JPS5935916B2 - Organic germanium compound and its manufacturing method - Google Patents
Organic germanium compound and its manufacturing methodInfo
- Publication number
- JPS5935916B2 JPS5935916B2 JP56087558A JP8755881A JPS5935916B2 JP S5935916 B2 JPS5935916 B2 JP S5935916B2 JP 56087558 A JP56087558 A JP 56087558A JP 8755881 A JP8755881 A JP 8755881A JP S5935916 B2 JPS5935916 B2 JP S5935916B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- organic germanium
- germanium compound
- lower alkyl
- general formula
- 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.)
- Expired
Links
- 150000002291 germanium compounds Chemical class 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 12
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- QJPXCEZHYSIWRD-UHFFFAOYSA-N C(C)[Ge](S)(S)S Chemical class C(C)[Ge](S)(S)S QJPXCEZHYSIWRD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 230000003009 desulfurizing effect Effects 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000013078 crystal Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- NLIJOIUVZBYQRS-UHFFFAOYSA-N 3-trichlorogermylpropanoic acid Chemical compound OC(=O)CC[Ge](Cl)(Cl)Cl NLIJOIUVZBYQRS-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- GIEAINOVPLDQPT-UHFFFAOYSA-N ethylgermanium Chemical compound CC[Ge] GIEAINOVPLDQPT-UHFFFAOYSA-N 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- -1 organogermanium compound Chemical class 0.000 description 3
- 230000001766 physiological effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- VLZFWMHRXCHTLY-UHFFFAOYSA-N trichloro(ethyl)germane Chemical class CC[Ge](Cl)(Cl)Cl VLZFWMHRXCHTLY-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VPMMMQIATACXDN-UHFFFAOYSA-N 1-carboxypropan-2-ylgermanium Chemical compound CC([Ge])CC(O)=O VPMMMQIATACXDN-UHFFFAOYSA-N 0.000 description 1
- IQULGZQMMPRBLA-UHFFFAOYSA-N 2-carboxyethylgermanium Chemical compound OC(=O)CC[Ge] IQULGZQMMPRBLA-UHFFFAOYSA-N 0.000 description 1
- RXFDWPOEIKTCTH-UHFFFAOYSA-N 2-cyanoethylgermanium Chemical compound [Ge]CCC#N RXFDWPOEIKTCTH-UHFFFAOYSA-N 0.000 description 1
- BBKZEYDTCMRBCR-UHFFFAOYSA-N 2-methyl-3-trichlorogermylpropanoic acid Chemical compound OC(=O)C(C)C[Ge](Cl)(Cl)Cl BBKZEYDTCMRBCR-UHFFFAOYSA-N 0.000 description 1
- YOPIFVUIPDPTNM-UHFFFAOYSA-N 3-trichlorogermylpropanamide Chemical compound NC(=O)CC[Ge](Cl)(Cl)Cl YOPIFVUIPDPTNM-UHFFFAOYSA-N 0.000 description 1
- LSFGNGLLMQZPFT-UHFFFAOYSA-N NC(=O)CC[Ge] Chemical compound NC(=O)CC[Ge] LSFGNGLLMQZPFT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- OICUMRKNVLLVNJ-UHFFFAOYSA-N [Ge]CC(C)C(O)=O Chemical compound [Ge]CC(C)C(O)=O OICUMRKNVLLVNJ-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003276 anti-hypertensive effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- XEABSBMNTNXEJM-UHFFFAOYSA-N propagermanium Chemical compound OC(=O)CC[Ge](=O)O[Ge](=O)CCC(O)=O XEABSBMNTNXEJM-UHFFFAOYSA-N 0.000 description 1
- 150000005599 propionic acid derivatives Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- YITSIQZHKDXQEI-UHFFFAOYSA-N trichlorogermanium Chemical compound Cl[Ge](Cl)Cl YITSIQZHKDXQEI-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Description
【発明の詳細な説明】
本発明は新規な有機ゲルマニウム化合物及びその製造方
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel organogermanium compound and a method for producing the same.
