JP5601789B2 - Carbohydrate compounds - Google Patents

Description

  The present invention relates to a novel carbohydrate compound, and relates to a carbohydrate compound having a sugar chain and a hydroxyl group as adjacent substituents in the molecule.

  A sugar-type surfactant in which a saccharide such as glucose or maltose and an alkyl group are glycoside-bonded exhibits excellent interface characteristics at a low concentration, has high foaming properties, and is widely used as a cleaning agent. In addition, alkyl N-methylglucamide type surfactants exhibit the same characteristics as the above surfactants, and have high detergency and emulsification ability. On the other hand, in food applications, there are highly practical surfactants that can control a wide range of HLB, such as sucrose fatty acid ester type, and have excellent biocompatibility and biodegradability. Among these, compounds obtained by reacting a sugar lactone or sugar carboxylic acid with a primary or secondary amine such as alkylaldamide type (Patent Document 1, Non-Patent Document 1) are known. In contrast to the single-chain surfactants described above, recently, surfactants containing two-chain two-hydrophilic groups known as gemini-type surfactants have been studied, and compared with single-chain surfactants. , Compounds with various structures that show much higher surface activity (Patent Document 2, Patent Document 3, Non-Patent Document 2), different types of hydrophilic groups, and structures with asymmetric alkyl chain length Gemini surfactants having asymmetric structures of hydrophilic groups and alkyl chain lengths have also been studied (Non-patent Document 3).

Japanese Patent Laid-Open No. 05-221946 Special table 2003-509571 gazette JP 2005-82555 A

L. Syper et al, Progress in Colloid and Polymer Science 110 (1998) 199-203. R. Zana, J. et al. Xia (Eds.), Gemini Surfactants, Synthesis, Interfacial and Solution-Phase Behavior, and Applications, Marcel Dekker, New York, 2003. Xia (Eds.), Gemini Surfactants, Synthesis, Interfacial and Solution-Phase Behavior, and Applications. E. Alami and K.M. Holberg, Advances in Colloid and Interface Science 100-102 (2003) 13-46

  However, when considering the molecular design of this 2-chain 2-hydrophilic group-containing surfactant on the premise of industrial implementation, it is not always easy to connect two molecules or introduce hydrophobic groups or polar groups, and the molecular design is limited. In many cases, the use of relatively expensive raw materials is unavoidable. In fact, there are no two-chain 2-hydrophilic group-containing surfactants having asymmetric hydrophobic groups. As a result of diligent research to solve the above-mentioned problems, the present inventors have found that a carbohydrate compound having a hydroxyl group adjacent to a sugar chain is useful for use as a two-chain, two-hydrophilic group-containing surfactant, The present invention has been completed.

  That is, the gist of the present invention is a carbohydrate compound represented by the following general formula (1) or (2).

However, in the above general formulas (1) and (2), R ₁ is an alkyl group having 1 or more carbon atoms, R ₂ is an alkylene group, and R ₁ —CH—CH—R ₂ — has 9 to 25 carbon atoms. Hydrocarbon group, R ₃ is hydrogen or methyl group, Z is allonolactone, altronolactone, gluconolactone, mannonolactone, gulonolactone, idnolactone, galactonolactone, talonolactone, lactobionolactone, maltobionolactone, cellobi A sugar lactone residue selected from onolactone, maltotrionolactone, panonolactone, and isomaltrionolactone (a sugar residue excluding the carbonyl group (C = O) of an aminolysed sugar), or alloic acid, altronic acid, gluconic acid , Mannonic acid, gulonic acid, idonic acid, galactonic acid, talonic acid, aralic acid, altaric acid, gluca Sugar carboxylic acid residues selected from oxalic acid, mannaric acid, idalic acid, galactaric acid, lactobionic acid, maltobionic acid, cellobionic acid, maltotrionic acid, panonic acid, isomaltrionic acid (dehydrated condensed carbonyl group (C Sugar residue excluding ═O) , C _n H _{2n + 1} is a linear alkyl group, and n is an integer of 1 to 20.

