JP2014070040A - Manufacturing method of glucopyranosides, or manufacturing method of galactopyranosides and manufacturing method of intermediate of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of 2,3,4,5-tetra-O-acetyl-α-D-glucopyranosylchloride or 2,3,4,5-tetra-O-acetyl-α-D-glucopyranosylbromide, and a manufacturing method of glucopyranosides using the method.SOLUTION: There is provided a manufacturing method of 2,3,4,5-tetra-O-acetyl-α-D-glucopyranosylchloride ("TAGC") or 2,3,4,5-tetra-O-acetyl-α-D-glucopyranosylbromide ("TAGB"), or 2,3,4,5-tetra-O-acetyl-α-D-galactopyranosylchloride ("TAGC'") or 2,3,4,5-tetra-O-acetyl-α-D-galactopyranosylbromide ("TAGB'") in which aqueous solution (HClaq.) of hydrogen chloride and acetic anhydride, or aqueous solution (HBraq.) of hydrogen bromide and acetic anhydride are reacted under the presence of penta-O-acetyl-D-glucopyranose or penta-O-acetyl-D-galactopyranose to create HCl/glacial acetic acid or HBr/glacial acetic acid, and then, the penta-O-acetyl-D-glucopyranose or the penta-O-acetyl-D-galactopyranose is chlorinated or brominated by the created HCl/glacial acetic acid or HBr/glacial acetic acid. There is also provided a manufacturing method of the glucopyranosides or galactopyranosides by using the manufacturing method.

Description

  The present invention relates to glucopyranosides (for example, ethyl vanillyl-β-D-glucopyranoside) used as a scent component in the fields of foods, cosmetics, etc., or used as an intermediate in the production of galactopyranosides. 3,4,5-tetra-O-acetyl-α-D-glucopyranosyl chloride or 2,3,4,5-tetra-O-acetyl-α-D-glucopyranosyl bromide, or 2,3 , 4,5-tetra-O-acetyl-α-D-galactopyranosyl chloride or 2,3,4,5-tetra-O-acetyl-α-D-galactopyranosyl bromide, The present invention relates to a method for producing the glucopyranoside or galactopyranoside using the production method.

Until now, 2,3,4,5-tetra-O-acetyl-α-D-glucopyranosyl chloride (hereinafter sometimes abbreviated as “TAGC”), or 2,3,4,5- Tetra-O-acetyl-α-D-glucopyranosyl bromide (hereinafter sometimes abbreviated as “TAGB”) is, for example, etherified with ethyl vanillin and then deacetylated. Ethyl vanillyl-β-D-glucopyranoside is produced and used as a scent component in foods, cosmetics and the like.
By the way, a method for synthesizing a glycosyl halide containing “TAGC” or “TAGB” has been well known, and for example, the following non-patent documents 1 and 2 are also reported as follows.
That is, in Non-Patent Document 1 below, “a. Glycosyl halides Conventionally, chlorides and bromides have been used exclusively as sugar donors. These are produced by reacting the corresponding 1-O-acylated sugars with hydrogen halide. Can be synthesized (formula (3.2)), and
Non-Patent Document 2 below (that is, the reference document shown on page 280 of Non-Patent Document 1) includes “penta-O-benzoyl-D-glucopyranose at 30 to 32% (W / W) Treatment with HBr / glacial acetic acid yielded tetra-O-benzoyl-α-D-glucopyranosyl bromide ”.
As can be seen from the above description, the conventional synthesis method of “TAGC” or “TAGB” is penta-O-acetyl as in the case of tetra-O-benzoyl-α-D-glucopyranosyl bromide. -D-glucopyranose at room temperature with HCl / glacial acetic acid (ie "glacial acetic acid absorbed HCl gas", the same) or HBr / glacial acetic acid (ie "absorbs HBr gas into glacial acetic acid) In the same manner, the processing method is widely used.
The 2,3,4,5-tetra-O-acetyl-α-D-galactopyranosyl chloride (hereinafter sometimes abbreviated as “TAGC ′”) or 2,3,4,5- The conventional synthesis method of tetra-O-acetyl-α-D-galactopyranosyl bromide (hereinafter sometimes abbreviated as “TAGB ′”) was also the same.