炭素の同族体であるゲルマニウム（Ｇｅ）という元素は
、同じく炭素の同族体であるシリコン（Ｓｉ）と同様に
半導体効果を有するという特殊性から、長年にわたつて
物理学や無機化学の分野で研究が行なす）れていたもの
であるが、近年になつてその有機化合物に関する研究や
その結果の発表が活発に行なすつれ、各方面から注目さ
れるようになつた。The element germanium (Ge), which is a homolog of carbon, has been studied in the fields of physics and inorganic chemistry for many years because of its unique property of having a semiconductor effect like silicon (Si), which is also a homolog of carbon. However, in recent years, with the active research on organic compounds and the publication of their results, they have started to attract attention from various quarters.
例えば、本発明の発明者は上記のような動向にさきがけ
て、ゲルマニウムのプロピオン酸誘導体であり、しかも
、該ゲルマニウム原子と酸素原子とが交互に結合した、
あたかもクラウンエーテルのような１２員環を単位構造
とする極めてユニークな有機巨大分子化合物であるカル
ボキシエチルゲルマニウムセスキオキサイド（ＧｅＱ−
Ｉ！ＣＨ２ＣＯＯＹＴ）２ｑ（以下、単にセスキオキサ
イドという）の合成に成功し（Ｊ、Ａ、Ｃ、Ｓ、９８、
８２８７、（７６））、このセスキオキサイドの薬理効
果を試験してみたところ、極めて強力な血圧降下作用、
抗腫瘍作用等の生理活性を発揮する反面、全く毒性や副
作用を示さないことが明らかとなり、薬学界や囲学界で
非常に注目されるようになつた。而して、上記セスキオ
キサイドの生理活性のメカニズムは明確には解明されて
いないか、セスキオキサイド中に構成されているゲルマ
ニウム−酸素結合によるものと推定されているので、こ
の酸素原子を他の近縁した原子と置換した有機ゲルマニ
ウム化合物を合成することができれば、その有機ゲルマ
ニウム化合物は前記セスキオキサイド等の従来公知の有
機ゲルマニウム化合物に比較して、新たな面でより強力
な生理活性を発揮することが充分期待できる。For example, the inventor of the present invention pioneered the above-mentioned trend and developed a propionic acid derivative of germanium, in which germanium atoms and oxygen atoms are alternately bonded.
Carboxyethylgermanium sesquioxide (GeQ-
I! CH2COOYT)2q (hereinafter simply referred to as sesquioxide) was successfully synthesized (J, A, C, S, 98,
8287, (76)), and when we tested the pharmacological effects of this sesquioxide, we found that it has an extremely strong antihypertensive effect,
Although it exhibits physiological activities such as antitumor effects, it has become clear that it does not exhibit any toxicity or side effects, and has attracted much attention in the pharmaceutical and academic circles. However, the mechanism of the physiological activity of the sesquioxide has not been clearly elucidated, or it is presumed that it is due to the germanium-oxygen bond formed in the sesquioxide. If it is possible to synthesize an organic germanium compound in which adjacent atoms are substituted, that organic germanium compound will exhibit stronger physiological activity in new aspects compared to conventionally known organic germanium compounds such as the sesquioxides. can be fully expected.
