Method of producing 1'a-methyl-1'a-ethylformyl-1'a-carba-1'(2')a-homo(c60-ih)[5,6]fullerene

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

 

The present invention relates to the field of organic synthesis, namely the method of production of 1 a-methyl-1 a-ethylpropyl-1 a-carb-1'(2')a-Homo(C60-Ih)[5,6]fullerene of formula (1):

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 (4) opening 42% response With60-fullerene (2) with diazacrown-ether (3) at a temperature of 5-10°C for 2-3 hours

The known method does not allow you to get 1 a-methyl-1 a-ethylpropyl-1 a-carb-1'(2')a-Homo(C60-Ih)[5,6]fullerene of formula (1).

The known method (R.Sijbesma, G.Srdanov, F.Wudl, J.A.Castoro, C.Wilkins, S.H.Friedman, D.L.DeCamp, G.L.Kenyon. J. Am. Chem. Soc. 1993, 115, 6510 [2]) get fullarticlenonav (6) with a yield of 93% response With60-fullerene (2) with 4,4'-bis(N-acetyl-2-amino-ethyl)diphenyldiazomethane (5) in dry pyridine in the presence of succinic anhydride at room temperature within 24 hours

The known method does not allow you to get 1 a-methyl-1 a-ethylpropyl-1 a-carb-1'(2')a-Homo(C60-Ih)[5,6]the fuller the formula (1).

We propose a new method of obtaining 1 a-methyl-1 a-ethylpropyl-1 a-carb-1'(2')a-Homo(C60-Ih)[5,6]fullerene (1).

The method consists in the interaction of fullerene (C60) with α-methyldiazonium ether of the formula N2C(Me)COOEt, in the presence of a three-component catalyst {Pd(acac)2:2PPh3:4Et3Al}, taken in a molar ratio With60:α-metildigoxin ether: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, in o-dichlorobenzene (o-DHB) as solvent at 40°C for 0.25-1.0 hours Get 1 a-methyl-1 a-ethylpropyl-1 a-carb-1'(2')a-Homo(C60-Ih)[5,6]fullerene (1) with a total yield 58-86%. The reaction proceeds according to the scheme:

The conduct of a specified reaction in the presence of a palladium catalyst [Pd] more than 20 mol.% in relation to the fullerene C60does not lead to a significant increase in the yields of the target product (1). 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 (in the example, 20°C) decreases the reaction rate.

Significant differences of the proposed method.

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

The proposed method, in contrast to the known, allows you to get 1 a-methyl-1 a-ethylpropyl-1 a-carb-1'(2')a-Homo(C60-Ih)[5,6]fullerene (1), the synthesis of which is 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 0.05 mmol of α-metildigoxin ester in 0.5 ml of o-DHB. After 0.5 h the reaction mass is then cooled and passed through a column with a small layer of silica gel. Get 1 a-methyl-1 a-ethylpropyl-1 a-carb-1'(2')a-Homo(C60-Ih)[5,6]fullerene (1) yield 72% (according to HPLC).

Spectral characteristics (1)

An NMR spectrum1N: 1.36 (t, 3H, CH3, J=7.2 Hz), 3.22 (3H, CH3), 4.23 (K, 2H, CH2, J=7.2 Hz).
An NMR spectrum 13With (CDCl3: CS2=1:5 (υ/υ)), δ, ppm: 14.08 (C6), At 25.52 (C7), 53.44 (C3), 61.50 (C5), 134.06, 134.64, 135.41, 136.61 (C1,2), 137.65, 138.31, 138.67, 138.72, 139.91, 140.56, 141.41, 141.58, 141.75, 141.90, 142.21, 142.56, at 142.59, 142.69, 142.88, 142.95, 143.15, 143.29, 143.48, 143.65, 143.83, 144.51, 144.73, 147.26, 168.88 (4).

Other examples of the method shown in the table.

