KR20070020326A - Solvent base plant extract - Google Patents

Abstract

The present invention relates to a process for preparing petrochemical-free aroma components, which method comprises extracting aroma components from plant materials using volatile esters such as ethyl acetate. The process produces unique concrete, wax and anhydrous ingredients useful for all types of perfume compositions that can be guaranteed to be organically verifiable in the absence of petrochemicals.

Description

Solvent based plant extracts {SOLVENT BASED PLANT EXTRACTS}

Field of invention

The present invention relates to a process for the preparation of natural aroma components and to the aroma components produced by such a method.

Background of the Invention

It has been known for hundreds of years that fragrances have been used as an attractant to the opposite sex by mankind, and modern commercially available perfumes have rapidly diversified over the years. Perfume is now not only an accessory for man, but also for a person's home or office environment. The idea that a person's mood can be changed or improved by exposure to certain perfumes has been for many years, and recently, even scientific tests exist that confirm this psychological impact of perfumes.

It is generally recognized in the perfume industry that natural perfumes are preferred over synthetic perfumes. In many cases, by chemical analysis, for example, perfumes such as strawberries or roses are broken down into their constituents and then synthetically prepared one or more such ingredients in an attempt to reproduce the aroma of the raw material. It is possible. However, the resulting synthetic products often lack the "essence" of the original natural product and are typically considered to be qualitatively inferior to the natural raw material. Unfortunately, the preparation of aroma compounds from natural sources is not a simple matter and can be very costly but does not always yield a product of optimum quality per se.

Natural perfumes are typically derived from plant extracts. The aromatic components of most plant materials are oils or oils. These can be separated in various ways. The first method is steam distillation, which is an old way in which plants are exposed to hot water or steam, leaving a liquid later called essential oils. This method is preferred in that it does not use petrochemicals at all, but has some limitations in that it is not useful for extracting essential oils from all types of plant materials. In particular, the aroma constituents of the flower are susceptible to change by this process, so the essential oils of the flower, which are in great demand as perfume components, can hardly be produced in this way.

The second method of obtaining perfume components from plant material is solvent extraction. This process typically uses non-polar, petrochemical (hydrocarbon) solvents such as benzene, toluene or hexane to dissolve wax and aromatic substances from the plants. The solvent then evaporates off, leaving behind a solid or semi-solid material known as "concrete". The concrete may then be rinsed with ethanol to dissolve the ethanol-soluble components and then cooled to filter the waxes. Ethanol is then evaporated under vacuum, leaving behind a substance known as "anhydride". All three of these components, namely waxes, concrete and anhydrides, are widely used in the perfume industry. The limitation of this method lies in the use of petrochemical solvents; Many perfume makers, especially aromatherapists, are not pleased to use these products due to petrochemical solvent residues. These residues may also prevent organic proof if it may be desirable to prove organic.

Another way of obtaining natural perfume ingredients is known as compression, in which the perfume ingredient is squeezed or squeezed out of the plant material. This method is often used to obtain natural oils from the peels of citrus fruits such as lemons, limes or oranges. However, it is not practical to apply to the fraction of sensitive flowers that are the raw materials of very much needed perfume ingredients.

A new way of extracting aromatic components is supercritical carbon dioxide. This method involves heating and pressurizing until CO ₂ reaches a supercritical state and using it as a solvent. Supercritical carbon dioxide has the advantage of being easily removed from the extract (it simply evaporates), but water in fresh plant materials such as leaves and flowers can inhibit the extract's solubility, making the process inefficient and of poor quality. Take the extract.

Therefore, a state of current interest in the perfume industry is that there is currently no way to produce organically demonstrable a variety of floral perfume anhydrides. However, the present invention now provides such a useful method, along with aromatic components having a unique perfume and chemical composition.

Summary of the Invention

The present invention relates to a method of extracting aroma components from a plant material, wherein the method comprises volatile esters, preferably R = CH ₃ , for a period of time sufficient for the aroma components to be transferred to the ester. Contacting with an ester of C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ or C ₅ H ₁₁ , wherein the general structure is CH ₃ COOR; Separating the plant material and ester; Evaporating the ester to produce concrete containing aromatic components; Optionally contacting the concrete with at least one alcohol rinse, cooling the rinse to separate an alcohol soluble fraction from a wax fraction, separating the wax fraction from an alcohol soluble fraction, And evaporating the alcohol from the alcohol soluble fraction to produce the anhydrous fraction. The present invention also provides novel aromatic concrete, wax and anhydrous components produced by this method.

