CN111187312A - Simple preparation method of alkyl maltoside surfactant - Google Patents

Simple preparation method of alkyl maltoside surfactant Download PDF

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CN111187312A
CN111187312A CN202010029568.1A CN202010029568A CN111187312A CN 111187312 A CN111187312 A CN 111187312A CN 202010029568 A CN202010029568 A CN 202010029568A CN 111187312 A CN111187312 A CN 111187312A
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陈朗秋
张静
陈凯奋
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Xiangtan University
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Abstract

The invention belongs to the technical field of fine chemicals, and particularly discloses a preparation method of glycosyl nonionic surfactant alkyl- β -D-maltoside.

Description

Simple preparation method of alkyl maltoside surfactant
Technical Field
The invention relates to the field of fine chemicals, in particular to a method for preparing alkyl maltoside.
Technical Field
The alkyl glycoside is prepared from carbohydrate and natural fatty alcohol as raw materials (ACS Catalysis,2017,7(4), 2990-. Relevant production units such as Shanghai Kai chemical industry Co., Ltd utilize the advantages of the alkyl glycoside raw material such as being renewable, mild and good in degradability, and the alkyl glycoside is applied to the formulas of cosmetics and detergents.
With the development of research, on the basis of the existing alkyl glycoside development, it is necessary to further design and synthesize anomeric pure alkyl glycoside to develop the application value (j. org. chem.,2019,84(17), 10606-10614). The existing research shows that the anomeric pure 1, 2-trans alkyl maltoside has excellent performance (anal. chem.,2019,91(20),13071-13079) and potential application value (Liquan, etc. lipopeptide self-assembly property and the compound research of the lipopeptide and dodecyl maltoside, chemical and biological engineering, 2017, 34 (10): 16-19). Therefore, it is necessary to develop a synthetic process thereof.
The starch from natural sources can be subjected to controlled hydrolysis to obtain a large amount of cheap maltose products, and the maltose products are widely applied to cakes, medicaments and the like due to the characteristics of good water solubility, heat resistance, low viscosity and the like. Meanwhile, the method can also be used for preparing downstream products such as glycosides with practical values (J.Am.chem.Soc., 2019,141(50), 19677-19687). However, with the enhancement of environmental awareness of people, people are urgently required to reduce the usage amount of toxic and harmful substances and the pressure of reducing the production cost (Carbohydrate Research, 2010, 345, 2438-.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and adopts a short synthetic route to prepare the 1, 2-trans-isocephalic pure alkyl- β -D-maltoside, which is characterized by short synthetic route, low price and easy obtaining of raw materials, simple and convenient operation, green and environmental protection, and simultaneously, the obtained alkyl- β -D-maltoside contains a plurality of hydrophilic hydroxyl groups, has good hydrophilicity and water solubility, strong surface activity and good application value.
The glucoside prepared by the invention is 1, 2-trans-isocephalic pure alkyl- β -D-maltoside, and the structure of the glucoside is shown as the formula (I):
Figure BDA0002363799500000011
in the formula (I), the hydrocarbon group (R) is any one of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-pentadecyl and n-hexadecyl; the glycosyl is maltose glycosyl.
The invention adopts a chemical synthesis method, takes maltose as a raw material, obtains 1, 2-trans alkyl- β -D-maltoside through acylation protection, condensation with fatty alcohol and deacylation protection, and has the corresponding reaction formula as follows:
Figure BDA0002363799500000021
the invention provides a preparation method of alkyl- β -D-maltoside, which is characterized by comprising the following steps:
(1) in the presence of a catalyst, carrying out acylation reaction on maltose and a protective agent to obtain acyl-protected D-maltose (octa-O-acetyl-D-maltose); the protective agent used comprises at least one of acetic anhydride, propionic anhydride, benzoic anhydride, acetyl chloride, propionyl chloride and benzoyl chloride; when the acyl protective agent is acyl chloride, the corresponding catalyst is any one of pyridine and triethylamine; when the acyl protective agent is acid anhydride, the corresponding catalyst is anhydrous sodium salt corresponding to the acid anhydride, preferably, the protective agent is acetic anhydride, and the corresponding preferred catalyst is anhydrous sodium acetate; when acetic anhydride is adopted as the acylating reagent, the temperature is controlled to be between 80 and 140 ℃, preferably between 90 and 130 ℃, and more preferably between 110 and 120 ℃; the maltose is as follows: a protective agent: the molar ratio of the catalyst is 1:8-20:0.3-1.2, preferably 1:10-18:0.5-1.2, more preferably 1:10-17: 0.5-1.1.