Table
№ p/pThe molar ratio of C60:N2C(Me)COOEt:Pd(acac)2:PPh3:Et3Al, mmolReaction time, hThe yield of the target product (1), %
10.01:0.05:0.002:0.004:0.0080.572
20.01:0.10:0.002:0.004:0.0080.579
30.01:0.01:0.002:0.004:0.0080.567
40.01:0.05:0.0025:0.005:0.010.586
50.01:0.05:0.0015:0.003:0.0060.5 58
60.01:0.05:0.002:0.004:0.008184
70.01:0.05:0.002:0.004:0.0080.2563

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

The method of obtaining 1 a-methyl-1 a-ethylpropyl-1 a-carb-1'(2')a-Homo(C60-Ih)[5,6]fullerene of formula (1):

characterized by the fact that With60-fullerene interacts with α-methyldiazonium ether of the formula N2C(Me)COOEt, in o-dichlorobenzene in the presence of a three-component catalyst {Pd(acac)2: 2PPh3: 4Et3Al}, taken in a molar ratio With60: α-metildigoxin ether : 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 40°C for 0.25 to 1.0 hours



 

Same patents:

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: 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: organic chemistry.

SUBSTANCE: invention relates to method for production of 1-hydroxy-2,3-[60]fullerocyclopentanecarboxylic acid ethyl ester of formula 1 , wherein n = 1-2. Claimed method includes reaction of fullerene[60] (C60) with triethylaluminum (AlEt3) in C60:AlEt3 molar ratio of 1:(25-35) in presence of Cp2ZrCl2 as catalyst in amount of 15-25 mol.% based on C60 in argon atmosphere, in toluene medium under atmospheric pressure and at room temperature for 8 hours followed by addition to reaction mass at -15°C copper chloride (CuCl) catalyst in amount of 15-20 mol % based on C60 and oxalic acid diethyl ester (EtO2C-CO2Et) in equimolar amount in relation to AlEt3. Further reaction mass is agitated at room temperature followed by hydrolysis of reaction mass.

EFFECT: method for production of 1-hydroxy-2,3-[60]fullerocyclopentanecarboxylic acid ethyl ester with high yield.

1 tbl, 1 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing compound of the formula (I): , wherein R means (C1-C6)-alkyl; R1 and R2 mean independently hydrogen atom or (C1-C4)-alkyl. Method involves interaction of compound of the formula (II): , wherein R means (C1-C6)-alkyl; X means halogen atom or group -OCOCH3 with compound of the formula (III): , wherein R1 and R2 mean independently hydrogen atom or (C1-C4)-alkyl in the presence of (C1-C4)-carboxylic acid salt in polar solvent medium. Method provides preparing the end compound for a single stage using available reagents. Also, invention relates to a method for preparing fungicide benzophenone compound of the formula (IV): , wherein R1 and R2 mean independently hydrogen atom or (C1-C4)-alkyl; R3, R4, R5 and R6 mean independently (C1-C6)-alkyl using compound of the formula (I).

EFFECT: improved preparing method.

11 cl, 2 sch, 1 tbl, 12 ex

The invention relates to an improved method of dewatering solution of formaldehyde containing formaldehyde, water and methanol, including the distillation of the specified solution of formaldehyde in the presence of exciting water connection with obtaining the formaldehyde-containing product that contains significantly less water than the original solution, and use a solution of formaldehyde containing methanol at a molar ratio of methanol to formaldehyde 0.3 to 1.5:1, obtaining the formaldehyde-containing product in the form of a complex with methanol

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The invention relates to an improved process for the preparation of methyl methacrylate, comprising the stages of (i) interaction propionic acid or its ester with formaldehyde or its predecessor in the condensation reaction with the formation of the stream of gaseous products containing methyl methacrylate, residual reactants, methanol and by-products, (ii) processing at least one portion of the stream of gaseous products with the formation of a stream of liquid products containing almost all of the methyl methacrylate and at least one impurity, which melts at a temperature above the melting temperature of pure methyl methacrylate, run over the flow of the liquid product at least one operation fractional crystallization, which contains the stage (iii) cooling the specified flow of liquid product to a temperature between about -45oAnd about -95oSo that the flow of liquid product forms solid crystals of methyl methacrylate and uterine fluid, and these crystals have a higher content of methyl methacrylate than the specified stream of liquid products or uterine fluid, (iv) the separation of these crystals of solid methyl methacrylate from the specified match Azania impurity in a lower concentration, than the specified stream of liquid products

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: 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: 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: 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

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

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