JP5408926B2 - Process for producing polymethoxyflavones - Google Patents

Description

  The present invention relates to a simple method for producing polymethoxyflavones derived from natural products. Specifically, polymethoxyflavone is obtained by further distilling the residue after removing volatile components such as terpenes by atmospheric distillation or vacuum distillation from pericarp oil present in the peel of the mandarin orange plant, using a thin film vacuum distillation apparatus. It is a manufacturing method which distills and separates. According to this method, polymethoxyflavones can be produced efficiently and in a short time without using an organic solvent or the like.

（式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、及びＲ₅は各々独立して水素又はメトキシ基である。）
特にノビレチン（上記式(Ｉ)でＲ₁、Ｒ₂、Ｒ₃、Ｒ₄、及びＲ₅の全てがメトキシ基）に関しては、発ガン抑制作用等の生理活性が明らかにされている物質である（非特許文献１）。 Conventionally, it has been known that polymethoxyflavones represented by the structural formula of the following general formula (I) are contained in a large amount in the pericarp of mandarin orange plants, that is, citrus fruits.

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are each independently hydrogen or a methoxy group.)
In particular, nobiletin (all of R ₁ , R ₂ , R ₃ , R ₄ , and R _{5 in} the above formula (I) is a methoxy group) is a substance whose physiological activity such as carcinogenesis-inhibiting action has been clarified. (Non-Patent Document 1).

  Furthermore, polymethoxyflavones have been attracting attention in the field of foods, as they have found various useful effects such as a taste improving agent and a taste improving method (Patent Document 1) and a flavor deterioration inhibitor (Patent Document 2). Yes.

  In addition to polymethoxyflavones, the peel oil of the mandarin orange plant contains a wide variety of components with very different properties (for example, Non-Patent Document 2 and Non-Patent Document 3). For example, it contains hydrocarbon compounds such as terpenes, carbonyl compounds such as aldehydes and esters, volatile components such as alcohols, and non-volatile components such as waxes and carotenoid pigments that do not volatilize under normal conditions. It is difficult to selectively separate polymethoxyflavones by the method.

  As a conventional technique for producing polymethoxyflavones from pericarp oil of mandarin orange plants, raw materials such as citrus fruits, pericarp, pericarp oil, leaves, etc. are heated and extracted using organic solvents such as methanol, ethanol or chloroform. Or a method of extraction using a supercritical fluid solvent has been proposed (Patent Document 1, Patent Document 2).

  However, in the above method, in addition to polymethoxyflavones, hydrocarbon compounds such as limonene, linalool, geraniol, nerol, α-tapineol and citral derived from raw materials, carbonyl compounds, esters, alcohols, other aromatic components, and carotenoids Thus, it was not possible to obtain polymethoxyflavones having high purity. Therefore, when polymethoxyflavones obtained by the conventional extraction method are used for applications such as taste improvers or flavor deterioration inhibitors, problems such as flavor, off-flavour, coloring due to impurities in the extract arise. The application was extremely limited.

  Therefore, in order to obtain higher-purity polymethoxyflavones, in the prior art, an extract containing polymethoxyflavones is applied to a column packed with a carrier such as silica gel, aluminum oxide, alkylsilylated silica gel, or allylsilylated silica gel. It is supported and separated and purified by a column chromatography method using a developing solvent such as ethyl acetate-hexane or water-acetonitrile or high performance liquid chromatography. Further, liquid-liquid partition chromatography using hexane or pentane or the like and water-containing methanol or ethanol, or liquid-liquid countercurrent extraction chromatography using hexane or pentane or the like and water-containing methanol or ethanol may be used.

  However, the polymethoxyflavones obtained by these methods are very high in purity, but it is difficult to separate and purify a large amount of polymethoxyflavones at a time. In addition, it takes a very long time to prepare a large amount of polymethoxyflavones, and also requires a large amount of expensive organic solvent and special equipment. This method is not suitable for industrial production. Furthermore, in the above method, an organic solvent that may adversely affect the human body, such as n-hexane, ethyl acetate, tetrahydrofuran, acetonitrile, etc. is used. This is also an inappropriate method from the viewpoint of safety.

