Method for decomposing amide compounds and method for producing amines

Abstract

To provide an amide compound decomposing method that can decompose an amide compound having a glycosidic bond to efficiently produce an amine having a glycosidic bond, and an amine production method that can produce an amine having an amide bond in high yield.SOLUTION: An amide compound decomposing method includes a decomposing step for applying a hydrothermal treatment to a reaction liquid that contains raw materials containing an amide compound having a glycosidic bond and water, thereby decomposing the amide compound into an amine having a glycosidic bond, where the reaction liquid has a pH of 8.0 or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for decomposing an amide compound and a method for producing an amine. [Background technology]

[0002] Psychosine, for example, is known as an amine having a glycosidic bond. Psychosine exhibits physiological activity and is thought to be involved in the pathogenesis of, for example, degradative enzyme deficiency.

[0003] From the viewpoint of obtaining research reagents for clarifying the physiological activities of such amines having glycosidic bonds, it is important to produce amines having glycosidic bonds.

[0004] As a method for obtaining an amine having a glycosidic bond, for example, Patent Document 1 discloses a method for extracting psychosine tartrate from bovine brain tissue. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP-A-2-200691 Summary of the Invention [Problem to be solved by the invention]

[0006] Amide compounds obtained by dehydration condensation of the amino group of an amine having a glycosidic bond with the carboxyl group of a fatty acid are widely present in nature and are contained in the flowers, leaves, roots, stems, fruits, seeds, etc. of various plants. Therefore, if such amide compounds could be decomposed and recovered as amines having a glycosidic bond, it would be possible to produce amines having a glycosidic bond from various raw materials.

[0007] One possible method for decomposing an amide compound and recovering an amine having a glycosidic bond is to hydrolyze the amide bond of the amide compound. However, according to the studies of the present inventors, when an amide compound having a glycosidic bond is hydrolyzed, the hydrolysis reaction of the glycosidic bond proceeds, and the desired amine having a glycosidic bond cannot be obtained.

[0008] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a method for decomposing an amide compound, which can efficiently produce an amine having a glycosidic bond by decomposing an amide compound having a glycosidic bond, and a method for producing an amine, which can produce an amine having an amide bond in high yield. [Means for solving the problem]

[0009] In order to achieve the above object, the present invention provides a method for decomposing an amide compound, which includes a decomposition step of hydrothermally treating a reaction solution containing a raw material including an amide compound having a glycosidic bond and water to decompose the amide compound and produce an amine having a glycosidic bond, wherein the pH of the reaction solution is 8.0 or higher.

[0010] According to the above method, an amide compound having a glycosidic bond can be decomposed to efficiently produce an amine having a glycosidic bond.

[0011] The present inventors have found that when an amide compound having a glycosidic bond is decomposed by hydrothermal treatment, the hydrolysis reaction of the glycosidic bond proceeds, resulting in a decrease in the yield of an amine having a glycosidic bond. For example, when glucosylceramide is used as the amide compound having a glycosidic bond, the hydrolysis reaction of the glycosidic bond proceeds, resulting in the by-product of free ceramide. To solve this problem, the present inventors have conducted extensive research and found that by adjusting the pH of the reaction solution to 8.0 or higher, the hydrolysis reaction of the glycosidic bond is suppressed and the hydrolysis reaction of the amide bond in the amide compound is promoted. As a result, an amide compound having a glycosidic bond can be decomposed to efficiently produce an amine having a glycosidic bond.

[0012] In the above method, the amide compound may contain a glycosphingolipid. According to the above method, glycosphingolipids can be decomposed particularly efficiently.

[0013] In the above method, the amide compound may include glucosylceramide. According to the above method, glucosylceramide can be decomposed particularly efficiently.

[0014] In the above method, the raw material may be a plant material.

[0015] In the above method, the content of the amide compound in the reaction solution may be 0.05% by mass or more based on the total amount of the reaction solution. When the mass proportion of the amide compound is 0.05% by mass or more, the amide compound can be decomposed particularly efficiently.

[0016] In the above method, the hydrothermal treatment may be carried out under conditions of 110 to 300° C. When the temperature is within the above range, the decomposition of the amide compound can be further promoted.

[0017] The present invention also provides a method for producing an amine, which comprises a decomposition step of decomposing an amide compound by the method of the present invention and an extraction step of extracting an amine having a glycosidic bond from the decomposition product obtained in the decomposition step. According to this production method, an amine having a glycosidic bond can be produced in high yield. [Effects of the Invention]

[0018] According to the present invention, it is possible to provide a method for decomposing an amide compound, which can efficiently produce an amine having a glycosidic bond by decomposing an amide compound having a glycosidic bond, and a method for producing an amine, which can produce an amine having an amide bond in high yield. DETAILED DESCRIPTION OF THE INVENTION

[0019] The present invention will be described in detail below based on preferred embodiments thereof, but the present invention is not limited to the following embodiments.

