JPH0812633A - Glycine ca bicarbonate and monohydrate thereof, their production and ca-replenishing nutriment containing the same - Google Patents

Abstract

PURPOSE:To obtain a new compound highly stable in its dry state, convertible into readily soluble glycineCa through being readily decomposed by e.g. gastric acid, thus useful as e.g. a Ca-replenishing nutriment. CONSTITUTION:The objective glycineCa bicarbonate of the formula and monohydrate thereof. The monohydrate is obtained in the form of crystal by blowing carbon dioxide into an aqueous alkaline solution of glycineCa pref. with pH 10-12 or so. This monohydrate is dried under heating at 120-150 deg.C to eliminate the crystal water to obtain the objective anhydrous glycineCa bicarbonate. The anhydrous compound, if left to stand in the atmosphere, absorbs the moisture in the atmosphere into the monohydrate, thus being stabilized. The monohydrate does not decline in quality not only in the atmosphere but also in a high-temperature atmosphere at about <=80 deg.C, therefore can be preserved stably.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel compound consisting of glycine Ca bicarbonate and its monohydrate, a process for producing them and a nutritional supplement for Ca supplement containing them as an active ingredient.

[0002]

2. Description of the Related Art Ca is an essential component for humans to maintain the formation of bones and teeth. Deficiency of Ca not only causes poor growth of bones and teeth and osteoporosis in which bones become scum, but also high blood pressure and arteriosclerosis. It has been confirmed that it causes diseases such as diabetes, immune diseases and obesity.

Foods containing Ca include dried sardines, sardines,
Various foods such as hijiki and roasted seaweed are known, and milk is widely consumed as the most representative Ca-containing beverage. Recently, various soft drinks containing Ca, such as steel-framed drinks, are commercially available, and many Ca agents composed of Ca salts of various amino acids such as lactic acid and aspartic acid are also commercially available.

However, the conventional Ca-containing beverage, even if it is milk, has a Ca content of 100 mb at most.
/ 100 ml, and even a beverage containing a Ca salt of an amino acid such as lactic acid or aspartic acid has a very low solubility in water, and a large amount must be drunk to ingest a sufficient amount of Ca. .

[0005]

DISCLOSURE OF THE INVENTION The present invention focused on the above circumstances, and as a result of earnest research to develop a Ca supplement supplemented beverage capable of ingesting a large amount of Ca at a small drinking dose, Glycine Ca has a very high solubility in water, for example, a very high solubility of 30 to 50% by weight in neutral water, and if it is about 10% by weight, drinking water, various soft drinks, lactic acid drinks, fruit trees, etc. By including it as a source of Ca in beverages, further alcoholic beverages, etc.
Knowing that a Ca-supplemented beverage with a very high content can be obtained, we applied for a patent based on these findings.

Since then, the present inventors have been conducting various studies utilizing the characteristics of the glycine Ca, but when carbon dioxide gas was blown into the alkaline aqueous solution of the glycine Ca this time, it was unknown so far. It was confirmed that a new compound was obtained.

[0007]

That is, the present invention provides a glycine Ca bicarbonate represented by the following chemical formula (A) and its 1
Hydrate

[0008]

Embedded image

The glycine Ca bicarbonate monohydrate is an alkaline aqueous solution of glycine Ca, preferably p
It is obtained as a crystal by blowing carbon dioxide into an aqueous solution of H10 to 12 or so. And this is 120 ~ 15
When dried by heating at 0 ℃, water of crystallization is released and glycine Ca
A bicarbonate is obtained. When the above-mentioned glycine Ca bicarbonate and its monohydrate according to the present invention are taken, it is decomposed by gastric acid to become glycine Ca which is easily soluble in water, and becomes a useful nutritional supplement as a Ca source.

[0010]

The glycine Ca bicarbonate monohydrate according to the present invention is specified by the following constants. (1) Molecular weight (measured by X-ray diffraction analysis and X-ray photoelectron spectroscopy analysis): 194 (2) Ca: glycine ratio = 20.38: 38.17 (weight ratio) ≈
1: 1 (molar ratio) However, the amount of Ca was determined by EDTA titration, and the amount of glycine was determined by liquid chromatography by dissolving the sample in HCl. (3) Melting point and decomposition point: exotherm was seen around 400 ° C. , Not clear. (4) Solubility in water: 0.1% by weight or less at 25 ° C (5) When a hydrochloric acid aqueous solution is dropped, foaming (generates carbon dioxide gas)
While dissolving. (6) Thermobalance chart: Figure 1, 1 crystal water is released near 150 ° C (7) IR chart: Figure 2 IR (nujol) 3379.7, 1581.8, 1529.7, 1419.8,
1309.8,1244.2,808.3 (8) ESCA chart: Fig. 3, Ca: N: C (carbonyl) ≈ 1: 1: 2 (9) XRD chart: Fig. 4