  As a simple method for separating polymethoxyflavones, a method of extracting a volatile component from the peel oil of a mandarin orange plant by distillation and extracting the residue with an aqueous alcohol solution has been proposed (Patent Document 3). According to this method, a high content methoxyflavone composition can be obtained from a black brown tar-like distillation residue by a simple operation. However, the composition obtained by this method is an alcohol solution, which is a useful method for use as it is as an aqueous preparation, but lacks versatility in other preparations. That is, when the solvent is distilled off from the alcohol solution, the methoxyflavone composition is solidified in a bowl shape, making it difficult to handle and making it difficult to formulate into an oil-soluble preparation or a powder preparation. .

Therefore, it is possible to develop a method for producing a simple, economically advantageous and versatile polymethoxyflavone composition that can be used in foods without worrying about safety from the peel oil of the mandarin orange plant. There are currently no successful examples yet, and there are expectations for the provision of new production methods.
JP-A-6-335362 JP-A-11-169148 JP 2003-292488 A Journal of the Japanese Society for Agricultural Chemistry, Vol. 75, No. 12, 2001, pp. 1283-1290 Perfumery Chemistry Guide (I) 232 pages, Yodogawa Shoten, 1967 Fruit Science, 130 pages, Asakura Shoten, 1991

  The object of the present invention is to solve the above-mentioned problems in the prior art, and to separate polymethoxyflavones from other components in large quantities at one time from the peel oil of the mandarin orange plant, which is cheap and safe for use in foods. And a versatile method for producing a polymethoxyflavone composition.

  In addition, the pericarp oil of the mandarin orange plant that is the raw material, especially orange pericarp oil, is industrially used in large quantities as a fragrance raw material for terpenes such as limonene and essential oils (terpeneless oil) excluding terpenes. In reality, the residue is discarded without being effectively used. However, a large amount of polymethoxyflavones are contained in the residue after collection of a fragrance such as limonene, and the present invention can be applied as an inexpensive raw material that is almost free of charge, which also contributes to the purpose of effective use of waste. .

  The present inventors paid attention to the fact that polymethoxyflavones have various effects such as physiological activity and taste-improving effect, and as a result of earnest research on their simple and efficient separation method, the fruit peel of the mandarin orange plant The residue after removal of volatile components such as terpene compounds from oil is further distilled with a thin-film vacuum distillation device to distill polymethoxyflavones with high versatility and to be manufactured at low cost and extremely simply. As a result, the present invention has been completed.

（式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、及びＲ₅は各々独立して水素又はメトキシ基である）で表される化合物、より具体的にはポリメトキシフラボン類が、ペンタメトキシフラボン、ノビレチン、テトラメトキシフラボン、タンゲレチン、ヘプタメトキシフラボンからなる群より選ばれた少なくとも１種であることを特徴とする。 That is, the present invention provides a process for producing polymethoxyflavones characterized by further distilling and distilling the residue after removing volatile components from the peel oil of a mandarin orange plant by thin film vacuum distillation apparatus In detail, the raw material of the genus Cannabis plant is sweet orange (Citrus sinensis), sour orange (Citrus aurantium), tangerine (Citrus reticlata Blanco var. Tangerine), mandarin (Citrus reticlata Blanco var. depressa Hayata), and more specifically, the removal step of the first volatile component by distillation is performed under conditions of a pressure of 1 to 100 Pa and a temperature of 120 to 220 ° C., and the second thin film The distillation step in the vacuum distillation apparatus is characterized in that the pressure is from 0.4 to 2 Pa and the temperature is from 190 to 260 ° C.
Furthermore, polymethoxyflavones are represented by the following general formula (I):

Wherein R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are each independently hydrogen or a methoxy group, more specifically, polymethoxyflavones are pentamethoxy It is at least one selected from the group consisting of flavone, nobiletin, tetramethoxyflavone, tangeretin and heptamethoxyflavone.

  Further, the present invention is a polymethoxyflavone composition containing 20% by mass or more of the polymethoxyflavone produced by the above production method, and further comprising the polymethoxyflavone composition. Oral composition. Further, the present invention is a powder formulation of polymethoxyflavones characterized by powdering the polymethoxyflavones composition.