[0020] In this specification, a numerical range indicated using "to" indicates a range that includes the numerical values before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this specification, the upper or lower limit of a numerical range in a certain stage can be arbitrarily combined with the upper or lower limit of a numerical range in another stage. In the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in the examples. "A or B" may include either A or B, or may include both. Unless otherwise specified, the materials exemplified in this specification can be used alone or in combination of two or more.

[0021] (Method for decomposing amide compounds) The method for decomposing an amide compound according to this embodiment includes a decomposition step of hydrothermally treating a reaction solution containing a raw material containing an amide compound having a glycosidic bond (hereinafter also simply referred to as "amide compound") and water to decompose the amide compound to produce an amine having a glycosidic bond. The pH of the reaction solution is 8.0 or higher.

[0022] An amide compound is a hydrophilic compound in which an amino group (-NH) in an amine having a glycosidic bond is linked to a carboxyl group (-COOH) of a fatty acid via an amide bond (-CONH-). Examples of amide compounds used in the present invention include, but are not limited to, glycosphingolipids.

[0023] Glycosphingolipids are composed of sugars and sphingosine bound together via glycosidic bonds, and examples of glycosphingolipids include glucosylceramide.

[0024] The sugar that is the source of the amide compound is not particularly limited, and examples thereof include the known sugars that can form the above-mentioned amide compounds.

[0025] The raw material to be subjected to the decomposition treatment of the amide compound may contain components other than the amide compound. Examples of such components include amines having a glycosidic bond, water-soluble dietary fiber, sparingly soluble dietary fiber, sugars, proteins, organic acids, etc. The content of the amide compound in the raw material is preferably 0.1% by mass or more, more preferably 0.25 to 30% by mass, and even more preferably 0.5 to 15% by mass, based on the total solid content of the raw material. When the raw material further contains an amine having a glycosidic bond, the content of the amide compound is preferably 0.25 parts by mass or more, more preferably 0.5 to 100 parts by mass, and even more preferably 5 to 50 parts by mass, per part by mass of the content of the amine.

[0026] Examples of raw materials include plants and seaweed. Specifically, flowers, leaves, roots, stems, fruits, seeds, etc. of plants and seaweed can be used. Examples of plants include legumes such as soybeans, cucurbits such as melons, grasses such as rice and corn, amaranthaceae plants such as beets, fagaceae plants such as chestnuts, Asteraceae plants such as sunflowers, and Rosaceae plants such as peaches. The method for decomposing amide compounds according to this embodiment decomposes amide compounds, so even raw materials with a low content of amines having glycosidic bonds can be used as raw materials.

[0027] The reaction solution may contain a solvent other than water. Examples of the solvent other than water include alcohol, dimethylformamide, dimethyl sulfoxide, etc. When the reaction solution contains a solvent other than water, the proportion of water in the water and the solvent other than water may be 5% by mass or more.

[0028] The hydrothermal treatment can be carried out by sealing the raw materials together with water in a pressure-resistant sealed container and heating the sealed container at a temperature exceeding 100°C. By heating the reaction solution containing the raw materials and water in the sealed container, the inside of the sealed container becomes a heated and pressurized environment, and hydrothermal treatment (hydrothermal synthesis) is carried out using subcritical water. The hydrothermal treatment may be carried out while stirring the reaction solution. As the pressure-resistant sealed container, any known container usable for hydrothermal treatment can be used without any particular limitation. From the viewpoint of obtaining high decomposition efficiency, the filling rate of the reaction solution in the sealed container is preferably 20% by volume or more, more preferably 40 to 80% by volume, based on the volume of the sealed container.

[0029] The content of the amide compound in the reaction solution is not particularly limited, but is, for example, preferably 0.05% by mass or more, more preferably 5% by mass or more, and preferably 25% by mass or less, more preferably 15% by mass or less, based on the total amount of the reaction solution. When the content of the amide compound in the reaction solution is within the above range, the decomposition of the amide compound can be carried out efficiently.