"Experimental Chemistry Lecture 26 Organic Synthesis VIII Asymmetric Synthesis / Reduction / Sugar / Labeled Compound" June 30, 1994 (2nd edition issued) Maruzen Co., Ltd., pp. 271-272 Adjustment methods and characteristics " "HG Fletcher, Jr., Methods Carbohydr. Chem., 2, 226-227 (1963)"

However, the conventional synthesis method of “TAGC” or “TAGB” or “TAGC ′” or “TAGB ′” has a problem (problem) that the yield is not sufficient.
Also, high concentrations of HBr / glacial acetic acid, such as 30-32% (W / W) HBr / glacial acetic acid, are difficult to obtain, and 20% (W / W) HBr / glacial acetic acid that is generally commercially available is It is expensive and is not an advantageous method in industrial production.
Furthermore, HBr / glacial acetic acid having a higher concentration than 20% (W / W) HBr / glacial acetic acid has a high volatility of HBr gas and is not preferable for industrial production in terms of working environment.

The present invention replaces conventional HCl / glacial acetic acid or HBr / glacial acetic acid with HClaq./acetic anhydride (ie, “a specific ratio mixture of an aqueous solution of HCl and acetic anhydride to produce HCl / glacial acetic acid. ”, The same shall apply hereinafter), or HBraq./acetic anhydride (ie, a specific ratio mixture of an aqueous solution of HBr and acetic anhydride, which produces HBr / glacial acetic acid”, hereinafter the same), The inventors have found that the yield of “TAGC”, “TAGB”, or “TAGC ′” or “TAGB ′” is improved, and have completed the present invention.
The reason why the yield is improved by using the HClaq./acetic anhydride or the Hbraq./acetic anhydride, the mechanism has not been fully elucidated, but the HClaq./acetic anhydride or the Hbraq./acetic anhydride is When changing to HCl / glacial acetic acid (“glacial acetic acid absorbed HCl gas”) or HBr / glacial acetic acid (“glacial acetic acid absorbed HBr gas”), some halogenation reaction was performed. It is presumed that a promoting action, for example, a catalytic action occurs, and the yield of the “TAGC” or “TAGB” or the “TAGC ′” or “TAGB ′” is improved.

The present inventor has discovered the fact that the yield has been improved by chance after many trials and errors in order to solve the above problems (problems), and has led to the completion of the present invention. is there.
The gist of the present invention is as follows.
1. An aqueous solution of hydrogen chloride in the presence of penta-O-acetyl-D-glucopyranose represented by the following general formula (1) or penta-O-acetyl-D-galactopyranose represented by the following general formula (1 ′) (HClaq.) And acetic anhydride are reacted to produce HCl / glacial acetic acid, and then the penta-O-acetyl-D-glucopyranose or the penta-O-acetyl-D is produced with the produced HCl / glacial acetic acid. -Tetra-O-acetyl-α-D-glucopyranosyl chloride ("TAGC") represented by the following general formula (2), or the following general formula (2), characterized by chlorinating galactopyranose A method for producing tetra-O-acetyl-α-D-galactopyranosyl chloride (“TAGC ′”) represented by ′).

  2. In the presence of penta-O-acetyl-D-glucopyranose represented by the following general formula (1) or penta-O-acetyl-D-galactopyranose represented by the following general formula (1 ′), hydrogen bromide An aqueous solution (HBraq.) And acetic anhydride are reacted to form HBr / glacial acetic acid, and then the penta-O-acetyl-D-glucopyranose or the penta-O-acetyl- D-galactopyranose is brominated, and tetra-O-acetyl-α-D-glucopyranosyl bromide ("TAGB") represented by the following general formula (3), or the following general formula ( 3 ′), a method for producing tetra-O-acetyl-α-D-galactopyranosyl bromide (“TAGB ′”).

