Method for preparing phyton

FIELD: organic chemistry, chemical chemistry.

SUBSTANCE: invention relates to a method for synthesis of compound of the formula (I): . Method involves interaction of compound of the formula (II)

with compound of the formula (III) in the presence of a catalyst chosen from cationic complexes of bivalent ruthenium and polar organic solvent. Also, invention relates to a novel compound of the formula (I) that is used in synthesis of phyton and vitamin E, and to a method for synthesis of phyton also.

EFFECT: improved method of synthesis.

20 cl, 3 ex

 

The present invention relates to a method for producing intermediates used in the preparation of Fitna and/or vitamin E.

For a long period of time vitamin E synthesized using many different chemical methods. Usually this vitamin is obtained from intermediate compounds, known as fitton, which has the following chemical structure:

FITTON

In the European patent 0544588 disclosed is a method of obtaining vitamin E derived by condensation of polyunsaturated allyl alcohol. In U.S. patent No. 3867408 described getting new katalevich compounds that can be used to obtain Fiona, which, in turn, is an intermediate connection when receiving vitamin E.

Applicants currently have synthesized a new compound that can be used as intermediate compounds in the synthesis of Fiona and optionally in the synthesis of vitamin E.

Accordingly, in the present invention, a method of obtaining the compounds of formula (I)

which includes the interaction of the compounds of formula (II)

with the compound of the formula (III)

in the presence of a catalyst and a polar RA is the maker.

The compound (I) is a new connection and represents another aspect of the present invention.

The method of obtaining the compound (I) is carried out in the presence of a polar solvent. Suitable solvents include aprotic polar solvents such as dimethylacetamide, dimethylformamide, N-organic and dimethylsulfoxide. The preferred solvent is dimethylacetamide. The solvent may be present in a concentration of from 0.01 to 5 mol/l, preferably from 0.1 to 1 mol/L.

The solvent can be added to water, although this is not essential. When added to the solvent water suitable concentration is from 10 to 50% in volume percentage.

The method is carried out in the presence of a catalyst. Suitable catalysts include cationic complexes of divalent ruthenium. The preferred catalyst is hexafluorophosphate Tris-oceanicinstitute.org.

The preferred embodiment of the present invention is to add the reagents in the solution of the catalyst. This method is preferred to prevent decomposition of the reactants.

In addition, this method can be carried out in the presence of a second solvent that is not miscible with the polar solvent. Solvents corresponding to this is the condition, include non-polar solvents. Suitable nonpolar solvents include aromatic hydrocarbons such as toluene, benzene and xylene; and aliphatic hydrocarbons such as pentane, heptane, hexane, and octane; and single-phase mixture of hydrocarbon solvent and a simple ether. The second solvent may be present in a volume ratio from 0.01 to 10, preferably from 0.5 to 2, in the calculation of the polar phase of the catalyst.

The method can be carried out at a temperature of from 20 to 100°C, preferably from 20 to 60°and at atmospheric or elevated pressures. Preferably, the process is performed at atmospheric pressure.

Preferably, the compound (III) is added slowly to the reaction mixture, in order to avoid the formation of side reaction products.

The compounds of formula (I)obtained by the method according to the present invention are particularly suitable for use as starting material in the synthesis of Fiona. Thus, according to another aspect of the present invention, a method of obtaining Fiona, which includes (a) the first stage of hydrolysis of the following compound (I)

with the aim of obtaining the hydrolysis product; and (b) the second stage hydrogenation of the product of hydrolysis.

The first stage of this method, namely article is Dios hydrolysis, it is advisable to use an acid catalyst, such as sulfonic acid, sulfuric acid or hydrogen chloride. The catalyst may be present in amounts of from 0.001 to 0.5 molar equivalent, preferably between 0.05 and 0.1 molar equivalent, based on the compound of formula (I).

In addition, hydrolysis, it is advisable to carry out in the presence of an organic solvent, such as toluene or ether, for example diethyl ether or tetrahydrofuran. The reaction temperature may be between -50 and +150°C, preferably between 20 and 100°C.