  The carbohydrate compound of the present invention has a higher surface activity than conventional one-chain / one-hydrophilic group-containing surfactants. For example, when used as a cleaning agent or an emulsifier, a small amount of addition is useful. The carbohydrate compound of the present invention can be used as a compounding base for personal care products such as cosmetics that come into direct contact with the human body because of low irritation to the skin. Further, since the carbohydrate compound of the present invention is a two-chain type and similar to a ceramide structure, it has a high skin permeability, enters into intercellular lipids, and prevents skin roughness and the like. It can be expected to have a moisture retention function, stabilize antibodies and enzymes, and can be used as a next-generation biochemical surfactant that does not affect living cells. Further, the carbohydrate compound of the present invention can be further functionalized by introducing a polyoxyethylene group which is a hydrophilic group, a sulfonate group, a phosphate group or the like into the remaining hydroxyl group or the hydroxyl group of the sugar. It is also possible to synthesize saccharide compounds with increased levels and use them as raw materials.

  The saccharide compound of the present invention represented by the general formula (1) or (2) is a reaction between an unsaturated fatty acid having 10 double carbon atoms having one double bond and an alkylamine having 1 to 20 carbon atoms. After the epoxidation of the double bond portion of the unsaturated fatty acid alkylamide represented by the following general formula (3) obtained by the following formula, the amino group and the hydroxyl group are introduced adjacent to each other, which is represented by the general formula (4) or (5) It can be obtained as a mixture of (1) and (2) by the reaction of the aminohydroxy fatty acid alkylamide and sugar lactone or sugar carboxylic acid.

  Examples of the unsaturated fatty acid having 10 double carbon atoms that constitutes the unsaturated fatty acid alkylamide represented by the general formula (3) include decenoic acid (C′10) such as caproleic acid, and undecene. Acid (C'11), dodecenoic acid (C'12) such as lauroleic acid, tridecenoic acid (C'13), tetradecenoic acid (C'14) such as myristoleic acid, pentadecenoic acid (C'15), palmitoleic acid Hexadecenoic acid (C′16), heptadecenoic acid (C′17), octadecenoic acid (C′18) such as elaidic acid, nonadecenoic acid (C′19), eicosenoic acid (C′20) such as gondonoic acid, Heneicosenoic acid (C'21), docosenoic acid (C'22) such as erucic acid, tricosenoic acid (C'23), tetracosenoic acid (C'24) such as ceracoleic acid, pentacosenoic acid C'25), although such hexacosenoic acid (C'26) can be mentioned, decenoic acid, octadecenoic acid, docosenoic acid. Examples of the alkylamine having 1 to 20 carbon atoms include methylamine, ethylamine, propylamine, isopropylamine, butylamine, pentylamine, heptylamine, hexylamine, octylamine, decylamine, dodecylamine, octadecylamine, and eicosylamine. Aliphatic primary amines are mentioned, but butylamine, octylamine, decylamine, dodecylamine and octadecylamine are preferred. In the unsaturated fatty acid alkylamide represented by the general formula (3), the total number of carbon atoms of the unsaturated fatty acid and the aliphatic primary amine is 11 to 46, preferably 16 to 32, particularly preferably. The total number of carbon atoms is 20 to 28.

  The aminohydroxy fatty acid alkylamide represented by the general formulas (4) and (5) is an unsaturated fatty acid alkylamide represented by the general formula (3), m-chloroperbenzoic acid, hydrogen peroxide and formic acid, hydrogen peroxide. After epoxidizing the double bond part by reacting with tungstic acid etc., the epoxy ring is opened by reacting with ammonia or methylamine, the hydroxyl group adjacent to the opened part of the epoxy ring, the amino group and Can be obtained.

  The saccharide compounds of the present invention represented by the general formulas (1) and (2) are prepared by aminolysis of an aminohydroxy fatty acid alkylamide represented by the general formulas (4) and (5) and a sugar lactone, or a sugar carboxylic acid. It can be obtained by dehydration condensation with an acid. Therefore, the sugar chain Z in the general formulas (1) and (2) is a sugar residue excluding the carbonyl group (C═O) of the sugar subjected to aminolysis or dehydration condensation.