Detailed description of the invention

The present invention provides a novel solvent extraction means for the preparation of perfume components. Unlike the solvent extraction methods currently used, the present invention uses organic esters, in particular volatile organic esters, as solvents. Volatile in this paragraph means esters having a boiling point of about 130 ° C. or lower. Esters useful for the purposes herein are represented by the general formula CH ₃ COOR, wherein R = CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ or C ₅ H ₁₁ . Particularly preferred esters for this purpose are ethyl acetate because of their greater volatility (boiling point of about 77 ° C., similar to the more traditional solvents used in the process). However, other esters of the indicated structural formulas, which may also have higher boiling points, such as, for example, isobutyl acetate, may provide the same results, but some greater effort is required to remove the solvent and the process There is a risk of losing some of your top notes.

Of course ethyl acetate is a well known solvent often used in the preparation of plant extracts for the separation of biologically active substances such as proteins, polysaccharides, etc., but to the inventors' knowledge, this has not previously been used for the separation of perfume components. Indeed, it is generally counterintuitive to use polar solvents such as ethyl acetate to extract the perfume substances from plants, given the bulk of perfume components of oily or non-polar nature. However, this not only effectively yields the same classification of typical aromatic substances as non-polar solvent extraction, but also unexpectedly provides substantially higher yields of up to two to three times that achieved by traditional hexane extraction.

More importantly, the resulting fractions also have hexane, toluene or benzene extractions, very different physical properties, are more aromatic overall, and have different flavor profiles than the same fractions obtained using petrochemical solvent extraction Has In particular, the extract prepared by this method is advantageous in that it is organically verifiable. Ethyl acetate is an organic ester obtainable by the reaction of two natural substances, namely ethyl alcohol and vinegar. Therefore, the aromatic components separated in this way are undesirable petrochemical residues that make other commercially available concrete, waxes or anhydrides undesirable for certain perfumery industries and make them more organically unprovable. It does not contain

The extraction method of plant material is relatively simple. Plant materials known to contain the aromatic components of interest are collected. These may be any part of the plant, for example flowers, stems, leaves, or roots. Porous plant materials, such as leaves and flowers, can be used as a whole or milled, and non-porous materials such as nuts or seeds must be milled prior to extraction. The plant material is then impregnated in the ester solvent and allowed to stay together for a short period of time, as short as 15 seconds, but typically up to 5 to 10 minutes. Longer residence times of 30-60 minutes, more typical for hexane-based processes, can extract materials that are incompatible with other aromatic components, such as certain essential oils. In such a rinse, the ratio of solvent to plant material is not strict, but may be just enough to cover the plant material. As an example, however, when relatively light materials such as flowers are used, about 3 kilograms of solvent per kilogram of plant material provide good results. Since the ratio can vary with the density of the raw material, fewer solvents can be used for very dense materials and more solvents can be used for lighter materials. Generally speaking, the use of more solvent leads to faster extraction of the material. However, there is no criticality in this amount since the ability to remove solvent at the end of the process is only one limitation.

After impregnation, the solvent fraction and plant fraction of the mixture are then separated. Surprisingly, unlike hexane extraction, large amounts of aromatic material can be extracted with a very short exposure as described above, and more rinsing is not necessary to obtain an acceptable output. However, if necessary, it is also possible to rinse the plant fraction with a second solvent and separate the two fractions, this time for another 5 minutes or less, this time at a solvent: plant ratio of about 2: 1. Optionally, a third rinse of plant material is performed at a solvent to plant ratio of about 1: 1 for a slightly longer period of time, such as for example about 10 minutes or more. If multiple rinses are performed, the following steps will be combined. However, it should be noted that since the first rinse extracts most of the aromatic material, the yield will not increase very significantly, typically with multiple rinses.

After rinsing, after discarding the plant material, the solvent is evaporated from the rinse liquid, leaving concrete. Concrete is a mixture of waxes and aromatics, which can also be used in cosmetics such as lipsticks or lotions (as wax can be further purified from concrete or residual extracts), to modify physical properties such as viscosity or structure. The same way as other waxes are used, but at the same time has the added advantage of providing aromas.