According to the present invention, high purity polymethoxyflavones can be separated from other components in large quantities at once from the peel oil of the easy-to-obtain raw material mandarin plant, and it is inexpensive and highly safe for food use. Furthermore, a versatile method for producing polymethoxyflavones can be provided.
Further, the polymethoxyflavone composition of the present invention contains 20% by mass or more of the above polymethoxyflavones and is a transparent liquid composition having a low viscosity, so that it is easy to handle and easily oil-soluble. It is a highly useful composition that can be processed into a preparation or a powder preparation.

  The present invention includes (a) a step of removing volatile components from the peel oil of the mandarin orange plant by distillation, and then (b) a residue after distillation removal in the above step (hereinafter referred to as “distillation residue”) is further subjected to a thin film vacuum distillation apparatus. Is a process for producing polymethoxyflavones comprising a step of distilling and distilling and separating.

  The form of the food containing the polymethoxyflavones of the present invention may be a capsule, granule, tablet, paste or beverage. In addition, the polymethoxyflavones can be mixed with known preparation additives and the like, if necessary.

  Known formulation additives include excipients, bases, binders, disintegrants, disintegration aids, lubricants, fluidizing agents, coating agents, plasticizers, antifoaming agents, dragees, skins, gloss Agent, foaming agent, moisture-proofing agent, surfactant, solubilizer, buffering agent, solubilizer, solubilizer, solvent, stabilizer, emulsifier, suspending agent, dispersant, antioxidant, filler, viscosity Examples include thickeners, thickeners, pH adjusters, preservatives, preservatives, sweeteners, flavoring agents, refreshing agents, flavoring agents / fragrances, fragrances, and coloring agents.

  In addition, DHA (docosahexaenoic acid), EPA (eicosapentaenoic acid), phosphatidylserine, phosphatidylcholine, soybean lecithin, egg yolk lecithin, tocotrienol, GABA (γ-aminobutyric acid), theanine, lycopene, yamabushitake, ginkgo biloba, tomorrow, Hops, chrysanthemum flowers, gadgets, saffron, garlic, germinated brown rice, vitamin C, vitamin E, coenzyme Q10, royal jelly, propolis, collagen, plant sterols, vegetable oils and fats (olive oil, soybean oil, etc.), unsaturated fatty acids, beeswax , Zinc yeast, selenium yeast and the like.

（式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、及びＲ₅は各々独立して水素又はメトキシ基である）で表される化合物であり、具体的には、ペンタメトキシフラボン（Mp １７９℃）、ノビレチン（Mp １３４℃）、テトラメトキシフラボン（Mp １２８℃）、ヘプタメトキシフラボン（Mp １２９〜１３１℃）、タンゲレチン（Mp １５４℃）が該当する。 Embodiments of the present invention will be described below.
[1] Polymethoxyflavones and their raw materials:
The polymethoxyflavones extracted and separated in the present invention are represented by the following general formula (I):

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are each independently hydrogen or a methoxy group), specifically, pentamethoxyflavone (Mp 179 ° C), nobiletin (Mp 134 ° C), tetramethoxyflavone (Mp 128 ° C), heptamethoxyflavone (Mp 129-131 ° C), tangeretin (Mp 154 ° C).

  The polymethoxyflavones are contained in a large amount in the peel oil contained in the pericarp of the mandarin orange plant. Among them, sweet orange (Citrus sinensis), sour orange (Citrus aurantium), tangerine (Citrus reticlata Blanco var. Mandarin), mandarin (Citrus reticlata Blanco var. Mandarin), Shikuwasha (Citrus depressa Hayata) It is preferable to use the pericarp oil as a raw material. The method for collecting pericarp oil is not particularly limited, and examples thereof include a method for obtaining pericarp oil (cold press oil) by squeezing pericarp at cold or normal temperature. Natural limonene residues produced industrially from orange peel oil can also be used.

