Stereoselective method of producing norbornadiene-based stressed skeleton carbocyclic compounds

FIELD: chemistry.

SUBSTANCE: invention relates to a stereoselective method of producing norbornadiene-based stressed skeleton carbocyclic compounds. The method is characterised by that it involves codimerisation of norbornadiene with acrylic esters. The catalyst used is a bis(allyl)nickel-based single-component system.

EFFECT: use of the present method increases stereoselectivity of the codimerisation reaction and increases product output.

1 cl, 5 ex, 1 tbl


The invention relates to the field of homogeneous-catalytic transformations of organic compounds and more particularly to catalytic codimerization of norbornadiene (hereinafter NBD) with esters of acrylic acid (hereinafter EAK) with the formation of intense frame carbocyclic compounds (ademero NBD with EAK).

Tense frame carbocyclic compounds, are known to be intermediates in obtaining components of motor fuel of high octane number, low pour point, and high calorific value methodest along with high storage stability.

In addition to fuel intense frame carbocyclic compounds on the basis of EAK and NDS can be used as fragrances in the production of motor fuels.

Given that one of the main sources of environmental pollution is transportation, in recent times there are specific requirements for the composition of the fuel, which causes an increased demand for fuel in the high-octane fuel, not containing aromatic derivatives, such as tense frame carbocyclic compounds, the most acceptable from an environmental point of view.

It is known that codimerization NBD with EAK proceeds in the presence of bis(Acrylonitrile)Nickel (0) [R. Noyori, I. Umeda, H. Kawauchi, H. Takaya Nickel (0) catalyed reaction of quadricyclane with electron deficient olefins. // J. Am. Chem. Soc., 1975, 97, 812-819]. The authors carried out the reaction at different temperatures with different EAK. However, they note that the formation of ademero time-consuming and obtaining ademero with high yields and selectivity is a synthetic problem.

In [Pardigon O., Tenaglia, A., G. Buono Influence of aluminum Lewis acids on the diastereoselectivity of the nickel-catalyzed [2+2+2] cycloaddition of norbomadiene and electron deficient alkenes // Tetrahedron Lett. 2000, 41, 4089-4092] described a method in which the reaction codimerization NBD with methyl ester of acrylic acid (hereinafter MAAC) is carried out in the presence of a three-component catalytic systems on the basis of Nickel acetylacetonate, alkylamine (alkylalkoxysilane) and triphenylphosphine (hereinafter THF). Depending on the temperature it is possible to achieve output of ademero NBD with MAAC up to 60% for 12 hours. The disadvantages of this system are the low reaction rate, a large number of components of the catalytic system, including phosphine ligands, high sensitivity one of the components of the catalytic system (alkylamine) to water and hydroxyl-containing compounds.

There is a method of obtaining ademero NBD with MEEK in the presence of a three-component catalytic system consisting of acetylacetonate Nickel chloride alkylamine and triphenylphosphine [US Patent 4139714, 13.02.1979]. The disadvantages included the system are also low reaction rate and consequently low yield codimerization NBD with MAAC, a large number of components of a catalytic system comprising phosphine ligands, high sensitivity one of the components of the catalytic system (alkylamine chloride) to impurities hydroxyl-containing compounds, such as water and alcohols.

The closest technical solution of the invention is a method which uses two-component catalytic system based acetylacetonate and Nickel chloride alkylamine [US Patent 4142055, 27.02.1979].

In the said method fast codimerization NBD with MAAC is achieved through the use of two-component catalytic systems on the basis of Nickel acetylacetonate and chlorides alkylamine. The final product stimer NBD with MAAC can be used in the production of motor fuels.

The proposed method involves the use of a catalytic composition containing as a catalyst of Nickel acetylacetonate and going into the second component chloride alkylamine, choose from the following range: diethylaluminium chloride, ethylaluminum dichloride and ethylaluminum sesquichloride (preferably use diethylaluminium chloride).

As solvents in the specified method used aromatic hydrocarbons, cycloparaffin, ethers, halogenated hydrocarbons, halogenated aromatic hydrocarbons and halogen is rowanne cycloparaffin. The reaction is carried out under anaerobic conditions, in the absence of water, alcohols and other compounds, methods to inactivate the catalyst.