Further, the above-mentioned glycine Ca bicarbonate monohydrate is sparingly soluble in water by blowing carbon dioxide into an alkaline (particularly about pH 10-12) aqueous solution of glycine Ca as will be described later. Although obtained as crystals, pK of glycinium ion, carbonate ion and bicarbonate ion
a is as the respective following ionizing reaction ^{_{pKa N + H 3 CH 2 COO}} - → NH 2 CH 2 COO - + H + 9.78 H 2 CO 3 → HCO 3 - + H + 6.35 HCO 3 - → CO 3 2 ^- + H ⁺ 10.33 NH ₂ CH ₂ COO ⁻ and HCO ₃ ⁻ are present in large amounts near pH = 9.5, and when the above analytical values are combined, the glycine Ca weight shown by the following chemical formula (B) is obtained. It can be confirmed that it is a carbonate monohydrate.

[0012]

Embedded image

Ca ions have a hexacoordinate octahedral structure, glycine can be coordinated with both carbonyl oxygen and an amino group, and bicarbonate ions have a planar structure centered on carbon and have three oxygen atoms. It has been confirmed that it is possible to coordinate with the above, and that the water of crystallization can be coordinated to the surplus area, and these are comprehensively combined, and the glycine Ca bicarbonate monohydrate according to the present invention When the structure is estimated, it is considered that the structure is represented by the following formula.

[0014]

[Chemical 4]

From the characteristic (6), the above glycine C
The a-bicarbonate monohydrate heated and dried to release the water of crystallization becomes the glycine Ca bicarbonate represented by the chemical formula (A).

Glycine Ca bicarbonate having the above chemical structure. 1
Hydrates are alkaline (preferably pH) of glycine Ca.
It can be easily obtained by blowing carbon dioxide gas into an aqueous solution of about 10 to 12). That is, when carbon dioxide gas is blown into the above aqueous solution, the pH of the liquid is absorbed by the absorption of carbon dioxide gas.
Gradually decreases, but Ca: glycine: bicarbonate = 1: as insoluble crystals at a pH of about 9.5 to 9.0.
1: 1 glycine Ca bicarbonate monohydrate precipitates. When carbon dioxide gas is further blown in thereafter, the pH of the reaction solution gradually decreases, and the crystals formed by the pH up to about 8.5 are Ca: glycine = 1.12: 1 (molar ratio), pH
The crystals formed by about 8.0 are Ca: glycine = 2.
Although it is 86: 1 (molar ratio), these are a mixture of glycine Ca bicarbonate monohydrate and calcium carbonate. When calcium carbonate is separated and removed from the precipitate, the glycine Ca bicarbonate of the present invention is obtained. -Although a monohydrate can be obtained, calcium carbonate hardly precipitates in the pH range of the reaction solution of about 9.5 to 9.0 as described above, and glycine Ca bicarbonate monohydrate. Since only the product is produced, the desired product of the present invention can be easily and efficiently obtained without any subsequent separation / purification operation.

The precipitate thus obtained is washed with water, and preferably dried under reduced pressure to dry off the adhering water, whereby glycine Ca bicarbonate monohydrate in the form of white powder is obtained. The white powder does not deteriorate in the air atmosphere at room temperature or in a high temperature atmosphere of about 80 ° C. or less and can be stably stored. Then, when the glycine Ca bicarbonate monohydrate is heated to about 120 to 150 ° C. under reduced pressure, the water of crystallization is released as described above, and anhydrous glycine Ca bicarbonate is obtained. The anhydride is also chemically stable, but when left in the air atmosphere, it gradually absorbs moisture in the atmosphere and becomes a monohydrate and is stabilized.

The glycine Ca bicarbonate and its monohydrate of the present invention are very stable in the air atmosphere and hardly soluble in water as described above, but in the presence of a strong acid such as hydrochloric acid. It easily decomposes into glycine Ca, which is easily soluble in water.
Therefore, if this characteristic is utilized, it can be effectively utilized as a nutrient for enhancing Ca supplementation. That is, glycine Ca
When bicarbonate or its monohydrate is taken, it is rapidly decomposed by gastric acid into glycine Ca, which can be easily absorbed as a Ca source. Therefore, the glycine Ca bicarbonate and / or its monohydrate is itself Ca
It can be effectively used as a nutritional supplement for strengthening source supplementation, and also as an excipient for drugs having various pharmacological effects (powder, tablets, capsules, etc.) It is also possible to utilize it for various supplements.

