JPS59227895A - Production of glycoside - Google Patents

Abstract

PURPOSE:To reduce the amount of hydrochloric acid having disadvantages of corrosiveness, coloring, etc. and obtain efficiently a glycoside, by reacting a compound hydrolyzable into a monosaccharide with an alcohol in the presence of hydrochloric acid and a thermally stable sulfonic acid type cation exchange resin. CONSTITUTION:A compound hydrolyzable into a monosaccharide, e.g. starch or cellulose, and an alcohol containing preferably 5-20wt% thermally stable sulfonic acid type cation exchange resin and 0.5-1wt% hydrochloric acid are put into a reaction vessel, e.g. an autoclave and reacted at 120-150 deg.C for 2hr to give a monosaccharide, e.g. methyl glucoside.

Description

[Detailed description of the invention] This invention relates to the production of glicondes.

Compounds of this type are very useful as raw materials for glycoside polyethers used in the production of polyurethane foam. (e.g. US, '4359573, US, 4366265
, US, 4342864, Modern Plast
ics International-Lional August,
1982, page 45 etc.). Compounds in which the sugar moiety in the glycoside is composed of glucone are generally known as glucosides, and these can be used as raw materials for cosmetics (for example, US, 4323).
468) Of these, methyl glucoside is particularly important (
Soap, Per-fumery & Cosmet
ics 47(9) 406 (1974), and US,
4,324,703, etc.] Methyl gelconde is also used as a plasticizer for thermosetting resins.

(Described in Japanese Patent Publication No. 50-13770) Many methods of synthesizing such compounds are known up to now, and representative examples are listed below: 1) Method for producing glycosides using hydrochloric acid as a catalyst (Organic 5ynLhes-is
, C-ollcc also ive Vol (I) 35
4. CanLor et al. US.

2390507, Roudier et al. FR11143
82) I+) Method for producing methyphleglucoside using sulfuric acid as a catalyst (Langl-ois US, 227662
1)nl) Lewis acid catalyzed process, (Kai
aer et al. US 3296245) lv) Process for producing glycosides using cation exchange resin as catalyst (Cado-Lt
e et al. J, Amer, Cbem Soc, 741501
(1952), Dean et al. US, 2606186) V
) Glycoside production method using water-soluble sulfonic acid (Nev
in et al. US, 3375243. Roth et al. US, 422
3129 and 4329449) vl) Other Borinel Glycocytono manufacturing methods (0 also eyra uS: 3165
508RO also Jl et al. US, 3:346558), the preparation of methylmannoside (Hamilton et al.
853 and 3531461), Process for producing higher alkyl glycosides (LeMUS 3598865.37'0
7535 and 3772269).

As mentioned above, a wide variety of methods are known for the production of glicondes. Catalysts that have been widely used in the past are mineral acids, with hydrochloric acid being the most preferred. This is because because the molecules are small, the number of hydrogen ions per unit volume of acid is enormous, making it very effective as an acid catalyst. However, mineral acids are extremely corrosive, and not only do acid-resistant equipment have to be used, but the use of highly volatile acids, such as hydrochloric acid, has the disadvantage that the emitted gas may damage other equipment in the plant. These drawbacks also apply to certain Lewis acids. Although the reaction using a water-soluble sulfonic acid largely alleviates the above-mentioned disadvantages, it generally requires a high temperature of 140° C. or higher and has the disadvantage that the reaction solution is considerably colored. In either case, the acid remains in the reaction system and requires steps of neutralization and salt removal.

In order to improve these drawbacks, methods using cation exchange agents have been proposed. It does not have sufficient catalytic ability to completely hydrolyze polysaccharides such as The ability to smoothly proceed with glycosylation in reactions;
When using tamarinds as a raw material, it is preferable to use a mineral acid or hydrochloric acid.Also, hydrolysis tends to proceed slowly at high temperatures, but if the temperature is too high, problems such as coloring and a decrease in yield may occur. In order to allow the hydrolysis and glycosidation reactions to proceed completely within an appropriate temperature range (it is sufficient to use a sufficient amount of strong acids such as hydrochloric acid), as mentioned above, corrosion problems and neutralization and salt removal can be avoided. Strength; becomes a heavy burden.