In alternative embodiments, all or some of the concrete obtained can also be further treated by rinsing at least once with alcohol to separate the anhydride and wax fractions, then cooling and filtering. One rinse will extract a substantial portion of the aromatic material, but multiple rinses, preferably at least two rinses, will typically increase the separation efficiency. Ethanol is the preferred alcohol for this step, but the alcohol can be a monohydric or polyhydric alcohol such as, for example, isopropanol or propylene glycol, which is compatible with cosmetic and / or perfume use of the final product. The alcohol used is preferably relatively volatile; However, if evaporation of the solvent is not necessary for the intended end use, non-volatile solvents such as glycerin may also be used in this case provided that the non-volatile material will significantly dilute the final anhydride. The cooling step after rinsing results in separation from the wax fraction, which can then be separated from the alcohol rinse, for example by filtration. The resulting alcohol fraction is then evaporated to produce anhydride, which can optionally be filtered to remove the remaining small solids. An exemplary procedure for this rinsing process is as follows: 10 parts by weight of alcohol of standard strength 200 are added per part by weight of concrete. The mixture is mixed with the propeller mixture at room temperature for about 1 hour and then cooled with slow mixing to -30 ° C. The mixture is filtered to clear. The solid extract is then added back to the mixing vessel and additional alcohol is added, typically about 8 parts by weight of alcohol is added to 1 part by weight of the solid extract. After the mixing, cooling and filtration steps are repeated, a third rinse is performed with about 6 parts by weight of alcohol with respect to 1 part by weight of the solid extract. Those skilled in the art will readily understand that the conditions of the foregoing procedures are not necessarily stringent, and may, for example, modify the residence time in the solvent, the ratio of solvent to material, the number of rinses, and the like; Modifications may result in differences in final yields, but will nevertheless result in qualitatively similar products at the end of the procedure.

The resulting fractions, namely concrete, waxes and anhydrides are unexpectedly chemically distinguished from the corresponding petrochemical solvents of the same material as discussed above. Early observations of the perfume quality of anhydrides by perfume makers showed a very qualitative difference between hexane derived extracts and ethyl acetate derived extracts. This suggests that there may be chemical differences in the composition of the extracts. To confirm this hypothesis, two types of extracts were analyzed by GC / MS. Repeating with several different types of flower extracts shows that the chemical components of the hexane extracts are quite different from the ethyl acetate extracts. These differences are found both in the proportion of components common in both extracts and in the overall identity of the components in each extract. For example, in the jasmine extract, a total of 60 components are found between the two extracts, with only seven components found in both extracts, and in many cases even in common cases, in very different amounts. . A more detailed analysis of this experiment is provided in Example 3 below. Another observation is that anhydrides prepared by the process of the present invention typically exhibit lower indole contents than the corresponding petrochemically separated anhydrides. This is quite important because the proportion of indole in the perfume means "animal content", which indole features perfumes that are not particularly desirable in high quality flowers. Similar tests also show higher benzyl acetate content in the hexane extract.

Another difference is that the concentration of wax obtained in this extraction procedure is significantly higher than the concentration of wax observed in hexane extraction. Since the wax itself has cosmetic utility apart from the utility of the anhydride (ie, cosmetic or pharmaceutical use in which the wax is commonly applied), it provides additional efficiency to the process. In addition, the properties of the waxes obtained are distinct: The waxes produced by the ethyl acetate process are generally darker and more aromatic than typical hexane process waxes. Therefore, each of the fractions obtained from the process is a unique product that is chemically distinct from the comparative fractions obtained by the more typical petrochemical-based extraction procedure.