Then the product of the hydrolysis step hydronaut. Hydrogenation is advisable to carry out in the presence of gaseous hydrogen and in the presence of metal or metal salt. Suitable metals and metal salts include Raney Nickel (an alloy of Nickel and aluminum), optionally in the presence of iron, manganese, cobalt, copper, zinc or chromium; zinc in the presence of acetic acid; chloride tin (II); and salts of molybdenum (III). In addition, this reaction can be carried out in the presence of palladium or platinum, which can be deposited on a suitable inert carrier, such as charcoal. The hydrogenation is preferably carried out in the presence of palladium on an inert carrier, such as charcoal. Usually the number of meth is the lia or metal salt is from 0.01 to 3 molar equivalents, preferably, from 0.05 to 2 molar equivalents.

Usually stage hydrogenation is carried out in a solvent which may be selected from alcohols, such as methanol or ethanol; linear or cyclic ethers, such as tetrahydrofuran; and aromatic hydrocarbons. The preferred solvent is a simple ether, especially tetrahydrofuran.

Typically, the temperature at the stage hydrogenation is from 20°to 150°C, preferably from 20°to 90°and the gas pressure is from 1 to 50 bar (0.1-5 MPa), it is generally preferable to use a pressure from 5 to 10 bar (0.5 to 1.0 MPa).

The processes of hydrolysis and hydrogenation can be carried out as two separate stages or combined in a single stage reaction system.

Expediently, the method of producing fitone be implemented during the period of time from 30 minutes to 24 hours, preferably from 30 minutes to 6 hours at the above reaction conditions, to ensure complete conversion of the reacting compounds.

Vitamin E can be synthesized from Fitna, which is obtained by the method of the present invention.

Further, the present invention is illustrated with reference to the following examples.

Example 1. Obtaining the compound (I)

In argon atmosphere, dissolve the catalyst (22 mg) in a mixture you dimethylacetamide and 250 microliters water (so-called solution more polar phase). The resulting solution is heated at a temperature of 60°C. Then slowly add a solution of 1 ml of heptane (containing 63 mg of compound (II) and 77 mg of compound (III) within 90 minutes. The solution is stirred for 3 hours at 60°C and cooled to 20°C. Heptane phase is separated from the polar phase and add 1 ml of pure heptane to the polar phase. The resulting mixture is stirred for 15 minutes at 20°and heptane phase is separated. This operation is repeated 4 times, then combine the four heptane phase; the heptane is distilled off and the remaining oily residue purified using chromatography on silica gel (eluent: a mixture of pentane/diethyl ether = 2/1 by volume). Get a pure compound (I) in the form of a yellow oil, yield 84 mg (60%).

Example 2. Getting Fiona

From the compound obtained in example 1, to synthesize fitton in two stages using the following quantities of reagents:

ConnectionNumberMolar massThe mmol
The connection I0,689 g2802,46
Toluene30 ml92-
PTSC·H2About1)0.01 g190,220,053 (0.02 equiv.)
15 ml46-
5% Pd on coal (weight/weight)0,g106,420,055 (0.02 equiv.)
1)PTSC·H2O this is a pair of toluensulfonate, monohydrate

The compound (I), toluene and monohydrate PTSC placed in a round bottom flask with a capacity of 25 ml and incubated for 3 hours at a low boil toluene (reflux) to carry out the reaction. Then add 10 ml of a saturated aqueous solution of sodium carbonate and the resulting product is extracted 3 times with simple ether. After simple distillation of the ether get a residue, which immediately placed in a glass ampoule containing palladium mobile and ethanol in an argon atmosphere. The ampoule was placed in an autoclave of stainless steel. The autoclave is sealed and rinsed with hydrogen. The hydrogen pressure support is 5±0.2 bar (0,5±0.02 MPa) under stirring the contents of the autoclave. The process of hydrogenation is continued for 6 hours at ambient temperature. Then the autoclave Tegaserod and poured its contents into a small column containing the filtering agent celite. The column is washed with ethanol and the filtrate concentrated. Get 0,587 g Fiona; yield, having a purity of 95%, is 89%.