In the present invention, a heat-stable sulfonic acid type cation exchange resin is used as a main ingredient, and a small amount of hydrochloric acid is used in combination when polysaccharide, which is relatively difficult to hydrolyze, is subjected to glycondation as a raw material.

The amount of hydrochloric acid used alone is 10 to 15 parts by weight (
100 parts by weight of a compound that can be hydrolyzed into monosaccharides (hereinafter the same) is required, but when used in combination with an ion exchange resin,
Even if the amount is less than 1 part by weight, the reaction can be carried out at a higher temperature and therefore the reaction time can be shortened. The reaction proceeds in a short time. Considering post-treatment of the reaction solution, the amount is preferably 4 parts by weight or less.

The concentration of hydrochloric acid in the reaction medium is preferably 0.5% by weight or more, preferably 1% by weight.

The present invention relates to a process for producing glycoside compounds, which comprises reacting a compound hydrolyzable to monosaccharides with a monohydric or polyhydric alcohol in the presence of hydrochloric acid and a heat-stable sulfonic acid type cation exchange resin. Specific embodiments of this method are shown below, and the desired product can be obtained in either case. Namely, 1) a compound that can be hydrolyzed into a monosaccharide is heated and reacted with alcohol in the presence of hydrochloric acid and the resin, and after cooling, the resin is separated in a furnace to obtain a glycoside solution, and the recovered resin can be used repeatedly. . Hydrochloric acid contained in the glycoside solution is removed by passing it through a column of anion exchange resin (eg Amberlystom-21 etc.), excess alcohol is evaporated and water is added to form an aqueous solution of glycoside. In some cases, the crude reaction solution may be concentrated to a certain extent to precipitate the glycoside as crystals directly from the alcohol solution. In this case, the P solution is dechlorinated, the alcohol is evaporated, and water is added to form an aqueous glycoside solution containing a large amount of amorphous glycoside. If purification is required, the product can be prepared after removing a very small amount of saccharide remaining in the glycoside, or it may be decolorized with activated carbon or the like depending on the case. Although the above reaction method is a batch method, the reaction can also be carried out by a continuous method. 2) A compound that can be hydrolyzed into a monosaccharide, previously suspended in an alcohol containing hydrochloric acid, is pumped into a column filled with a perfluorosulfonic acid resin or a heat-stable sulfonic acid type cation exchange resin. It can be carried out continuously by heating the reaction mixture and extracting the reaction solution from the bottom to obtain a glycoconde solution. The above embodiment 1) is a typical embodiment of the present invention, and when the reaction can be carried out under pressure, it is preferable to use a pressure-resistant container such as an autoclave.

Compounds that can be hydrolyzed into monosaccharides used as raw materials are not easily hydrolyzed by solid acids such as cation exchange resins. For example, it refers to polysaccharides such as starch and cellulose. Alcohols useful in this invention for reacting with these compounds are m-alcohols and polyhydric alcohols. Particularly preferred m-alcohols are those having from 1 to 8 carbon atoms, such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, methyl alcohol, and amyl alcohol. , 2-ethylhexyl alcohol, phenol and hyoctyl alcohol. Suitable polyhydric alcohols are ethylene glycol propylene glycol, butylene glycol and glycerol. The relative amount of alcohol to sugar used varies widely.

It can be changed depending on the individual ingredients used. The necessary linear excess of alcohol must be used to react with the sugars. This is because +i an excess of alcohol is required to shift the equilibrium in which the produced glycoside is hydrolyzed by the water present in the system and returned to sugar. Here, the water existing in the system refers to both water that already contains sugars and water that is generated from monosaccharides through a glycosidation reaction. In addition, an excess of alcohol is required to prevent the reaction from precipitating the glycoside from solution. Generally speaking, the molar ratio of alcohol to sugar can vary from 3°1 to 50=1 depending on the system used. As mentioned above, the glycosidation reaction is reversed, and the presence of water in the reaction mixture inhibits the production of glycosides. Therefore, although it is preferable to use anhydrous raw materials in step 4, it is by no means an essential condition that the raw materials be anhydrous. This is because satisfactory results can be obtained even when using sugars with a water content of about 12 parts.