(2) Condensing the acyl-protected D-maltose obtained in the step (1) with fatty alcohol in the presence of a catalyst to obtain alkyl-2, 3,6,2 ', 3', 4 ', 6' -hepta-O-acyl- β -D-maltoside, wherein in the step, the fatty alcohol comprises methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol,Any one of n-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol and n-hexadecanol; the catalyst for the condensation reaction may include boron trifluoride diethyl etherate (BF)3·Et2O), trimethylsilyl trifluoromethanesulfonate (TMSOTf) and tin tetrachloride, preferably boron trifluoride diethyl etherate; the solvent is molecular sieve dried dichloromethane; when boron trifluoride diethyl etherate is used as a catalyst, controlling the temperature to be-10-40 ℃, preferably-10 ℃, adding the catalyst, and then reacting for 6 hours at normal temperature; the acyl group-protected maltose: fatty alcohol: the molar ratio of the catalyst is 1: 1-6: 1-6, preferably 1: 1-3: 3-5, more preferably 1: 1.3-2: 3.5-4.5.
(3) Deacylation protection is carried out on the alkyl-2, 3,6,2 ', 3', 4 ', 6' -hepta-O-acyl- β -D-maltoside obtained in the step (2) in the presence of a catalyst to obtain the alkyl- β -D-maltoside, wherein the deacylation catalyst used is at least one of ammonia, triethylamine, sodium methoxide, sodium ethoxide, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium carbonate and potassium carbonate, preferably at least one of ammonia and sodium methoxide, more preferably sodium methoxide, the selected solvent is anhydrous methanol, the temperature is controlled to be-5-45 ℃, preferably 5-38 ℃, more preferably normal temperature when the sodium methoxide is used as the catalyst, and the pH of the solution is 8-14, preferably 8.5-12, more preferably 9-10.5.
For the step (2), a series of post-treatment processes such as washing, drying, filtering, concentrating, column chromatography separation and crystallization are adopted to obtain the alkyl-2, 3,6,2 ', 3', 4 ', 6' -hepta-O-acyl- β -D-maltoside.
And (3) neutralizing the reaction mixture reaching the reaction end point by using an acidic substance as a neutralizing agent, wherein the neutralizing agent is at least one of cation exchange resin, acetic acid, hydrochloric acid, phosphoric acid and p-toluenesulfonic acid, preferably at least one of cation exchange resin and acetic acid, more preferably acetic acid, and performing a series of post-treatment processes such as concentration and column chromatography separation to obtain the alkyl- β -D-maltoside.
In the invention, the reactions are all carried out under stirring conditions, and the stirring speed is not limited in the invention; meanwhile, the reaction time in the method of the present invention is not particularly limited, and those skilled in the art can select the reaction time according to actual conditions, and detect the degree of reaction progress by means of TLC plates and the like, and when the conversion of the raw material is no longer changed and the size of the spot of the produced desired intermediate and product is no longer increased by detection, the reaction end point is determined.
The invention has the advantages of short synthetic route, simple process, low production cost, renewable, cheap and easily-obtained raw materials, mild reaction conditions, easy operation and environmental protection.
Detailed Description
Unless otherwise specified, various reagents used in the following preparations and examples were commercially available.