The sugar lactone, monosaccharides lactone is monosaccharide, disaccharide lactone is oligosaccharides, trisaccharides lacto down, and examples of the sugar carboxylic acid, monosaccharide aldonic acid which is a monosaccharide, a monosaccharide aldaric, O Examples include disaccharide aldonic acid and trisaccharide aldonic acid which are ligosaccharides.
As a single sugar lactone, Aronorakuton, alto Lono lactone, gluconolactone, Man Nono lactone, gulonolactone, Idonorakuton, galactosamine concert lactone, Taronorakuto down, but also as a disaccharide lactone, lactobionolactone, maltodextrin Biot gluconolactone, Serobionorakuto emissions is, as the trisaccharide lactone, maltotriosyl gluconolactone, Panonorakuton, isobutanol maltotriosyl Bruno lacto down.
The monosaccharide aldonic acid, Aaron acid, altronic acid, gluconic acid, mannonic acid, gulonic acid, idonic acid, galactonic acid, Talon acid, the monosaccharide aldaric, Aral acid, Arutoraru acid, glucaric acid, mannaric acid , Idar acid, galactaric acid, as the disaccharide aldonic acid, lactobionic acid, maltobionic acid, Serobion acid, as the trisaccharide aldonic acid, maltodextrin trione acid, Pannon acid, isomalt trione acid. Among these, monosaccharide lactone gluconolactone, galactonolactone, disaccharide lactone lactobionolactone, maltobionolactone, disaccharide aldonic acid lactobionic acid, maltobionic acid, trisaccharide lactone maltotrionolactone, The trisaccharide aldonic acid maltotrionic acid is preferred.

  The reaction shown in the following chemical formula 6 shows a case where 9-octadecenoic acid alkylamide is used as a starting material as a more specific example of producing the carbohydrate compound of the present invention. The 9-octadecenoic acid alkylamide is prepared by reacting, for example, 9-octadecenoic acid with 1 to 10 equivalents of oxalyl chloride or thionyl chloride at 0 to 30 ° C. with stirring for 1 to 10 hours to obtain excess oxalyl chloride or thionyl. After removing the chloride, a base such as pyridine or triethylamine is used, and an organic solvent such as tetrahydrofuran (THF) is added dropwise with 1 to 5 equivalents of an alkylamine, followed by reaction at 10 to 50 ° C. for 1 to 10 hours. Can be obtained.

In the reaction shown in Chemical Formula 6, in Step 1, 9-octadecenoic acid alkylamide is epoxidized with a peracid such as m-chloroperbenzoic acid (mCPBA) in a chlorinated organic solvent such as chloroform. The process of obtaining 10-epoxy octadecanoic acid alkylamide is shown. Step 2 is an aminohydroxyoctadecanoic acid obtained by opening the epoxy ring of 9,10-epoxyoctadecanoic acid alkylamide and introducing a hydroxyl group at the 9-position (or 10-position) and an amino group at the 10-position (or 9-position). The process of obtaining an alkylamide is shown. Aminohydroxyoctadecanoic acid alkylamide is prepared by dissolving 9,10-epoxyoctadecanoic acid alkylamide in an organic solvent such as THF, aqueous ammonia or a methylamine (R ₃ NH ₂ ) aqueous solution and, if necessary, lithium perchlorate (LiClO ₄ ). And is allowed to react at 100 to 180 ° C. for 5 to 50 hours, preferably 10 to 20 hours. Step 3 shows the step of obtaining the carbohydrate compound of the present invention from aminohydroxyoctadecanoic acid alkylamide. The carbohydrate compound of the present invention comprises aminohydroxyoctadecanoic acid alkylamide and 1 to 5 equivalents of sugar lactone or sugar carboxylic acid in a polar solvent such as methanol, ethanol, n-propanol, or 2-propanol. It can be obtained by reacting at 100 ° C., preferably 20 to 80 ° C. with stirring for 1 to 72 hours. The obtained saccharide compound can be purified by recrystallization using a solvent such as ethyl acetate or column chromatography using silica gel as a stationary phase and chloroform / methanol / water mixed solvent as a mobile phase.

  EXAMPLES Next, although an Example is given and this invention is demonstrated still in detail, this invention is not limited only to these Examples.

Example 1
1) Amidation reaction 150 g (1.17 mol) of oxalyl chloride was added dropwise to 80.1 g (0.285 mol) of 9-octadecenoic acid, and after stirring for 2 hours at room temperature, unreacted oxalyl chloride was reduced in pressure from the reaction solution. Distilled off to give 9-octadecenoic acid chloride. To this was added 660 ml of tetrahydrofuran and 22.8 g (1.17 mol) of pyridine, and the mixture was stirred under ice-cooling, and 45.6 g (0.288 mol) of n-decylamine was added dropwise. The reaction was further carried out at room temperature for 3 hours. The precipitated crystals were removed by suction filtration, the filtrate was distilled off under reduced pressure, 600 ml of diethyl ether was added to the residue of the filtrate and dissolved, and washed twice with 5% hydrochloric acid and once with water. After diethyl ether was distilled off, recrystallization was performed twice with ethyl acetate to obtain 84 g (yield 70%) of 9-octadecenoic acid decylamide as a white solid.