本発明は上記のような事情を背景として、ゲルマニウム
原子と酸素の近縁原子との結合を含む新規な有機ゲルマ
ニウム化合物を提供することを目的として、鋭意研究の
結果完成されたもので、その有機ゲルマニウム化合物は
、一般式〔式中、Ａ及びＢは水素原子若しくは低級アル
キル基を、ＺはＣＯＯＨ，ＣＮ，ＣＯＮＨ２，ＣＨＯ及
びＣＯＯＲ（Ｒは低級アルキル基を表わす）のうちいず
れかを、それぞれ表わす〕で示されることを特徴とする
ものであり、又、その製造方法は、一般式〔式中、Ａ及
びＢは水「原子若しくは低級アルキル基を、ＺはＣＯＯ
Ｈ，ＣＮ，ＣＯＮＨ２，ＣＨＯ及びＣＯＯＲ（Ｒは低級
アルキル基を表わす）のうちいずれかを、それぞれ表わ
す〕で示されるエチルトリクロルゲルマニウム誘導体ど
硫化水素とを、無水状態でビリジン等の塩基存在下に反
応させることにより、一般式〔式中、Ａ，Ｂ及びＺは（
１）と同一である〕で示されるエチルトリメルカプトゲ
ルマニウム誘導体となし、これを分子間で脱硫化水素す
ることを特徴とするものである。Against the background of the above-mentioned circumstances, the present invention was completed as a result of intensive research with the aim of providing a novel organic germanium compound containing a bond between a germanium atom and an atom closely related to oxygen. The germanium compound has a general formula [wherein A and B represent a hydrogen atom or a lower alkyl group, and Z represents one of COOH, CN, CONH2, CHO and COOR (R represents a lower alkyl group)] It is characterized by being represented by the general formula [where A and B are water atoms or lower alkyl groups, and Z is COO
H, CN, CONH2, CHO, and COOR (R represents a lower alkyl group)] and hydrogen sulfide in an anhydrous state in the presence of a base such as pyridine. By reacting, the general formula [wherein A, B and Z are (
This is the same as 1)] and is characterized by intermolecular desulfurization of the ethyltrimercaptogermanium derivative.
以下、本発明を詳細に説明する。The present invention will be explained in detail below.
本発明の有機ゲルマニウム化合物は、一般式（１）で表
わされるように、エチルトリクロルゲルマニウム誘導体
と硫黄原子とが２：３の割合で結合したエチルゲルマニ
ウムセスキスルフイドを基本的構造とするものであり、
例えば次のような化合物である。The organic germanium compound of the present invention has a basic structure of ethylgermanium sesquisulfide in which an ethyltrichlorogermanium derivative and a sulfur atom are bonded in a ratio of 2:3, as represented by general formula (1). can be,
Examples include the following compounds.
上記のような構造を有する本発明有機ゲルマニウム化合
物は、一般式（１）で表わされるエチルトリクロルゲル
マニウム誘導体と硫化水素とを、無水状態でピリジン等
の塩基存在下に反応させることにより得ることができ、
これを上記化合物中（１）の場合について詳しく述べれ
ば、２−カルボキシエチルトリクロルゲルマン（Ｃ４Ｇ
ｅＣＨ２ＣＨ２ＣＯＯＨ）を無水ベンゼンに溶解し、無
水ピリジンを加えてかくはんした後、乾燥硫化水素を通
することにより２−カルボキシエチルトリメルカプトゲ
ルマンとなし、これに水又
はメタノールを加えることにより分子間で脱硫化水素す
るのであるが、本発明有機ゲルマニウム化合物を製造す
るに当つては、一般式（）で示される中間体の口メルカ
プト体は単離しても良いし、又、単離しなくても良い。The organic germanium compound of the present invention having the above structure can be obtained by reacting the ethyltrichlorogermanium derivative represented by the general formula (1) with hydrogen sulfide in an anhydrous state in the presence of a base such as pyridine. ,
To explain this in detail in the case of (1) among the above compounds, 2-carboxyethyltrichlorogermane (C4G
eCH2CH2COOH) is dissolved in anhydrous benzene, anhydrous pyridine is added and stirred, and then dried hydrogen sulfide is passed through to form 2-carboxyethyltrimercaptogermane, which is intermolecularly desulfurized by adding water or methanol. However, in producing the organic germanium compound of the present invention, the mercapto form of the intermediate represented by the general formula () may or may not be isolated.