[2] Step of removing volatile components The volatile components in the peel oil are removed by atmospheric pressure or vacuum distillation, but vacuum distillation is preferred from the viewpoint of removing volatile components at as low a temperature as possible. The vacuum distillation can be performed by a general method such as simple distillation, rectification, or molecular distillation.
Further, a low-boiling component having a particularly high volatility such as limonene (bp 175 to 176 ° C.) is preliminarily removed by distillation (preferably at a pressure of 1000 to 10,000 Pa and a temperature of 50 to 200 ° C.), and then obtained. Multi-stage distillation in which the residual liquid is subjected to this step, that is, distilled under high vacuum conditions to sufficiently remove the hardly volatile components remaining in the residual liquid is desirable in that a product with high purity can be obtained.

  Distillation in this volatile component removal step is preferably vacuum distillation performed at a pressure of 1 to 100 Pa and a distillation temperature of 120 to 220 ° C, and particularly preferably a pressure of 10 to 50 Pa and a distillation temperature of 160 to 200 ° C. When the temperature is lower than 120 ° C., volatile components tend not to be sufficiently removed.

  Here, in the present invention, the volatile components removed from the peel oil are limonene, linalool (bp 198 ° C.), geraniol (bp 229 to 230 ° C.), and nerol (bp 225 to 226 ° C.) contained in the peel oil. , Α-tapineol (bp 217-218 ° C.), citral (bp 229 ° C.) and other hydrocarbon compounds, carbonyl compounds, esters, alcohols, and other aromatic components, which are more volatile than the polymethoxyflavones. Is a component having a high boiling point, that is, a lower boiling point.

[3] Step of separating polymethoxyflavones In this step, polymethoxyflavones are obtained by further distilling the residue (hereinafter referred to as “distillation residue”) after distillation removal in the previous volatile component removal step with a thin-film vacuum distillation apparatus. Is a step of distilling and separating.
Distillation used in this step is performed by thin film distillation. Thin film distillation is a method in which a product to be distilled (the distillation residue) is continuously supplied onto a surface heated to a certain temperature to form a uniform thin film, and the product to be distilled is only on the surface. It is a distillation method in which a volatile component and a non-volatile component are separated by heating and evaporating the volatile component.

  In this step, the pressure and temperature conditions are 0.1-5 Pa, 190-260 ° C., preferably 0.4-2 Pa, 190-260 ° C. When the temperature is lower than 190 ° C., it takes time to distill the polymethoxyflavones. On the other hand, when the temperature exceeds 260 ° C., components other than the polymethoxyflavones are distilled and the polymethoxyflavone content decreases.

  The polymethoxyflavones obtained by the production method described above can be used as a food taste improver, a flavor deterioration inhibitor or the like, even if they are a mixture of various polymethoxyflavone compounds. Therefore, in many cases, it is only necessary to separate the polymethoxyflavones from the other components from the peel oil of the mandarin orange plant, and it is not always necessary to isolate and purify the individual components of the polymethoxyflavones for each compound.

  However, if a single product such as polymethoxyflavones with high purity, for example, heptamethoxyflavone, is required, it can be easily purified by recrystallization or column chromatography methods. An appropriate purification method known in the art can be appropriately selected and used.

  The present invention will be described in more detail with reference to the following examples. However, the following examples are used only for illustrative purposes, and the present invention is not limited thereto.

[Measurement example]
Commercial orange peel oil ("ORANGE PEEL OIL" manufactured by FISCHER S / A) was diluted 5-fold with ethyl acetate, and the content of polymethoxyflavones was quantified using the following high performance liquid chromatography (HPLC). .
The quantified results are shown in Table 1 below. The HPLC conditions used in this experimental example are shown below:
Equipment: “Agilent 1100 HPLC system” manufactured by Agilent Technologies
Column: “CAPCELL PAK C18MG” manufactured by Shiseido Co., Ltd. (column temperature: 40 ° C)
Eluent: A. Acetonitrile
B. 10% acetonitrile aqueous solution (pH 2.5 H ₃ PO ₄ )
Gradient condition: 0 min → 25 min A. Acetonitrile 0% 100%
B. 10% acetonitrile aqueous solution
(PH2.5 H ₃ PO ₄ ) 100% 0%
Flow rate: 1 ml / min Detection wavelength: 325 nm

  The content of each component was calculated using a calibration curve prepared with a pure product isolated in advance. The content of polymethoxyflavones in Table 1 indicates the total content of pentamethoxyflavone, nobiletin, tetramethoxyflavone, heptamethoxyflavone, and tangeretin.