2) Epoxidation reaction 1080 ml of chloroform was added to 50.7 g (0.12 mol) of 9-octadecenoic acid decylamide and dissolved by stirring. On the other hand, 39.3 g (0.228 mol) of m-chloroperbenzoic acid was dissolved in 600 ml of chloroform, and this was added dropwise to the 9-octadecenoic acid decylamide solution at room temperature over 1 hour. After the dropping, the mixture was stirred for 12 hours under reflux. The reaction solution is cooled to room temperature, washed with an aqueous sodium hydrogen carbonate solution three times, magnesium sulfate is added and the solution is dried. The solvent is then distilled off under reduced pressure, and a white solid 9,10-epoxyoctadecanoic acid decylamide is obtained. 49.5 g (yield 94%) was obtained.

3) Aminoalcoholization reaction 30 ml of tetrahydrofuran was added to 10 g (0.0228 mol) of 9,10-epoxyoctadecanoic acid decylamide and dissolved by heating. The solution was transferred to an autoclave, 2.4 g (0.0228 mol) of lithium perchlorate was added, 30 g (0.5 mol) of 28% aqueous ammonia was added, and the mixture was immediately sealed. The autoclave was placed in an oil bath and stirred at a set temperature of 150 ° C. for 18 hours. After the reaction, the mixture was allowed to cool, and the reaction solution was transferred to a beaker and cooled with ice to precipitate a white solid. After suction filtration, the solid was washed with water. The obtained solid was dried under reduced pressure, recrystallized three times with ethyl acetate, and a mixture of 9-amino-10-hydroxyoctadecanoic acid decylamide and 10-amino-9-hydroxyoctadecanoic acid decylamide (hereinafter simply referred to as aminohydroxyoctadecane). Acid decylamide) 7.3g (yield 70%) was obtained.

4) Sugar amidation 125 ml of dehydrated methanol was added to D-(+)-glucono-1,5-lactone (2.7 g, 0.0152 mol) and stirred at room temperature until dissolved, and then the aminohydroxyoctadecanoic acid was added. Decylamide (5.8 g, 0.0126 mol) was added, and the mixture was stirred at room temperature for 44 hours. Thereafter, refluxing was performed for 3 hours.
After confirming the disappearance of aminohydroxyoctadecanoic acid decylamide by thin layer chromatography (TLC), methanol was distilled off under reduced pressure, chloroform was added and suction filtered to remove excess sugar, and the filtrate was distilled off under reduced pressure. An ointment-like solid was obtained. By repeating recrystallization with ethyl acetate, 5.0 g (yield 62%) of a white solid was obtained.

The structure of the obtained white solid was confirmed by FT-IR (KBr method), ¹ H-NMR, and ESI-MS, and the purity was confirmed by elemental analysis.

FT-IR results:
Absorption of 3323 cm ⁻¹ (O—H, st), 1642 cm ⁻¹ (C═O, st), 1555 cm ⁻¹ (N—H, δ) was observed.
¹ H-NMR (500 MHz, CD ₃ OD) results:
δ 0.90 (t, 6H), 1.29-1.58 (m, 42H), 2.15 (t, 2H), 3.15 (t, 2H), 3.57-3.82 (m, 6H), 4.10-4.11 (m, 1H), 4.24-4.25 (m, 1H).
ESI-MS results:
[M + Na] ⁺ = 6555.4870 (calc.6555.4873)
Elemental analysis _{(C 34 H 68 N 2 O} 8):
Actual value (%) C: 64.46%, H: 10.56%, N: 4.13%
Calculated value (%) C: 64.52%, H: 10.83%, N: 4.43%

  From these results, it was confirmed that the mixture was a compound having a structure represented by the following general formula (1a) or (1a ′).