As the thermally stable sulfonic acid type cation exchange resin used as an acid catalyst in the present invention, perfluorosulfonic acid resins are typically tetrafluoroethylene and perfluoro-3.
, 6-dioxa-4-methy)v-7-octensulfonic acid, which is sold by DuPont under the trade name 1nafion.Other resins other than fluorine-based resins, such as styrene-based and acrylic-based Ion-exchange resins with improved heat resistance can also be used, but the above ones are most preferred.Whether the resin is in the form of a cube or a powder, the reaction will not occur. However, it is preferable to use a powdered form.

The target product obtained by the present invention varies depending on the saccharide and alcohol used, but it is an alkyl glycoconde such as methyl glycoside, ethyl glycoside, glycol glyphsite, and the like.

Compounds that can be hydrolyzed to monosaccharides and 100 percent by weight of a heat-stable sulfonic acid type cation exchange resin, preferably 5 to 20 percent by weight, and 0.5 to 10 percent by weight of hydrochloric acid. A 3 to 50 mole amount of the alcohol contained in the saccharide is introduced into the reaction vessel. An acid-resistant container such as a glass-lined container is preferably used, and when the reaction is carried out under pressure, a pressure-resistant container such as an autoclave is preferably used. When using a high boiling point alcohol such as ethylene glycol, propylene glycol, glycerol phenol, etc., it is preferable to carry out the heating reaction under reduced pressure while water is allowed to flow out of the system. To describe the method for producing methyl glucoside as an example of a reaction method, 120 parts of starch (98 parts of dry purity), 395 parts of methanol containing 198 parts of hydrochloric acid, and 10-12 parts of heat-stable sulfonic acid type cation exchange resin are used. Place the remaining portion in a 1e glass-lined crepe. 12 while stirring at 600 r-p-m.
The reaction is carried out at 0°C for 2 hours. The gauge pressure in the system is 6.
0 #/d. After cooling to room temperature, the resin is separated by P to obtain a methylgelcondotanol solution. The reaction time varies depending on the raw materials used and the reaction temperature, but an example for the production of methyl glucoside is 120-
At 130°C, approximately 2 hours is appropriate, and the reaction temperature varies depending on the alcohol used, but is generally 100°C to 180°C, preferably 120°C to 150°C.

After the reaction is completed, the resin is separated by P and passed through a column of non-aqueous anion exchange resin such as "Amberlyst" A-21 to remove hydrochloric acid contained in the system, and then alcohol and water are removed. In addition, it is made into a gliconde aqueous solution. By adjusting the amount of water added, the solid content is adjusted to obtain an aqueous gliconde solution suitable for the purpose. In some cases, decolorization and purification are performed using activated carbon, etc. It has been found through mass spectrographic analysis that in general, crude glycosides are not a single component, but contain everything from glycoside monomers to trace amounts of tetramers. If the main product has good crystallinity (17z), an alcoholic solution of 1 nitric acid can be concentrated to a certain extent and directly crystallize the glycond. If only the main product with good crystallinity is desired, the mother liquor (more cycled.

As described above, the present invention not only simplifies the post-treatment of the reaction solution by reducing the amount used when using hydrochloric acid alone (compared to the case where hydrochloric acid is used alone) while maintaining the reaction rate and glycode production rate, but also simplifies the post-treatment of the reaction solution. When used alone, unreacted substances remain, but it has been found that the method of the present invention has the advantage that unreacted substances can be reduced to almost zero.

Next, the present invention will be explained using specific examples.

Example 1 Botetoscouch 12 oy (moisture content 18.3%), Nafion powder 1 2. OF and hydrochloric acid gas 19s
Methanol 3952 containing y (2% by weight based on dry starch) is charged into a glass-lined autoclave 1e.

2 at 120°C with stirring at 600 rpm.
.

Allow time to react. The pressure in the system is 6. 0 # / d
; (gauge pressure). After cooling to room temperature, Nafion is separated in a furnace to obtain a pale yellow methanol solution of methyl glucoside. This solution was passed through a column packed with Amberlyst A-21 to remove hydrochloric acid, water was added, and methanol was evaporated at 40° C. under reduced pressure to obtain an aqueous solution of methyl glucoside. The solid content was 1162, and as a result of determination of glucose by liquid chromatography and oxygen method, the composition of the solid content and molar yield were as follows.