[Distillation example]
1000 kg of commercially available orange peel oil used in the measurement example was subjected to pre-reduced vacuum distillation at a pressure of 1330 Pa and a kettle temperature of 150 ° C. to obtain 50 kg of a kettle residue from which high-volatile low-boiling components such as limonene were removed. .
100 g of the kettle residue obtained by the pretreatment distillation was subjected to vacuum distillation under various temperature and pressure conditions to remove volatile components.
Table 2 shows the results of analysis of the fraction and distillation residue thus obtained.

In the table, “yield” represents the weight of the fraction obtained by distillation under reduced pressure and the weight of the distillation residue as a percentage of the weight of the residual liquid of the pretreatment distillation, and the recovery rate of polymethoxyflavones refers to the orange peel oil. The recovery rate of the polymethoxyflavones contained in the kettle residue was shown and calculated using the following formula (I).
Recovery rate (%) = (c × d) / (a × b) × 100 (%) (I)
[Wherein, a: weight (kg) of oil used for distillation, b: content (%) of polymethoxyflavone (s) in oil used for distillation, c: weight of distillation residue (kg), d: polymethoxy of distillation residue Flavonone (s) content (%)]

  Further, 500 g of a 30% aqueous ethanol solution was added to 25 g of the distillation residue obtained by distillation, and extraction was performed by heating under reflux for 1 hour. After cooling to 25 ° C., the upper oil part and the ethanol aqueous solution layer were separated. After filtering the ethanol aqueous solution layer, the polymethoxyflavones obtained by concentrating to dryness under reduced pressure were diluted to 1% with 50% ethanol aqueous solution, and the diluted solution was added to 0.1% glucose to 10% aqueous solution. Table 2 shows the results of evaluating the presence or absence of off-flavors and odors.

  As shown in Table 2, when the distillation temperature exceeds 200 ° C., the polymethoxyflavones distill off in the fraction, and the recovery rate of the polymethoxyflavones in the distillation residue decreases. On the other hand, when the distillation temperature is 160 ° C. or lower, an orange-like fragrance remains.

[Example 1]
(1) Volatile component removal process As a pretreatment, 1000 kg of commercially available orange peel oil used in the measurement example was distilled under reduced pressure at a pressure of 1330 Pa and a kettle temperature of 150 ° C. to remove low boiling components such as limonene. A residual liquid of 50 kg was obtained.
Distillation of 50 kg of the residual liquor obtained in the above pretreatment was performed at a pressure of 40 Pa and a temperature of 190 ° C. using a thin film distillation apparatus (“CEH-400BII” manufactured by ULVAC-TECHNO INC.) To remove hardly volatile components. 25.6 kg of distillation residue was obtained.
The obtained distillation residue was diluted 1000 times with ethyl acetate and measured under the same conditions as in the measurement example. The results are shown in Table 3.

The recovery rate represents the recovery rate of polymethoxyflavones contained in orange peel oil to the distillation residue, and was calculated using the following calculation formula (I).
Recovery rate (%) = (c × d) / (a × b) × 100 (%) (I)
[Wherein, a: weight (kg) of oil used for distillation, b: content (%) of polymethoxyflavone (s) in oil used for distillation, c: weight of distillation residue (kg), d: polymethoxy of distillation residue Flavonone (s) content (%)]

  As shown in Table 3, in the volatile component removal step, polymethoxyflavones were recovered from the orange peel oil in the distillation residue without loss. The polymethoxyflavones separation step shown below was performed using the distillation residue obtained in the above volatile component removal step.

