Diol compound, method for producing diol compound, and moisturizing agent composition

Abstract

An object of the present invention is to provide a novel diol compound using a compound derived from a bioproduct.SOLUTION: The present invention is a diol compound represented by the following formula (1). (In the formula, R1 represents a single-bond, an alkylene group having 1 to 8 carbon atoms, or an arylene group having 6 to 10 carbon atoms.). ) SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a diol compound, a method for producing a diol compound, and a moisturizing composition. [Background technology]

[0002] In recent years, the development of products using bioproducts has been attracting attention from the perspectives of protecting the natural environment and using sustainable resources. Materials that have been processed as desired using biotechnology, such as microorganisms, enzymes, and cell cultures, are used as raw materials to produce a variety of products in a variety of fields, including pharmaceuticals, cosmetics, food additives, and industrial products. Summary of the Invention [Problem to be solved by the invention]

[0003] Therefore, an object of the present invention is to provide a novel diol compound using a compound derived from a bioproduct, a method for producing the same, and a moisturizing composition containing the diol compound. [Means for solving the problem]

[0004] As a result of intensive research aimed at solving the above problems, the present inventors discovered that a novel diol compound can be obtained by using a compound derived from xylitol as a bioproduct, thereby completing the present invention. That is, the present invention is as follows. [1] A diol compound represented by the following formula (1): [ka] (In the formula, R 1 represents a single bond, an alkylene group having 1 to 8 carbon atoms, or an arylene group having 6 to 10 carbon atoms. [2] R 1 represents a single bond or an alkylene group having 1 to 3 carbon atoms. [1] The diol compound according to [1]. [3] R 1 represents a single bond, the diol compound according to [1]. [4] R 1 represents an alkylene group having 3 carbon atoms. [1] The diol compound according to [1]. [5] R 1 represents a phenylene group. [6] A method for producing a diol compound according to any one of [1] to [5], comprising a step of reacting either one or a mixture of compounds represented by the following formula (2) and formula (3) with an acetalizing agent represented by the following formula (4) in the presence of an acid catalyst: [ka] (In the formula, R 1 represents a single bond, an alkylene group having 1 to 8 carbon atoms, or an arylene group having 6 to 10 carbon atoms. [7] The production method according to [6], wherein the reaction step includes a step of carrying out the reaction under conditions of 70 to 150°C while removing water present in the reaction system. [8] The method according to [6] or [7], wherein the acid catalyst is selected from the group consisting of sulfuric acid, alkylsulfonic acid, arylsulfonic acid, hydrochloric acid, nitric acid, and combinations thereof. [9] A moisturizing composition comprising the diol compound according to any one of [1] to [5]. [Effects of the Invention]

[0005] According to the present invention, it is possible to provide a novel diol compound using a compound derived from a bioproduct, a method for producing the same, and a moisturizing composition containing the diol compound. [Brief explanation of the drawings]

[0006] [Figure 1]1 is a H NMR spectrum of the diol compound (1-1) of Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0007] Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail, but the present invention is not limited to this embodiment. In this specification, "A to B" (A and B are numerical values) means "A or more and B or less." In addition, in this specification, for example, a compound described as "a compound represented by formula (X)" will also be referred to as "compound (X)."

[0008] 1. Diol compounds The diol compound of this embodiment is a diol compound represented by the following formula (1). [ka] (In the formula, R 1 represents a single bond, an alkylene group having 1 to 8 carbon atoms, or an arylene group having 6 to 10 carbon atoms.

[0009] The diol compound can be produced using a compound derived from xylitol, a bioproduct. Specifically, as shown in the following chemical reaction formula, it can be produced by acetalizing 1,4-anhydroxylitol, which is derived from xylitol, with a dialdehyde. [ka]

[0010] Xylitol is a biologically derived sugar alcohol that can be extracted from the fibers of many plants and certain trees, including various berries, corn husks, oats, birch, and mushrooms. More practically, xylitol can be obtained industrially by known hydrogenation processes of xylose. Xylose can also be produced from various non-food pentosan-containing biomass sources, such as corn cobs and stover, cereal straw, sugarcane bagasse, wood waste, and paper pulp processing liquor, using known hydrolysis techniques.

