KR100676262B1 - High purity organic germanium synthesis method - Google Patents

Abstract

The present invention relates to a method of synthesizing high purity organic germanium, wherein the organic solvent (germanium trichloride solution) is extracted by mixing germanium dioxide, sodium hypophosphite and concentrated hydrochloric acid solution and removing impurities. To obtain intermediate germanium trichloride propionic acid, and then add a little hydrochloric acid, or recrystallize through hydrogen chloride gas to obtain high purity organic germanium from which residual germanium dioxide is removed.

Description

High purity organic germanium synthesis method             

1 is a synthetic process diagram of the high purity organic germanium of the present invention

The present invention relates to a high purity organo germanium synthesis method.

Germanium (Ge: Atomic Number 32, Atomic Weight 72.59), which is present in trace amounts in nature, has been deeply interested in the carbides of paleozoic plants, and has analyzed germanium content in animals and plants. At the same time, the researchers succeeded in synthesizing organic germanium compounds that are soluble in water, as well as identifying and containing them. As a result, in 1967, he succeeded in developing an organic germanium (Bis-Carboxyethyl-germanium sesquioxide; Ge-132), which is not toxic and has a physiological activity not found in conventional synthetic drugs. The effects include erythrocyte production and antibacterial activity, and in recent years, studies on the anticancer effect and the immune formation promoting effect of organic germanium (Ge-132) have been reported, and organic germanium (Ge-132) is beta calboksi Ethyl germanium cescuoxide organo germanium compound, HOOCCH ₂ CH ₂ GeO _1.5, is a kind of factor inducer. It has the effect of transforming sleeping encroachment cells into tumor encroachment cells, which induces the activity of anti-cancer factors, inhibits the growth of multiple tumors, inhibits the development of starch degeneration, and causes them from various poisonous cells and protozoa. It cures various diseases and suppresses the growth of cancer cells in the reproductive system.

Recently, it is widely used in health care medicine, health food, cosmetics, etc. In particular, organic germanium (Ge-132) sodium salt is a component of skin lubricating agent to treat skin melanoma caused by women's pregnancy and overexposure to sunlight. Widely used.

In addition, derivatives of organic germanium (Ge-132) are used to treat diseases such as poultry, livestock (chicken, pigs), fish in fish farms, etc., especially for prolonging the spawning period of poultry chickens and treating chicken leukemia. have.

In view of this fact, organic synthesis of organic germanium (Ge-132) has a very important development value.

The manufacturing method according to organo germanium (Ge-132) synthesis has several synthesis methods as follows.

(1) A method for synthesizing, purifying and hydrolyzing acrylic acid and its derivatives using germanium trichloride (HGeCl ₃ ) as a raw material.

(2) Germanium tetrachloride (GeCl ₄ ) as a raw material, sodium chloride (NaCl) produced by treatment of germanium tetrachloride with a concentrated hydrochloric acid solution of sodium hypophosphite in methyl alcohol, filtered to remove the filtered solution at room temperature Direct hydrolysis by reaction with acrylic acid.

(3) A method of extracting a germanium trichloride solution obtained by mixing and reacting germanium dioxide, sodium hypophosphite and a concentrated hydrochloric acid mixture, and dropping acrylic acid on the extract and then hydrolyzing it again.

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Among the three methods described above (3) is easy to purchase raw materials and easy to operate, high development value.

2) 사용기기
EA는 240B 원소측정기로 측정.
IR은 Nicolet FT-IR 기기(KBr 압축편)로 측정.
¹H.nmr은 ER-360형 60MH_Z 핵자기 공명장치로 측정.
티 뉴트롤스펙트로는 VGZAB-HF-3F 기기로 측정함.
지금까지의 기존 합성법에 의하면 대부분 에틸에테르로 HGeCl₃을 추출하고 그 다음 아크릴산과 작용하여 생산을 하였던 것이다. 그러나 이 방법에 사용하는 에틸에테르는 매우 쉽게 휘발하여 폭발하기 쉬운 물질이므로 조작 중 위험을 피하기가 어려우며 안전문제와 환경오염문제가 심각하게 발생하므로 본 발명은 직접 생산된 HGeCl₃의 농염산 중에 아크릴산을 첨가한 결과 1차생산품인 삼염화게르마늄 프로피온산의 생산량에 아무런 영향을 미치지 않았으며 제조방법도 간편하면서 안전하고, 이 1차생산품이 침전된 후 농염산을 넣거나 염화수소(HCl)가스를 통과시킨 결고 표 1에서 비교되는 바와 같이 제품의 생산율이 3∼4.5% 증가하였다.
표 1
실험법 1 2 3 에틸에테르 축출법 89.0 87.3 88.7 아크릴산 직접 넣는 법 88.8 87.6 89.1 HCI 더 첨가하는 법 92.1 91.5 91.5
이산화게르마늄과 차아인산나트륨 및 농염산혼합액을 혼합 반응시켜 유기용제(삼염화게르마늄액)를 추출하고 그 추출물에 아크릴산을 집어 넣어 교반하여 얻은 삼염화게르마늄 피로피온산에 농염산을 넣거나, 염화수소가스를 통과시켜 잔존 이산화게르마늄을 제거한 고순도 유기게르마늄을 증산한다.Therefore, in the present invention, the synthesis method of the above 3 is easy to operate and very good in productivity, and the method of the present invention is reconsidered because the method consumes less raw materials and significantly reduces the contamination of waste water.
Materials and Equipment
1) material