(2) Polymethoxyflavone separation step Distillation residue 150 g obtained in the volatile component removal step is distilled at a pressure of 2 Pa and a temperature of 210 ° C. using a thin-film distillation apparatus (“MS-F” manufactured by Daishin Kogyo Co., Ltd.). And 56 g of polymethoxyflavones were obtained. The obtained polymethoxyflavones were orange-yellow highly viscous paste oil. The polymethoxyflavones thus obtained were diluted 1000 times with 99.5% aqueous alcohol solution, and the results of measuring the content of polymethoxyflavones in the solid content under the same conditions as in the above measurement example are shown in Table 4. Show. The recovery rate indicates the recovery rate of polymethoxyflavone (s) from the distillation residue obtained by pretreatment distillation, and was calculated in the same manner as the recovery rate calculation in the volatile component removal step.

  As shown in Table 4, it was possible to easily produce a high content polymethoxyflavone composition with a high recovery rate.

[Example 2]
(1) Volatile component removal process Exactly the same process as the volatile component removal process of Example 1 was performed to obtain 25.6 kg of a distillation residue from which volatile components were removed.

(2) Separation process of polymethoxyflavones 100 g of the obtained distillation residue was set to a pressure of 0.4 Pa, and vacuum thin film distillation was performed under various temperature conditions. Table 5 shows the results obtained by analyzing the fraction and distillation residue thus obtained under the same conditions as in Example 1. The recovery rate represents the weight of the fraction obtained by distillation under reduced pressure and the weight of the distillation residue as a percentage of the weight of the residual liquid in the volatile component removal step. The recovery rate of polymethoxyflavones is the recovery rate in the volatile component removal step. It calculated using the same method.

  As shown in Table 5, when the distillation temperature exceeds 260 ° C., components other than polymethoxyflavones distill out and the content of polymethoxyflavones decreases. On the other hand, when the distillation temperature is 190 ° C. or lower, the recovery rate of polymethoxyflavones decreases.

[Example 3] Oil-soluble preparation Using the polymethoxyflavones obtained in Example 1, an oil-soluble preparation was prepared according to the formulation shown in Table 6 below.

  The oil-soluble preparation thus obtained was a liquid composition having high fluidity and a preparation having high stability.

Example 4
Using the oil-soluble preparation obtained in Example 3, a soft capsule-shaped food having the composition shown in Table 7 below was prepared according to a conventional method.

[Example 5] Emulsified powder formulation After heating 65 parts by weight of gum arabic in 200 parts by weight of water, 5 parts by weight of microcrystalline cellulose was dispersed, and the polymethoxyflavones 30 obtained in Example 1 were added thereto. A part by mass was added and emulsified. This was spray-dried to prepare an emulsified powder formulation. This powder formulation was a fluid and highly stable formulation.

[Example 6] Adsorbed powder formulation An adsorbed powder formulation was prepared by adding 25 parts by mass of the polymethoxyflavones obtained in Example 1 to 75 parts by mass of maltose and stirring and mixing them. This powder formulation was a fluid and highly stable formulation.

Example 7
Using the powder formulation obtained in Example 5, tablets having the compositions shown in Table 8 below were prepared according to a conventional method.

[Example 8] Ethanol preparation 100 g of an aqueous ethanol solution was added to 10 g of the polymethoxyflavones obtained in Example 1, and the mixture was heated to 60 ° C and extracted with stirring for 1 hour. After cooling to −5 ° C., the upper oil part and the ethanol aqueous solution layer were separated, and the ethanol aqueous solution layer was filtered. Table 9 shows the results of analyzing the obtained polymethoxyflavone under the same conditions as in Example 1.

From Table 9, when the alcohol concentration used for extraction was 10% to 20%, although the purity of the separated polymethoxyflavones was high, the recovery rate was as low as 33 to 60%, which was inefficient.
On the other hand, when the alcohol concentrations were 60% and 80%, the recovery rate of the separated polymethoxyflavones was as high as 97 to 99%, but the purity was as low as 25 to 64%.
When the alcohol concentration is 30% to 50%, the purity of the separated polymethoxyflavones is as high as 73 to 87%, and the recovery rate is 78 to 94%, so that polymethoxyflavones can be obtained very efficiently. I was able to.

