JPS6317889A - Germanium-alkali mixed salt of organic acid and production thereof - Google Patents

Abstract

NEW MATERIAL:A germanium-alkali mixed salt of an organic acid composed of an alkali metal germanate and an organic acid. EXAMPLE:Germanium sodium citrate. USE:A component of herb used as a remedy for cancer, etc. It has excellent absorbability in living body, especially in vegetable because the germanium acts as an organic substance in place of inorganic substance. PREPARATION:An aqueous solution of an alkali metal germanate is produced by boiling germanium oxide and an alkali (e.g. sodium hydroxide) usually in water under agitation. 1mol of the produced alkali metal germanate is made to react with usually >=6 base equivalent of an organic acid (e.g. malic acid, citric acid, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a germanium-alkali mixed salt of an organic acid and a method for producing the same. More specifically, a method for obtaining an alkali germanate from germanium oxide, which is easy to handle among commercially available germanium compounds, and then producing a germanium-alkali mixed salt of an organic acid that is easily useful in high yield, and a method for producing a germanium-alkali mixed salt of an organic acid that is easily useful in high yield. Organic acid germanium
Regarding alkaline mixed salts.

[Prior Art] In recent years, germanium is said to be effective in treating cancer and other difficult-to-treat diseases, and many books have already been published on this subject. For example, “Germanium and Me” by Dr. Hiko Asai, “Germanium Health Method” by Dr. Toshiko Yamazaki
, ``Germanium Therapy,'' by Mr. Kai Ryo, etc., all describe the miraculous effects of germanium compounds on diseases that are considered difficult to treat with modern medicine.

Also, it's been like this for a long time! It is also said that germanium compounds are the components of medicinal herbs that have been said to be effective against I disease and are most responsible for their efficacy. However, medicinal herbs currently obtained through cultivation contain almost no germanium compounds. Therefore, many studies have been conducted to make medicinal herbs contain germanium compounds by mixing germanium compounds into the culture medium, but since plants cannot use inorganic germanium, organic chelates with EDTA etc. have been used. Although germanium is produced and absorbed, the utilization efficiency of germanium is not very high.

Generally, a major drawback of germanium compounds is that they are difficult to utilize due to their low chemical reactivity. For example, germanium oxide and germanium sulfide are both insoluble in water, so they are difficult to be absorbed and utilized by plants and animals, and even if organic chelates can be made, they do not have effective stability in the complexation equilibrium in aqueous solutions. Since the concentration is small, the rate at which it is absorbed and utilized by plants is low.

It is well known that in the section where Mendeleev devised the periodic table of elements, germanium had not yet been discovered, so he assumed an element tentatively named dikasilicon in the blank space for germanium. This is because germanium has low chemical reactivity.
Despite its wide distribution in the earth's crust, it was not possible to extract or separate it from ore using the technology available at the time, and its discovery was delayed.

[Objective and Structure of the Invention] In order to react germanium, which has low reactivity as described above, with an organic acid, the present inventor focused on the fact that germanium is an amphoteric element, and first reacted germanic acid, which is a germanium compound, as an anion. By making an aqueous alkaline salt solution and adding an organic acid to it to shift the pH from alkaline to acidic, germanium, which was previously dissolved in water as an anion, is easily changed to a cation, producing an organic acid germanium salt. At the same time, by converting one-third of the carboxyl groups of organic acids into alkali salts, they succeeded in synthesizing a stable mixed salt of germanium and alkali all at once.

For example, the reaction when using sodium hydroxide as the alkali and citric acid as the organic acid is as follows.

aO aOH H,C-C0OH → HO-C-COO0OC-C-OHHtC-CO
ONa Na00C-CH2 In this case, an aqueous solution containing 10 to 30% germanium sodium citrate is easily obtained, and upon evaporation to dryness, white crystals having 4 to 2 molecules of water of crystallization are obtained.

If germanium oxide and citric acid are not in accordance with the present invention,
When heated and stirred in water, germanium oxide remains almost unreacted as a precipitate even if boiling is continued for a long time, and germanium citrate cannot be obtained.

Other possible sources of germanium include germanium tetrachloride and germanium metal.

However, since the former easily releases chlorine, it is a difficult liquid to handle as it generates white smoke of hydrogen chloride gas in the air, and furthermore, when added to an aqueous organic acid solution, it immediately hydrolyzes to form a precipitate of germanium oxide. Moreover, the latter does not react at all and does not change even when heated for a long time.

Germanium oxide may be commercially available and is usually an orthorhombic crystalline powder or an amorphous powder.

Such germanium oxide powder may contain tetragonal crystals with poor reactivity, but when these are separated as precipitates and dissolved in an aqueous sodium peroxide solution, sodium germanate is produced. It can be used in the production method.

In the present invention, suitable alkalis to be reacted with germanium oxide to produce alkali germanates include hydroxides of alkali metals such as sodium and potassium, alkaline earth metals, and ammonia.

