JPS6023676B2 - β-carboxyethyl silicon (germanium) sesquioxide and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel compound of silicon and germanium, which is useful for the treatment of human cancer and high pressure treatment due to its unique physiological action, that is, a compound of the general formula 03 [Six (gold), SCH2CH
B-carboxyethyl silicon (germanium) expressed as 2COOH]2 (0.05<x<1.00)
The purpose of the present invention is to provide sesquioxide and a method for producing the same.

As is clear from the above general formula, the novel compound of the present invention has
It can be considered that some of the silicon (Si) atoms of B-carboxyethyl silicon sesquioxide are replaced with germanium (Q).

Silicon and germanium belong to the same group NB in the periodic table of elements, and although there are slight differences in atomic radius and electronegativity, their physical and chemical properties are extremely similar. The only material that has been widely put into practical use as a semiconductor material is The same applies to the fields of inorganic compounds and organometallic compounds, and although there are differences in the melting points, boiling points, thermal stability, etc. of the corresponding compounds, their chemical properties show good similarities. Therefore, replacing part of silicon with germanium, as in the novel compound of the present invention, can be achieved without much difficulty by ordinary chemical synthesis methods. Conventionally, B-carboxyethylgermani, which is a hydrolysis product of 8-cyanoethyltrichlorogermane or 3-carboxyetyltrichlorogermane,
Side 03 [Q/CQC
The compound 2COOH]2 is well known, and due to its unique physiological activity, it has been used effectively in the treatment of human cancer, hypertension, etc., and has attracted attention. However, the above-mentioned known compounds are obtained as white microcrystals that do not dissolve in organic solvents and are elutriated in water; however, when they are intended as physiologically active substances or for medicinal purposes, it is necessary to use pure water to further enhance their effects. It is desired to improve the solubility in Moreover, when it is intended for medicinal purposes, it has the drawback of high costs because it uses high-purity germanium alone or a compound with low levels of impurities such as heavy metals as a starting material.

The 8-carboxyetyl silicon (germanium) sesquioxide of the present invention improves the above-mentioned drawbacks of 3-carboxycetyl germanium sesquioxide, has improved solubility in pure water, and is a physiologically active substance with a higher healing effect. There are two methods for obtaining the above novel compound with high purity and high yield.

The first method is to mix P-cyanoethyl compounds of silicon and germanium that have been sufficiently purified by a fractional distillation method or the like in a predetermined molar ratio, and then hydrolyze the mixture without a catalyst or using a basic catalyst.

The second method is to mix an organic solvent solution of an 8-carpoxyethyl trichloro compound of silicon germanium sufficiently purified by a recrystallization method in a predetermined molar ratio, and add pure water to the mixture for hydrolysis.

The hydrolyzed product obtained by the above method is generally prone to vertical polymerization, and therefore the obtained B-carboxyethylsilicon (germanium) sesquioxide' does not consist only of a single pure green substance, but is It is a mixed composite containing ethyl silicon sesquioxide, 8-carboxyethyl germanium sesquioxide, 6-carboxyethyl silicon (germanium) sesquioxide, and subsequent polymers of duplexes or more of these. However, by repeating the usual recrystallization purification method for organic compounds using decolorizing charcoal 3 to 5 times using pure water as a solvent, the hydrolysis proceeds almost completely and almost all of the compounds of the present invention are removed. It is obtained as a pure white microcrystalline compound as a single compound,
Furthermore, by vacuum drying this microcrystalline body at 60 to 80 C, its chemical composition can be changed to the following general formula Q [Six(&)
,~CH2day2COOH]2 (however, 0.05<x<1.
00) is obtained.

As a result of research, it was found that the compound of the present invention has the general formula 03 [Six(Q)
, ~CH2CH2COOH]2 subscript ×, that is, B-carboxyethylgermanium sesquioxide 03 [C is also CH2CH2COOH]2 Corresponding to the increase in the substitution ratio of silicon atoms to germanium atoms, the pure water of the sesquioxide which is the compound of the present invention As shown in the table below, the solubility in Substitution rate of silicon atoms with solubility in pure water for germanium atoms (Solute phosphorus/solvent 10 degrees Celsius @25℃) - (X) 0.00 11○025
130 0.50 220 075 150 1.00 310 According to this, when x is 0.0, its solubility in pure water is substantially equal to the solubility of silicon-free sesquioxide alone equivalent to x = 0.0q. No significant difference was observed, and therefore, effective improvement of physical properties cannot be expected unless x is 0.05 or more.