このようにして得られる本発明の有機ゲルマニウム化合
物は、すでに述べたようにエチルゲルマニウム誘導体と
硫黄原子とが２：３の割合で結合した巨大分子であるか
ら、前記セスキオキサイドや無機化合物の二酸化ケイ素
ＳｉＯ２と同様に、構成単位とその割合を用いて一般式
（１）のように示したが、該構成単位をモノマーとする
ポリマーの様に把握して、若しくは、
のように示すこともできる。The organic germanium compound of the present invention obtained in this way is a macromolecule in which an ethylgermanium derivative and a sulfur atom are bonded in a ratio of 2:3, as described above, and therefore, the organic germanium compound of the present invention is a large molecule in which an ethylgermanium derivative and a sulfur atom are bonded in a ratio of 2:3. Similar to SiO2, it is expressed as the general formula (1) using the structural units and their ratios, but it can also be understood like a polymer using the structural units as monomers, or expressed as follows.
然し乍ら、上記（１つ（″）のように示した場合には、
ｎの範囲が特定できないので、適当とは言いがたい。而
して、本発明化合物は、前記セスキオキサイドと同様に
、種々の生物活性を示し、医薬品の主剤として多方面に
わたつて応用されることが期待されるが、例えば本発明
化合物のうち（２），（５），（７），についてその抗
菌力を試験してみたところ、次のような結果を得た。However, in the case of (1) shown above,
Since the range of n cannot be specified, it is difficult to say that it is appropriate. The compounds of the present invention, like the sesquioxides described above, exhibit various biological activities and are expected to be applied in a wide range of fields as main ingredients of pharmaceuticals. ), (5), and (7) were tested for their antibacterial activity, and the following results were obtained.
次に本発明の実験例について述べるが、本発明有機ゲル
マニウム化合物の原料となるエチルトリクロルゲルマニ
ウム誘導体（）は、いずれもトリクロルゲルマニウムＨ
ＧｅＣムとアクリル酸誘導体との付加反応により合成す
ることができ、例えば本発明化合物（１）を製造する際
の原料となる２−カルボキシエチルトリクロルゲルマン
ＣムＧｅＣＨ２ＣＨ２ＣＯＯＨは特公昭４６−２９６４
号公報に開示されている方法等により容易に合成するこ
とができる。Next, experimental examples of the present invention will be described. Ethyltrichlorogermanium derivatives (), which are the raw materials for the organic germanium compounds of the present invention, are all trichlorogermanium H
For example, 2-carboxyethyltrichlorogermane C, GeCH2CH2COOH, which can be synthesized by an addition reaction between GeC and an acrylic acid derivative, and is a raw material for producing the compound (1) of the present invention, is synthesized from Japanese Patent Publication No. 46-2964.
It can be easily synthesized by the method disclosed in the above publication.
実験例 １
２−カルボキシエチルトリクロルゲルマンＣムＧｅＣＨ
２ＣＨ２ＣＯＯＨ２５．２ｙ（ ０．１モル）を無水ベ
ンゼン２００ゴに溶解し、無水ピリジン２４ｇ（ ０．
１モル）を加えてかくはん後、乾燥硫化水素ガスを６０
分間通じた。Experimental example 1 2-carboxyethyl trichlorogermane C GeCH
25.2y (0.1 mol) of 2CH2COOH was dissolved in 200 g of anhydrous benzene, and 24 g (0.1 mol) of anhydrous pyridine was dissolved.
1 mol) and stirred, add 60 mol of dry hydrogen sulfide gas.
It lasted for a minute.
生じた油状物に注意し乍らベンゼンを除き、該油状物を
メタノール１００ｍｉに溶解し、これを精製水３００ｗ
Ｌ１！に加え、析出した結晶をメタノールから再結晶し
たところ、２−カルボキシエチルゲルマニウムセスキス
ルフイド（１）（ ＧｅＣＨ２ＣＨ２ＣＯＯＨ）２Ｓ３
の無色板状結晶１６．８θが得られた。収率は８６．７
％であつた。実験例 ２２−シアノエチルトリクロルゲ
ルマン
ＣムＧｅＣＨ２ＣＨ２ＣＮ２３．３ｇ（ ０．１モル）
を氷冷し乍ら無水ベンゼン２００ゴに溶解し、無水ピリ
ジン２４９（０．３モル）を加えてかくはん後、乾燥硫
化水素を６０分間通じた。Benzene was removed while being careful of the oily substance formed, the oily substance was dissolved in 100ml of methanol, and this was dissolved in 300w of purified water.