The following will explain in detail the embodiments of the present invention by means of preparation examples and examples.
Preparation example: synthesis of octa-O-acetyl-D-maltose
Adding 30.00g of anhydrous maltose and 132.55ml of acetic anhydride into a three-neck round-bottom flask, heating to 90-100 ℃ under stirring, adding 7.19g of anhydrous sodium acetate in batches, heating to 120-130 ℃, and carrying out reflux reaction under the condition of heat preservation until TLC (V)Petroleum ether：VEthyl acetate1: 1) the reaction was detected to be complete (6 h). And quickly pouring the reaction solution into crushed ice water while the reaction solution is hot, stirring for 12 hours, washing with water, carrying out suction filtration, and drying filter residues to obtain the octa-O-acetyl-D-maltose white solid with the yield of 83.9 percent. This product was used directly in the reactions in the subsequent examples.
Examples
Example 1 Synthesis of n-octyl- β -D-maltoside
(1) In a round-bottomed flask, 5.00g of octa-O-acetyl-D-maltose prepared in preparation example and 1.74mL of n-octanol were charged, and 25mL of molecular sieve-dried dichloromethane was added, and stirred in an ice-water bath to dissolve, 3.72mL of boron trifluoride diethyl ether was added at low temperature, and after reaction for half an hour, the ice-water bath was removed, and reaction was carried out at normal temperature for 6 hours, TLC (V)Petroleum ether：VEthyl acetate1: 1) the reaction was detected to be complete. The mixed solution is used in turnNeutralizing with saturated sodium bicarbonate water solution, washing with brine, drying with anhydrous sodium sulfate, filtering, concentrating the filtrate, and performing column chromatography (V)Petroleum ether：VEthyl acetate2,3,6,2 ', 3', 4 ', 6' -hepta-O-acetyl- β -D-maltoside was obtained in 43.6% yield.
(2) Adding 2.00g of n-octyl-2, 3,6,2 ', 3', 4 ', 6' -hepta-O-acetyl- β -D-maltoside prepared as above and 50mL of anhydrous methanol into a round-bottom flask, stirring for dissolving, dropwise adding a sodium methoxide/methanol solution with the mass fraction of 15%, adjusting the pH value of the solution to be about 10, stirring for reacting for 4h, and TLC (V)Ethyl acetate：VMethanol3: 1) the reaction was detected to be complete. Adjusting pH of the reaction solution to 7 with acetic acid, concentrating, and performing column chromatography (V)Ethyl acetate： VMethanolSeparation as 13: 1) gave n-octyl- β -D-maltoside in 86.9% yield.
Example 2 Synthesis of n-decyl- β -D-maltoside
(1) In a round-bottomed flask, 5.00g of octa-O-acetyl-D-maltose prepared in preparation example and 2.11mL of n-decanol were charged, and 25mL of molecular sieve-dried dichloromethane was added, and stirred in an ice-water bath to dissolve, 3.72mL of boron trifluoride diethyl ether was added at low temperature, and after reaction for half an hour, the ice-water bath was removed, and reaction was carried out at normal temperature for 6 hours, TLC (V)Petroleum ether：VEthyl acetate1: 1) the reaction was detected to be complete. The mixture was neutralized with saturated aqueous sodium bicarbonate solution, washed with brine, dried over anhydrous sodium sulfate, filtered, the filtrate was concentrated, and column chromatography (V) was performedPetroleum ether：VEthyl acetate2,3,6,2 ', 3', 4 ', 6' -hepta-O-acetyl- β -D-maltoside was obtained in 41.3% yield.
