propionic acid (T-5224), having anti-arthritic action and osteoclast inhibitory action. One of the versions of the method involves reaction of a benzophenol derivative of general formula: 3 , where R2a and R3b are as described above, or salts thereof with a 6-(halogenmethyl)-1,2-benzisoxazol-3(2H)-one derivative of general formula: , where R5 is as described above, and X is a halogen atom. The disclosed method can be used as a method for simple and safe synthesis of T-5224 with high output. The invention also relates to methods of producing intermediate compounds and novel intermediate compounds.

EFFECT: high efficiency of the composition.

28 cl, 23 ex

FIELD: chemistry.

SUBSTANCE: invention relates to organic chemistry and specifically to a method of producing functionally substituted fullerenes used as complexing agents, sorbents and biologically active compounds. The method of producing 1'a-methyl-1'a-ethylformyl-1'a-carba-1'(2')a-homo(C60-Ih)[5,6]fullerene of formula (1) is characterised by that C60-fullerene reacts with α-methyldiazoacetic ester of formula N2C(Me)COOEt, in α-dichlorobenzene in the presence of a three-component catalyst {Pd(acac)2 : 2PPh3:4Et3Al}, taken in molar ratio C60:α-methyldiazoacetic ester :Pd(acac)2:PPh3:Et3Al = 0.01:(0.01-0.10):(0.0015-0.0025):(0.003-0.005):(0.006-0.01), preferably 0.01:0.05:0.002:0.004:0.008 at temperature 40°C for 0.25-1.0 hours.

EFFECT: desired product is obtained with 58-86% output.

1 tbl

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