3. 1. The hydrogen chloride concentration in the hydrogen chloride aqueous solution (HClaq.) Is 10 to 35% (W / W). The manufacturing method as described in.
4). 2. The hydrogen bromide concentration in the aqueous solution of hydrogen bromide (HBraq.) Is 10 to 48% (W / W). The manufacturing method as described in.
5. The chlorination treatment or bromination treatment is performed at 0 to 60 ° C. for 1 to 18 hours. ~ 4. The manufacturing method in any one of.
6). The chlorination treatment or the bromination treatment is penta-O-acetyl-D-glucopyranose represented by the general formula (1) or penta-O-acetyl-D- represented by the general formula (1 ′). 1. The above-mentioned 1. characterized by being carried out by dripping the produced HCl / glacial acetic acid or the produced HBr / glacial acetic acid into a solvent solution of galactopyranose. ~ 5. The manufacturing method in any one of.
7). Above 1. ~ 6. The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method described in any of the above, and then the “TAGC” or “TAGB”, or the “TAGC ′” or A cis-3-hexenyl-β-D obtained by etherifying “TAGB ′” with cis-3-hexenol and then deacetylating the etherification reaction product. -Production method of glucopyranoside or cis-3-hexenyl-β-D-galactopyranoside.
8). Above 1. ~ 6. The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method described in any of the above, and then the “TAGC” or “TAGB”, or the “TAGC ′” or Citronellyl-β-D-glucopyranoside or citronellyl-β-D-, which is obtained by subjecting “TAGB ′” and citronellol to an etherification reaction, followed by a deacetylation reaction of the etherification reaction product. A method for producing galactopyranoside.

9. Above 1. ~ 6. The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method described in any of the above, and then the “TAGC” or “TAGB”, or the “TAGC ′” or A geranyl-β-D-glucopyranoside or geranyl-β-D-characterized by subjecting “TAGB ′” and geraniol to an etherification reaction, followed by a deacetylation reaction of the etherification reaction product. A method for producing galactopyranoside.
10. Above 1. ~ 6. The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method described in any of the above, and then the “TAGC” or “TAGB”, or the “TAGC ′” or Anisyl-β-D-glucopyranoside or anisyl-β-D, which is obtained by subjecting “TAGB ′” and anis alcohol to an etherification reaction, followed by a deacetylation reaction of the etherification reaction product. -Manufacturing method of galactopyranoside.
11. Above 1. ~ 6. The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method described in any of the above, and then the “TAGC” or “TAGB”, or the “TAGC ′” or Phenethyl-β-D-glucopyranoside or phenethyl-β-D, which is obtained by etherifying “TAGB ′” with phenethyl alcohol and subsequently deacetylating the etherification reaction product. -Manufacturing method of galactopyranoside.
12 Above 1. ~ 6. The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method described in any of the above, and then the “TAGC” or “TAGB”, or the “TAGC ′” or Cinnamyl-β-D-glucopyranoside or cinnamyl-β-, which is obtained by subjecting “TAGB ′” to ether alcohol and then deacetylating the etherification reaction product. A method for producing D-galactopyranoside.

13. Above 1. ~ 6. The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method described in any of the above, and then the “TAGC” or “TAGB”, or the “TAGC ′” or Menthyl-β-D-glucopyranoside or menthyl-β-D-, characterized in that “TAGB ′” and menthol are subjected to an etherification reaction, followed by a deacetylation reaction of the etherification reaction product. A method for producing galactopyranoside.
14 Above 1. ~ 6. The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method described in any of the above, and then the “TAGC” or “TAGB”, or the “TAGC ′” or 3-Tuanyyl-β-D-glucopyranoside, which is obtained by subjecting “TAGB ′” and 3-tyanol to an etherification reaction and then deacetylating the etherification reaction product, or 3- A method for producing tsuyanyl-β-D-galactopyranoside.
15. Above 1. ~ 6. The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method described in any of the above, and then the “TAGC” or “TAGB”, or the “TAGC ′” or Eugenyl-β-D-glucopyranoside or eugenyl-β-D-, characterized in that “TAGB ′” and eugenol are subjected to an etherification reaction, followed by a deacetylation reaction of the etherification reaction product. A method for producing galactopyranoside.