As the organic acid, select one or more organic acids known as food ingredients, such as citric acid, malic acid, tartaric acid, succinic acid, lactic acid, linoleic acid, lyluic acid, butyric acid, acetic acid, and ascorbic acid. It can be used in

In the product obtained by the present invention, an alkali salt is mixed in the germanium organic acid salt, or in the case of a polybasic acid, an alkali is bonded to other carboxyl groups in the same organic acid molecule as germanium. One of the characteristics is that In such a chemical structure, the dissociation constant of the alkali component is large, so the alkali salt portion is strongly dissociated in water, and this suppresses the dissociation of the germanium bonding portion. Therefore, the mineralization of the product can be suppressed, and the product acts as organic germanium, so the rate of absorption and utilization by living things, especially plants, is high, and the coexistence of alkali salts is a germanium compound that is useful for health. It is producing good results.

The reaction between germanium oxide and the alkali component can be carried out by simply heating and stirring both components in water, and an alkali germanate can be obtained in the form of an aqueous solution. This aqueous solution can be used as it is for reaction with an organic acid.

The reaction between the alkali germanate and the organic acid can be carried out by adding the organic acid at a predetermined ratio to the aqueous solution of the alkali germanate prepared as described above. Although the reaction may be carried out at room temperature, it is preferably carried out under heating and stirring. Six base equivalents of organic acid are reacted per mole of alkali germanate, but the amount of organic acid used may be greater than six base equivalents.

Next, examples will be shown to specifically explain the present invention.

Example 1 Production of germanium sodium citrate 8 g of sodium hydroxide is dissolved in 200 ml of water, 10.46 g of germanium oxide is added thereto, and the mixture is stirred and boiled to obtain an aqueous solution of sodium germanate.

42 g of citric acid is added to this aqueous solution, and the mixture is stirred and boiled to obtain a transparent aqueous solution. The clear aqueous solution was freeze-dried overnight to obtain 57 g of white crystalline product. The analytical values of this crystalline product are shown below.

Elemental analysis: C,H analysis C: 26.0%, H: 3.5%.

Luminescence analysis Ge: 13.0%.

Assuming that the structural formula of the white crystalline product is Ge(CsHsOtNa)t-3HtO, when the above-mentioned measured values and calculated values are compared, they almost match as follows.

C (%) H (%) Ge (%) Calculated value: 26.
0 2.9 13.2 Actual value: 26.0 3.
The infrared absorption spectrum of the 513.0 product is shown in FIG.

Example 2 Production of germanium/potassium ascorbate 52.3 g (0.5 mol) of germanium oxide was added to 561 g (1 mol potassium hydroxide) of an approximately 10% potassium hydroxide aqueous solution.
Add to the solution while stirring, boil and dissolve, then dilute the total amount with water to about 2Q. After cooling, 528 g of ascorbic acid was added and stirred to obtain a colorless and transparent aqueous solution.
fi3630m (diluted to 2.1 m of this solution contained 10 mg of germanium and 145 mg of ascorbic acid.

Example 3 Production of sodium germanium malate Dissolve 8 g of sodium hydroxide in 200 m of water and add 5 g of germanium oxide to obtain a suspension. This suspension is heated for about 30 minutes. After boiling to obtain an aqueous solution of sodium germanate, add 40 g of malic acid (C4HI05) to an aqueous solution of 200 m of hot water with stirring.
Boil for another 30 minutes to obtain a clear liquid. This was evaporated to dryness to obtain about 55 g of crystalline powder.

1 g of this crystal contained 132+++ g of germanium. Figure 2 shows the infrared absorption spectrum of the crystalline powder.

Example 4 Production of sodium germanium lactate A sodium germanate aqueous solution (approximately 100 m
(96 g of a 70% lactic acid aqueous solution is added to the solution, stirred and homogenized, and then diluted to 726 mC with water to obtain an aqueous solution of sodium germanium lactate containing 10 mg of germanium per mf7.

Example 5 Production of sodium germanium acetate A sodium germanate aqueous solution prepared by the method of Example 3 (approximately 100 i
Add 36g of water vinegar to (1), stir to homogenize, and then dilute to 363mQ with water.
An aqueous solution of sodium germanium acetate is obtained containing mg of sodium germanium acetate.

[Brief explanation of the drawing]

Figure 1 shows the germanium citrate obtained in Example 1.
Infrared absorption spectrum of sodium, Figure 2 is Example 3
This is an infrared absorption spectrum of sodium germanium malate obtained in .

Claims (1)

[Claims] 1. A germanium-alkali mixed salt of an organic acid consisting of an alkali germanate and an organic acid. 2. The germanium-alkali mixed salt according to claim 1, which comprises 6 base equivalents of organic acid per mole of alkali germanate. 3. A method for producing a germanium/alkali mixed salt of an organic acid, which is characterized by reacting an alkali germanate with an organic acid. 4. The method according to claim 3, wherein at least 6 base equivalents of organic acid are reacted per mole of alkali germanate.