JPS58174391A - Tetrakis(1-(n-carboxymethylcarbamoyl)ethylmercapto) germane and preparation thereof - Google Patents
Tetrakis(1-(n-carboxymethylcarbamoyl)ethylmercapto) germane and preparation thereofInfo
- Publication number
- JPS58174391A JPS58174391A JP57057730A JP5773082A JPS58174391A JP S58174391 A JPS58174391 A JP S58174391A JP 57057730 A JP57057730 A JP 57057730A JP 5773082 A JP5773082 A JP 5773082A JP S58174391 A JPS58174391 A JP S58174391A
- Authority
- JP
- Japan
- Prior art keywords
- soluble
- water
- carboxymethylcarbamoyl
- tetrakis
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 title claims description 5
- 229910000078 germane Inorganic materials 0.000 title description 2
- YTGJWQPHMWSCST-UHFFFAOYSA-N Tiopronin Chemical compound CC(S)C(=O)NCC(O)=O YTGJWQPHMWSCST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 108010058907 Tiopronin Proteins 0.000 claims abstract description 6
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 abstract description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004458 analytical method Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 229940121363 anti-inflammatory agent Drugs 0.000 abstract 1
- 239000002260 anti-inflammatory agent Substances 0.000 abstract 1
- 230000003327 cancerostatic effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 238000010792 warming Methods 0.000 abstract 1
- 229910052732 germanium Inorganic materials 0.000 description 8
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 206010028980 Neoplasm Diseases 0.000 description 3
- BJXXCOMGRRCAGN-CLFAGFIQSA-N [2,2-bis(hydroxymethyl)-3-[(z)-octadec-9-enoyl]oxypropyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(CO)(CO)COC(=O)CCCCCCC\C=C/CCCCCCCC BJXXCOMGRRCAGN-CLFAGFIQSA-N 0.000 description 3
- 201000011510 cancer Diseases 0.000 description 3
- 201000004624 Dermatitis Diseases 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- REFJWTPEDVJJIY-UHFFFAOYSA-N Quercetin Chemical compound C=1C(O)=CC(O)=C(C(C=2O)=O)C=1OC=2C1=CC=C(O)C(O)=C1 REFJWTPEDVJJIY-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 208000019425 cirrhosis of liver Diseases 0.000 description 2
- 208000006454 hepatitis Diseases 0.000 description 2
- 231100000283 hepatitis Toxicity 0.000 description 2
- 208000027866 inflammatory disease Diseases 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YDCFOUBAMGLLKA-UHFFFAOYSA-N 2,6,7-trihydroxy-9-phenylxanthen-3-one Chemical compound C1=2C=C(O)C(O)=CC=2OC2=CC(=O)C(O)=CC2=C1C1=CC=CC=C1 YDCFOUBAMGLLKA-UHFFFAOYSA-N 0.000 description 1
- 208000002874 Acne Vulgaris Diseases 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 206010016654 Fibrosis Diseases 0.000 description 1
- 201000005505 Measles Diseases 0.000 description 1
- 240000004371 Panax ginseng Species 0.000 description 1
- 235000002789 Panax ginseng Nutrition 0.000 description 1
- ZVOLCUVKHLEPEV-UHFFFAOYSA-N Quercetagetin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=C(O)C(O)=C(O)C=C2O1 ZVOLCUVKHLEPEV-UHFFFAOYSA-N 0.000 description 1
- HWTZYBCRDDUBJY-UHFFFAOYSA-N Rhynchosin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=CC(O)=C(O)C=C2O1 HWTZYBCRDDUBJY-UHFFFAOYSA-N 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 206010000496 acne Diseases 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- 230000007882 cirrhosis Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- -1 ethyl mercapto Chemical compound 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 241000411851 herbal medicine Species 0.000 description 1
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 description 1
- 230000007721 medicinal effect Effects 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229960001285 quercetin Drugs 0.000 description 1
- 235000005875 quercetin Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
Landscapes
- Cosmetics (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は炎症性疾患及び癌の治療効果を有し、又皮膚を
なめらかにし、其の他皮膚のあれを防ぐ効果を有する、
下記式ＣＩ）で示される新規なテトラキス（１−（Ｎ−
カルボキシメチルカルバモイル）エチルメルカプ°ト〕
ゲルマンＣＴｇｔｒａｋｉｓ（１−（Ｎ −ｃａｒＡｏ
ｘｙｎｓｇｔＡｙｌ ｃｑｒｂａｎｔｏｙｌ−） ｇ
ｔＡｙｌ−ｍｔｒｃａｐｔｏ ） ｇｅｒｍａｎｅ 、
以下Ｔ、、Ｃ，Ｅ、 Ｑ、と略称す司及びその製造法に
関する。DETAILED DESCRIPTION OF THE INVENTION The present invention has a therapeutic effect on inflammatory diseases and cancer, and also has an effect on smoothing the skin and preventing other skin roughness.
