JP2590447B2 - Monosaccharide selective transport agent and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel selective transport agent for monosaccharides and a method for producing the same. More specifically, the present invention provides an inexpensive fat-soluble calcium that has the ability to efficiently transport a specific monosaccharide from an aqueous solution containing various monosaccharides through a liquid membrane, and that can be selectively and continuously extracted. The present invention relates to a monosaccharide selective transport agent comprising a complex and a method for efficiently producing the same.

[0002]

2. Description of the Related Art Monosaccharides such as D-glucose and D-ribose are widely distributed in nature and are used for various purposes as biochemical products. In particular, D-glucose (glucose) is used as a pharmaceutical, a sweetener, a reducing agent such as dyeing and tanning, an analytical reagent, and D-ribose is used as a riboflavin (vitamin B2 )) Are in great demand as raw materials, and these are currently industrially produced by fermentation.

By the way, to selectively extract a desired monosaccharide from an aqueous solution containing many types of monosaccharides,
It is industrially important as a method for obtaining high-purity monosaccharides. Therefore, the present inventors have conducted intensive studies on a method for selectively extracting monosaccharides. First, D-ribose was selectively used by a chloroform-soluble complex obtained from a lanthanum salt and a phosphodiester. Transported through the liquid membrane. However, in this method, a lanthanum complex used as a selective transport agent is expensive, and is not necessarily an industrially advantageous method.

[0004]

Under such circumstances, the present invention has the ability to efficiently transport a specific monosaccharide from an aqueous solution in which various monosaccharides are present through a liquid membrane. The purpose of the present invention is to provide an inexpensive selective transport agent for monosaccharides that can be extracted continuously and continuously.

The present inventors have conducted intensive studies on selective transport agents for monosaccharides. As a result, fat-soluble calcium complexes obtained by reacting calcium hydroxide or calcium chloride with a specific phosphoric diester are inexpensive, In particular, they have found that they have excellent ability to selectively transport D-ribose, and based on this finding, have completed the present invention.

That is, the present invention relates to a compound represented by the general formula: Ca [OPO (OR) ₂ ] ₂ (I) wherein R is a 2-ethylhexyl group or 4- (1,1,
3,3-tetramethylbutyl) -phenyl group]. The present invention provides a selective transport agent for a monosaccharide comprising a fat-soluble calcium complex represented by the formula:

According to the present invention, the monosaccharide selective transport agent comprising the fat-soluble calcium complex represented by the general formula (I) is selected from calcium hydroxide or calcium chloride and the general formula HOPO (OR) ₂ (II) (Wherein R in the formula has the same meaning as described above).

The fat-soluble calcium complex represented by the general formula (I) is produced by reacting the phosphoric diester represented by the general formula (II) with calcium hydroxide or calcium chloride. The reaction is advantageously carried out in the presence of a basic substance such as an inorganic base such as sodium carbonate or sodium hydrogen carbonate, or an organic base such as pyridine, 4-dimethylaminopyridine or triethylamine as a dehydrochlorinating agent.

The above reaction is preferably carried out in a solvent, such as an aromatic hydrocarbon such as benzene, toluene and xylene; an aliphatic hydrocarbon such as n-hexane, cyclohexane and n-heptane; Examples thereof include alicyclic hydrocarbons, halogenated hydrocarbons such as chloroform and ethylene chloride, and ethers such as dioxane and tetrahydrofuran. Of these, chloroform is particularly preferred. When a dehydrochlorinating agent is used, an organic base such as triethylamine or pyridine can also be used as a solvent.

In the above reaction, the proportion of the phosphoric diester to calcium hydroxide or calcium chloride is at least 2 mol, preferably 2 mol, per mol of calcium hydroxide or calcium chloride.
It is desirable to use it in a proportion of ４4 mol, more preferably in a proportion of 2２．５2.5 mol. The reaction temperature varies depending on the type of the raw material to be used and the type of dehydrochlorination when used, but is generally 0 to 100 ° C, preferably 10 to 50 ° C.
Is selected in the range.

In this way, a fat-soluble calcium complex represented by the general formula (I) is formed, and this may be isolated from the reaction completed solution by a known means and purified. In the method using calcium hydroxide, the reaction mixture may be used as it is or after adjusting the concentration as required, for selective transport of monosaccharides. On the other hand, in the method using calcium chloride, since a salt of a dehydrochlorinating agent and hydrogen chloride is usually precipitated, it is removed by filtration or the like, and then the monosaccharide is selectively transported as it is or after adjusting the concentration as required. May be provided.

The fat-soluble calcium complex represented by the general formula (I) can selectively convert monosaccharides, particularly D-ribose, in one volume A in a liquid membrane system consisting of solution A-solution M-solution B. It has the effect of transporting to solution B.

