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[4.3.0.02,4.03,7]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.

Table
№ p/pEAKThe yield of reaction products, %Stereoselectivity Exo/endo
1MMA8148/52
2the acrylate6449/51
3n-butyl acrylate6051/49
4tert-butyl acrylate4856/44
52-methyl-adamantylamine2571/29

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.



 

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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.

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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.

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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

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61 cl, 4 tbl, 16 dwg, 5 ex

FIELD: chemistry.

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1 tbl

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28 cl, 23 ex

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18 ex, 4 tbl

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1 tbl, 10 ex

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1 tbl, 7 ex

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

1 cl, 1 tbl, 1 dwg, 4 ex

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