Examples will be described in detail below. 1st Example 3 8 which was boiled under reduced pressure of Yamawaki Hg at 105o ~ 110℃
P-cyanoethyltrichlorogermane (0.1 mole) was distilled into 66 moles (0.35 mol) of -cyanoethyltrichlorosilane at 132°C to 136°C under a vacuum of 22 chest Hg.
5 mol) and diisopropyl ether 30
Adding the above gives a clear homogeneous solution.

When 200 g of shaved ice is added to this ether solution, hydrochloric acid gas is generated and a white precipitate is formed in the aqueous layer.
Add 1 part of 30% sodium hydroxide solution as a basic catalyst to this.
The white precipitate was redissolved, the aqueous layer was separated and cooled to 10-20, and acetic acid was added to adjust the pH to 3.
．． 00 to 5.00, white microcrystals are produced. The white microcrystals were distilled to obtain about 300 g of white microcrystals. To this, about 500 g of pure water was added, and the mixture was heated to 80 to 100°C to re-dissolve it, and about 20 g of activated carbon was added to it, and it was treated with a monkey. If the monkey solution is left to cool, white microcrystals will form again.
The above recrystallization process was repeated two more times, and about 200 final white microcrystals were separated and thoroughly soaked in cold water.
When one liquid is vacuum dried at 80 to 150 qo with enemy Hg, x =
Sesquioxide 11 of the compound of the present invention corresponding to 0.7
Two evenings were obtained.

03 [Si〇. 7(W)o. 3CH2C ratio COOH]2
This product is in the form of white microcrystals, and is insoluble or soluble in organic solvents such as ether, acetone, and alcohol, and readily soluble in pure water even at room temperature.

Further, no change was observed even after short-time heating at 70° C. or less and long-term heat treatment at 60° C. for 2 hours. The experimental values and theoretical values of the elemental analysis of this sample are shown in the table below, and the experimental values are within ±5% of the theoretical value, indicating good agreement.

By element Experimental value Theoretical value Grandson) C 27.06 25.992
Sun 3.74 3.61
0 38.95 40.43
Si 14.35 14.22G
e 15.90 15.74 The infrared absorption spectrum (K-trajectory tablet method) of this sample is shown in Figure 1. As is clear from this infrared absorption spectrum, Ge
-1 absorption of 800-900 based on -○ bond and Si
Absorption at -1 of 900 to 1150 based on the -○ bond and absorption around 1700 to -1 based on the carboxyl group are characteristically shown.

Also, the experimental value of the molecular weight by the neutralization equivalent method of the carboxylic acid group is 2
The square shows good agreement with the theoretical value of 277 with an error of less than 5%.

Second Example 47 mol of B-cyanoethyltrichlorogermane granule (0.2 mol) was mixed with the same 8-cyanoethyltrichlorosilane granule (0.2 mol) as in the first example. When 500% of diethyl ether is added to this, a transparent and homogeneous solution is obtained.

A white precipitate forms when this solution is slowly added to a water/solvent mixture consisting of about 400 g of shaved ice and 200 g of diethyl ether.

Next, a 30% aqueous sodium hydroxide solution as a basic catalyst was added thereto to redissolve the white precipitate, and the aqueous layer was separated, and at 10 to 2 psi, a 10% aqueous hydrochloric acid solution was added to adjust the pH to 3.
．． When neutralized to 0.00 to 5.00, white microcrystals are produced.

The white microcrystals were recrystallized and purified in the same manner as in the first example, and the final white microcrystals were separated and thoroughly washed with cold water. After drying under vacuum overnight at 15°C, a sesquioxide compound of the present compound corresponding to x=0.5 was obtained.

The resulting compound is white microcrystalline and contains ether, acetone,
It is insoluble or poorly soluble in organic solvents such as alcohol, and easily soluble in pure water even at room temperature. In addition, short-term heating below 6 pi 0, 50
No change was observed even after long-term heat treatment at 2°C. The experimental values and theoretical values of the elemental analysis of this sample are as shown in the table below, and the experimental values are all within 5% of the theoretical value, showing good agreement.

By element Experimental value association Theoretical value association C 25.8
1 24.43 days 3.4
5 3.390 36.2
3 38.0OSi9.
71 9.54Ge 24.
80 24.64 The infrared absorption spectrum (KBr tablet method) of this sample is shown in FIG.