The plant raw material for extraction can be any type of plant useful as a source of aromatic components. These include, for example, fruits (strawberries, apples, melons, lemons, limes, oranges, and grapes), herbs or leaves (such as tomatoes, basil, patchouli, citrus fruits, sage, violets, rosemary or hay), seeds ( For example, coriander, caraway, cocoa, tongka beans, nutmeg, mace cardamom, and anise), spices (star anise, pepper, allspice), trees (e.g. birch, cedar, sandalwood, juniper, larch and Pine), bark (eg broilers), roots (eg ginger, vetiver or iris) and flowers. However, when applied to flowers, this is particularly advantageous due to the typical difficulty in obtaining good quality essential oils from flowers, with the high demands on the floral components and the high costs associated with them. Essential oils are usually defined as oils obtained by steam distillation of plant materials. Peppermint, sandalwood, basil, and rose oils are all essential oils obtained by steam distillation; In some cases, though not all, roses are an important exception, since the essential oils of roses are the most abundant and the most complex, making them the most important aroma component of certain plants. However, many flowers will not yield essential oils by steam distillation. Jasmine is probably the best known of these flowers. Steam distillation attempts of jasmine flowers produce a non-flowery, perfumed water condensate that is free of essential oils. The only way to get the aroma of jasmine flower is by extracting the jasmine flower with a solvent, which has been done so far petrochemically, which is unacceptable for some consumers. Advantageously, the present invention now provides for the first time a means by which essential oils can be obtained from certain plant raw materials without the use of petrochemical solvents.

As an additional advantage, the method of the present invention provides a higher yield of specific classification. In comparative extraction, the yield of concrete is much higher for ethyl acetate concrete compared to hexane concrete (see Example 2 below). Since the yields of aromatic anhydrides are almost the same in the hexane process and in the ethyl acetate process, an increase in the amount of concrete indicates a greater amount of wax extracted by ethyl acetate. This is particularly unexpected because the waxes are generally nonpolar, and the process also extracts more of them using more polar solvents and shorter solvent residence times than petrochemical solvents. In addition, the process cost to achieve this result is substantially the same as the cost incurred when using hexane, thereby reducing the cost of the final product. Perhaps more importantly, however, this method also provides a means to obtain an organically verifiable floral fragrance, which could not be achieved using more than one handful of flower raw materials up to now due to the flower oil damaging effect of steam distillation. This more natural quality of the perfume ingredients can be an important feature for both aromatherapists and perfume makers, and will also enhance the enjoyment of the perfume by the ultimate consumer of the product. Examples of flowers that are a popular source of aromatic ingredients and that would be useful in this extraction procedure include roses, jasmine, orange blossoms, carnations, geraniums, mimosa, peony, violet, lavender, lilac, honeysuckle, blue chamomile, orchid and mu There is, but is not limited to. While the present invention is particularly important in separating the aromatic components from the flower or a portion of the flower, it will also be appreciated that the present invention can be used with plant materials containing aromatic or wax components soluble in volatile esters. Examples of other useful plant raw materials include trees, shrubs, herbs and vegetables, and the plant parts used for extraction include fruits, berries, leaves, stems, twigs, bark, trees, snow, seeds, roots, and pods. It may be any part of the plant, including but not limited to. Examples of natural raw materials for perfume ingredients are, for example, Perfumery , Practice and Principles , Calkin and Jellinek (1994), or Perfumery and Flavoring Materials , Bedoukian (1995), the contents of which are incorporated herein by reference.

Concrete, anhydrides and waxes produced by this method can be used in numerous ways in perfume products. Each may be used alone or in admixture with one another, or in combination with a topically acceptable carrier in combination with one or more ingredients suitable for the intended end use, for example, cosmetic or pharmaceutical use. Examples of products in which the ingredients may be used include personal care products such as perfumes, cologne, perfumed body sprays and splashes; Products for treating hair such as shampoos, conditioners, setting gels, hair sprays and the like; Products for treating skin such as cosmetic creams, lotions, milks, sticks, gloss, gels and powders; Or color cosmetics such as lipstick, lip gloss, foundation, blusher, eyeshadow, eyeliner or mascara; Household aroma products such as candles, room sprays, perfume dispersers, wax tarts, perfumes, and the like; And aromatherapy products such as perfumed massage oils. The manufacture of such products is known in the art; For example, formulations of cosmetic compositions and pharmaceutical compositions are described in Harry's Cosmeticology , Eighth Edition, M. Reiger, ed. (2000), and Remington : The Science and Practice of Pharmacy , Twentieth Edition, A. Gennaro, ed., (2003), which are incorporated herein by reference. The components prepared by the present invention can be readily used in any type of formulation in place of traditionally prepared components. Those skilled in the art will readily recognize other applications of the aroma components made in accordance with the present invention and will recognize that traditional perfume ingredients may be used anywhere that may be used.