[Example 9] Preparation of water-soluble preparation Using the polymethoxyflavones of the present invention, a water-soluble preparation was prepared as follows.
100 g of 40% aqueous ethanol solution was added to 10 g of the polymethoxyflavones obtained in Example 1, and the mixture was heated to 60 ° C. and extracted with stirring for 1 hour. After cooling to −5 ° C., the upper oil part and the ethanol aqueous solution layer were separated, and the ethanol aqueous solution layer was filtered to obtain 99.0 g of a filtrate. The obtained filtrate was concentrated to 10.1 g, and 11.0 g of 99% ethanol was added to obtain 21.1 g of an ethanol preparation. Table 10 shows the results of analyzing polymethoxyflavones of the obtained ethanol preparation under the same conditions as in Example 1.

  The ethanol preparation thus obtained was a yellow liquid with low taste and no off-flavors.

[Example 10] Preparation of orange beverage An orange beverage was prepared according to the formulation shown in Table 11 below.

  According to the present invention, by combining distillation (especially vacuum distillation) and purification by vacuum thin-film distillation, polymethoxyflavones with few impurities and no off-flavor can be easily and very efficiently separated from the peel oil of the mandarin orange plant. be able to. In addition, the present invention makes it possible to industrially obtain inexpensive and highly safe polymethoxyflavones that can be used in foods. Furthermore, if the present invention is applied, it becomes possible to use orange peel oil residue after collecting terpenes such as limonene and essential oils (terpeneless oil) excluding terpenes, which have been discarded so far. It can make a great contribution to use.

Claims (12)

The following steps,
(I) a step of removing a volatile component from the peel oil of a mandarin orange plant by distillation under conditions of a pressure of 1 to 100 Pa and a temperature of 120 to 220 ° C. to obtain a distillation residue;
(Ii) The distillation residue obtained in the step (i) is distilled using a thin film vacuum distillation apparatus under conditions of a pressure of 0.1 to 5 Pa and a temperature of 190 to 260 ° C. to contain 20% by mass or more of polymethoxyflavones. Separating the liquid composition;
(Iii) a step of mixing the liquid composition obtained in step (ii) with a medium chain fatty acid triglyceride or vegetable oil to form an oil-soluble preparation,
A process for producing a polymethoxyflavone-containing oil-soluble preparation, comprising: The following steps,
(I) A step of first obtaining the residue (1) by subjecting the peel oil of the mandarin orange plant to distillation under conditions of a pressure of 1000 to 10000 Pa and a temperature of 50 to 200 ° C.,
(Ii) subjecting the residue (1) to distillation under conditions of a pressure of 1 to 100 Pa and a temperature of 120 to 220 ° C. to obtain a residue (2);
(Iii) A liquid composition containing 20% by mass or more of polymethoxyflavones by distilling and distilling the residue (2) using a thin film distillation apparatus under conditions of a pressure of 0.4 to 2 Pa and a temperature of 190 to 260 ° C. Separating the process,
(Iv) a step of mixing the liquid composition obtained in step (iii) with a medium-chain fatty acid triglyceride or vegetable oil to form an oil-soluble preparation,
A process for producing a polymethoxyflavone-containing oil-soluble preparation, comprising:   Tangerine genus plant is selected from sweet orange (Citrus sinensis), sour orange (Citrus aurantium), tangerine (Citrus reticlata Blanco var. Tangerine), mandarin (Citrus reticlata Blanco var. Mandarin), Shikuwasha (Citrus depressa Hayata) The method for producing an oil-soluble preparation containing polymethoxyflavones according to claim 1 or 2, wherein there are two or more kinds. Polymethoxyflavones are represented by the following general formula (I):