L1! In addition, when the precipitated crystals were recrystallized from methanol, 2-carboxyethylgermanium sesquisulfide (1) (GeCH2CH2COOH)2S3
Colorless plate-like crystals of 16.8θ were obtained. Yield is 86.7
It was %. Experimental example 23.3 g (0.1 mol) of 22-cyanoethyl trichlorogermane C GeCH2CH2CN
was dissolved in 200 g of anhydrous benzene while cooling on ice, and anhydrous pyridine 249 (0.3 mol) was added and stirred, followed by passing dry hydrogen sulfide through for 60 minutes.
生じた沈澱に注意し乍らベンゼンを除き、メタノール２
００ゴを加えて３０分間かくはんした後、析出した結晶
を精製水、メタノール，エチルエーテルの順で洗浄し、
乾燥したところ、２−シアノエチルゲルマニウムセスキ
スルフイド（２）（ＧｅＣＨ２ＣＨ２ＣＨ）２Ｓ３の無
色無定型結晶１５．８９が得られた。収率は９０．５％
であつた。実験例 ３
２−カルボキシ−２−メチルエチルトリクロルゲルマン
ＣムＧｅＣＨ２ＣＨ（ＣＨ３）ＣＯＯＨ２６．６９（０
．１モル）を無水ベンゼン４００ｍｊに溶解し、無水ピ
リジン２４９（ ０．３モル）を加えてかくはん後、乾
燥硫化水素を９０分通じた。Remove the benzene while being careful of the precipitate that has formed, and add methanol 2.
After adding 00g and stirring for 30 minutes, the precipitated crystals were washed with purified water, methanol, and ethyl ether in this order.
Upon drying, 15.89 g of colorless amorphous crystals of 2-cyanoethylgermanium sesquisulfide (2) (GeCH2CH2CH)2S3 were obtained. Yield is 90.5%
It was hot. Experimental example 3 2-carboxy-2-methylethyltrichlorogermane CM GeCH2CH(CH3)COOH26.69(0
．． 1 mol) was dissolved in 400 mj of anhydrous benzene, anhydrous pyridine 249 (0.3 mol) was added, and after stirring, dry hydrogen sulfide was passed through the solution for 90 minutes.
生じた油状物から注意し乍らベンゼンを除き、メタノー
ル１００ゴを加えて該油状物を溶解し、これを精製水３
００ゴ中に滴下すると結晶が析出するので、この結晶を
戸別してメタノールと精製水の１：１溶液から再結晶し
たところ、２−カルボキシ−２−メチルエチルゲルマニ
ウムセスキスルフイド（３）（ＧｅＣＨ２ＣＨ（ＣＨ３
）ＣＯＯＨ）２Ｓ３の無色針状結晶２０．０９が得られ
た。収率は９６．２％であつた。実験例 ４１−メチル
−２−カルボキシエチルトリクロルゲルマンＣムＧｅＣ
Ｈ（ＣＨ３）ＣＨ２ＣＯＯＨ２６．６ｇ（０．１モル）
を無水ベンゼン４００ゴに溶解し、無水ピリジン２４ｇ
（ ０．３モル）を加え１０分間かくはんした後、乾燥
硫化水素を９０分間通じた。Carefully remove benzene from the resulting oil, add 100 g of methanol to dissolve the oil, and add 3 g of purified water.
Crystals precipitate when added dropwise to 2-carboxy-2-methylethylgermanium sesquisulfide (3) (GeCH2CH (CH3
) COOH) 2S3 20.09 colorless needle crystals were obtained. The yield was 96.2%. Experimental example 41-methyl-2-carboxyethyl trichlorogermane C GeC
H(CH3)CH2COOH26.6g (0.1 mol)
was dissolved in 400 g of anhydrous benzene, and 24 g of anhydrous pyridine was added.