[0011] Here, R in equation (1) 1 represents a single bond, an alkylene group having 1 to 8 carbon atoms, or an arylene group having 6 to 10 carbon atoms. The alkylene group having 1 to 8 carbon atoms may be linear or branched. Examples of the alkylene group having 1 to 8 carbon atoms include, but are not limited to, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, and groups represented by the following formulas (A-1) to (A-14). In formulas (A-1) to (A-14), "*" represents a bond to a carbon atom. [ka]

[0012] The arylene group having 6 to 10 carbon atoms is a divalent aryl group, and the aryl group is a monovalent monocyclic or polycyclic aromatic group. Examples of the arylene group having 6 to 10 carbon atoms include, but are not limited to, an o-phenylene group, an m-phenylene group, a p-phenylene group, a 3,5-tolylene group, a 2,4-tolylene group, a 2,6-tolylene group, a 1,2-naphthylene group, a 1,8-naphthylene group, and a 2,3-naphthylene group.

[0013] Of these, R 1 is preferably a single bond, an alkylene group having 1 to 3 carbon atoms, or an arylene group having 6 to 7 carbon atoms. 1 is a single bond or an alkylene group having 1 to 3 carbon atoms, or a phenylene group.1 may be a single bond or an alkylene group having 3 carbon atoms. Examples of the alkylene group having 3 carbon atoms include a propylene group and a methylethylene group.

[0014] Examples of the diol compound of this embodiment include diol compounds represented by the following formulas (1-1) to (1-3). [ka]

[0015] In this embodiment, as described above, diol compound (1) is a compound produced using a compound derived from a bioproduct, and some of the carbon atoms constituting the molecule of diol compound (1) are carbons derived from the bioproduct. The proportion of carbon atoms derived from the bioproduct to all carbon atoms constituting the compound is also referred to as the bio-ratio. In this embodiment, the bio-ratio of diol compound (1) can be, for example, 50 to 83%. More specifically, the bio-ratio can be calculated by assuming that the raw material xylitol is 100% derived from bio-products and determining the ratio from the number of bio-based carbon atoms in the molecular formula of diol compound (1), using the following formula: Bio percentage (%) = carbon number derived from xylitol / total carbon number x 100 The bio-contents of the diol compounds (1-1) to (1-3) are 83%, 67%, and 56%, respectively.

[0016] The diol compound of the present embodiment may have stereoisomers due to the presence of multiple asymmetric carbon atoms in the molecule, but the diol compounds of the present embodiment represented by the above formula (1) and formulas (1-1) to (1-3), etc., include all stereoisomers, stereoisomer mixtures, and racemates.

[0017] 2. Method for producing diol compounds A method for producing the diol compound of this embodiment will be described. The method for producing the diol compound of this embodiment is a method for producing the diol compound of this embodiment described above, and includes a step of reacting either one of compounds (1,4-anhydroxylitol) represented by the following formula (2) and formula (3) or a mixture thereof with an acetalizing agent represented by the following formula (4) in the presence of an acid catalyst (hereinafter also referred to as the "acetalization step"). [ka] (In the formula, R 1 represents a single bond, an alkylene group having 1 to 8 carbon atoms, or an arylene group having 6 to 10 carbon atoms. According to the method for producing a diol compound of this embodiment (hereinafter also referred to as "production method"), a diol compound can be efficiently produced from a compound derived from xylitol, which is a bioproduct. The manufacturing method of this embodiment will be described in more detail below.

[0018] In the manufacturing method of this embodiment, when carrying out the above-mentioned acetalization step, a step of etherifying xylitol in the presence of an acid catalyst (hereinafter also referred to as the "etherification step") can be carried out, as shown in the chemical reaction formula below. [ka]

[0019] In the etherification step, 1,4-anhydroxylitol (2) and (3) can be obtained by forming an ether bond through a dehydration reaction between the two hydroxy groups attached to the carbon atoms at positions 1 and 4 of xylitol in the presence of an acid catalyst. This reaction yields the stereoisomers 1,4-anhydroxylitol (2) and (3) as racemates. More specifically, in the etherification step, although not particularly limited, xylitol can be reacted in the presence of an acid catalyst in water or an aprotic solvent while being stirred at a temperature in the range of 80 to 180°C (preferably 100 to 150°C, more preferably 110 to 130°C).

[0020] Examples of the acid catalyst include inorganic and organic acids. Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, and boric acid. Examples of organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, benzoic acid, p-aminobenzoic acid, alkylsulfonic acids, arylsulfonic acids (e.g., p-toluenesulfonic acid and benzenesulfonic acid), trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, citraconic acid, malic acid, and glutaric acid. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, and oxalic acid. These acid catalysts can be used alone or in combination of two or more.

[0021] The content of the acid catalyst is not particularly limited, but can be in the range of 0.01 to 5 mol or 0.05 to 3 mol per 1 mol of xylitol. The reaction time in the etherification step is not particularly limited, but may be, for example, 2 to 30 hours, or 2 to 10 hours.