In order to transport monosaccharides using the fat-soluble calcium complex represented by the general formula (I) of the present invention,
The two solutions A and B may be brought into indirect contact with each other via the fat-soluble calcium complex. For example, (1) a fat-soluble calcium complex is dissolved in an organic solvent substantially immiscible with the solution A and the solution B, and the solution A and the solution B are indirectly treated with the solution of the fat-soluble calcium complex as an intermediate solution. (2) a method of indirectly contacting solution A and solution B via a solution of a fat-soluble calcium complex accommodated in a compartment partitioned by a diaphragm, and (3) a polymer membrane or filter paper. For example, a method in which the solution A and the solution B are indirectly contacted via a fat-soluble calcium complex supported on a support such as can be used.

Next, a specific example in which the solution A and the solution B are brought into contact with each other via a solution M of a fat-soluble calcium complex to transport monosaccharides will be described with reference to the accompanying drawings.
FIG. 1 is an explanatory view of an example of a device for transporting monosaccharides using a selective transport agent comprising a fat-soluble calcium complex of the present invention, wherein a U-shaped device 1 comprises a cylindrical container 2. And 3 and a connecting pipe 4 connecting the lower portions thereof, and stirrers 5 and 6.

In this apparatus 1, first, a solution M of a fat-soluble calcium complex is put as an intermediate solution layer, and then, a solution A is put into one cylindrical container 2, and a solution B is put into the other cylindrical container 3. The solution M is substantially immiscible with the solutions A and B.

The solution A contains a monosaccharide to be transferred. Usually, an aqueous solution is used. However, the solution is not necessarily limited to the aqueous solution, but may be a mixed solution of an organic solvent and water, or an alcohol. Organic solvent solutions also apply.
On the other hand, the solution B is for receiving the transferred monosaccharide, and usually water is used. As the solvent used for preparing the solution M, those which are substantially immiscible with the solution A and the solution B, for example, when the solution A and the solution B are aqueous solutions,
Halogenated hydrocarbons such as chloroform, carbon tetrachloride and dichloroethane; hydrocarbons such as benzene and toluene;
Hardly water-soluble alcohols such as hexyl alcohol and octyl alcohol are exemplified.

In this way, by bringing the solution A and the solution B into indirect contact, the monosaccharide in the solution A is trapped by the fat-soluble calcium complex, and the trapped fat-soluble calcium complex is brought into contact with the solution B. And releases the entrapped monosaccharides. In this way, the monosaccharides in solution A are effectively transported into solution B.

The agent for selectively transporting monosaccharides comprising the fat-soluble calcium complex of the present invention transports D-ribose most efficiently, and also transports D-fucose, L-rhamnose, D-mannose, D-arabinose, D-xylose. Transports to some extent, whereas D-glucose and D-galactose transport little. It is considered that the relative arrangement of each hydroxyl group of the saccharide and the presence / absence of a hydrophobic group greatly influence the transport selectivity.

[0019]

Industrial Applicability The selective transport agent for monosaccharides comprising a fat-soluble calcium complex of the present invention has an ability to efficiently transport a specific monosaccharide, particularly D-ribose, from an aqueous solution containing various monosaccharides through a liquid membrane. And can be selectively and continuously extracted.

The fat-soluble calcium complex is inexpensive because it can be easily obtained from calcium hydroxide or calcium chloride and a phosphoric diester.

[0021]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 (1) Preparation of fat-soluble calcium complex solution In 300 ml of chloroform, 10 ml of calcium hydroxide was added.
Mmol and di-2-ethylhexyl phosphate 20 mmol were added, and the mixture was stirred at room temperature for 12 hours and reacted to obtain a fat-soluble calcium complex (Ca [OPO (OC
₈ H ₁₇ ) ₂ ] A solution containing ₂ ) ₂ ) was prepared. (2) Monosaccharide transport experiment As solution A, 0.5 M D-glucose, 0.5 M
D-galactose, 0.5M D-mannose, 0.5
MD-ribose, 0.5MD-arabinose, 0.
15 ml of an aqueous solution containing 5M D-xylose, 0.5M D-fucose and 0.5M L-rhamnose was prepared respectively.

Next, in the apparatus 1 shown in FIG. 1, 30 ml of the calcium complex solution obtained in (1) above as an intermediate liquid layer (solution M) was added as chloroform (calcium complex 1).
15 ml of the above solution A in one cylindrical container 2 and water as solution B in the other cylindrical container 3.
15 ml was charged, and a transport experiment was performed at 25 ° C. (rotation speed of a stirrer: 200 rpm). After a lapse of 10 days, the amount of monosaccharides transported from solution A to solution B was determined. Table 1 shows the results.