The main disadvantage of this method is the extremely high sensitivity of the catalytic system to water, alcohols, solvents, which may contain very small admixture of water more than 0.1%. Use reclaimed solvents with a high degree of drying is expensive and uneconomical procedure.

The technical result of the present invention is to improve the stereoselectivity of the reaction of codimerization, as well as increased product yield.

The technical result is achieved by codimerization of norbornadiene with esters of acrylic acid using a one-component catalyst based on bis(allyl)Nickel (0) (the BAN), is insensitive to the presence of hydroxyl-containing compounds such as water and alcohols in the original solvent, and is highly active. The nature of the used EAK (methyl, ethyl, butyl, tributyl, 2-methyldiphenylamine esters of acrylic acid) determines the stereoselectivity of the reaction of codimerization with NBD and output. The method involves carrying out the reaction of codimerization NBD with EAK in inert gas (nitrogen, argon or carbon dioxide) at temperatures on the 0 to 90°C. since the reaction is carried out in homogeneous conditions in the liquid phase, the lower temperature limit is determined by the melting and dissolution of the catalytic system, and the upper boiling point of the solvent and the original substances), atmospheric pressure or elevated pressure, and if you use any organic solvents, the reaction can be carried out in the mass of the initial reagents. The ratio of BAN/NBD is from 10 to 1000, but it is preferable to use a ratio of from 20 to 100, the ratio EAK/NBD depending on EAK can vary from 2 to 10, preferably from 2 to 5.

The BAN can be obtained by the method of Wilke [G.Wilke, .Bogdanovic, P.Hardt, P.Heimbach, W.Keim, M.Kroner, W.Oberkirch, Klapka, E.Steinrucke, D.Walter, H.Zimmermann. Allyl-Transition Metal Systems // Angew. Chem. Intern. Ed. 1966, 5, p.151-164].

The implementation of stereoselective method of obtaining intense frame carbocyclic compounds based on NBD and EAK carried out in a static vacuumized reactors in argon. The reaction products were isolated using preparative column chromatography and analyzed by gas chromatography. An example implementation of the method, and the yield and selectivity for various EAK below.

Example 1

To 1.1 ml of toluene, add 0.25 ml of NBD (2,47 mmol) and 0.45 ml (5 mmol) MEAC. After removal of oxygen from the reagents in the reactor is transferred a portion of 0.017 g (0.012 mmol) of BAN and C is discharging the reactor with dry argon (purity of 99.99%). The reaction is carried out at a temperature of 50°C for 4 hours. Then, the solution is blown with oxygen to decompose the catalyst, then it is filtered over a layer of silica gel and evaporated. The result is a yellow oil (number of 0.37 g). After dissolving the oil analyzed by gas-liquid chromatography. According to the analysis output methyltetrazole[,4.03,7]nonan-8-carboxylate is 81%, the ratio of the isomers endo/Exo =43/57.

Similarly (in the same molar ratios) conduct the reaction with other EAK, containing different substituents. The output of ademero NBD with EAK and stereoselectivity are presented in table.

№ p/pEAKThe yield of reaction products, %Stereoselectivity Exo/endo
2the acrylate6449/51
3n-butyl acrylate6051/49
4tert-butyl acrylate4856/44

Stereoselective method of obtaining intense frame of carbocyclic compounds based on norbornadiene, including codimerization of norbornadiene with esters of acrylic acid, characterized in that the catalyst used one-component system based on bis(allyl)Nickel.


Same patents:

FIELD: chemistry.

SUBSTANCE: present invention relates to methods for synthesis of bicyclo[3.1.0]hexane derivatives, used as mGIuR agonists having formulae ,

, where R1 and R2 represent hydrogen, X is a halogen, R3 is -O-Ra , Ra is C1-10alkyl, and R4 is (1) hydrogen or (2) Si-(R9)(R10)(R11), where each of R9, R10 and R11 is C1-10alkyl, as well as intermediate compounds obtained when realising the said methods.

EFFECT: design of an efficient method for synthesis of bicyclo[3,1,0]hexane derivatives.