16. Above 1. ~ 6. The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method described in any of the above, and then the “TAGC” or “TAGB”, or the “TAGC ′” or Vanillyl-β-D-glucopyranoside or vanillyl-β-D-, characterized in that “TAGB ′” and vanillin are subjected to an etherification reaction, followed by a deacetylation reaction of the etherification reaction product. A method for producing galactopyranoside.
17. Above 1. ~ 6. The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method described in any of the above, and then the “TAGC” or “TAGB”, or the “TAGC ′” or Ethyl vanillyl-β-D-glucopyranoside or ethyl vanillyl-β-D, which is obtained by etherifying “TAGB ′” with ethyl vanillin and subsequently deacetylating the etherification reaction product. -Manufacturing method of galactopyranoside.
18. Above 1. ~ 6. The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method described in any of the above, and then the “TAGC” or “TAGB”, or the “TAGC ′” or 2-butanone, 4- (characteristically characterized in that “TAGB ′” and raspberry ketone (also called p-hydroxyphenylbutane) are subjected to an etherification reaction, followed by a deacetylation reaction of the etherification reaction product. A method for producing 4-hydroxyphenyl) -β-D-glucopyranoside or 2-butanone, 4- (4-hydroxyphenyl) -β-D-galactopyranoside.
The cis-3-hexenol, citronellol, geraniol, anis alcohol, phenethyl alcohol, and cinnamic alcohol are primary alcohols, the menthol and 3-tuanol are secondary alcohols, and the eugenol, vanillin, and ethyl vanillin. Raspberry ketone (also known as p-hydroxyphenylbutane) is a compound belonging to phenol.

The present invention can provide a high yield that cannot be realized in the prior art in the synthesis method of “TAGC” or “TAGB” or “TAGC ′” or “TAGB ′”.
In addition, HClaq./acetic anhydride or HBraq./acetic anhydride is used instead of the conventional HCl / glacial acetic acid or HBr / glacial acetic acid, so that the cost is low and the gas of HCl and HBr is difficult to volatilize. This has the advantage that it is more preferable in terms of the working environment.

The penta-O-acetyl-D-glucopyranose represented by the general formula (1) or the penta-O-acetyl-D-galactopyranose represented by the general formula (1 ′) is D-glucose or D- It can be obtained by completely acetylating galactose.
Above 1. “TAGC” or “TAGC ′” or 2. above. In the production method of “TAGB” or “TAGB ′”, the mixing ratio of the aqueous solution of hydrogen chloride (HClaq.) Or the aqueous solution of hydrogen bromide (HBraq.) To acetic anhydride depends on the concentration of HCl or HBr. The amount of acetic anhydride converted to 100% glacial acetic acid is ideal and preferred, but may be less (in this case, excess acetic anhydride remains). However, if the blending ratio is too large, free water remains, which may be undesirable because glacial acetic acid dissolves to form an acetic acid aqueous solution.
The concentration of the aqueous hydrogen chloride solution (HClaq.) Is from 10 to 35% (W / W), preferably from 25 to 35% (W / W), more preferably from the viewpoint of halogenation yield, handling and the like. 35% (W / W).
The concentration of the aqueous solution of hydrogen bromide (HBraq.) Is 10 to 48% (W / W), preferably 35 to 48% (W / W), more preferably from the viewpoint of the yield of halogenation, handling, and the like. Is 48% (W / W).
The temperature and time of the chlorination treatment or bromination treatment reaction are 0 to 60 ° C. for 1 to 18 hours, preferably 10 to 30 ° C. for 4 to 18 hours, from the viewpoint of halogenation reaction rate, operation, etc. More preferably, it is 18 hours at 20 ° C.