A novel tetrakis (1-(N-
Carboxymethylcarbamoyl)ethyl mercapto]
Germanic CTgtrakis(1-(N-carAo
xynsgtAyl cqrbantoyl-) g
tAyl-mtrcapto) germane,
Hereinafter, the following will be abbreviated as T, C, E, and Q, and the manufacturing method thereof.
古来筋の治療に有効な薬として、一般に使用されている
漢薬類にはゲルマニウムが次表に示すように相当量含有
されている。Traditional Chinese medicines that have been used as effective medicines for muscle treatment contain considerable amounts of germanium, as shown in the table below.
表 漢薬類のゲルマニウム含有量
その他、朝鮮人参（朝鮮産）の良質のものにはゲルマニ
ウム含量が４０００ ｐｐｍに及ぶものがあると云う。Table: Germanium content in Chinese medicines In addition, it is said that some high-quality Korean ginseng (produced in Korea) has a germanium content of up to 4000 ppm.
これらの分析結果より想像するに生薬中のゲルマニウム
はどのような有機化合物となって含有されているかは不
明であるが、水溶性の有機化合物と、して含有されてい
ることが想像される。Based on these analysis results, it is unclear what kind of organic compound germanium is contained in herbal medicines, but it is assumed that it is contained as a water-soluble organic compound.
本発明者は、このような見地から水溶性ゲルマニウム化
合物について研究を重ねた結果、肝炎、肝硬変、電麻疹
、皮膚炎、雌、座瘉等に有効な２−メルカプトプロピオ
ニルグリシンとゲルマニウムのキレート化合物であるＴ
、 Ｃ，Ｅ、Ｇ、が上記炎症性疾患及び癌に有効である
ことを見出し、更に研究の結東好収率でＴ、 Ｃ０Ｅ、
Ｇ、を合成することに成功し、本発明を完成した。As a result of repeated research on water-soluble germanium compounds from this perspective, the present inventor has discovered that a chelate compound of 2-mercaptopropionylglycine and germanium is effective against hepatitis, cirrhosis, electric measles, dermatitis, acne, etc. A certain T
, C, E, and G were found to be effective against the above-mentioned inflammatory diseases and cancer, and further research showed that T, C0E,
We succeeded in synthesizing G, and completed the present invention.
まず本発明のＴ、 Ｃ，Ｅ、 Ｇ、の製造法について説
明する。First, the method for producing T, C, E, and G of the present invention will be explained.
酸化ゲルマニウム１分子量を１００倍の水に加熱溶解し
、透明に溶解した後、４分子量の２−メルカプトプロピ
オニルグリシンを加え、攪拌下１００℃で加熱反応せし
める。２〜３時間時間反応水分を減圧下で回収し殆んど
完全に水分を留去すると粘着性を有するＴ、 Ｃ，Ｅ、
Ｇ、が残る。One molecular weight of germanium oxide is heated and dissolved in 100 times the amount of water to make it transparent. After that, 4 molecular weight of 2-mercaptopropionylglycine is added and a reaction is caused by heating at 100° C. with stirring. When the reaction water is collected under reduced pressure for 2 to 3 hours and the water is almost completely distilled off, sticky T, C, E,
G remains.
これにペンツオールを加え約６０℃で攪拌溶解した後、
−夜冷蔵庫中に放置するとＴ、Ｃ，Ｂ、 Ｇ、の結晶が
析出する。結晶をｒ別し、更に冷ペンツオールで洗浄す
るか或は再結晶し、ｒ別後乾燥する。After adding pentol to this and stirring and dissolving it at about 60℃,
- If left in the refrigerator at night, crystals of T, C, B, and G will precipitate. The crystals are separated, further washed with cold pentol or recrystallized, and dried after separation.
今上記反応操作を次の通り行なう。Now, the above reaction operation is carried out as follows.
酸化ゲルマニウム１００Ｉに水１０，０００．９を加え
て、１００℃に加熱し攪拌する。約１時間半位で透明に
溶解する。これに、２−メルカプトプロピオニルグリシ
ン６２５Ｉ！を加え２〜３時間加熱下（１００℃）攪拌
反応させる。反応終了後、減圧下で水分を完全に留去す
る。粘着性を有する残渣にペンツオール約１ｋｇを加え
６０℃で１時間加温攪拌して溶解した後、−夜冷蔵庫中
に放置するとＴ、 Ｃ，Ｅ、 Ｑ、の結晶が析出する。Add 10,000.9 I of water to 100 I of germanium oxide, heat to 100° C. and stir. It dissolves transparently in about an hour and a half. In addition, 2-mercaptopropionylglycine 625I! is added and reacted with stirring under heating (100°C) for 2 to 3 hours. After the reaction is complete, water is completely distilled off under reduced pressure. Approximately 1 kg of pentol was added to the sticky residue, heated and stirred at 60°C for 1 hour to dissolve, and then left in the refrigerator overnight to precipitate crystals of T, C, E, and Q.
