JPS637192B2 - - Google Patents
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- Publication number
- JPS637192B2 JPS637192B2 JP8802781A JP8802781A JPS637192B2 JP S637192 B2 JPS637192 B2 JP S637192B2 JP 8802781 A JP8802781 A JP 8802781A JP 8802781 A JP8802781 A JP 8802781A JP S637192 B2 JPS637192 B2 JP S637192B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- general formula
- reaction
- germanium
- following general
- 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.)
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- 150000002291 germanium compounds Chemical class 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 9
- -1 Germanium halide Chemical class 0.000 claims description 7
- 229910052732 germanium Inorganic materials 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 16
- 235000019441 ethanol Nutrition 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 5
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229940047670 sodium acrylate Drugs 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MUDDKLJPADVVKF-UHFFFAOYSA-N trichlorogermane Chemical compound Cl[GeH](Cl)Cl MUDDKLJPADVVKF-UHFFFAOYSA-N 0.000 description 3
- VGUNRJRDVTYSCL-UHFFFAOYSA-N 2-hydroxyethylgermanium Chemical compound OCC[Ge] VGUNRJRDVTYSCL-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001766 physiological effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- IQULGZQMMPRBLA-UHFFFAOYSA-N 2-carboxyethylgermanium Chemical compound OC(=O)CC[Ge] IQULGZQMMPRBLA-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 208000007101 Muscle Cramp Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 208000004880 Polyuria Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 208000005392 Spasm Diseases 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- OEERIBPGRSLGEK-UHFFFAOYSA-N carbon dioxide;methanol Chemical compound OC.O=C=O OEERIBPGRSLGEK-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- DDKMFOUTRRODRE-UHFFFAOYSA-N chloromethanone Chemical group Cl[C]=O DDKMFOUTRRODRE-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 230000035619 diuresis Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229940093626 germanium sesquioxide Drugs 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 208000030603 inherited susceptibility to asthma Diseases 0.000 description 1
- 239000002799 interferon inducing agent Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 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