2) Equipment used
EA measured with 240B elementometer.
IR measured with Nicolet FT-IR instrument (KBr compression piece).
¹ H. nmr is measured by ER-360 type 60MH _Z nuclear magnetic resonance apparatus.
The tneutron spectrometer is measured on a VGZAB-HF-3F instrument.
According to the existing synthetic methods up to now, most of the extraction was HGeCl ₃ with ethyl ether and then produced by working with acrylic acid. However, because this way the ether is very easy because it is volatile and an explosive material it is difficult to avoid the risk of the operating serious safety problems and environmental pollution problems used for the acrylic acid in the present invention is directly produced in HGeCl ₃ of concentrated hydrochloric acid As a result of the addition, it did not affect the production of germanium trichloride propionic acid as the primary product, and the manufacturing method was simple and safe, and after the primary product was precipitated, concentrated hydrochloric acid was added or hydrogen chloride (HCl) gas was passed. As compared with, the product yield increased by 3 to 4.5%.
Table 1
Experimental method One 2 3 Ethyl Ether Extraction Method 89.0 87.3 88.7 How to add acrylic acid directly 88.8 87.6 89.1 How to add more HCI 92.1 91.5 91.5
The mixture of germanium dioxide, sodium hypophosphite, and concentrated hydrochloric acid is mixed to extract an organic solvent (germanium trichloride solution), and acrylic acid is added to the extract, followed by stirring. The high purity organic germanium is removed by removing residual germanium.

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Example;

Synthesis of Germanium Trichloride Propionic Acid (Cl ₃ GeCH ₂ CH ₂ COOH)

8.0 g of germanium dioxide (GeO ₂ ), 12.0 g of sodium hypophosphite, and 100 ml of concentrated hydrochloric acid were added to a reactor, followed by heating and stirring (2.5 h) to obtain a colorless transparent germanium hydrogen trichloride solution, followed by 1 night at 10 ° C. Precipitate is removed to remove the precipitate, and the filtrate (germanium trichloride) is poured in 5 g of acrylic acid while stirring in ice.
At this time, the temperature should be maintained at 10 ℃ to 15 ℃. A few minutes later, a precipitate (germanium trichloride propionic acid) is produced. A short time later, hydrochloric acid is added or a small amount of hydrogen chloride gas is passed to form sufficient precipitation of high purity products.

Immediately after vacuum filtration, recrystallized with ethyl ether to obtain about 18 g of white spherical crystals.

MP: 84 ° C. Molecular formula is C ₃ H ₅ Cl ₃ GeO ₂

Elemental analysis measured values (calculated): C14 ₂₁ (14.30H _2.04 (2.00))

IRvmax (cm ^-1 ): 1720 (C = O) 593 (Ge-C) 418 (GeCl)
¹ H.nmr 2.30 (2H, CH 2 CO), 2.88 (2H, Ge-CH 2) 11.70 (1H, COOH)
Purification of Organic Germanium (Ge-132)

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After stirring 12.0 g of germanium trichloride propionic acid (Cl ₃ GeCH ₂ CH ₂ COOH) in 50 ml of water, it immediately dissolves, becomes a uniform state and immediately precipitates. After a few minutes, the solid is separated by filtration and washed with ethyl alcohol.
When the first product is crystallized again with water and ethyl alcohol, white crystals of high purity are obtained.

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MP: 270 ~ 270.5 ℃ (decomposition)

Molecular Formula: (C ₃ H ₅ GeO _1.5 ) n

Elemental Analysis: Experimental Value (Calculated Value)
C _21.17 (21.24)
H _2.99 (2.97)

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lRvmax (cm ^-1 ): 3050 (OH) 1690, 1409, 1240 (C = O)
※ How to add acrylic acid directly in concentrated hydrochloric acid solution of HGeCl ₃
※ How to pass through concentrated hydrochloric acid or HCl gas

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When reacted with acrylic acid, the following reaction process is formed, and the presence of HCl is advantageous for the formation of ④.

In the synthesis of germanium trichloride propionic acid, the molecular formula C ₃ H ₅ GeO ₂ can easily know the presence of germanium dioxide (GeO ₂ ) miscellaneous, but in the present invention, the recrystallization of Cl ₃ GeCH ₂ CH ₂ COOH (refining method) ₂ ) by removing the presence of the world standard content of GeO ₂ content ≤ 0.005% to 0.001% to improve the quality of the product.

Germanium dioxide, sodium hypophosphite, and concentrated hydrochloric acid are mixed to obtain a germanium trichloride solution from which miscellaneous impurities have been removed, and acrylic acid is added to the filtrate at 10 ° C to 15 ° C to precipitate. It is effective to increase the organic germanium of 99.995% of high purity (world standard content 99.90%) from which germanium dioxide is removed.

Claims (1)

The reaction mixture of germanium dioxide, sodium hypophosphite and concentrated hydrochloric acid is heated to obtain a colorless and transparent germanium trichloride solution. The precipitate is removed, and the filtrate is poured into the acrylic acid while stirring in ice. Precipitation is formed after a few minutes. After a while, a high purity organic germanium synthesis method is obtained by adding hydrochloric acid or passing hydrogen chloride gas to obtain high purity organic germanium.

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