結晶をｒ別し、更に冷ベンツオールで洗浄し、再びＦ別
し、乾燥する。 収量的５９０〜６０（Ｌ９このＴ、
Ｃ９Ｅ、Ｇ、は前記式（１）に示す構造を有する文献未
記載の化合物であり、その理化学的性質は下記に示す通
りである。The crystals are separated by R, further washed with cold benzol, separated again by F, and dried. Yield 590-60 (L9 this T,
C9E,G is a compound having the structure shown in the above formula (1) that has not been described in any literature, and its physicochemical properties are as shown below.
（１）組成式’ ＣｔｏＨｓｔＮ＜Ｏ＋ｔＳ＊Ｑｇ（２
）分子量 ：’７２１．３２２４
（３）元素分析 、 Ｃ（％） Ｈ（１１Ｎ
＋１） Ｓ（餉計算値 ３３．３１ ４．４７ ７．
７７ １７．７９分析値 ３３５６ ４．３９ ７．５
３ １７．９１誤差０２５０．０８０．２４ ０．１２
このように分析結果は良く一致する。(1) Composition formula 'CtoHstN<O+tS*Qg(2
) Molecular weight: '721.3224 (3) Elemental analysis, C (%) H (11N
+1) S (calculated value 33.31 4.47 7.
77 17.79 Analysis value 3356 4.39 7.5
3 17.91 error 0250.080.24 0.12
The analysis results thus agree well.
（４）ペーパークロマトグラフ
Ｔ、 Ｃ，−Ｅ、 Ｇ、が単一物質であることが確認さ
れた。(4) Paper chromatographs T, C, -E, and G were confirmed to be a single substance.
（５）純 度 ：９９〜１００％
（６）融 点 ２１８０℃で分解
（７１解性 ：水、メタノール、エタノールに可溶クロ
ロホルム、＆！ｇ塩イシ炭素に不溶ペンツオールに溶け
にくい（加温すると溶解する。）
（８）水溶液のＰＨ： 濃度（チ） ｐＨＯ，５４
，３
１，０４，３
２，０４，３
（９）赤外吸収スペクトル：第１図参照３３４０ａＲ−
’の吸収は＞ＮＨノ吸収２５００ ｍ−ｌの吸収は一〇
Ｘ肘の−ＯＨの吸収１７２０イ１の吸収は一αＸ肘のン
ＣＯの吸収Ｑｌ ’Ｈ核磁気共鳴スペクトル：第２図参
照なお、純度の計算はゲルマニウムを指標として以下の
方法により行なう。(5) Purity: 99-100% (6) Melting point Decomposes at 2180℃ (71) Solubility: Soluble in water, methanol, ethanol, chloroform, &! (Dissolve.) (8) PH of aqueous solution: Concentration (ch) pHO, 54
,3 1,04,3 2,04,3 (9) Infrared absorption spectrum: See Figure 1 3340aR-
'The absorption of > NH absorption 2500 ml is 10X -OH absorption 1720 I1 absorption is - αX elbow CO absorption Ql 'H nuclear magnetic resonance spectrum: see Figure 2 Note that the purity is calculated by the following method using germanium as an indicator.
Ｔ、 Ｃ，Ｅ、 Ｇ、約１ｇを精密に秤量し、磁性ルツ
ボにとり、はじめは小さなバーナー炎で弱く加熱し炭化
させる。煙が出なくなったら電気炉で約７２０〜７４０
℃で約２〜３時間加熱すると白色ノ贈化ゲルマニウムか
のこる。この酸化ゲルマニウムの重量を測定し、次式〔
ｌＴ）により純度を求又、Ｔ、Ｃ，ｍ、 ａ、の添加加
工品に付いてはケルセチンスルフオン酸法或はフェニー
ルフルオロン法により求める。Precisely weigh approximately 1 g of T, C, E, and G, place in a magnetic crucible, and heat gently at first with a small burner flame to carbonize. When the smoke stops coming out, use an electric furnace for about 720-740 yen.
When heated at ℃ for about 2 to 3 hours, a white colored germanium substance appears. The weight of this germanium oxide was measured, and the following formula [
Purity is determined by T, C, m, a, etc., using the quercetin sulfonic acid method or the phenylfluorone method.