The invention is explained in more detail by the following non-limiting examples.

Example 1 This example describes the preparation of the aroma components of jasmine flower. 25 kilograms of jasmine flower is filled into a wire basket and pressurized so that the solvent cannot flow through the jasmine flower. The basket is immersed in a stainless steel of a steam jacket containing ethyl acetate at room temperature (approximately 22-27 ° C.) sufficient just to completely cover the flower. The combined ingredients are not stirred. After 15 seconds, the wire basket containing the jasmine flower is removed from the solvent, the solvent is drained for about 1 minute and the flower is discarded. Heat the extraction solution to 60-70 ° C. and mix slowly until most of the ethyl acetate is removed. Evaporated ethyl acetate can be collected through a condenser for reuse. When the extract is condensed to the point of about 50% ethyl acetate, the extract is cooled to minus 20 ° C. and the extract is held for at least 15 minutes, during which the bulk of the wax precipitates out and some additional wax, ethyl acetate And an extract having a aromatic compound. A small amount (about 10% of the extract amount) of 200 standard strength ethanol is added to the extract and mixed until uniform (approximately 15 minutes). The extract is added to a vacuum distillation apparatus and heated to 40-50 ° C. To remove the remaining ethyl acetate, a normal vacuum (20-100 mm mercury) is applied. At this stage, the extract represents concrete except some of the wax that was initially removed.

To separate the aromatic components from the wax, the extract can then be transferred to a tank of a stainless steel jacket and 10 parts by weight of alcohol of 200 standard strengths can be added to 1 part by weight of the extract. The components were mixed for 1 hour at room temperature with a propeller mixer and then cooled slowly to minus 30 ° C with slow mixing. The extract was filtered off to clear. The solid extract from the filter is added back to the tank and 8 parts by weight of alcohol is added to 1 part by weight of the solid extract. Repeat mixing, cooling and filtration. A third time repetition of the washing, with 6 parts Alcohol to 1 part by weight of the extract was carried out with a third repeated rinse using 6 parts by weight of alcohol. Pour alcohol rinse into vacuum distillation unit and warm to 40-55 ℃. Normal vacuum (20-100 mm mercury) is applied to remove the alcohol. After the alcohol is removed, the final aromatic ethyl acetate anhydride, a dark brown material, is left, and the remaining solid extracts represent a wax fraction.

Example 2:

One kilo of jasmine flower is extracted by a traditional hexane process (3 times rinse at room temperature, immersion 15 minutes each time, then evaporating the solvent) to produce approximately 2.5 grams of concrete. The concrete is then extracted using ethanol similar to the method described above. The yield of anhydride is approximately 1.3 grams. One kilo of jasmine flower was extracted with ethyl acetate by the method of Example 1 to produce approximately 6 grams of concrete, with higher amounts of concrete indicating a higher degree of wax extracted by this process as opposed to the hexane process. Indicates. The concrete is then further extracted with ethanol as in Example 1 to produce approximately 1.2 grams of anhydride and the remaining wax.

Example 3: This example shows qualitative and quantitative differences between hexane-extracted anhydride and ethyl acetate-extracted anhydride.

Hexane anhydride and ethyl acetate anhydride of different flowers are prepared as described above in Example 2. In a quality assessment by perfume experts, jasmine hexane anhydride is found to have flower notes with rich, nice, sweet but less gentle sweetness. Similarly, violet leaf hexane anhydride has very fresh, bright cucumber green colored notes, whereas violet leaf ethyl acetate anhydride has very heavy green, not cucumber green, notes similar to oak moss.

After this qualitative observation, the quantitative differences between the anhydrides prepared by the different extractions are evaluated. Comparison by gas chromatography / mass spectrometry. The instrument consists of an Agilent 6890N GC and an Agilent 5973 mass spectrometer with HP1MS (nonionic) columns manufactured by J & W. The experiment is carried out using a temperature ramp of 4 ° C. per minute from 50 ° C. to 250 ° C.