- 230000002685 pulmonary effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Description
本発明は有機ゲルマニウム化合物、特に下記一
般式〔〕
（但し式中Ｒは水素原子または炭素数１〜３のア
ルキル基を示す。）
で表わされる有機ゲルマニウム化合物の製造法に
関するものである。
本発明で目的とする前記一般式〔〕で表わさ
れる有機ゲルマニウム化合物は、その特有な性
質、水溶性、脂溶性のため生理活性物質として近
年注目されているものである。その生理活性は、
ヌクロフアージアクチベーター、インターフエロ
ンインジユーサーのなどの作用により制ガン、ア
レルギーの抑制、高血圧症、利尿、肺せんい症、
気管支喘息などが明らかとなつている。
この様な生理活性を有する前記有機ゲルマニウ
ム化合物の製造法として、例えば(A)特公昭46−
2964号公報記載のハロゲルマニウムヒドリドにア
クリロニトリルを反応させ、シアノエチルトリハ
ロゲルマニウムを得これを、酸分解により、カル
ボキシエチルゲルマニウムクロリドとなし、さら
にこれにチオニルクロリドを作用させ、カルボキ
シル基をカルボニルクロル基となし、次いでこれ
を加水分解して、カルボキシエチルゲルマニウム
セスオキシドを得る方法や(B)特開昭55−81890号
公報記載のカルボキシアルキルエチルトリハロゲ
ルマニウムを酸性加水分解することによりカルボ
キシエチルゲルマニウムセスキオキシドを得る方
法等がある。
しかし、前記(A)の方法は反応工程が多く複雑で
工業的には不利である。また(B)の方法は反応後に
メタノールの如き有機物が副生し、排水などの問
題が生起するとともに、例えばその原料として、
アクリル酸メチルの如き化合物を用いたときはそ
の臭気が問題となる。
本発明者はかかる欠点を克服すべく前記一般式
〔〕で表わされる有機ゲルマニウム化合物の製
造法を研究した結果、本発明に到達した。
すなわち、本発明は下記一般式〔〕
（但し式中Ｘはハロゲン原子、Ｒは水素原子また
は炭素数１〜３のアルキル基を示す。）
で表わされるハロ環状ゲルマニウム化合物をPH
1.5〜6.5の範囲で加水分解することを特徴とする
下記一般式〔〕
（但し式中Ｒは前記定義と同じ）
で表わされる有機ゲルマニウム化合物の製造法で
ある。
かゝる本発明方法によれば、前記一般式〔〕
のハロ環状ゲルマニウム化合物をPH0.5〜6.5の範
囲、好ましくはPH１〜６の範囲の酸性で加水分解
することにより収率よく、簡単に前記一般式
〔〕の有機ゲルマニウム化合物が得られる。
また本発明者らの研究によれば、前記一般式
〔〕は下記一般式〔〕
X3GeH ……〔〕
（但し式中Ｘは前記定義と同じ）
で表わされるハロゲン化ゲルマニウムと下記一般
式〔〕
（但し式中Ｒは前記定義と同じであり、Ｍはアル
カリ金属を示す。）
で表わされるアクリル酸誘導体とを反応せしめる
ことにより得られることがわかつた。
本発明は、前記の如くして前記一般式〔〕と
〔〕との反応によつて得られた下記一般式〔〕
（但し式中ＸおよびＲは前記定義と同じ）
で表わされるハロ環状ゲルマニウム化合物は、こ
れを含む反応混合物のPHを前記酸性状態として加
水分解することもできるが、特に特徴的なことは
その反応混合物から式〔〕のハロ環状ゲルマニ
ウム化合物を蒸留により単離できることであり、
かくすることにより高純度の式〔〕のハロ環状
ゲルマニウムを得、次いでこれを前記酸性条件下
で加水分解して純度の良好な目的とする式〔〕
の有機ゲルマニウム化合物を得ることが可能とな
る。
本発明において使用する前記一般式〔〕で表
わされるハロゲン化ゲルマニウムは、例えば(i)ケ
ミカルアブストラクト536996i（1959）記載の如
く、金属ゲルマニウムと塩化水素ガスとの反応に
よるトリクロルゲルマニウムハイドライドを得る
方法に従つて、金属ゲルマニウムとハロゲン化水
素との反応による方法、(ii)グメリン・ハンドブツ
ハ・デル・アンオルガニツシユ・ヘミーシステ
ム、No.45、520頁に記載されている如く、四塩化
ゲルマニウムを高温気相下、分子状水素と反応さ
せて、トリクロロゲルマニウムハイドライドを製
造する方法に従つて、四ハロゲルマニウムと分子
状水素とを反応させる方法などがある。式〔〕
のＸのハロゲンとしては塩素が好ましい。
しかし、この他いかなる方法で製造したもので
も使用は可能であり、特に製造法に限定されるも
のではない。
また前記式〔〕のハロゲン化ゲルマニウムと
反応せしめられるアクリル酸誘導体は下記式
〔〕で表わされる。
この式中Ｒは水素原子または炭素数１〜３のア
ルキル基であり、好ましくは水素原子またはメチ
ル基である。またＭはアルカリ金属を示し、殊に
周期律表Ａ属のものが好ましい。特にリチウ
ム、ナトリウム、カリウムなどが工業的見地から
好ましい。
この〔〕のアクリル酸誘導体は、〔〕のア
ルカリ塩に対応するアクリル酸の水溶液を、重合
防止剤の存在下、アルカリ金属の水溶液と接触反
応させることにより得ることもできるし、また例
えば、特公昭48−31085公報記載の如く、不飽和
酸のエステルに重合防止剤の存在下アルカリ水溶
液を反応させてつくることも出来る。しかし、一
般式〔〕に相当するものであれば、その製造法
は特に限定されるものではない。
以上の如き、原料〔〕と〔〕との反応によ
り化合物〔〕を製造するわけであるが、この反
応は無溶媒でもよいが、一般には溶媒が用いられ
る。かかる溶媒としては、アルコール、ケトン、
エーテル、炭化水素、ハロゲン化炭化水素、カル
ボン酸等があるが、かかる溶媒のうち、例えばエ
タノール、メタノール、プロピルアルコール、ア
セトン、エチルエーテル、プロピルエーテル、四
塩化炭素等が好んで用いられる。
かかる溶媒のもと、ほゞ化学量論量の反応物を
用いて、一般に反応は行なわれる。