(0.3 mol) was added and stirred for 10 minutes, and then dry hydrogen sulfide was passed through the mixture for 90 minutes.
反応液は二層に分離したので下層を分取し、メタノール
１５０ゴを加えて希釈後、このメタノール溶液に精製水
４００ゴを加えた。この水溶液を約半量になるまで濃縮
し、さらに乾燥硫化水素を３０分間通じて放置すると結
晶が析出するので、この結晶を炉取し、メタノールから
再結晶したところ、１−メチル−２−カルボキシエチル
ゲルマニウムセスキスルフイド（４）（ＧｅＣＨ（ＣＨ
３）ＣＨ２ＣＯＯＨ）２Ｓ３の無色板状結晶１０．１４
９が得られた。収率は４８．８％であつた。実験例 ５
２−カルバモイルエチルトリクロルゲルマンＣムＧｅＣ
Ｈ２ＣＨ２ＣＯＮＨ２２５．ｌｇ（ ０．１モル）を無
水ベンゼン５００ゴに溶解し、前記実険例１と同一条件
で硫化水素と反応させた後、後処理をしたところ、２−
カルバモイルエチルゲルマニウムセスキスルフイド（Ｇ
ｅＣＨ２ＣＨ２ＣＯＮＨ２）２Ｓ３のプリズム状結晶５
．３４ｇが得られた。The reaction solution was separated into two layers, so the lower layer was separated, diluted with 150 g of methanol, and 400 g of purified water was added to the methanol solution. When this aqueous solution was concentrated to about half its volume and further left in dry hydrogen sulfide for 30 minutes, crystals precipitated.When these crystals were collected in a furnace and recrystallized from methanol, 1-methyl-2-carboxyethyl Germanium sesquisulfide (4) (GeCH(CH
3) Colorless plate-like crystals of CH2COOH)2S3 10.14
9 was obtained. The yield was 48.8%. Experimental example 5 2-carbamoylethyl trichlorogermane C GeC
H2CH2CONH225. 1g (0.1 mol) was dissolved in 500 g of anhydrous benzene and reacted with hydrogen sulfide under the same conditions as in Practical Example 1, followed by post-treatment.
Carbamoylethylgermanium sesquisulfide (G
eCH2CH2CONH2)2S3 prismatic crystal 5
．． 34g was obtained.
収率は２７．５％であつた。実験例 ６
１−メチル−２−カルバモイルエチルトリクカルゲルマ
ンＣムＧｅＣＨ（ＣＨ３）ＣＨ２ＣＯＮＨ２２６．５ｇ
（ ０．１モル）を無水アセトン２００ゴに溶解し、前
記実険例１と同一の条件で硫化水素と反応させた後，後
処理をしたところ、１−メチル−２−カルバモイルエチ
ルゲルマニウムセスキスルフイド（ＧｅＣＨ（ＣＨ３）
ＣＨ２ＣＯＮＨ２）２Ｓ３の板状結晶４．２８Ｉが得ら
れた。The yield was 27.5%. Experimental Example 6 1-Methyl-2-carbamoylethyltriccalgermane C GeCH(CH3)CH2CONH226.5g
(0.1 mol) was dissolved in 200 g of anhydrous acetone and reacted with hydrogen sulfide under the same conditions as in Practical Example 1, followed by post-treatment. Feed(GeCH(CH3)
4.28I platelet crystals of CH2CONH2)2S3 were obtained.
収率は２０．７％であつた。実験例 ７２−ホリミルエ
チルトリクロルゲノｖマニウムＣムＧｅＣＨ２ＣＨ２Ｃ
ＨＯ２９．ｌｌ（ ０．１モル）を無水ベンゼン２００
ゴに溶解し、氷冷し乍ら無水ピリジン２４９（ ０．３
モル）を加えてかくはん後、実験例１と同一の条件で硫
化水素と反応させた後、後処理をしたところ、２−ホル
ミルエチルゲルマニウムセスキスルフイド（ＧｅＣルＣ
Ｈ２ＣＨＯ）２Ｓ３の無色無定結晶１０．２５ｙが得ら
れた。The yield was 20.7%. Experimental example 72-Horimylethyl trichlorgeno-manium C GeCH2CH2C
HO29. ll (0.1 mol) of anhydrous benzene 200
Anhydrous pyridine 249 (0.3
2-formylethylgermanium sesquisulfide (GeC) was reacted with hydrogen sulfide under the same conditions as in Experimental Example 1, and then post-treated.