26 cl, 17 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention is related to the field of organic chemistry, in particular, to method for production of methyl ethers of 2-thiophen carbonic acid intended for use in synthesis of optical whiteners, dyes for cotton, wool, artificial fibers, medical preparations, and also as additive to oils or hydraulic liquids. Substance of the method consists in thiophen interaction with methanol in presence of carbon tetrachloride under action of catalysts - oxo-bis-(2,4-pentanodionato)vanadium VO(acac)2 or tris (2,4-pentanodionato)iron Fe(acac)3, or molybdenum hexacarbonyl Mo(CO)6 at the temperature of 130-170°C for 3-6 hours at the following mole ratio - catalyst:thiophen:CCl4:methanol equal to 1:100:200-300:200-300.

EFFECT: suggested method makes it possible to produce target product with yield of 63-85%, using simplified technology.

1 tbl, 14 ex

The invention relates to new derivatives of esters of carboxylic acids of General formula I, where R1represents an alkyl group branched or non-branched chain having 1-4 carbon atoms; R2represents a group of formula IV, in which R4represents a hydrogen atom or etinilnoy group; R5and R6are the same or different selected from the group consisting of a hydrogen atom or a methyl group; R7represents a hydrogen atom; R8selected from propargyl, methoxymethyl or methylthio

The invention relates to a new process for the preparation of esters cyclopropanecarbonyl acid of the formula I

< / BR>
where R is the ester residue, split in neutral or acid medium and which WITH1-18the alkyl possibly substituted with halogen or benzyl radical, possibly substituted on the tops of the aromatic ring by one or more halogen atoms, or a radical of formula (a) -(g),

< / BR>
where R2Is h or methyl;

R3- aryl;

R4- CN, N.;

R5- fluorine, chlorine, bromine or hydrogen;

R6, R7, R8, R9is hydrogen or methyl;

S/1 symbolizes tetrahedrite

The invention relates to a new method of obtaining some of esters of cyclopropane used in the synthesis of important pesticides

FIELD: medicine.

SUBSTANCE: invention refers to new compounds of formula (I) where X is carboxylic acid, carboxylates, carboxylic anhydride, diglyceride, triglyceride, phospholipid, or carboxamides, or to any their pharmaceutically acceptable salt. The invention particularly refers to (4Z, 7Z, 10Z, 13Z, 16Z, 19Z)-ethyl 2-ethyldocosa-4,7,10,13,16,19-hexanoate. The invention also refers to a food lipid composition and to a composition for diabetes, for reducing insulin, blood glucose, plasma triglyceride, for dislipidemia, for reducing blood cholesterol, body weight and for peripheral insulin resistance, including such compounds. Besides, the invention refers to methods for treating and/or preventing diabetes, dislipidemia, peripheral insulin resistance, body weight reduction and/or weight gain prevention, insulin, blood cholesterol, blood glucose and/or plasma triglyceride reduction.

EFFECT: higher clinical effectiveness.

61 cl, 4 tbl, 16 dwg, 5 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

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.

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40 cl, 1 ex

FIELD: chemistry.

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1 tbl, 7 ex

FIELD: chemistry.

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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: chemistry.

SUBSTANCE: invention relates to a method of forming a high-efficiency catalyst based on a cationic complex of nickel for addition polymerisation of norbornene (NB). One of the modern trends in addition polymerisation of norbornene is production of high-purity polynorbornenes for optoelectronics, machine-building and medicine. There are high requirements for purity of polynorbornenes owing to the specific nature of fields of application. The method is realised by forming a norbornene polymerisation catalyst based on a cationic complex, where the complex used is nickel complex (O) Ni(COD)2 combined with boron trifluoride etherate (B) with ratio Ni:B ranging from 2 to 10, followed by addition of a monomer. Depending on the task, the reaction is carried out in toluene with different concentration of nickel and ratio Ni:B:NB and at temperature from 0 to 50°C. The reaction product is polynorbornene which is soluble in cyclohexene, toluene, chlorobenzene and chloroform. The method enables to reduce the amount of boron compounds in the system by 200 times, while preserving high catalyst activity.

EFFECT: simple, cheap, intense method of producing a polymer and high purity of the end product.

1 cl, 1 tbl, 1 dwg, 4 ex