Similar to the infrared absorption spectrum of the first example, this infrared absorption spectrum characteristically shows absorption based on the Q-○ bond and carpoxyl group. Also, the experimental value of the molecular weight by the neutralization equivalent method of the carboxylic acid group is 238, and the theoretical value is 247.
This shows good agreement with an error of less than 5%.

Third Example 65 parts (0.3 mol) of the same 8-cyanoethyltrichlorosilane distillate as in the first example was dissolved in 200 parts of diisopropyl ether.

Hereinafter, by the same operation as in the first example, 8-carboxyethyl silicon sesquioxide 03 (SIC day 2CH2CO
OH) 264 hours were obtained. This product is 8-carboxyethylsilane of the present invention. This is a compound corresponding to x=1.00 of con(germanium) sesquioxide Q [Six (戊), CH2CH2COOH]2.

This compound is a white microcrystal. It is insoluble or slightly soluble in organic solvents such as ether, ketone, and alcohol, and extremely easily soluble in water. No change was observed even with time treatment.

However, at temperatures above 80 oo, decomposition occurred and the melting point could not be measured.

The experimental values and theoretical values of the elemental analysis of this sample are shown in the table below, and the experimental values are all within 5% of the theoretical value, indicating agreement.

By element Experimental values Theoretical values) C 27.50 28.7
8th 3.88 4.00
0 45.78 44.76S
i 22.84 22.46
Further, the infrared absorption spectrum (KBr tablet method) of this sample is shown in FIG. 3. This red cough absorption spectrum characteristically shows absorption based on Si-○ bonds and carboxyl groups.

In addition, the experimental value of the molecular weight by the neutralization equivalent method of the carboxyl group is 2
40 shows good agreement with the theoretical value of 250, with an error of less than 5%.

Fourth Example 8-carpoxyethyltrichlorosilane 10 moles (0.05 mol) purified by recrystallization with diisopropyl ether;
Similarly, 8-carboxyethyltrichlorogermane (0.15 mol), which had been recrystallized and purified, was added to diethyl ether 2.
When dissolved in 0.00ml of water, a transparent and homogeneous solution is obtained.

When this solution is added to a mixture of about 300 g of shaved ice and 100 g of ethyl ether, a white precipitate is formed in the aqueous layer while generating hydrochloric acid gas. Next, a 30% aqueous sodium hydroxide solution was added as a basic catalyst to redissolve the white precipitate, and the aqueous layer was separated and treated in the same manner as in Example 2 to obtain the present invention represented by the following formula. 8-Carboxyethyl silicon (germanium) sesquioxide 03 [Si. ．． 25(Q)〇. 10,000 C&CH2COO
H] 256 days were obtained. The above-produced 8-carboxyethyl silicon (germanium) sesquioxide is white, microcrystalline, and is insoluble or eluent-soluble in organic solvents such as ethers, ketones, and alcohols, and readily soluble in water.

Further, no change was observed even after short-time heating at 5 pi○ or less and long-time heat treatment at 40q○/2. The experimental and theoretical values of the elemental analysis of this sample are as follows.
22.72 days 2.97
3.160 35.74
35.34Si 4.71
4.43Ge 35.03
34.36 The experimental values are all within 5% of the theoretical values, indicating good agreement.

The experimental value of the molecular weight determined by the carboxylic acid group neutralization equivalent method was 305, which showed good agreement with the theoretical value of 317 with an error of less than 5%.

[Brief explanation of the drawing]

FIG. 1 is the first embodiment in the specification of the present invention, and FIG. 2 is the second embodiment.
FIG. 3 of the example shows an infrared absorption spectrum diagram (Hata-koshi) of the 8-carboxyethyl silicon (germanium) sesquioxide sample obtained in the third example. Rudder chart N Ship chart N Ship

Claims (1)

[Claims] 1 General formula O_3 [Six(Ge)_1_-_xCH_2CH_2
β-carboxyethyl silicon (germanium) expressed as COOH]_2 (0.05<x<1.00)
Sesquioxide. 2 General formula O_3 [Six(
Ge)_1_-_xCH_2CH_2COOH〕_2(
However, 0.05 < x < 1.00) A method for producing β-carboxyethyl silicon (germanium sesquioxide). , the general formula O_3 [Six(Ge)_1_-_xCH_2CH_
2COOH]_2 (0.05<x<1.00) A method for producing β-carboxyethyl silicon (germanium) sesquioxide.