[0019]

EXAMPLES Next, examples of the present invention will be shown, but the present invention is not limited by the following examples, and may be carried out with appropriate modifications within a range compatible with the gist of the preceding and following description. Of course, it is possible, and all of them are included in the technical scope of the present invention.

Example 1 59.57 g (0.26 mol) of glycine Ca dihydrate
A solution of 340.5 g of water (12.5 wt% as glycine Ca, pH 11.61) was stirred at room temperature, and purified carbon dioxide gas was blown into the solution. As the blowing of carbon dioxide continues, the pH of the reaction solution gradually decreases, and when the pH reaches about 9.5, precipitation starts to occur.
Collect the precipitate that forms by 9.0. Then further pH
Precipitates generated in the pH range of 9.0 to 8.5 and pH 8.5 to 8.0 were collected, dried under reduced pressure at 80 ° C., and then subjected to chemical analysis. As a result, the molar ratio of Ca: glycine: bicarbonate in the precipitate formed up to pH 9.0 is 1: 1: 1.
As a result of chemical analysis, it was confirmed that the product had the characteristic values shown above and was glycine Ca bicarbonate monohydrate. The XRD chart of this product was as shown in FIG.

Further, the pH is 9.0 to 8.5 and the pH is 8.5.
For the precipitate formed at ~ 8.0 C in the same manner as above.
When the molar ratio of a: glycine was examined, it was 1.12:
1 and 2.86: 1. Also, these XRD
The charts are as shown in FIGS. 5 and 6, and the diffraction peaks obtained by subtracting the CaCO ₃ peaks from these spectra are in agreement with those in FIG. 4 above, and the precipitate formed in the above pH range is glycine Ca bicarbonate. -It was confirmed to be a mixture of monohydrate and CaCO ₃ formed thereafter.

Of the above crystals, 20 g of the dried precipitate obtained up to pH 9.0 was heated at 150 ° C. for 5 hours to give 18 g of white powder of anhydrous glycine Ca bicarbonate.

The glycine Ca bicarbonate and its monohydrate obtained above are hardly dissolved in water,
When 2 g of each was added to 18 ml of 1N hydrochloric acid aqueous solution,
All were completely dissolved while foaming. From this,
The glycine Ca bicarbonate and its monohydrate of the present invention are
It was confirmed that when it is taken in a solid state, it is easily decomposed by gastric acid and converted into easily soluble glycine Ca, which can be utilized as a nutrient for Ca supplementation, a pharmaceutical excipient, and the like.

[0024]

EFFECTS OF THE INVENTION The present invention is constituted as described above, and it is extremely stable in a dry state and is easily decomposed by gastric acid or the like to be changed into easily soluble glycine Ca, which is useful as a Ca supplement enhancer and the like. It has become possible to provide the compound glycine Ca bicarbonate and its monohydrate.

[Brief description of drawings]

FIG. 1 is a thermobalance chart of glycine Ca bicarbonate monohydrate according to the present invention.

FIG. 2 is an IR chart of glycine Ca bicarbonate monohydrate according to the present invention.

FIG. 3 is an ESCA chart of glycine Ca bicarbonate monohydrate according to the present invention.

FIG. 4 is an XRD chart of glycine Ca bicarbonate monohydrate according to the present invention.

FIG. 5 is an XRD chart of a mixture of glycine Ca bicarbonate monohydrate and CaCO ₃ obtained in the example.

FIG. 6 is an XRD chart of a mixture of glycine Ca bicarbonate monohydrate and CaCO ₃ obtained in the example.

Claims (4)

[Claims] 1. Glycine Ca bicarbonate and its monohydrate represented by the following chemical formula (A): Embedded image 2. A method for producing glycine Ca bicarbonate monohydrate, which comprises blowing carbon dioxide gas into an alkaline aqueous solution of glycine Ca. 3. Glycine Ca bicarbonate 1 obtained in claim 2.
A method for producing glycine Ca bicarbonate, which comprises drying a hydrate. 4. A nutritional supplement for Ca supplementation, which contains the glycine Ca bicarbonate described in claim 1 and / or its monohydrate.