[0022] In the etherification step, for example, in order to shorten the reaction time, the etherification reaction may be carried out while dehydrating using a Dean-Stark apparatus, etc. Furthermore, a dehydrating agent may be used in the etherification reaction.

[0023] In addition to 1,4-anhydroxylitols (2) and (3), the reaction product obtained in the etherification step may also contain a small amount of the compound of the following formula (5) (1,5-anhydroxylitol) as a by-product. [ka] When the etherification step is performed, a purification step for removing by-products such as 1,5-anhydroxylitol from the obtained reaction product may be performed after the etherification step, or the next step, the acetalization step, may be performed without performing the purification step. Furthermore, since 1,4-anhydroxylitol (2) and (3) in the reaction product obtained in the etherification step are optical isomers, the reaction product may be used in the next step as a racemate.

[0024] The method for producing a diol compound of this embodiment then involves an acetalization step in which either one or a mixture of 1,4-anhydroxylitols (2) and (3) is acetalized in the presence of an acetalizing agent (4) and an acid catalyst to obtain a diol compound of formula (1). [ka]

[0025] In the above acetalization reaction, the hydroxymethyl group bonded to the carbon atom at position 2 of the tetrahydrofuran ring of 1,4-anhydroxylitol (2) and (3) and the hydroxy group bonded to the carbon atom at position 3 are bonded in a cis configuration (i.e., in the same direction), so the formyl group of the acetalizing agent (4) undergoes a substantially selective acetalization reaction with these two hydroxy groups. The two hydroxy groups bonded to the carbon atoms at positions 3 and 4 of the tetrahydrofuran ring are in a trans configuration and hardly undergo acetalization. Then, in the acetalization step, the two formyl groups of the acetalizing agent (4) undergo an acetalization reaction with two molecules of 1,4-anhydroxylitol (2) and (3), producing the diol compound of formula (1). In this acetalization step, the reaction may be carried out using either the compound of formula (2) or the compound of formula (3) as 1,4-anhydroxylitol, or a mixture of the compounds of formula (2) and formula (3).

[0026] Furthermore, in the above etherification step, in addition to 1,4-anhydroxylitols (2) and (3), 1,5-anhydroxylitol (5) may also be present as a by-product in the resulting reaction product. 1,5-anhydroxylitol (5) has three hydroxy groups attached to the tetrahydropyran ring, but since adjacent hydroxy groups are in a trans configuration, it hardly undergoes acetalization reaction with the acetalizing agent (4). Therefore, in the acetalization step, the reaction product obtained in the etherification step can be used without purification, i.e., it can be used as it is, containing 1,5-anhydroxylitol (5).

[0027] The acetalizing agent is a dialdehyde compound represented by the following formula (4), where R 1 represents a single bond, an alkylene group having 1 to 8 carbon atoms, or an arylene group having 6 to 10 carbon atoms. 1 is the R of diol compound (1). 1 Since this corresponds to R in Eq. (4), 1 is R in Eq. (1). 1 can be similarly done. [ka]

[0028] The acid catalyst is not particularly limited, but examples thereof include inorganic acids and organic acids. Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Examples of organic acids include alkylsulfonic acids, arylsulfonic acids, and trifluoroacetic acid. Examples of acid catalysts include solid acids such as cation exchange resins, zeolites, and heteropolyacids (e.g., phosphotungstic acid and phosphomolybdic acid), as well as various Lewis acids. In this embodiment, the acid catalyst may be selected from the group consisting of sulfuric acid, alkylsulfonic acids, arylsulfonic acids, hydrochloric acid, nitric acid, and combinations thereof. The acid catalyst preferably includes arylsulfonic acid, more preferably paratoluenesulfonic acid.

[0029] The content of the acid catalyst is not particularly limited, but can be in the range of 0.01 to 1 mol, or in the range of 0.01 to 0.1 mol, per 1 mol of the total amount of 1,4-anhydroxylitol (2) and (3).

[0030] In the acetalization step, the molar ratio of the total amount of 1,4-anhydroxytols (2) and (3) to 1 mole of the acetalizing agent (4) is preferably 0.25 to 1, more preferably 0.3 to 0.7, and even more preferably 0.45 to 0.55.

[0031] A solvent can be used as needed, and examples thereof include aromatic hydrocarbon solvents such as toluene and xylene, and aprotic polar solvents such as N-methylpyrrolidone. For example, at the start of the reaction, a water solvent may be used to dissolve the raw materials in water to form an aqueous solution, in order to make it easier to add the raw materials to a reaction vessel.

