SU914061A1 - Method of producing beta-d-glycoside of pyromeconic acid - Google Patents

Description

The invention relates to the chemical-pharmaceutical industry and relates to the production of drugs from plant materials.

The method of obtaining / -1) -glycoside pyromeconic acid is not described in the literature.

The purpose of the invention is the preparation of g-glycoside of pyromeconic acid.

This goal is achieved by the fact that, according to the method of producing p-γ-glycoside of pyromeconic acid, the leaves of the small-brighter caustic (E. ace I) are extracted with chloroform, then 75-85% ethanol at a temperature of 20-50 ° C, followed by purification of the extract propanol and lower alcohol.

. ^> - ϋ-Γ Pyromeconic acid glucose, which has hemostatic activity, is obtained from the dry, crushed leaves of the small-broom pickle, caustic P. ase b. What are the chopped leaves extracted with organic

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a solvent, for example chloroform. Extraction is carried out in order to remove chlorophyll, resinous substances and other related impurities, which is determined by the absence of the color of the extractant. Next, the extraction is carried out 75-85% alcohol, for example ethyl, in the ratio of 1: 8.

The extraction with alcohol is carried out many times until the extraction is negative with a 1% solution of iron trichloride. The resulting extraction is evaporated, the residue is dissolved in hot water, the resulting solution is kept at 4–8 ° C for 1215 hours. The precipitate is filtered and the filtrate is treated with chloroform in order to remove impurities. The resulting aqueous solution of the desired product is concentrated in vacuo at 50 ° 6 ° C to a syrup consistency. This is then dissolved by heating in a water bath in n-propanol when heated. n-pro- ^:

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Panol dissolves pyromeconic glycoside under these conditions and precipitates higher molecular weight compounds, which are then removed by filtration, for example, through alumina.

The purified solution of the desired product in propanol is evaporated in vacuo at 5 ° C ~ 6 ° C until the onset of crystallization, which is determined visually by the appearance of turbidity in the solution. Then, the crystallization occurs at room temperature, the precipitate is separated by filtration and recrystallized from alcohol, such as methyl or ethyl, to yield -P-glycoside piromekonovoy acid as a white crystalline powder, odorless and tasteless, having the formula C44 H ^ 0 _{A J} 0 , 5 N ₂ 0. (Pyromeconic acid d-Glycosid acid is highly soluble in water and when heated in ethyl and methyl alcohols. The substance reacts with a 1% alcoholic solution of ferric chloride, forms a red-brown color, which is enhanced by heating.

Melting point 197 ~ 19θ C.

Example 1. 1 kg of crushed leaves of the small-apertured food auger, counting on absolutely dry webs, are loaded into a flow-through or Socklet-type extraction vessel, filled with chloroform, and extraction is carried out to complete the extraction of chlorophyll and resinous substances. The end of the extraction set visually for the absence of color of the extractant.

The raw materials thus treated are dried at 25 ° C, extracted with 75% ethyl alcohol by the method of fractional maceration in the ratio 1: 8 at room temperature. Insist 3 times.

I.

The first time is 48 hours, the second and the third are 24 hours each. The combined extracts are evaporated in vacuum at 55 ° C to a thick syrup, which is diluted with 1 liter of hot distilled water and kept at 4 ° C for 14 hours. The precipitate formed is separated. The filtrate is treated in a separating funnel three times with 1 l of chloroform. The aqueous layer is evaporated to a syrup consistency, then dissolved by heating in a boiling water bath in 200 ml of n-propanol. The resulting hot filter filter914061 4

through a small layer of aluminum oxide. The resulting solution is evaporated in vacuo until crystals appear. After that, evaporation is stopped and the solution is left at 20 ° C. The precipitated precipitate is separated by filtration. Recrystallized from ethyl or methyl alcohol, dried to constant weight. Get 8.7 g of the finished product in the form of a white crystalline powder.

Example 2. 1 kg of crushed leaves of the small-apertured caustic, counting on absolutely dry weight, are loaded into an extraction vessel of the flow type or Soxlet, filled in with chloroform and extracted to complete extraction of chlorophyll and resinous substances. The end of extraction 20 is set visually by the absence of color of the extractant.

The raw material thus treated is dried at 25 ° C, extracted with 85% ethyl alcohol by the method of 25 fractional maceration in a ratio of 1: 8 at 20-50 ° C.

Insist 3 times. The first time is 48 hours, the second and the third are 24 hours each. The combined extracts are evaporated in vazoukoum at 55 ° C to a thick syrup, which is diluted with 1 liter of hot water and kept at 4 ° C for 14 hours. The precipitated precipitate is separated.

The filtrate is treated in a separating funnel three times with 1 l of chloroform. The aqueous layer is evaporated to a syrup consistency, then dissolved by heating in a water bath in 200 ml of n-propanol. The resulting hot 40 solution is filtered through

a small layer of aluminum oxide. The resulting solution is evaporated in vacuo until crystals appear. Then stop the evaporation and the solution 45 is left at 20 ° C. The precipitation is separated by filtration, recrystallized from ethyl or methyl alcohol, dried to constant weight. 8.9 g of finished product _{50 are} obtained in the form of a white crystalline powder.

Example 3. 1kg of crushed leaves of the small-brighter of the caustic, counting on absolutely dry weight, are loaded into a flow-type extraction vessel or Sockslet, poured with chloroform and extracted to fully remove chlorophyll and smo914061

sheet substances. The end of the extraction set visually for the absence of color of the extractant.

The raw material thus treated is dried at 25 ° C, extracted with 5 to 80% ethyl alcohol by the method of fractional maceration in a ratio of 1: 8 at 20-50 ° C.

Insist 3 times. The first time is 48 hours, the second and the third are 24 hours each. 'Θ The combined extracts are evaporated in vacuum at 55 ° C to a thick syrup, which is diluted with 1 liter of hot water and kept at 4 ° C for 14 hours. The precipitate formed is separated. The filtrate is formed in ’5 in a separatory funnel three times 1 liter of chloroform. The aqueous layer is evaporated to a syrup consistency, then dissolved by heating in a water bath in 200 ml of n-propanol. 20 The resulting hot solution is filtered through a small layer of alumina. The resulting solution is evaporated in vacuo until crystals appear. After that, evaporation is stopped and the solution is left at 20 ^ 0.

The precipitation is separated by filtration, recrystallized from ethyl or methyl alcohol, dried to constant weight. 9.1 g of the finished product are obtained in the form of a white crystalline powder.

Physico-chemical properties of β-ϋ-glycoside pyromeconic acid.

-ϋ-Glycoside pyromeconic acid is a white crystalline powder, odorless and tasteless, soluble in water and when heated in ethyl and methyl alcohol. The substance gives a reaction with a 1% alcoholic solution of ferric chloride, forms a red-brown color, which is enhanced when heated. Melting point 197 “198 ° С.

Elemental analysis:

Found,%: C 47.0; 46.79; H 5.2;

5.16.

C, u 0.5 H ₂ 0

Calculated,%: C 46.64; H 5.33 · IR spectrum (liquid paraffin):

3500-2500 (broad band, OH groups 1720 and 1680 (CO - groups).

UV spectrum (alcohol): λ max 215 nm (E 11000,260 / 9200), with the addition of sodium ethylate, the appearance of an additional peak at 313 nm.

Spectrum I / 4P (CB ^ OEm.d.): 3.3-4.0 (band of bands, 6H, = CHOH, -CH ОO), 4.96 multiplet (1H, glycosidic atom), 6.54 doublet / ΙΗ, 3 5.6 Hz H-atom at ¢ 5 /, 8.15 doublet (ΙΗ, "7 6.5 Hz H-atom at Sat), 8.36 singlet

(,-Atom at C ₂ ).

Mass spectrum / 90 ^e , 70 eU /: 274 / M,

10% /, 112/83% /, 111/100%, 83/23% · ₄₅

Substance I, upon acid hydrolysis, gives pyromeconic acid and glucose.

These two materials prepared by hydrolysis with pomodyu -P-glucosidase, therefore, the connection wish to set up ⁵⁰ I yav- glucoside piromekonovoy acid.

The fact that compound II is pyromeconic acid confirms m.p. 116-117 ° C (from alcohol), ⁵⁵

Mass Spectrum / 200.70 / C ^ HcO ^:

112 / M ⁴ , 100% / 84 / M ¹ '-28.30% / 71/42%,

69/41%, 55/57%, 4 3/72%, 4 2/75% / ·

In accordance with its structure, substance I gives tetraacetate when treated with acetic anhydride in pyridine.

It's confirmed:

1. NMR spectrum (C1) C? ₄ ppm): 20.4 singlet (6Н, 2СНзС00-groups), 2, О singlet (ЗН, СН $ СОО-group), 2.12 singlet (ЗН, СНаС00-group). Groups

π

(3.71 multiplet / ΙΗ), 4.08 multiplet (2H), 5.08-5.4 band group (4H), 6.40 doublet (1H, 39 Hz), 7, 71 doublet (, L 9 Hz), 7.88 singlet mon). .

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2. Mass spectrum.

Molecular weight 442 (tetraacetate).

Aqueous and alcoholic extracts of caustic from the small-aperiate, containing 0.1-0.15% of pyromeconic acid B-glycoside, have pronounced antiprotease activity, reduce the erythrocyte permeability of the fluorescein test, inhibit

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inflammatory response to the introduction of formalin rats.

Claims (1)

The invention method for producing d> -ϋ-glycoside ⁵ piromekonovoy acid comprising that the sodium erigeron leaves (E.aseg L) was extracted with chloroform, followed 75-8524 nym ethanol at 20 ~ ⁵⁰ C. ^{, 0} followed by purification of the extract with propanol and lower alcohol. SP