Example 2
Steps 1) and 2) were the same as in Example 1. 3) Aminoalcoholation reaction 40 ml of tetrahydrofuran was added to 12 g (0.0274 mol) of 9,10-epoxyoctadecanoic acid decylamide and dissolved by heating. The solution was transferred to an autoclave, 2.9 g (0.0274 mol) of lithium perchlorate was added, 42.7 g (0.55 mol) of a 40% aqueous solution of methylamine was added, and the mixture was immediately sealed. The autoclave was placed in an oil bath and stirred at a set temperature of 170 ° C. for 15 hours. After the reaction, the mixture was allowed to cool, and the reaction solution was transferred to a beaker and cooled with ice to precipitate a white solid. After suction filtration, the solid was washed with water. The obtained solid was dried under reduced pressure, recrystallized three times with ethyl acetate-hexane, and then a mixture of 9-methylamino-10-hydroxyoctadecanoic acid decylamide and 10-methylamino-9-hydroxydecyloctadecanoic acid decylamide (hereinafter referred to as “a”). 7.7 g (yield 60%) of mere methylaminohydroxyoctadecanoic acid decylamide).

4) Sugar amidation 125 ml of dehydrated methanol was added to D-(+)-glucono-1,5-lactone (3.4 g, 0.0192 mol), stirred at room temperature until dissolved, and then methylaminohydroxyoctadecanoic acid 6 g (0.0128 mol) of decylamide was added and stirred at room temperature for 60 hours.
After confirming the disappearance of methylaminohydroxyoctadecanoic acid decylamide by TLC, methanol was distilled off under reduced pressure to remove excess sugar, ethanol was added to the viscous body, the precipitated crystals were removed, suction filtered, and the filtrate was distilled under reduced pressure. On leaving, an ointment-like solid was obtained. Column chromatography purification was performed using chloroform, methanol, and water to obtain 2.6 g (yield 32%) of a viscous body.

The structure of the viscous body was confirmed by FT-IR (KBr method), ¹ H-NMR, and ESI-MS, and the purity was confirmed by elemental analysis.

FT-IR results:
Absorption of 3325 cm ⁻¹ (O—H, st), 1643 cm ⁻¹ (C═O, st) was observed.
¹ H-NMR (500 MHz, CD ₃ OD) results:
δ 0.90 (t, 6H), 1.29-1.58 (m, 42H), 2.15 (t, 2H), 2.85 (s, 3H), 3.15 (t, 2H) The peaks of 55-3.80 (m, 6H), 4.10-4.11 (m, 1H), 4.24-4.25 (m, 1H) were observed.
ESI-MS results:
[M + Na] ⁺ = 6699.4998 (calc. 669.5029)
Elemental analysis _{(C 35 H 70 N 2 O} 8):
Actual value (%) C: 64.98%, H: 10.91%, N: 4.33%
Calculated value (%) C: 64.90%, H: 11.02%, N: 4.27%

  From these results, it was confirmed that the mixture was a compound having a structure represented by the following general formula (2a) or (2a ′).

Example 3
Steps 1) to 3) were the same as in Example 1. 4) Sugar amidation 200 ml of dehydrated methanol was added to 4.3 g (0.012 mol) of lactobionic acid and stirred. To this was added 4.7 g (0.0104 mol) of aminohydroxyoctadecanoic acid decylamide, and the mixture was stirred at room temperature for 64 hours, and then refluxed for 3 hours. The disappearance of aminohydroxyoctadecanoic acid decylamide was confirmed by TLC. When methanol was distilled off under reduced pressure, a glossy white solid was obtained. This solid was purified by column chromatography with chloroform / methanol / water to obtain 5 g of white solid (yield 62%).

The structure of the white solid was confirmed by FT-IR (KBr method), ¹ H-NMR, and ESI-MS, and the purity was confirmed by elemental analysis.

FT-IR results:
Absorption at 3388 cm ⁻¹ (O—H, st), 1644 cm ⁻¹ (C═O, st), 1545 cm ⁻¹ (N—H, δ) was observed.
¹ H-NMR (500 MHz, CD ₃ OD) results:
δ 0.90 (t, 6H), 1.29-1.60 (m, 42H), 2.16 (t, 2H), 3.14 (t, 2H) 3.47-3.94 (m, 12H) ), 4.22-4.23 (m, 1H), 4.36 (s, 1H), 4.48-4.49 (d, 1H).
ESI-MS results:
[M + Na] ⁺ = 817.5386 (calc. 817.5402)
Elemental analysis _{(C 40 H 78 N 2 O} 13) Result:
Actual value (%) C: 60.3%, H: 9.92%, N: 3.37%
Calculated value (%) C: 60.43%, H: 9.89%, N: 3.52%

  From these results, it was confirmed that the mixture was a compound having a structure represented by the following general formula (3a) or (3a ′).