[0032] Incidentally, the acetalization step preferably includes a step of carrying out the reaction under conditions of 70 to 150° C. while removing water present in the reaction system. Specifically, the reaction may be carried out while dehydrating using, for example, a Dean-Stark apparatus, or a dehydrating agent may be used. The reaction temperature is preferably in the range of 70 to 150°C, more preferably in the range of 90 to 140°C, and even more preferably in the range of 110 to 130°C.

[0033] The reaction time in the acetalization step is not particularly limited, but may be, for example, 1 to 10 hours, or 1 to 6 hours.

[0034] In this embodiment, the reaction in the acetalization step is stopped by a known method, and then a purification step is carried out as necessary, whereby the diol compound can be obtained.

[0035] 3. Moisturizing composition The moisturizing composition of this embodiment will be described. The moisturizing composition of the present embodiment is a moisturizing composition containing the diol compound of the present embodiment. Since the diol compound of the present embodiment has a moisturizing effect, for example, by applying the moisturizing composition of the present embodiment to the skin, the user can obtain a moisturizing effect. The moisturizing composition of the present embodiment may contain, in addition to the above-mentioned diol compound, other ingredients commonly used in cosmetics and the like, such as hyaluronic acid, glycerin, surfactants, liquid oils, aqueous solution thickening components, alcohols, glycols, lipophilic active agents, semi-solid oils, solid oils, pharmaceuticals, buffers, fragrances, preservatives, colorants, sequestering agents, antioxidants, ultraviolet absorbers, powders, and the like, without being particularly limited thereto. Furthermore, the moisturizing composition of the present embodiment can be used as a cosmetic material such as a moisturizing cream or lotion, although there are no particular limitations thereon.

[0036] Although the embodiments of the present invention have been described above, the present invention is not limited to the above examples and can be modified as appropriate. [Example]

[0037] The present invention will be described in more detail below with reference to examples, but the materials, amounts used, proportions, treatment contents, treatment procedures, etc. shown in the examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0038] <Production Example 1> 1,4-Anhydroxylitol was prepared as follows. 200 g (1.31 mol) of xylitol, 336 g (18.7 mol) of water, and 11.9 g (0.15 mol) of sulfuric acid were added to a recovery flask. The reaction mixture was heated to 115°C while stirring, and the evaporated solvent was refluxed using a Dimroth condenser. After the reaction continued for 24 hours, the pH of the reaction mixture was adjusted to 7 by adding aqueous sodium hydroxide. The reaction mixture was concentrated using an evaporator, and the residue was purified by column chromatography to obtain 130 g of anhydroxylitol. The purity of the resulting anhydroxylitol was determined using gas chromatography (GC) and nuclear magnetic resonance (NMR) spectroscopy, confirming that the mixture consisted of 93% racemic 1,4-anhydroxylitol and 7% 1,5-anhydroxylitol. In the following examples, the mixture obtained in this production example was used as the raw material "1,4-anhydroxylitol."

[0039] <Experiment 1> The diol compounds of the examples were prepared as follows.

[0040] [Example 1] A recovery flask reactor was charged with 5.0 g (37.3 mmol) of 1,4-anhydroxylitol, 2.77 g (18.64 mmol) of 40% aqueous glyoxal solution (acetalizing agent), and 0.35 g (1.86 mmol) of p-toluenesulfonic acid monohydrate. The flask was heated to 120 °C and stirred for 5 hours while removing water from the reaction system using a Dean-Stark apparatus. After completion of the reaction, the reaction mixture was analyzed by gas chromatography (GC), confirming the formation of the desired diol compound (1-1) in 84% yield. The reaction mixture was allowed to cool, filtered, and washed with water to obtain 1.2 g of the desired product. [ka] In the above formula, one stereoisomer is shown as 1,4-anhydroxylitol, but in Example 1 and Examples 2 and 3 described below, the racemic mixture was used for the investigation.