Example 1 (Manufacturing method of said "TAGC")
In a eggplant-shaped flask having a capacity of 300 ml, 27 g of penta-O-acetyl-D-glucopyranose represented by the above general formula (1) was dissolved in 150 ml of chloroform, and 35% (W / W) hydrogen chloride was dissolved in this dissolved solution. A mixture of 18 g of aqueous solution (HClaq.) / 66.5 g of acetic anhydride was added dropwise, the inside of the flask was replaced with nitrogen gas, and the mixture was stirred at 20 ° C. for 18 hours to be reacted.
Thereafter, the reaction mixture was poured into a 500 ml Erlenmeyer flask containing saturated saline and stirred with a magnetic stirrer so that the aqueous layer and the organic layer were well mixed, and then the stirring was stopped and the aqueous layer was removed. To the remaining reaction mixture, 100 ml of a saturated aqueous sodium carbonate solution was added and stirred, and then the aqueous layer was removed. Further, 100 ml of saturated saline was added and stirred, and then only the organic layer was taken out with a separatory funnel.
The organic layer was placed in a 300 ml eggplant type flask and the solvent was removed by evaporation using a rotary evaporator. 50 ml of n-hexane was added to the concentrate to remove the solvent, and 12.7 g of tetra-O-acetyl-α-D-glucopyranosyl chloride (“TAGC”) represented by the above general formula (2) was added. It was collected.
The yield of “TAGC” represented by the above general formula (2) with respect to penta-O-acetyl-D-glucopyranose represented by the above general formula (1) is 50.0% (molar conversion ratio, the same applies hereinafter). there were.

Example 2 (Manufacturing method of said "TAGB")
Instead of 18 g of 35% (W / W) hydrogen chloride aqueous solution (HClaq.) Used in Example 1 and 66.5 g of acetic anhydride, 48% (W / W) aqueous solution of hydrogen bromide (HBraq.) 29 .2 g / Acetic anhydride was used in the same manner as in Example 1 except that 26.2 g of “TAGB” represented by the general formula (3) was recovered.
The yield of “TAGB” represented by the general formula (3) relative to penta-O-acetyl-D-glucopyranose represented by the general formula (1) was 95.6%.

Comparative Example 1 (Manufacturing method of the above “TAGB”)
20% (W / W) HBr / glacial acetic acid (ie, 48% (W / W) aqueous solution of hydrogen bromide (HBraq.) 29.2 g / acetic anhydride 86.2 g used in Example 2) “A product obtained by absorbing 20% (W / W) HBr gas in glacial acetic acid”) Except for using 69.0 g, the same operation as in Example 2 was carried out, and “TAGB” 26 of the above general formula (3) was .6 g was recovered.
The yield of “TAGB” represented by the general formula (3) with respect to penta-O-acetyl-D-glucopyranose represented by the general formula (1) was 93.5%.