(2) Adding 2.00g of n-decyl-2, 3,6,2 ', 3', 4 ', 6' -hepta-O-acetyl- β -D-maltoside prepared as above and 50mL of anhydrous methanol into a round-bottom flask, stirring for dissolving, dropwise adding 15% by mass sodium methoxide/methanol solution, adjusting the pH value of the solution to be about 10, stirring for reacting for 4h, and TLC (V)Ethyl acetate：VMethanol3: 1) detecting until the reaction is finishedAnd (4) completing. Adjusting pH of the reaction solution to 7 with acetic acid, concentrating, and performing column chromatography (V)Ethyl acetate： VMethanolSeparation at 13: 1) gave n-decyl- β -D-maltoside in 85.3% yield.
Example 3 Synthesis of n-dodecyl- β -D-maltoside
(1) A round-bottomed flask was charged with 5.00g of octa-O-acetyl-D-maltose prepared in preparation example and 2.06g of n-dodecanol, and 25mL of molecular sieve-dried dichloromethane was added, stirred in an ice-water bath to dissolve, 3.72mL of boron trifluoride diethyl etherate was added at low temperature, the ice-water bath was removed after reaction for half an hour, and the reaction was carried out at room temperature for 6 hours, TLC (V)Petroleum ether：VEthyl acetate1: 1) the reaction was detected to be complete. The mixture was neutralized with saturated aqueous sodium bicarbonate solution, washed with brine, dried over anhydrous sodium sulfate, filtered, the filtrate was concentrated, and column chromatography (V) was performedPetroleum ether：VEthyl acetate2,3,6,2 ', 3', 4 ', 6' -hepta-O-acetyl- β -D-maltoside was obtained in 46.8% yield.
(2) Adding 2.00g of n-dodecyl-2, 3,6,2 ', 3', 4 ', 6' -hepta-O-acetyl- β -D-maltoside prepared as above and 50mL of anhydrous methanol into a round-bottom flask, stirring for dissolving, dropwise adding a sodium methoxide/methanol solution with the mass fraction of 15%, adjusting the pH value of the solution to be about 10, stirring for reacting for 4h, and TLC (V)Ethyl acetate：VMethanol3: 1) the reaction was detected to be complete. Adjusting pH of the reaction solution to 7 with acetic acid, concentrating, and performing column chromatography (V)Ethyl acetate：VMethanolSeparation as 13: 1) gave n-dodecyl- β -D-maltoside in 88.7% yield.
Example 4 Synthesis of n-tetradecyl- β -D-maltoside
(1) In a round-bottomed flask, 5.00g of octa-O-acetyl-D-maltose prepared in preparation example and 2.37g of n-tetradecanol were charged, and 25mL of molecular sieve-dried dichloromethane was added, dissolved with stirring in an ice-water bath, 3.72mL of boron trifluoride diethyl ether was added at low temperature, the ice-water bath was removed after reaction for half an hour, and reaction was carried out for 6 hours, TLC (V)Petroleum ether：VEthyl acetate1: 1) the reaction was detected to be complete. The mixed solution is saturated in turnNeutralizing with sodium bicarbonate water solution, washing with brine, drying with anhydrous sodium sulfate, filtering, concentrating the filtrate, and performing column chromatography (V)Petroleum ether：VEthyl acetate2,3,6,2 ', 3', 4 ', 6' -hepta-O-acetyl- β -D-maltoside was obtained in 40.7% yield.
(2) Adding the prepared n-tetradecyl-2, 3,6,2 ', 3', 4 ', 6' -hepta-O-acetyl- β -D-maltoside 2.00g and anhydrous methanol 50mL into a round-bottom flask, stirring for dissolving, adding sodium methoxide/methanol solution with mass fraction of 15%, adjusting pH to about 10, stirring for reaction for 4h, and TLC (V)Ethyl acetate：VMethanol3: 1) the reaction was detected to be complete. Adjusting pH of the reaction solution to 7 with acetic acid, concentrating, and performing column chromatography (V)Ethyl acetate：VMethanolSeparation at 13: 1) gave n-tetradecyl- β -D-maltoside in 86.9% yield.