[0041] The diol compound of Example 1 was analyzed using a nuclear magnetic resonance (NMR) device. 1 H NMR spectra were recorded on a JASCO JMN-ECZN 500 MHz spectrometer. All chemical shifts are reported in parts per million (δ) relative to dimethylformamide. The following abbreviations are used to denote signal patterns: S = singlet, d = doublet, t = triplet, q = quartet, quin = quintet, M = multiplet, and br = broad. 1 HNMR: 3.48-3.52ppm (2H, d), 3.70-3.73ppm (2H, S), 3.88-3.91ppm (2H, q), 3.99-4.03ppm (8H, M), 4.36-4.38 (2H, S), 5.20-5.35 (2H, br)

[0042] [Example 2] A recovery flask reactor was charged with 5.0 g (37.3 mmol) of 1,4-anhydroxylitol, 3.73 g (18.64 mmol) of a 50% aqueous glutaraldehyde solution (acetalizing agent), and 0.35 g (1.86 mmol) of p-toluenesulfonic acid monohydrate. The flask was heated to 120 °C and stirred for 2 hours while removing water from the reaction system using a Dean-Stark apparatus. After completion of the reaction, the reaction solution was analyzed by GC, confirming the formation of the desired diol compound (1-2) in a 70% yield. The reaction solution was allowed to cool, filtered, and the filtrate was subjected to silica gel column chromatography to obtain 1.0 g of the desired product. [ka]

[0043] [Example 3] A recovery flask reactor was charged with 5.0 g (37.3 mmol) of 1,4-anhydroxylitol, 2.5 g (18.64 mmol) of terephthalaldehyde (acetalizing agent), 0.35 g (1.86 mmol) of p-toluenesulfonic acid monohydrate, and 5.0 mL of N-methylpyrrolidone. The flask was heated to 120 °C and stirred for 2 hours while removing water from the reaction system using a Dean-Stark apparatus. The reaction mixture was allowed to cool, filtered, and washed with water to obtain 3.2 g of the target diol compound (1-3). [ka]

[0044] <Experiment 2> The moisturizing test of the diol compound (1-1) of Example 1 was carried out in the following manner. An aqueous solution of 2% by mass (69 mM) of the diol compound (1-1) of Example 1 was prepared as Example 4. Furthermore, aqueous solutions of petrochemically derived glycols, ethylene glycol, 1,4-butanediol, and 1,6-hexanediol, were prepared to a concentration of 69 mM (the same concentration as Example 4) as Comparative Examples 1 to 3. 10 g of each of the aqueous solutions of Example 4 and Comparative Examples 1 to 3 and pure water were placed in a glass vial. These glass vials were left to stand in a constant temperature oven at 60°C for 3 hours. After 3 hours, the mass loss of each solution was measured, and the moisture retention rate of each test solution was calculated as follows: Moisture retention rate (%) = (1 - (mass loss of aqueous solution) / (mass loss of pure water)) x 100

[0045] As a result of the moisture retention test, the mass loss and moisture retention rate of the pure water in the example and comparative examples were as follows: Pure water: mass reduction 1.97g Example 4: Mass loss 1.75 g, moisture content = 11% Comparative Example 1: Mass loss 1.69 g, moisture retention rate = 14% Comparative example 2: mass reduction 1.79g, moisture retention ratio = 9% Comparative Example 3: Mass loss 1.85 g, moisture retention rate = 6% Therefore, it was found that the diol compound of Example 1 has moisturizing properties equivalent to those of glycols generally used in cosmetics. [Industrial Applicability]

[0046] According to the present invention, a novel diol compound can be produced using a compound derived from a bioproduct, a method for producing the same, and a moisturizing composition containing the diol compound. Thus, the diol compound can be used as a moisturizing agent and is industrially applicable.

Claims

1. A diol compound represented by the following formula (1): 【Chemistry 1】 (In the formula, R １ represents a single bond, an alkylene group having 1 to 8 carbon atoms, or an arylene group having 6 to 10 carbon atoms.

2. R １ represents a single bond or an alkylene group having 1 to 3 carbon atoms.

3. R １ The diol compound according to claim 1 , wherein represents a single bond.

4. R １ The diol compound according to claim 1 , wherein represents an alkylene group having 3 carbon atoms.

5. R １ The diol compound according to claim 1 , wherein represents a phenylene group.

6. A method for producing the diol compound according to any one of claims 1 to 5, comprising a step of reacting one or a mixture of compounds represented by the following formula (2) and formula (3) with an acetalizing agent represented by the following formula (4) in the presence of an acid catalyst: 【Chemistry 2】 (In the formula, R １ represents a single bond, an alkylene group having 1 to 8 carbon atoms, or an arylene group having 6 to 10 carbon atoms.

7. The method according to claim 6, wherein the reaction step comprises a step of carrying out the reaction at 70 to 150°C while removing water present in the reaction system.

8. 7. The process of claim 6, wherein the acid catalyst is selected from the group consisting of sulfuric acid, alkylsulfonic acid, arylsulfonic acid, hydrochloric acid, nitric acid, and combinations thereof.

9. A moisturizing composition comprising the diol compound according to any one of claims 1 to 5.

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