[0030] The reaction conditions for the hydrothermal treatment are not particularly limited, but can be, for example, 110 to 300°C and 0.5 to 20 hours. The reaction temperature is preferably 120 to 200°C, and more preferably 140 to 195°C. A reaction temperature of 110°C or higher tends to facilitate the hydrolysis reaction of the amide bond, while a temperature of 300°C or lower tends to inhibit the carbonization of the raw materials and the amine having a glycosidic bond, resulting in a more improved yield. The reaction time is preferably 0.2 to 20 hours, and more preferably 0.5 to 10 hours. A reaction time of 0.2 hours or longer tends to facilitate the reaction, while a reaction time of 20 hours or shorter tends to facilitate a balance between reaction progress and costs.

[0031] The pressure inside the container during the hydrothermal treatment may be equal to or higher than the saturated vapor pressure corresponding to the reaction temperature, but is preferably saturated vapor pressure from the viewpoint of the pressure resistance of the apparatus. When steam is supplied into the sealed container, it is preferable to supply saturated steam at the reaction temperature described above. The pressure inside the sealed container during the hydrothermal treatment can be, for example, 0.2 to 1.6 MPa.

[0032] The pH of the reaction solution is 8.0 or higher, preferably 9.0 or higher, more preferably 10.0 or higher, and even more preferably 11.0 or higher, in order to more efficiently decompose the amide compound and produce an amine having a glycosidic bond. The pH of the reaction solution may be 13.5 or lower. That's fine.

[0033] The pH of the reaction solution can be adjusted by dissolving an acid or base in an aqueous solution of raw material powder containing a specific amide compound. The acid or base used is preferably a substance approved as a food additive. Examples of acids include citric acid, acetic acid, and malic acid. Examples of bases include sodium hydroxide.

[0034] By carrying out the hydrothermal treatment under the above conditions, the amide compound can be decomposed to efficiently produce an amine having a glycosidic bond.

[0035] (Method for producing amines having glycosidic bonds) The method for producing an amine according to this embodiment includes a decomposition step of decomposing an amide compound and an extraction step of extracting an amine having a glycosidic bond from the decomposition product obtained in the decomposition step. The decomposition step is a step of decomposing an amide compound by the method for decomposing an amide compound according to this embodiment described above.

[0036] In the extraction step, amines having glycosidic bonds are extracted from the degradation products obtained in the degradation step. The degradation products contain, in addition to amines having glycosidic bonds, sugars, amide compounds remaining after degradation, water-soluble and hardly soluble cellulose, and degradation products thereof. The amines having glycosidic bonds can be extracted, for example, with ethanol heated to 60°C. [Example]

[0037] The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited to the following examples.

[0038] <Manufacturing of Psychosine> Example 1 3 g of Nippon Ceramide CP (trade name, manufactured by Nippon Flour Mills Co., Ltd.), which has a free ceramide content of 0.5% by mass and a glucosylceramide content of 3% by mass, was dissolved / dispersed in 147 g of ultrapure water, and 0.134 g of sodium hydroxide powder (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was further added to obtain a reaction solution. The pH of the obtained reaction solution was measured with a pH meter and found to be 12.0. This reaction solution was placed in a Teflon (registered trademark) container with a capacity of 200 ml. Next, the vessel was filled with 2 ml of water. 3The container was placed in a hot air circulation autoclave (manufactured by Ashida Manufacturing Co., Ltd.), and the reaction solution was hydrothermally treated at 180°C for 1 hour. The hydrothermal treatment was performed by supplying saturated steam at 180°C from a boiler into the autoclave's tank (pressure vessel) and adjusting the steam supply rate and pressure valve so that the pressure inside the tank reached 1 MPa, which is the saturated steam pressure of water at 180°C. After hydrothermal treatment, the pressure inside the tank was 0.9 MPa and the temperature inside the tank was 180°C. The autoclave was allowed to cool naturally for 10 minutes until the pressure inside the tank reached 0.7 MPa and the temperature inside the tank reached 165°C. After natural cooling, the valve was opened, and compressed air at a pressure of 1 MPa was introduced into the tank using a compressor attached to the device. Since the pressure inside the tank immediately after the compressed air was introduced exceeded 1 MPa, compressed air was introduced into the tank by manually opening and closing the exhaust valve while maintaining the pressure at or above 0.75 MPa, and cooling with compressed air was initiated. During cooling, the pressure inside the tank was reduced as needed to maintain the temperature above the saturated vapor pressure at that time. Two hours after the start of cooling with compressed air, the solution temperature fell below 100°C (the saturated vapor pressure of the aqueous dispersion fell below normal pressure (0.1 MPa)). The lid of the tank was opened, the container was removed, and the container was allowed to cool naturally to room temperature (25°C). After cooling, the decomposition products of the amide compound that had precipitated or adhered to the inner surface of the container were removed using a medicine spoon.