Example 5 Synthesis of n-dodecyl-2, 3,6,2 ', 3', 4 ', 6' -hepta-O-acetyl- β -D-maltoside
(I) on the basis of the molar ratio of octa-O-acetyl-D-maltose to fatty alcohol to catalyst of 1: 1.5: 4 in example 3, the charge amounts and charge ratios of octa-O-acetyl-D-maltose and n-dodecanol were unchanged, and the influence of the change in the charge amounts of the catalyst on the yield of n-dodecyl-2, 3,6,2 ', 3', 4 ', 6' -hepta-O-acetyl- β -D-maltoside synthesized was examined.
(1) octa-O-acetyl-D-maltose: fatty alcohol: the molar ratio of the catalyst is 1: 1.5: 3
A round-bottomed flask was charged with 5.00g of octa-O-acetyl-D-maltose prepared in preparation example and 2.06g of n-dodecanol, and 25mL of molecular sieve-dried dichloromethane was added, stirred in an ice-water bath to dissolve, 2.79mL of boron trifluoride diethyl etherate was added at low temperature, the ice-water bath was removed after reaction for half an hour, and the reaction was carried out at room temperature for 6 hours, TLC (V)Petroleum ether：VEthyl acetate1: 1) the reaction was detected to be complete. The mixture was neutralized with saturated aqueous sodium bicarbonate solution, washed with brine, dried over anhydrous sodium sulfate, filtered, the filtrate was concentrated, and column chromatography (V) was performedPetroleum ether：VEthyl acetate2,3,6,2 ', 3', 4 ', 6' -hepta-O-acetyl- β -D-maltoside was obtained in 44.3% yield.
(2) octa-O-acetyl-D-maltose: fatty alcohol: the molar ratio of the catalyst is 1: 1.5: 5
In a round-bottomed flask, 5.00g of octa-O-acetyl-D-maltose prepared in preparation example and 2.06g of n-dodecanol were added, and 25mL of molecular sieve-dried dichloromethane was added, stirred in an ice-water bath to dissolve, 4.65mL of boron trifluoride diethyl ether was added at low temperature, the ice-water bath was removed after reaction for half an hour, reaction was carried out at normal temperature for 6 hours, TLC (V)Petroleum ether：VEthyl acetate1: 1) the reaction was detected to be complete. The mixture was neutralized with saturated aqueous sodium bicarbonate solution, washed with brine, dried over anhydrous sodium sulfate, filtered, the filtrate was concentrated, and column chromatography (V) was performedPetroleum ether：VEthyl acetate2,3,6,2 ', 3', 4 ', 6' -hepta-O-acetyl- β -D-maltoside was obtained in 45.2% yield.
(3) octa-O-acetyl-D-maltose: fatty alcohol: the molar ratio of the catalyst is 1: 1.5: 6
A round-bottomed flask was charged with 5.00g of octa-O-acetyl-D-maltose prepared in preparation example and 2.06g of n-dodecanol, and 25mL of molecular sieve-dried dichloromethane was added, stirred in an ice-water bath to dissolve, 5.58mL of boron trifluoride diethyl etherate was added at low temperature, the ice-water bath was removed after reaction for half an hour, and the reaction was carried out at room temperature for 6 hours, TLC (V)Petroleum ether：VEthyl acetate1: 1) the reaction was detected to be complete. The mixture was neutralized with saturated aqueous sodium bicarbonate solution, washed with brine, dried over anhydrous sodium sulfate, filtered, the filtrate was concentrated, and column chromatography (V) was performedPetroleum ether：VEthyl acetate2,3,6,2 ', 3', 4 ', 6' -hepta-O-acetyl- β -D-maltoside was obtained in 44.9% yield.
(II) in example 3, the effect of the change in the amount of the octa-O-acetyl-D-maltose to be added on the yield of n-dodecyl-2, 3,6,2 ', 3', 4 ', 6' -hepta-O-acetyl- β -D-maltoside was examined on the basis of the molar ratio of octa-O-acetyl-D-maltose to fatty alcohol to catalyst being 1: 1.5: 4 and the addition ratio of octa-O-acetyl-D-maltose, n-dodecanol and boron trifluoride diethyl etherate being unchanged.