Example 3 (Synthesis of ethyl vanillyl-β-D-glucopyranoside using TAGB obtained in Example 2) (Example of Claim 17)
27.2 g of TAGB obtained in Example 2 was placed in a 500 ml eggplant-shaped flask, dissolved in 80 ml of chloroform, 124.2 g of 10% (W / W) NaOH aqueous solution, 18.9 g of ethyl vanillin, and tetrabutylammonium. 3.0 g of bromide was added, and the mixture was vigorously stirred at 40 ° C. for 1 hour to be reacted.
Then, after transferring to a separatory funnel and removing the aqueous layer, the organic layer was washed 3 times with 10% (W / W) NaOH aqueous solution to remove ethyl vanillin. Furthermore, it washed with water 3 times and was made neutral.
The organic layer was placed in a eggplant type flask having a capacity of 300 ml, and the solvent was removed with a rotary evaporator. 30 ml of chloroform was added to the concentrate and recrystallization was performed to obtain 20.4 g of ethyl vanillyltetra-O-acetyl-β-D-glucopyranoside. The yield was 62.1%.
Subsequently, 20.4 g of ethyl vanillyltetra-O-acetyl-β-D-glucopyranoside obtained was placed in a 300 ml eggplant type flask, dissolved in 230 ml of methanol, and 16 g of 5% (W / W) aqueous sodium carbonate solution. And stirred vigorously at room temperature for 1 hour to react.
Thereafter, the mixture was neutralized with a 5% (W / W) acetic acid methanol solution, and the solvent was removed with a rotary evaporator. 11.8 g of ethyl vanillyl-β-D-glucopyranoside was obtained by adding 200 ml of methanol to the concentrated liquid and performing recrystallization. The yield was 87.4%.

Claims (18)