[0039] Next, the solution and solids in the container were filtered under reduced pressure using a 0.2 μm mesh hydrophilized PTFE membrane filter (Omnipore 0.2 μm JG (Merck Millipore, product name)) with a diaphragm pump. The resulting solids were dried in an oven at 120°C for 5 hours to obtain a powder of the decomposition product of the amide compound. The decomposition product of the amide compound was then prepared into a 5% dispersion in ethanol, refluxed at 60°C for 1 hour, and filtered under reduced pressure using a 0.2 μm mesh hydrophilized PTFE membrane filter (Omnipore 0.2 μm JG (Merck Millipore, product name)) with a diaphragm pump. The resulting solution was vacuum dried using a diaphragm pump at 60°C to obtain 0.04 g of a powder of psychosine concentrate.

[0040] (Comparative Example 1) Except for not adding sodium hydroxide when preparing the reaction solution, 0.115 g of psychosine concentrate powder was obtained in the same manner as in Example 1. The pH of the reaction solution was 7.0.

[0041] (Comparative Example 2) The reaction solution used was a solution prepared by dissolving / dispersing 3 g of Nippon Ceramide CP (trade name, manufactured by Nippon Flour Mills Co., Ltd.) in 147 g of ultrapure water, to which 0.005 g of citric acid was further added, and 0.156 g of psychosine concentrate powder was obtained in the same manner as in Example 1. The pH of the reaction solution was 4.0.

[0042] (Comparative Example 3) The reaction solution used was a solution prepared by dissolving / dispersing 3 g of Nippon Ceramide CP (trade name, manufactured by Nippon Flour Mills Co., Ltd.) in 147 g of ultrapure water, to which 0.266 g of citric acid was further added, in the same manner as in Example 1 to obtain 0.115 g of psychosine concentrate powder. The pH of the reaction solution was 2.6.

[0043] <Measurement of psychosine, glucosylceramide, and free ceramide content> (Example 1 and Comparative Examples 1 to 3) The contents of psychosine, glucosylceramide, and free ceramide in the resulting psychosine concentrate powder were measured using the following method. First, 20 mg of psychosine concentrate powder was diluted 50 times with a chloroform:methanol (2:1) mixed solvent to obtain a solution. Psychosine, glucosylceramide, and free ceramide were separated from 0.1 mL of the resulting solution by thin-layer chromatography (TLC). A 95:12 chloroform:methanol (95:12) mixed solvent was used to separate free ceramide and glucosylceramide, and a 80:20:2 chloroform:methanol:2N aqueous ammonia solution (80:20:2) mixed solvent was used to separate psychosine. The separated psychosine, glucosylceramide, and free ceramide were quantitatively analyzed using gas chromatography. Commercially available free ceramide, glucosylceramide, and psychosine standard production samples were used as standard substances, and a sphingoid base was added as an internal standard substance to perform quantitative analysis using the internal standard method. The results are shown in Table 1. The contents shown in Table 1 represent the amounts (mmol) of free ceramide, glucosylceramide, and psychosine contained in 100 g of psychosine concentrate powder. The psychosine yield is also shown in Table 1. The psychosine yield is the amount of psychosine in the obtained psychosine concentrate powder divided by the amount of glucosylceramide in the raw material.

[0044] [Table 1]

Claims

1. a decomposition step of hydrothermally treating a reaction solution containing a raw material containing an amide compound having a glycosidic bond and water to decompose the amide compound and produce an amine having a glycosidic bond, the pH of the reaction solution is 8.0 or higher, the reaction solution does not contain any solvent other than water, the content of the amide compound in the raw material is 0.25 to 30 mass% based on the total amount of solids in the raw material; A method for decomposing an amide compound, wherein the amide compound includes a glycosphingolipid.

2. The degradation method according to claim 1 , wherein the amide compound comprises glucosylceramide.

3. The decomposition method according to claim 1 or 2, wherein the raw material is a plant raw material.

4. The decomposition method according to any one of claims 1 to 3, wherein the content of the amide compound in the reaction solution is 0.05 mass% or more based on the total amount of the reaction solution.

5. The decomposition method according to any one of claims 1 to 4, wherein the hydrothermal treatment is carried out at a temperature of 110 to 300°C.

6. a decomposition step of decomposing an amide compound by the method according to any one of claims 1 to 5; an extraction step of extracting amines having glycosidic bonds from the degradation products obtained in the decomposition step; A method for producing an amine, comprising:

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