10.25y of colorless amorphous crystals of H2CHO)2S3 were obtained.
Claims (1)
及びＢは水素原子若しくは低級アルキル基を、ＺはＣＯ
ＯＨ、ＣＮ、ＣＯＮＨ＿２、ＣＨＯ及びＣＯＯＲ（Ｒは
低級アルキル基を表わす）のうちいずれかを、それぞれ
表わす〕で示されることを特徴とする有機ゲルマニウム
化合物。 ２ 一般式 ▲数式、化学式、表等があります▼（II）〔式中、Ａ及
びＢは水素原子若しくは低級アルキル基を、ＺはＣＯＯ
Ｈ、ＣＮ、ＣＯＮＨ＿２、ＣＨＯ及びＣＯＯＲ（Ｒは低
級アルキル基を表わす）のうちいずれかを、それぞれ表
わす〕で示されるエチルトリクロルゲルマニウム誘導体
と硫化水素とを、無水状態でピリジン等の塩基存在下に
反応させることにより、一般式▲数式、化学式、表等が
あります▼（III）〔式中、Ａ、Ｂ及びＺは（II）と同
一である〕で示されるエチルトリメルカプトゲルマニウ
ム誘導体となし、これを分子間で脱硫化水素することを
特徴とする有機ゲルマニウム化合物の製造方法。[Claims] 1. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, A
and B is a hydrogen atom or a lower alkyl group, Z is CO
OH, CN, CONH_2, CHO, and COOR (R represents a lower alkyl group), respectively. 2 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (II) [In the formula, A and B are hydrogen atoms or lower alkyl groups, Z is COO
H, CN, CONH_2, CHO and COOR (R represents a lower alkyl group)] and hydrogen sulfide in an anhydrous state in the presence of a base such as pyridine. By reacting, it becomes an ethyltrimercaptogermanium derivative represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (III) [In the formula, A, B and Z are the same as (II)], and this A method for producing an organic germanium compound, which comprises intermolecularly desulfurizing the organic germanium compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56087558A JPS5935916B2 (en) | 1981-06-09 | 1981-06-09 | Organic germanium compound and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56087558A JPS5935916B2 (en) | 1981-06-09 | 1981-06-09 | Organic germanium compound and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57203090A JPS57203090A (en) | 1982-12-13 |
| JPS5935916B2 true JPS5935916B2 (en) | 1984-08-31 |
Family
ID=13918312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56087558A Expired JPS5935916B2 (en) | 1981-06-09 | 1981-06-09 | Organic germanium compound and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5935916B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3424107A1 (en) * | 1983-07-01 | 1985-01-10 | Asai Germanium Research Institute, Tokio/Tokyo | ORGANOGERMANIUM COMPOUND AND THIS ACTIVE INGREDIENT OPIOID PEPTIDAS INHIBITOR |
| JPS6016924A (en) * | 1983-07-11 | 1985-01-28 | Asai Gerumaniumu Kenkyusho:Kk | Antineoplastic agent |
| JPS60226592A (en) * | 1984-04-25 | 1985-11-11 | Asai Gerumaniumu Kenkyusho:Kk | Antioxidant |
| JPS63107920A (en) * | 1986-06-18 | 1988-05-12 | Asai Gerumaniumu Kenkyusho:Kk | Osteroblast activator |
| JPS62142189A (en) * | 1986-12-12 | 1987-06-25 | Asai Gerumaniumu Kenkyusho:Kk | Organogermanium compound |
-
1981
- 1981-06-09 JP JP56087558A patent/JPS5935916B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57203090A (en) | 1982-12-13 |
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