_{4. The} compound according to claim 1, wherein R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are each independently hydrogen or a methoxy group. Of producing an oil-soluble preparation containing polymethoxyflavones. The following steps,
(I) a step of removing a volatile component from the peel oil of a mandarin orange plant by distillation under conditions of a pressure of 1 to 100 Pa and a temperature of 120 to 220 ° C. to obtain a distillation residue;
(Ii) The distillation residue obtained in the step (i) is distilled using a thin film vacuum distillation apparatus under conditions of a pressure of 0.1 to 5 Pa and a temperature of 190 to 260 ° C. to contain 20% by mass or more of polymethoxyflavones. Separating the liquid composition;
(Iii) adding and emulsifying the liquid composition obtained in step (ii) to an aqueous gum arabic solution in which microcrystalline cellulose is dispersed;
(Iv) a step of spray-drying the emulsion obtained in step (iii) to form an emulsified powder;
A process for producing an emulsified powder preparation containing polymethoxyflavones, comprising: The following steps,
(I) A step of first obtaining the residue (1) by subjecting the peel oil of the mandarin orange plant to distillation under conditions of a pressure of 1000 to 10000 Pa and a temperature of 50 to 200 ° C.,
(Ii) subjecting the residue (1) to distillation under conditions of a pressure of 1 to 100 Pa and a temperature of 120 to 220 ° C. to obtain a residue (2);
(Iii) A liquid composition containing 20% by mass or more of polymethoxyflavones by distilling and distilling the residue (2) using a thin film distillation apparatus under conditions of a pressure of 0.4 to 2 Pa and a temperature of 190 to 260 ° C. Separating the process,
(Iv) adding and emulsifying the liquid composition obtained in step (iii) to an aqueous gum arabic solution in which microcrystalline cellulose is dispersed;
(V) a step of spray-drying the emulsion obtained in step (iv) to form an emulsified powder;
A process for producing an emulsified powder preparation containing polymethoxyflavones, comprising:   Tangerine genus plant is selected from sweet orange (Citrus sinensis), sour orange (Citrus aurantium), tangerine (Citrus reticlata Blanco var. Tangerine), mandarin (Citrus reticlata Blanco var. Mandarin), Shikuwasha (Citrus depressa Hayata) The method for producing a polymethoxyflavone-containing emulsified powder preparation according to claim 5 or 6, wherein there are two or more kinds. Polymethoxyflavones are represented by the following general formula (I):

8. The compound according to claim 5, wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently hydrogen or a methoxy group. Of producing an emulsified powder preparation containing polymethoxyflavones. The following steps,
(I) a step of removing a volatile component from the peel oil of a mandarin orange plant by distillation under conditions of a pressure of 1 to 100 Pa and a temperature of 120 to 220 ° C. to obtain a distillation residue;
(Ii) The distillation residue obtained in the step (i) is distilled using a thin film vacuum distillation apparatus under conditions of a pressure of 0.1 to 5 Pa and a temperature of 190 to 260 ° C. to contain 20% by mass or more of polymethoxyflavones. Separating the liquid composition;
(Iii) a step of adding the liquid composition obtained in step (ii) to maltose, stirring and mixing to form an adsorbed powder,
A process for producing an adsorbent powder preparation containing polymethoxyflavones, comprising: The following steps,
(I) A step of first obtaining the residue (1) by subjecting the peel oil of the mandarin orange plant to distillation under conditions of a pressure of 1000 to 10000 Pa and a temperature of 50 to 200 ° C.,
(Ii) subjecting the residue (1) to distillation under conditions of a pressure of 1 to 100 Pa and a temperature of 120 to 220 ° C. to obtain a residue (2);
(Iii) A liquid composition containing 20% by mass or more of polymethoxyflavones by distilling and distilling the residue (2) using a thin film distillation apparatus under conditions of a pressure of 0.4 to 2 Pa and a temperature of 190 to 260 ° C. Separating the process,
(Iv) adding maltose to the liquid composition obtained in step (iii), stirring and mixing to form an adsorbed powder;
A process for producing an adsorbent powder preparation containing polymethoxyflavones, comprising:   Tangerine genus plant is selected from sweet orange (Citrus sinensis), sour orange (Citrus aurantium), tangerine (Citrus reticlata Blanco var. Tangerine), mandarin (Citrus reticlata Blanco var. Mandarin), Shikuwasha (Citrus depressa Hayata) The method for producing an adsorbent powder preparation containing polymethoxyflavones according to claim 9 or 10, wherein there are two or more kinds. Polymethoxyflavones are represented by the following general formula (I):

12. The compound according to claim 9, wherein the compound is represented by the formula: wherein R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are each independently hydrogen or a methoxy group. Of producing an adsorbent powder preparation containing polymethoxyflavones.