(1) 2.00g of octa-O-acetyl-D-maltose prepared in preparation example and 0.83g of n-dodecanol were added into a round bottom flask, 13mL of molecular sieve dried dichloromethane was added, stirred and dissolved in an ice water bath, 1.49mL of boron trifluoride diethyl ether was added at low temperature, the ice water bath was removed after reaction for half an hour, the reaction was carried out at normal temperature for 6 hours, TLC (V)Petroleum ether：VEthyl acetate1: 1) the reaction was detected to be complete. The mixture was neutralized with saturated aqueous sodium bicarbonate solution, washed with brine, dried over anhydrous sodium sulfate, filtered, the filtrate was concentrated, and column chromatography (V) was performedPetroleum ether：VEthyl acetate2,3,6,2 ', 3', 4 ', 6' -hepta-O-acetyl- β -D-maltoside was obtained in 46.8% yield.
(2) In a round-bottomed flask, 10.00g of octa-O-acetyl-D-maltose prepared in preparation example and 4.12g of n-dodecanol were charged, 30mL of molecular sieve-dried dichloromethane was added, stirred in an ice-water bath to dissolve, 7.44mL of boron trifluoride diethyl ether was added at low temperature, the ice-water bath was removed after reaction for half an hour, reaction was carried out at normal temperature for 6 hours, TLC (V)Petroleum ether：VEthyl acetate1: 1) the reaction was detected to be complete. The mixture was neutralized with saturated aqueous sodium bicarbonate solution, washed with brine, dried over anhydrous sodium sulfate, filtered, the filtrate was concentrated, and column chromatography (V) was performedPetroleum ether：VEthyl acetate2,3,6,2 ', 3', 4 ', 6' -hepta-O-acetyl- β -D-maltoside was obtained in 46.3% yield.
The above examples show the reaction conditions and the corresponding yields, respectively, in view of the fact that the alkyl glycosides obtained by this process are a series of 1, 2-trans alkyl- β -D-maltosides with hydrophilic sugar-based heads and hydrophobic alkyl chains, which have a good potential market as environmentally friendly sugar-based neutral surfactants.
It is to be noted that the amount of methylene chloride used as a solvent in the present invention is determined as appropriate, as long as the relevant raw materials are sufficiently dissolved.
The raw materials are easy to obtain, the cost is low, the synthetic route is short, the process is simple, the reaction conditions are mild, the preparation method is green and environment-friendly, meanwhile, when the preparation method is used for preparing the alkyl- β -D-maltoside, the condensation yield of various alkyl-2, 3,6,2 ', 3', 4 ', 6' -hepta-O-acetyl- β -D-maltoside reaches more than 40%, and the yield of the alkyl- β -D-maltoside obtained through deacylation protection reaction reaches more than 85%.
The embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (6)

1. Preparation of alkyl-β-D-a method of maltoside, characterised in that it comprises the following steps:
(1) reacting maltose with a protective agent in the presence of a catalyst to obtain acyl-protected maltose;
(2) reacting the acyl-protected maltose obtained in step (1) with a fatty alcohol in the presence of a catalyst to obtain alkyl-2, 3,6,2 ', 3', 4 ', 6' -hepta-O-acyl-β-D-maltoside;
(3) reacting the alkyl-2, 3,6,2 ', 3', 4 ', 6' -hepta-O-acyl-ketone obtained in the step (2) in the presence of a catalystβ-DDeprotection of maltoside to give alkyl-β-DMaltoside, the alkyl group-β-D-the maltoside structure is of formula (I):
Figure 478551DEST_PATH_IMAGE001
formula (I);
wherein the hydrocarbyl (-R) is any one of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-pentadecyl, and n-hexadecyl; the glycosyl moiety is maltosyl.