以上述べたように本発明のテトラキス〔１−（Ｎ−カル
ボキシメチルカルバモイル）エチルメルカプトコゲルマ
ンは癌茫有効とされるゲルマニウムと肝炎、肝硬変、炎
症性皮膚疾患に有効である２−メルカプトプロピオニル
グリシンとのキレート化合物であり、両者の薬効を有す
る新規化合物である。又、このＴ、 Ｃ，Ｅ、 Ｇ、は
０．２％含有のクリームを作ると皮膚をやわらかにし、
スベスベした感じを与え、水を使用しても手があれるこ
となくひび、あ１．かぎれ等の皮膚のあれを防ぐことが
できる。As mentioned above, the tetrakis[1-(N-carboxymethylcarbamoyl)ethylmercaptocogermane of the present invention] contains germanium, which is said to be effective against cancer, and 2-mercaptopropionylglycine, which is effective against hepatitis, liver cirrhosis, and inflammatory skin diseases. It is a chelate compound of both, and is a new compound that has the medicinal effects of both. Also, when a cream containing 0.2% of T, C, E, and G is made, it softens the skin.
Gives a smooth feel and prevents cracks even when used with water.A1. It can prevent skin irritation such as cuts.
又、本発明の製造法によれば、答易に入手し得る原料に
より、比較的簡単な方法で好収率にＴ、 Ｃ，Ｅ、Ｇ、
を製造することができる。Furthermore, according to the production method of the present invention, T, C, E, G,
can be manufactured.
＃！１図は本発明のＴ、Ｃ，Ｅ、 Ｑ、の赤外吸収スペ
クトル（ＫＢｒ）の図、第２図は本発明のＴ、 Ｃ６Ｅ
、Ｇ。
のｍ磁ｘ共鳴スペクトルの図である。
特許出願人
第一薬品産業株式会社
特許出願人代理人#! Figure 1 shows the infrared absorption spectra (KBr) of T, C, E, Q of the present invention, and Figure 2 shows the T, C6E of the present invention.
,G. FIG. 2 is a diagram of the m magnetic x resonance spectrum of Patent applicant Daiichi Yakuhin Sangyo Co., Ltd. Patent applicant agent
Claims (1)
イル）エチルメルカプトコゲルマン。 ２）酸化ゲルマニウム１分子量と２−メルカプトプロピ
オニルグリシン４分子量とを水溶液中で加熱反応させる
ことによりテトラキスＣＩ −（Ｎ−カルボキシメチル
カルバモイル）エチルメルカプトコゲルマンを製造する
方法。[Claims] 1) Tetrakis[1-(N-carboxymethylcarbamoyl)ethylmercaptocogermane. 2) A method for producing tetrakis CI -(N-carboxymethylcarbamoyl)ethylmercaptocogermane by heating and reacting one molecular weight of germanium oxide and four molecular weights of 2-mercaptopropionylglycine in an aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57057730A JPS58174391A (en) | 1982-04-07 | 1982-04-07 | Tetrakis(1-(n-carboxymethylcarbamoyl)ethylmercapto) germane and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57057730A JPS58174391A (en) | 1982-04-07 | 1982-04-07 | Tetrakis(1-(n-carboxymethylcarbamoyl)ethylmercapto) germane and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58174391A true JPS58174391A (en) | 1983-10-13 |
| JPS6212797B2 JPS6212797B2 (en) | 1987-03-20 |
Family
ID=13064032
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57057730A Granted JPS58174391A (en) | 1982-04-07 | 1982-04-07 | Tetrakis(1-(n-carboxymethylcarbamoyl)ethylmercapto) germane and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58174391A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2549066A1 (en) * | 1983-07-11 | 1985-01-18 | Asai Germanium Res Inst | NOVEL ORGANOGERMANIUM COMPOUND USEFUL AS ANTINEOPLASTIC AGENT |
| WO1998009975A1 (en) * | 1996-09-05 | 1998-03-12 | Primamedic Limited | 1,3-dicarboxylic germanium complex and its therapeutic use |
-
1982
- 1982-04-07 JP JP57057730A patent/JPS58174391A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2549066A1 (en) * | 1983-07-11 | 1985-01-18 | Asai Germanium Res Inst | NOVEL ORGANOGERMANIUM COMPOUND USEFUL AS ANTINEOPLASTIC AGENT |
| WO1998009975A1 (en) * | 1996-09-05 | 1998-03-12 | Primamedic Limited | 1,3-dicarboxylic germanium complex and its therapeutic use |
| US6204276B1 (en) | 1996-09-05 | 2001-03-20 | Primamedic Ltd. | Dicarboxylic germanium complex and its therapeutic use |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6212797B2 (en) | 1987-03-20 |
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