Example 3. Getting fit is on

Fitton sitesabout in one stage from the compound obtained in example 1, using the following quantities of reagents:

ConnectionNumberMolar massThe mmol
The connection I138 mg2800,493
Tetrahydrofuran2 ml72-
Sulfuric acid (96% in water)7 mg980,07 (0,14 equiv.)
5% Pd on coal (weight/weight)105 mg106,420,049 (0.1 EQ. Pd)

The process is carried out in a glass flask with a capacity of 5 ml, which is placed in a stainless steel autoclave under hydrogen pressure of 5 bar (0.5 MPa), for 1.5 hours at a temperature of 65°With (external heating of the autoclave). The autoclave Tegaserod, rinsed with argon and then open. After filtering and processing simple ether and water to carry out the analysis of the crude sample. The output of Fiona exceeds 95%.

1. The method of obtaining the compounds of formula (I)

which includes the interaction of the compounds of formula (II)

with the compound of the formula (III)

in the presence of a catalyst selected from cationic complexes of divalent ruthenium, and a polar organic solvent.

2. The method according to claim 1, wherein the polar solvent is selected from dimethylformamide, dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone.

3. The method according to claim 1, wherein the catalyst is chosen from cationic complexes of divalent ruthenium, such as hexafluorophosphate Tris-acetonitrile-cyclopentadienylsodium or hexafluorophosphate Tris-acetonitrile-cyclopentadienylsodium.

4. The method according to claim 2, in which the catalyst is chosen from cationic complexes of divalent ruthenium, such as hexafluorophosphate Tris-acetonitrile-cyclopentadienylsodium or hexafluorophosphate Tris-acetonitrile-cyclopentadienylsodium.

5. The method according to claim 1, which is carried out in the presence of the second solvent, and the specified second solvent immiscible with the first solvent.

6. The method according to claim 2, which is carried out in the presence of the second solvent, and the specified second solvent immiscible with the first solvent.

7. The method according to claim 3, which is carried out in the presence of the second solvent, and the specified second solvent immiscible with the first solvent.

8. The method according to claim 4, which is carried out in the presence of the second solvent, and indicated the second solvent immiscible with the first solvent.

9. The method according to claim 5, in which the second solvent is a nonpolar solvent selected from aliphatic or aromatic hydrocarbons.

10. The method according to claim 6, in which the second solvent is a nonpolar solvent selected from aliphatic or aromatic hydrocarbons.

11. The method according to claim 7, in which the second solvent is a nonpolar solvent selected from aliphatic or aromatic hydrocarbons.

12. The method according to claim 8, in which the second solvent is a nonpolar solvent selected from aliphatic or aromatic hydrocarbons.

13. The method according to any one of claims 1 to 12, which is carried out at a temperature of from 20 to 100°and at atmospheric pressure.

14. Connection, characterized by the following structure

15. The method of producing Fiona, which includes (a) a first stage hydrolysis connection 14 in the presence of an acid catalyst and an organic solvent to obtain a product of hydrolysis; and (b) the second stage of the hydrogenation product of the hydrolysis stage (a).

16. The method according to item 15, in which the first stage is carried out in the presence of an acid catalyst selected from sulfonic acid, sulfuric acid and hydrogen chloride.

17. The method according to item 15, in which the first stage about the W ill result in the presence of an organic solvent, selected from organic hydrocarbon and simple ether.

18. The method according to clause 16, in which the first stage is carried out in the presence of an organic solvent selected from organic hydrocarbon and simple ether.

19. The method according to any of PP-18, in which the second stage is carried out in the presence of hydrogen and a metal or metal salt selected from palladium or platinum, Raney Nickel, optionally in the presence of iron, manganese, cobalt, copper, zinc or chromium; of zinc in the presence of acetic acid; chloride tin (II); and salts of molybdenum (III).

20. The method according to claim 19, in which the catalyst is a palladium deposited on charcoal.



 

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