Example 4
Steps 1) to 3) are the same as those in Example 2. 4) Sugar amidation 125 ml of dehydrated methanol was added to 6.9 g (0.0192 mol) of lactobionic acid, and the mixture was stirred at room temperature until dissolved. 6 g (0.0128 mol) of octadecanoic acid decylamide was added, and the mixture was stirred at room temperature for 70 hours.
After confirming the disappearance of methylaminohydroxyoctadecanoic acid decylamide by TLC, methanol was distilled off under reduced pressure, ethanol was added to remove excess sugar, the precipitated crystals were removed, suction filtered, and the filtrate was distilled off under reduced pressure. The obtained solid was subjected to column chromatography purification using chloroform / methanol / water to obtain 2.5 g of white solid (yield 24%).

The structure of the obtained white solid was confirmed by FT-IR (KBr method), ¹ H-NMR, and ESI-MS, and the purity was confirmed by elemental analysis.

FT-IR results:
Absorption of 3330 cm ⁻¹ (O—H, st), 1644 cm ⁻¹ (C═O, st) was observed.
¹ H-NMR (500 MHz, CD ₃ OD) results:
δ 0.90 (t, 6H), 1.29-1.60 (m, 42H), 2.16 (t, 2H), 2.87 (s, 3H), 3.15 (t, 2H) Peaks of 47-3.94 (m, 12H), 4.22-4.23 (m, 1H), 4.36 (s, 1H), 4.48-4.49 (d, 1H) are observed. It was.
ESI-MS result: [M + Na] ⁺ = 831.5591 (calc. 831.5557)
Elemental analysis _{(C 41 H 80 N 2 O} 13) Result:
Actual value (%) C: 61.00%, H: 9.94%, N: 3.50%
Calculated value (%) C: 60.86%, H: 9.97%, N: 3.46%

  From these results, it was confirmed that the mixture was a compound having a structure represented by the following general formula (4a) or (4a ′).

Example 5
1) Amidation reaction 52.7 g (0.443 mol) of thionyl chloride was added dropwise to 100 g (0.295 mol) of 13-docosenoic acid, and after stirring at room temperature for 3 hours, unreacted thionyl chloride was reduced in pressure from the reaction solution. Distilled off to obtain 13-docosenoic acid chloride. To this was added 750 ml of tetrahydrofuran and 35.0 g (0.443 mol) of pyridine, and the mixture was stirred with ice cooling. The reaction was further carried out at room temperature for 3 hours. The precipitated crystals were removed by suction filtration, the filtrate was distilled off under reduced pressure, 500 ml of diethyl ether was added to the residue of the filtrate and dissolved, and washed twice with 5% hydrochloric acid and once with water. After diethyl ether was distilled off, recrystallization was performed twice with ethyl acetate to obtain 87.1 g (yield 75%) of 13-docosenoic acid butyramide as a white solid.

2) Epoxidation reaction 600 ml of chloroform was added to 13-docosenoic acid butyramide (60 g, 0.152 mol), and dissolved by stirring. On the other hand, 49.9 g (0.289 mol) of m-chloroperbenzoic acid was dissolved in 400 ml of chloroform, and this was added dropwise to the 13-docosenoic acid butyramide solution at room temperature over 1 hour. After the dropping, the mixture was stirred for 12 hours under reflux. After cooling the reaction solution to room temperature, washing with an aqueous sodium hydrogen carbonate solution was performed three times, magnesium sulfate was added, the solution was dried, the solvent was distilled off under reduced pressure, and white solid 13,14-epoxydosanoic acid butyramide 57 .3 g (yield 92%) was obtained.