An aqueous solution of hydrogen chloride in the presence of penta-O-acetyl-D-glucopyranose represented by the following general formula (1) or penta-O-acetyl-D-galactopyranose represented by the following general formula (1 ′) (HClaq.) And acetic anhydride are reacted to produce HCl / glacial acetic acid, and then the penta-O-acetyl-D-glucopyranose or the penta-O-acetyl-D is produced with the produced HCl / glacial acetic acid. -Tetra-O-acetyl-α-D-glucopyranosyl chloride ("TAGC") represented by the following general formula (2), or the following general formula (2), characterized by chlorinating galactopyranose A method for producing tetra-O-acetyl-α-D-galactopyranosyl chloride (“TAGC ′”) represented by ′).
In the presence of penta-O-acetyl-D-glucopyranose represented by the following general formula (1) or penta-O-acetyl-D-galactopyranose represented by the following general formula (1 ′), hydrogen bromide An aqueous solution (HBraq.) And acetic anhydride are reacted to form HBr / glacial acetic acid, and then the penta-O-acetyl-D-glucopyranose or the penta-O-acetyl- D-galactopyranose is brominated, and tetra-O-acetyl-α-D-glucopyranosyl bromide ("TAGB") represented by the following general formula (3), or the following general formula ( 3 ′), a method for producing tetra-O-acetyl-α-D-galactopyranosyl bromide (“TAGB ′”).
  2. The production method according to claim 1, wherein the hydrogen chloride concentration in the aqueous solution of HCl (HClaq) is 10 to 35% (W / W).   The method according to claim 2, wherein the hydrogen bromide concentration in the aqueous solution of hydrogen bromide (HBraq.) Is 10 to 48% (W / W). The said chlorination process or a bromination process is performed at 0-60 degreeC for 1 to 18 hours, The manufacturing method of any one of Claims 1-4 characterized by the above-mentioned. The chlorination treatment or the bromination treatment is penta-O-acetyl-D-glucopyranose represented by the general formula (1) or penta-O-acetyl-D- represented by the general formula (1 ′). The production method according to any one of claims 1 to 5, wherein the production is performed by dropping the produced HCl / glacial acetic acid or the produced HBr / glacial acetic acid into a solvent solution of galactopyranose. .   The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method according to claim 1, and then the “TAGC” or “TAGB”, Alternatively, the above-mentioned “TAGC ′” or “TAGB ′” and cis-3-hexenol are subjected to an etherification reaction, followed by a deacetylation reaction of this etherification reaction product. A method for producing 3-hexenyl-β-D-glucopyranoside or cis-3-hexenyl-β-D-galactopyranoside.   The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method according to claim 1, and then the “TAGC” or “TAGB”, Or citronellyl-β-D-glucopyranoside, wherein the above-mentioned "TAGC '" or "TAGB'" and citronellol are etherified and then the etherified reaction product is deacetylated. Alternatively, a method for producing citronellyl-β-D-galactopyranoside.   The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method according to claim 1, and then the “TAGC” or “TAGB”, Alternatively, geranyl-β-D-glucopyranoside, characterized in that the above-mentioned “TAGC ′” or “TAGB ′” and geraniol are subjected to an etherification reaction, followed by a deacetylation reaction of this etherification reaction product, Alternatively, a method for producing geranyl-β-D-galactopyranoside.   The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method according to claim 1, and then the “TAGC” or “TAGB”, Alternatively, the above-mentioned “TAGC ′” or “TAGB ′” and anis alcohol are subjected to an etherification reaction, followed by a deacetylation reaction of the etherification reaction product, and anisyl-β-D-glucopyranoside Or Anisyl-β-D-galactopyranoside production method.   The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method according to claim 1, and then the “TAGC” or “TAGB”, Alternatively, the phenethyl-β-D-glucopyranoside is obtained by etherifying the above-mentioned “TAGC ′” or “TAGB ′” with phenethyl alcohol, and subsequently deacetylating the etherification reaction product. Or a process for producing phenethyl-β-D-galactopyranoside.   The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method according to claim 1, and then the “TAGC” or “TAGB”, Alternatively, the above-mentioned “TAGC ′” or “TAGB ′” and a cinnamic alcohol are subjected to an etherification reaction, and then this etherification reaction product is subjected to a deacetylation reaction. Cinnamyl-β-D- A method for producing glucopyranoside or cinnamyl-β-D-galactopyranoside.   The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method according to claim 1, and then the “TAGC” or “TAGB”, Alternatively, the above-mentioned “TAGC ′” or “TAGB ′” and menthol are subjected to an etherification reaction, followed by a deacetylation reaction of this etherification reaction product, menthyl-β-D-glucopyranoside, Alternatively, a method for producing menthyl-β-D-galactopyranoside.   The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method according to claim 1, and then the “TAGC” or “TAGB”, Alternatively, the above-mentioned "TAGC '" or "TAGB'" and 3-tyanol are subjected to an etherification reaction, followed by a deacetylation reaction of this etherification reaction product. A method for producing D-glucopyranoside or 3-tuyanyl-β-D-galactopyranoside.   The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method according to claim 1, and then the “TAGC” or “TAGB”, Alternatively, eugenyl-β-D-glucopyranoside, characterized in that the above-mentioned “TAGC ′” or “TAGB ′” and eugenol are subjected to an etherification reaction, followed by a deacetylation reaction of this etherification reaction product, Alternatively, a method for producing eugenyl-β-D-galactopyranoside.   The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method according to claim 1, and then the “TAGC” or “TAGB”, Alternatively, vanillyl-β-D-glucopyranoside, which is obtained by etherifying the above-mentioned “TAGC ′” or “TAGB ′” with vanillin and subsequently deacetylating the etherification reaction product, Or the manufacturing method of vanillyl- (beta) -D-galactopyranoside.   The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method according to claim 1, and then the “TAGC” or “TAGB”, Alternatively, ethyl vanillyl-β-D-glucopyranoside is obtained by etherifying the above-mentioned “TAGC ′” or “TAGB ′” with ethyl vanillin and subsequently deacetylating the etherification reaction product. Or a process for producing ethyl vanillyl-β-D-galactopyranoside.   The “TAGC” or “TAGB”, or the “TAGC ′” or “TAGB ′” is manufactured by the manufacturing method according to claim 1, and then the “TAGC” or “TAGB”, Alternatively, the above-mentioned "TAGC '" or "TAGB'" and raspberry ketone (also called p-hydroxyphenylbutane) are subjected to an etherification reaction, and then this etherification reaction product is subjected to a deacetylation reaction. A method for producing 2-butanone, 4- (4-hydroxyphenyl) -β-D-glucopyranoside or 2-butanone, 4- (4-hydroxyphenyl) -β-D-galactopyranoside.