The same jasmine flowers were extracted in the same field and extracted with hexane and ethanol or ethyl acetate and ethanol. GC / MS analysis finds 60 identifiable and quantifiable compounds. Of course, only seven are found in both anhydrides; The other 54 are found in one anhydride and not in another. All seven compounds common to both extracts (benzyl acetate, benzyl benzoate, benzindan-1,2,2-trione 2-oxime, isopititol, palmitic acid, phytol and dioctyl phthalate) are significantly different in both materials. It is found at different concentrations. For example, benzyl acetate is found at 16.99% in hexane anhydride and only 0.98% in ethyl acetate anhydride. Benzyl benzoate (another compound common to many flower essences) is found at 12.6% in hexane anhydride and only 0.46% in ethyl acetate anhydride. 34 compounds are found only in hexane anhydride and 20 compounds are found only in ethyl acetate anhydride.

Comparison of orange flower anhydrides shows similar results. 58 compounds were identified. 19 are common to both anhydrides, 34 are found only in hexane anhydride, and 5 are found only in ethyl acetate anhydride.

Violet leaf extract shows a more significant difference. Of the 14 compounds found in the extract, only one octadecadienoic acid is common to both extracts. Eight are found only in hexane anhydride, and six are found only in ethyl acetate anhydride. These results account for the significant differences observed in the qualitative aroma profile, and it also clearly shows that the products of the two different extractions have chemically distinct entities.

The present invention relates to a process for preparing petrochemical-free aroma components, which method comprises extracting aroma components from plant materials using volatile esters such as ethyl acetate. The process produces unique concrete, wax and anhydrous ingredients useful for all types of perfume compositions that can be guaranteed to be organically verifiable in the absence of petrochemicals.

Claims (20)

Contacting the plant material containing the aromatic components with a volatile ester for a period of time sufficient to allow the transfer of the aromatic components from the plant material to the ester, separating the ester containing the aromatic components from the plant material, and Evaporating the ester to produce a concrete fraction containing the wax and the aromatic components; Optionally alcohol rinsing the concrete one or more times, cooling the rinse solution to separate an alcohol soluble fraction containing aromatic components from a wax fraction, and separating the wax fraction from an alcohol soluble fraction And evaporating the alcohol from the alcohol soluble fraction to produce anhydrous fraction. A method of extracting an aromatic component from plant material, comprising. The method of extracting an aromatic component from plant material according to claim 1, characterized in that the period of contact time between the plant material and the volatile solvent is less than 30 minutes. The method of claim 1, wherein the plant material is in contact with the volatile ester once more, and the ester contains aromatic components separated from the plant material. The method of claim 1, wherein the concrete is rinsed and cooled with alcohol to produce a wax fraction and an alcohol soluble fraction. 5. A method according to claim 4, wherein the alcohol is ethanol. 5. The method of claim 4, wherein the wax fraction is separated from an alcohol soluble fraction. 7. The method of claim 6, wherein the alcohol is evaporated from the alcohol soluble fraction to produce anhydrous fraction. The aroma from plant material according to claim 1, wherein the ester has a structural formula of CH ₃ COOR, and R = CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ or C ₅ H ₁₁ . Extraction method of ingredients. The method of extracting an aromatic component from plant material according to claim 1, wherein the ester is ethyl acetate. Concrete prepared by the method of claim 1.  Wax prepared by the method of claim 6. Anhydrides prepared by the method of claim 7. The plant of claim 1, wherein the plant material is selected from at least one of the group consisting of fruit, strawberry, flower, leaf, stem, twig, bark, tree, snow, seed, root, and pod. Method for Extracting Aromatic Components from Ingredients. The method of extracting an aromatic component from plant material according to claim 1, wherein the plant material is a flower. 15. The flower of claim 14, wherein the flower is selected from the group consisting of roses, jasmine, orange blossoms, carnations, geraniums, mimosa, moonshine, violets, lavender, lilac, honeysuckle, blue chamomile, orchids and muew The extraction method of an aromatic component from plant material. Perfume composition comprising the concrete of claim 10. Perfume composition comprising the wax of claim 11. Anhydrous composition comprising the anhydride of claim 12.  A topical composition comprising at least one of anhydrides, waxes or concretes prepared according to claim 1, in combination with a topically acceptable carrier. Organically Proven Perfume Composition.