3) Aminoalcoholization reaction 30 ml of tetrahydrofuran was added to 10 g (0.0244 mol) of 13,14-epoxydocosanoic acid butyramide and dissolved by heating. The solution was transferred to an autoclave, 2.6 g (0.0244 mol) of lithium perchlorate was added, 30 g (0.5 mol) of 28% aqueous ammonia was added, and the mixture was immediately sealed. The autoclave was placed in an oil bath and stirred at a set temperature of 150 ° C. for 18 hours. After the reaction, the mixture was allowed to cool, and the reaction solution was transferred to a beaker and cooled with ice to precipitate a white solid. After suction filtration, the solid was washed with water. The obtained solid was dried under reduced pressure, recrystallized three times with ethyl acetate, and a mixture of 13-amino-14-hydroxydocosanoic acid butyramide and 14-amino-13-hydroxydocosanoic acid butyramide (hereinafter simply referred to as amino). 7.1 g (68% yield) of hydroxydocosanoic acid butyramide) was obtained.

4) Sugar amidation After adding 150 ml of dehydrated methanol to 3.0 g (0.0169 mol) of D-(+)-glucono-1,5-lactone and stirring at room temperature until dissolved, the aminohydroxy docosanoic acid was added. 6 g (0.0141 mol) of butyramide was added and stirred at room temperature for 44 hours. Thereafter, refluxing was performed for 3 hours.
After confirming the disappearance of aminohydroxydocosanoic acid butyramide by TLC, methanol was distilled off under reduced pressure to remove excess sugar, chloroform was added to the viscous body, suction filtered, and the filtrate was distilled off under reduced pressure. A solid was obtained. By repeating recrystallization with ethyl acetate, 5.5 g (yield 65%) of a white solid was obtained.

The structure of the white solid was subjected to FT-IR (KBr method), ¹ H-NMR, ESI-MS, and the purity was confirmed by elemental analysis.

FT-IR results:
Absorption was observed at 3322 cm ⁻¹ (O—H, st), 1643 cm ⁻¹ (C═O, st), and 1554 cm ⁻¹ (N—H, δ).
¹ H-NMR (500 MHz, CD ₃ OD) results:
δ 0.88-0.95 (m, 6H), 1.31-1.64 (m, 38H), 2.15 (t, 2H), 3.15 (t, 2H), 3.56-3. Peaks were observed at 81 (m, 6H), 4.10-4.11 (m, 1H), 4.24-4.26 (m, 1H).
ESI-MS results:
[M + Na] ⁺ = 627.44552 (calc. 627.4560)
Elemental analysis (C ₃₂ H ₆₄ N ₂ O ₈ ) results:
Actual value (%) C: 63.48%, H: 10.76%, N: 4.55%
Calculated value (%) C: 63.54%, H: 10.66%, N: 4.63%

  From these results, it was confirmed that the mixture was a compound having a structure represented by the following general formula (1b) or (1b ′).

Example 6
The steps 1) to 3) were the same as in Example 5. 4) Sugar amidation 200 ml of dehydrated methanol was added to 4.3 g (0.012 mol) of lactobionic acid and stirred. To this was added 4.4 g (0.0104 mol) of aminohydroxydocosanoic acid butyramide, and the mixture was stirred at room temperature for 64 hours, and then refluxed for 3 hours.
After confirming disappearance of aminohydroxydocosanoic acid butyramide by TLC, methanol was distilled off under reduced pressure to obtain a glossy white solid. This solid was purified by column chromatography with chloroform / methanol / water to obtain 4.8 g (yield 60%) of a white solid.

The structure of the obtained white solid was confirmed by FT-IR (KBr method), ¹ H-NMR, and ESI-MS, and the purity was confirmed by elemental analysis.

FT-IR results:
Absorption was observed at 3386 cm ⁻¹ (O—H, st), 1645 cm ⁻¹ (C═O, st), and 1544 cm ⁻¹ (N—H, δ).
¹ H-NMR (500 MHz, CD ₃ OD) results:
δ 0.88-0.95 (t, 6H), 1.31-1.64 (m, 38H), 2.16 (t, 2H), 3.14 (t, 2H), 3.47-3. Peaks were observed at 94 (m, 12H), 4.22-4.23 (m, 1H), 4.36 (s, 1H), 4.48-4.49 (d, 1H).
ESI-MS results:
[M + Na] ⁺ = 789.5102 (calc. 789.5088)
Elemental analysis (C ₃₈ H ₇₄ N ₂ O ₁₃ ) results:
Actual value (%) C: 59.48%, H: 9.71%, N: 3.63%
Calculated value (%) C: 59.51%, H: 9.72%, N: 3.65%

  From these results, it was confirmed that the mixture was a compound having a structure represented by the following general formula (2b) or (2b ′).