[0024]

[Table 1]

As is evident from Table 1, D-ribose is transported most efficiently, while D-fucose, L-rhamnose, D-mannose, D-arabinose and D-xylose are also transported to some extent. D-glucose and D-galactose were hardly transported.

Examples 2 to 4 (1) Preparation of fat-soluble calcium complex solution The amounts of calcium hydroxide and di-2-ethylhexyl phosphate shown in Table 2 were added to 30 ml of chloroform, and the mixture was stirred at room temperature for 12 hours. Then, a solution containing a fat-soluble calcium complex (Ca [OPO (OC ₈ H ₁₇ ) ₂ ] ₂ ) was prepared.

(2) D-Ribose Transport Experiment Solution A containing 0.5M D-ribose-containing aqueous solution 15
Using the calcium complex solution (30 ml as chloroform) obtained in the above (1) as solution M and water as solution B, a transport experiment was carried out in the same manner as in Example 1- (2), and 10 days passed. The amount of D-ribose transported later was determined. The results are shown in Table 2 together with the results when D-ribose was used as the monosaccharide in Example 1.

[0028]

[Table 2]

Example 5 (1) Preparation of a fat-soluble calcium complex solution 1 mmol of calcium hydroxide and di- [4- (1,1,3,3-tetramethylbutyl) -phenyl] phosphate in 30 ml of chloroform Add 2 mmol and add 1 at room temperature.
The mixture was stirred for 2 hours and reacted to prepare a solution containing a fat-soluble calcium complex.

(2) D-Ribose Transport Experiment 0.5 M D-ribose-containing aqueous solution as solution A 15
Using the calcium complex solution (30 ml as chloroform) obtained in the above (1) as solution M and water as solution B, a transport experiment was carried out in the same manner as in Example 1- (2), and 10 days passed. The amount of D-ribose transported later was determined. As a result, the transport amount of D-ribose was 2.2 mmol.

Example 6 (1) Preparation of fat-soluble calcium complex solution 1 mmol of calcium chloride, 2 mmol of di-2-ethylhexyl phosphate and 2 mmol of triethylamine were added to 30 ml of chloroform, and the mixture was stirred at room temperature for 6 hours to react. Thereafter, the precipitated triethylamine hydrochloride was removed by filtration, and the fat-soluble calcium complex (Ca
A solution containing [OPO (OC ₈ H ₁₇ ) ₂ ] ₂ ) was prepared.

(2) D-Ribose Transport Experiment A 0.5 M D-ribose-containing aqueous solution was used as solution A.
Using the calcium complex solution (30 ml as chloroform) obtained in the above (1) as solution M and water as solution B, a transport experiment was carried out in the same manner as in Example 1- (2), and 10 days passed. The amount of D-ribose transported later was determined. As a result, the transport amount of D-ribose was 2.2 mmol.

COMPARATIVE EXAMPLE As solution A, an aqueous solution containing 0.5 M D-ribose 15
Using a solution prepared by dissolving 2 mmol of di-2-ethylhexyl phosphate in 30 ml of chloroform as a solution M and water as a solution B, a transport experiment was carried out in the same manner as in Example 1- (2), and 10 days passed. When the amount of D-ribose transported later was determined, D-ribose was not transported at all.

[Brief description of the drawings]

FIG. 1 is an explanatory view of an example of an apparatus in the case of transporting a monosaccharide using a selective transport agent comprising a fat-soluble calcium complex of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 U-shaped apparatus 2, 3 Tubular container 4 Connecting pipe 5, 6 Stirrer A Solution A B Solution B M Solution M

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location // C07B 61/00 7419-4H C07B 61/00 Z C07H 1/06 C07H 1/06 3/02 3/02 (72) Inventor Kazuhisa Hiratani 1-1-1 Higashi, Tsukuba City, Ibaraki Pref.

Claims (2)

(57) [Claims] A compound of the general formula Ca [OPO (OR) ₂ ] _{2 wherein} R is a 2-ethylhexyl group or 4- (1,1,
3,3-tetramethylbutyl) -phenyl group], a selective transport agent for a monosaccharide comprising a fat-soluble calcium complex represented by the formula: 2. A compound of the general formula HOPO (OR) _{2 wherein} R is a 2-ethylhexyl group or 4- (1,1,
A phosphoric acid diester represented by the formula (3,3-tetramethylbutyl) -phenyl group) and calcium hydroxide or calcium chloride, characterized by reacting with a general formula Ca [OPO (OR) ₂ ] ₂ ( Wherein R in the formula has the same meaning as described above), a method for producing a monosaccharide selective transport agent comprising a fat-soluble calcium complex represented by the formula: