HU204884B - Process for obtaining sclareol from sage - Google Patents

Abstract

Sclareol is obtd. from Hibiscus tiliaceus, following the removal of essential oils. The dried plant is extracted by 5-7 quantities of solvent pref. ethanol or petroleum spirit for 1-3 hrs. at 20-30 deg.C. The concentrated extract's residue is hydrolysed pref. with 3-5 quantities of 10% ethanolic KOH soln. at reflux temp.. Alcohol is distilled off and the residue is extracted with 10-15 quantities of boiling petroleum ether or acetone. The soln. is clarified with active-carbon, concentrated and cooled and sclareol crystals are sepd..

Description

The present invention relates to a novel process for the extraction of scalarol from a muscatel plant.

The process according to the invention is carried out by extracting chopped, pre-volatile and then dried muscatel oil plant by steam distillation with 57 times the amount of solvent, preferably ethanol or gasoline, at 20-30 ° C for 1-3 hours, evaporating the extract and the extract is hydrolyzed by boiling with an alcoholic base, preferably 3-5 times with 10% w / v KOH in ethanol, then the residue after distillation of the alcohol is extracted with 10 to 15 times the amount of hot benzene or acetone and the resulting solution after carbon clarification, concentration and cooling, it is crystallized in known manner.

Sclareol is a very important ingredient in the perfume industry because it can be used to produce products with a smell similar to gray amber by oxidation.

A number of extraction methods are known for the extraction of sclareol from Muscovy Sage (Salvia sclarea). In the known methods, two consecutive extractions are performed to obtain the clarareol. In the first step, aliphatic hydrocarbons (such as trichlorethylene) are used, and the resulting extract is, after concentration, methanol containing 10-20% water (British Patent No. 879,958, 1960), 60% ethanol (161,842). (U.S. Pat. No. 1960, 1960) or 70% ethanol (U.S. Patent No. 417,408, 1974).

Soviet authors also report the use of ethylene glycol (U.S. Patent No. 167,931 (1965)).

In all of these processes, 0.1 to 0.2% by weight of clarareol is recovered per essential oil-free sage. The present invention relates to a novel extraction-hydrolytic-recrystallization process for the recovery of sclareol from muscatel sage. By this method, clarareol is obtained in a simpler, less expensive, higher purity and higher yield than dried and de-oiled sage, compared to prior art processes. In our experiments, the essential oil-free air-dried muscatel sage was extracted with various solvents, methanol, ethanol, alcohol-water mixtures and gasoline at 20-60 ° C, and the solvent was distilled off. No difference was found between batch and continuous extraction methods. The simple soaking method also works well. The cut crop was layered with enough solvent to cover the plant parts, and after soaking for a specified time and temperature, the extract was filtered off and the filtrate washed with solvent.

For 3 hours, soaking at room temperature is the most appropriate method for recovering clarareol. With further increase in soaking time, the amount of extract is barely changed. As the temperature increases, the amount of extract is increased, but the content of the clarareol remains unchanged, and isolation is difficult.

According to our studies, ethanol and extraction gasoline are the most suitable solvents, 5-10 times that of dried sage. These are the ones that give the clarareol with the best yield and purity.

After concentration of the extract, the residue (2.5 to 3.2% by weight of the extract relative to dried sage, 1.92.8% by weight of ethanol) is subjected to alkaline alcoholic hydrolysis in order to saponify and not saponify the extract. parts - such as sclareol. Preferably, the extract is refluxed with 3-5 times the amount of 10% w / w KOH in ethanol for 1-3 hours. The ethanol was then distilled off and the residue was removed in vacuo and then extracted with 310 times hot gasoline or acetone. The resulting extract was clarified with activated carbon, concentrated until crystalline precipitation started, and allowed to stand at 10 ° C for 5 hours. The precipitated clarareol was punctured and recrystallized from gasoline.

The clarareol obtained by the novel process of the present invention is a highly pure material. White hair, m.p. 10025 102 'C. It can be used as a perfume ingredient without further purification.

EXAMPLE I 30 kg of crushed, pre-steam-distilled 30 oil-free and then air-dried Muscle Sage plants were ethanol-layered. kg of ethanol. After combining, the alcoholic solution is concentrated to 2.15 kg. Its dry matter content (extract content) is 620 g.

Potassium hydroxide (170 g) was added and the mixture was heated under reflux for 3 hours. The alcohol was distilled off under 40 atmospheric pressure and the solvent traces were removed under vacuum.

The residue - weighing 790-800 g - is extracted with 3 · 4 kg of hot gasoline. The petrol solution was clarified with activated carbon, filtered and evaporated until crystallization started. After cooling and standing at 10 ° C for 5 hours, the crystalline material is filtered off, washed with a little cold petrol and dried.

Further recrystallization (usually 1 to 2) of the resulting material gives 80-110 g of white crystalline clarareol, m.p. 10050-102 ° C.

Example 2 kg of chopped, pre-oiled steam oil distillation and air-dried sage 55 muscles were extracted with 100 kg of 30 ° C gasoline, circulating through the plant for 1 hour. The petrol extract is then separated, the plant parts are washed with 20 kg of petrol and the combined petrol solution is evaporated to dryness. The solvent eye is removed by vacuum evacuation.

HU 204 884 B

To the extract (525 g) was added 2625 g of a 10% w / w solution of KOH in ethanol and the mixture was heated under reflux for 1 hour. The ethanol is then distilled off under normal pressure and the alcohol traces are removed under vacuum.

The residue - weighing 680-690 g - was extracted with hot acetone (3 x 2.3 kg). The acetone solution was clarified with charcoal, filtered and concentrated until crystallization began. After cooling and standing at 10 ° C for 5 hours, the crystalline material is filtered off, washed with a little cold acetone and dried.

Further recrystallization (usually 1 to 2) of the resulting material gave 75-90 g of white crystalline clarareol, m.p. 100-102 ° C.

Comparative study

Our procedure was compared with the method described in Hungarian Patent No. 181,595. The recipe of Example 1, which describes the preparation of crystalline scolarol, was compared with Example 1 of our patent application. In both sets of experiments we started from chopped, pre-oiled steam-distilled and then air-dried muscatel sage, obtained in the same way. The reported results are averages of 5-5 experiments.

1. A181,595. Example 1 of the Hungarian patent

100 kg of dried drug were extracted with 2 x 1001, 40 vol% ethanol water at room temperature for 10-10 hours. The filtrate was concentrated in vacuo (30 mm Hg) and the residue was extracted with 3 x 301 n-hexane.

The hexane was distilled off under normal pressure and the solvent was removed in vacuo.

1.46 kg of a residue are obtained, which is recrystallized 2-3 times with hexane to give the clarareol.

Yield: 0.24 kg (0.24%).

M.p. 100-102 'C.

2. The method of the invention (described in Example 1)

For a 100 kg dry drug - after compression - 600 kg

Ethanol (96%) was layered after soaking for 3 hours at room temperature, the alcoholic extract was separated and the plant parts were washed with 100 kg of ethanol.

After pooling, the alcoholic solution is concentrated to 11 kg. Its dry matter content is 3 kg.

Then 0.8 kg KOH was added and the mixture was heated under reflux for 3 hours. The ethanol was distilled off at normal pressure and the solvent traces were removed under vacuum. The residue is extracted with 3.8 kg of 3 · 20 kg of hot gasoline. The gasoline solution was clarified with activated carbon, filtered and evaporated until crystallization started.

After cooling and standing at 10 ° C for 5 hours, the crystalline material is filtered off, washed with a little cold petrol and dried. The resulting material is recrystallized 1-2 times with petrol to give the clarareol.

Yield: 0.45 kg (0.45%).

M.p. 100-102 'C.

Claims (1)

PATIENT PERSONALITY Method for Extracting Scarletol From Muscat Sage Plant by Extraction Method by Extracting Chopped, Steamed Oil Steam Oil-Dissolved Oil Dried and Dried Muscat Sage Plant 5-7-fold Organic Solvent, preferably Ethanol or Petrol at 20-30 ° C for 1-3 Hours , extracting the extract and distilling off the alcohol after distillation of the alcohol in a known manner using a known amount of spinning gasoline or acetone and crystallizing from the resulting solution by known methods of crystallization of the scarlet after activated charcoal clarification, concentration and cooling, characterized in that the extract after evaporation of the first extraction extract is hydrolyzed by boiling with an alcoholic solution, preferably 3 to 5 times with 10% ethanol in ethanol.