Example 7
The solubility test with respect to the various solvent of the carbohydrate compound obtained in Examples 1-6 was evaluated.
0.01 g of a saccharide compound was added to 9.99 g of the solvent, and the mixture was stirred at 25 ° C. for 3 hours, and then visually determined based on the following criteria. The results are shown in Table 1.

Evaluation criteria for solvent solubility ○: Soluble ×: Insoluble, swelling

  The saccharide compounds of Example 1 and Example 5 were insoluble in water at 25 ° C., but were soluble in alcohol solvents such as ethanol and 2-propanol, and applied to various forms of cosmetics. Formulation is possible.

Example 8
Among the saccharide compounds obtained in Examples 1 to 6, the saccharide compounds of Example 2, Example 3, Example 4, and Example 6 that showed solubility in water and the following chemical formulas 13 (Comparative) Example 1), surface tension was measured at 25 ° C. by the Wilhelmy method using a single-chain surfactant represented by Chemical Formula 14 (Comparative Example 2), and the surface at a critical micelle concentration (cmc) and cmc The tension (γ _cmc ) was determined. The results are shown in Table 2.

The saccharide compounds of Examples 2, 3, 4, and 6 show a critical micelle concentration (cmc) that is about 1/10 to 1/100 lower than that of the compound of the comparative example, and surface tension (γ _cmc in cmc). ) Was also lower than that of the compound of the comparative example, and showed a high surface tension reducing ability. From these results, when used as a cleaning agent or an emulsifier, a small amount can be added compared to conventional surfactants containing one chain and one hydrophilic group. It can be used as a next-generation biochemical surfactant that can stabilize water.

Example 9
Skin irritation was evaluated using the carbohydrate compounds obtained in Examples 1-6. A 1 wt% ethanol solution of each carbohydrate compound and glycerin mixed at a weight ratio of 1: 1 were used as test samples. After applying the test sample to the inner side of the upper arm of 10 panels and performing an occlusion patch for 24 hours, whether or not there was any problem in the skin condition (redness, tingling, rough skin) was determined as a control sample (ethanol And the same weight mixture of glycerin), each panel was evaluated by the following 0 to 3 points, and skin irritation was evaluated according to the following criteria based on the evaluation points. The results are shown in Table 3.
Evaluation of skin irritation 0 point: When no abnormality was observed.
1 point: When a slight redness is observed.
2 points: When a problem is recognized in 2 or more items among redness, tingling and rough skin.
3 points: Remarkable abnormalities such as papules are observed.
Evaluation criteria for skin irritation ○: Average score of 10 panelists: less than 0.2 Δ: Average score of 10 panelists: 0.2 or more and less than 0.3 ×: Evaluation score of 10 panelists Average value: 0.3 or more

  In any of the carbohydrate compounds obtained in Examples 1 to 6, the evaluation of skin irritation is ○, skin irritation is not recognized, and since it is highly safe, personal care that directly contacts the human body It can be used as a compounding base for products.

Claims (1)

A carbohydrate compound represented by the following general formula (1) or (2).

However, in the above general formulas (1) and (2), R ₁ is an alkyl group having 1 or more carbon atoms, R ₂ is an alkylene group, and R ₁ —CH—CH—R ₂ — has 9 to 25 carbon atoms. Hydrocarbon group, R ₃ is hydrogen or methyl group, Z is allonolactone, altronolactone, gluconolactone, mannonolactone, gulonolactone, idnolactone, galactonolactone, talonolactone, lactobionolactone, maltobionolactone, cellobi A sugar lactone residue selected from onolactone, maltotrionolactone, panonolactone, and isomalttrionolactone (a sugar residue excluding the carbonyl group (C = O) of an aminolysed sugar), or aroic acid, altronic acid, and gluconic acid , Mannonic acid, gulonic acid, idonic acid, galactonic acid, talonic acid, aralic acid, altaric acid, gluca Sugar carboxylic acid residues selected from oxalic acid, mannaric acid, idalic acid, galactaric acid, lactobionic acid, maltobionic acid, cellobionic acid, maltotrionic acid, panonic acid, isomaltrionic acid (dehydrated condensed carbonyl group (C Sugar residue excluding ═O) , C _n H _{2n + 1} is a linear alkyl group, and n is an integer of 1 to 20.