2. The method according to claim 1, wherein in step (1), the protecting agent comprises at least one of acetic anhydride, propionic anhydride, benzoic anhydride, acetyl chloride, propionyl chloride, and benzoyl chloride; when the acyl protective agent is acyl chloride, the corresponding catalyst is any one of pyridine and triethylamine; when the acyl protective agent is acid anhydride, the corresponding catalyst is anhydrous sodium salt corresponding to the acid anhydride, preferably, the protective agent is acetic anhydride, and the corresponding preferred catalyst is anhydrous sodium acetate; when acetic anhydride is adopted as the acylating reagent, the temperature is controlled to be between 80 and 140 ℃, preferably between 90 and 130 ℃, and more preferably between 110 and 120 ℃; the maltose is as follows: a protective agent: the molar ratio of the catalyst is 1:8-20:0.3-1.2, preferably 1:10-18:0.5-1.2, more preferably 1:10-17: 0.5-1.1.
3. The method according to claim 1, wherein in the step (2), the aliphatic alcohol comprises any one of methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, and n-hexadecanol; the catalyst may comprise boron trifluoride diethyl etherate (BF)3•Et2O), trimethylsilyl trifluoromethanesulfonate (TMSOTf) and tin tetrachloride, preferably boron trifluoride diethyl etherate; the solvent is molecular sieve dried dichloromethane; when boron trifluoride diethyl etherate is used as a catalyst, controlling the temperature to be-10-40 ℃, preferably-10 ℃, adding the catalyst, and then reacting for 6 hours at normal temperature; what is needed isThe acyl group-protected maltose: fatty alcohol: the molar ratio of the catalyst is 1: 1-6: 1-6, preferably 1: 1-3: 3-5, more preferably 1: 1.3-2: 3.5-4.5.
4. The process according to claim 1, wherein in step (3), the catalyst is at least one of ammonia, triethylamine, sodium methoxide, sodium ethoxide, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium carbonate and potassium carbonate, preferably at least one of ammonia and sodium methoxide, more preferably sodium methoxide; the selected solvent is absolute methanol; controlling the temperature to be-5-45 ℃ when sodium methoxide is used as a catalyst, preferably 5-38 ℃, and more preferably normal temperature; the solution pH =8-14, preferably pH =8.5-12, more preferably pH = 9-10.5.
5. The method as set forth in claim 1 and claim 3, wherein in the step (2), a series of post-treatments of washing, drying, filtering, concentrating, column chromatographic separation and crystallization are used to obtain the alkyl-2, 3,6,2 ', 3', 4 ', 6' -hepta-O-acyl-β-D-maltoside.
6. The method according to claim 1 and claim 4, characterized in that in the step (3), the reaction mixture reaching the end point of the reaction is neutralized with an acidic substance as a neutralizing agent, the neutralizing agent being at least one of cation exchange resin, acetic acid, hydrochloric acid, phosphoric acid and p-toluenesulfonic acid, preferably at least one of cation exchange resin, acetic acid, more preferably acetic acid; adopts a series of post-treatment processes of concentration, column chromatography separation and the like to obtain alkyl-β-D-maltoside.
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Citations (2)

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Publication number Priority date Publication date Assignee Title
CN103265586A (en) * 2013-06-06 2013-08-28 济南卡博唐生物科技有限公司 Method for preparing dodecyl maltoside from maltose
CN105622681A (en) * 2016-02-29 2016-06-01 湘潭大学 Method for preparing alkyl-beta-D-maltoside

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CN103265586A (en) * 2013-06-06 2013-08-28 济南卡博唐生物科技有限公司 Method for preparing dodecyl maltoside from maltose
CN105622681A (en) * 2016-02-29 2016-06-01 湘潭大学 Method for preparing alkyl-beta-D-maltoside

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Application publication date: 20200522