Weight composition Molar yield methyl-α-gelcond s7.7 weight 1% 5
7.1 Monorostral methyl-β-glucoside 30.0
'/29,4 //Dextrose
2.5 High-grade oligosides and others
3,0〃100,0'/Comparative example 1 Potato starch 120F (moisture content 183%) and hydrochloric acid gas 198F (2% by weight based on dry starch)
methanol/l/3952 containing 1e is charged into a glass-lined autoclave. 6 0 0 r-
The reaction was carried out at 120°C for 2 hours while stirring at pm, and after cooling to room temperature, 2.72% of the unreacted raw material was separated by P.
A pale yellow methano-/I/liquid of methyl glucoside was obtained. Post-treatment was carried out in the same manner as in the example, and the product was quantitatively determined. As a result, the composition of the solid content was as follows.

Weight composition Soluble yield methyl-α-glucoside 49.4% by weight 4
8.07-4-methyl-β-gelcond 29.7
'/29,0 //Dextrose
24 〃High-grade Olibond Others
10.3'/100, 0// Comparative Example 2 Under exactly the same raw material composition and reaction conditions as Comparative Example 1.

In order to carry out the reaction and obtain the same results as in Examples 1 and 2, the reaction time was required to be 4 hours or more.

Comparative example 3 Potato starch 120? In Example 1, methanol 3952 containing (moisture content 18.3%) and hydrochloric acid gas 3.959 (4% by weight based on dry starch) was charged into an autoclave and the reaction was carried out in the same manner at 110°C for 15 hours. , 2 was obtained.

Comparative Example 4 Commercially available cornstarch SO, OR (containing 12% water), Nafion Powcler 4.42 and methanol 1302 were mixed in an autoclave with stirring for 14 hours.
Heat the reaction at 0 to 145°C for 2 hours. Nafion 4.4
2 and the unreacted raw material 3.12 are separated in a furnace to obtain a light brown gelcondo crude liquid. The yield was as follows.

Methyl-α-glucoside 48.6 mol% Methyl-β-glucoside 26.5//Methyl-α-maltonde & Methyl-β-maltoside 7.2/Dextrose 2.0 Comparative Example 5 Potato starch 54.92 (moisture content 19.8% content),
Nafion powder 2. Oy and methano-/
16 l/133 t with stirring in an autoclave.
A heating reaction is carried out at 00±2° C. for 2.5 hours. The pressure is 16
．． The pressure was 5±10# (gauge pressure). Nafion and unreacted raw material (3,62F) were separated by furnace to obtain a yellow glucoside crude liquid.

The yield was as follows.

Methyl-α-glucoside 45.5 mol% Methyl-β-crilecoside 26.7'/Methyl-α-
Maltoside & Methyl-β-maltoside 88 〃Dextrose 3.6〃Procedural amendment (spontaneous) August 11, 1980 Director-General of the Patent Office Kazuo Wakasugi L Case Indication Patent Application No. 102711-1988 2, Invention Manufacturing method of the name Glicondo 3, Person making the amendment 4, Detailed description of the invention in the specification subject to amendment 5, Contents of the amendment (1) Changed the word ``made'' to ``made'' on page 2, line 4 of the specification. (1) Page 3, line 1, “Us, 31655
0'8j was corrected to "l'-US, 316550.8," (1) "It is difficult to be done." on page 7, line 9 was corrected to "hard to be done." fil Same page 7, line 10 was "cellulose"
(1) Corrected "Glycol Pro..." to "Glycol, Pro..." on page 7, line 20. ``ha'' is ``...''
(1) Corrected "powder-like" on page 9, line 13 to "powder-like" (1) Corrected "glycerol phenol" on page 10, line 13 as "powder-like".
(1) Corrected "List" A-21J to "List A-21" on page 11, line 13.

Claims (1)

[Claims] The presence of hydrochloric acid and a thermostable nulphonic acid-type cation exchange resin that hydrolyzes vine compounds into monosaccharides.