本発明におけるかゝる反応温度は、特に限定は
されないが、例えば０℃以上、好ましくは常温〜
200℃の範囲がよい。
かくして得られたハロ環状ゲルマニウム〔〕
を加水分解するのであるが、前記の如くして得ら
れた〔〕を含有する反応混合物に対して加水分
解を行うこともできるし、また前記反応混合物か
ら〔〕を単離して加水分解することもできる。
この単離の方法としては蒸留によつて行うことが
できる。例えば〔〕式中Ｘが塩素原子でありＲ
が水素原子のものは２mmHgの圧力において85℃
の沸点を有している。
本発明における式〔〕の加水分解反応におい
ては特に加水分解液のPHが重要であり、一定の範
囲PHで加水分解を行う必要がある。すなわち加水
分解はPH0.5以上6.5以下、好ましくはPH１以上、
６以下の範囲で行なわれ、これ以外のPHにおいて
は、加水分解により、目的生成物をうることがで
きないか、生成物が非常に少なくしか得ることが
できない。
以下本発明を実施例をかかげて詳述する。
実施例 １
（トリクロロゲルマニウムハイドライドの合
成）
内径直10mmφ×長さ250mmの石英管に、石英ウ
ールをつめ、管内温度を900℃に保つ。これにH2
ガスと四塩化ゲルマニウムの混合物を供給し、反
応液をドライアイス−メタノールトラツプで捕集
する。反応終了後、60〜70℃でトラツプを加熱
し、単蒸発させこれを別のトラツプに移し、精製
する。無色透明な液体が得られる。沸点75℃。
実施例 ２
内容量50c.c.のフラスコに、アクリル酸ナトリウ
ム1.0ｇｒ、ハイドロキノン10mg、エチルアルコ
ール20c.c.を仕込み、氷冷しつつ、前記実施例１で
得られたGeHCl31.26c.c.を５分間で滴下する。一
時間常温で撹拌したのち、60℃で更に１時間反応
さす。反応終了後、エタノールを追い出し、クロ
ロゲルマニウム環状化合物
The present invention relates to organic germanium compounds, particularly the following general formula [] (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) The present invention relates to a method for producing an organic germanium compound represented by the following formula. The organic germanium compound represented by the general formula [], which is the object of the present invention, has recently attracted attention as a physiologically active substance due to its unique properties, water solubility, and fat solubility. Its physiological activity is
Due to the effects of nucleophage activator and interferon inducer, it is effective against cancer, suppresses allergies, hypertension, diuresis, pulmonary spasms, etc.
Bronchial asthma has become evident. As a method for producing the organic germanium compound having such physiological activity, for example, (A)
The halogermanium hydride described in Publication No. 2964 is reacted with acrylonitrile to obtain cyanoethyltrihalogermanium, which is converted into carboxyethylgermanium chloride by acid decomposition, and further treated with thionyl chloride to convert the carboxyl group into a carbonylchlor group. Then, this is hydrolyzed to obtain carboxyethyl germanium sesoxide, and (B) carboxyethyl germanium sesquioxide is obtained by acidic hydrolysis of carboxyalkylethyl trihalogermanium described in JP-A-55-81890. There are methods etc. However, method (A) is complicated and has many reaction steps, and is industrially disadvantageous. In addition, in method (B), organic substances such as methanol are produced as by-products after the reaction, causing problems such as drainage.
When a compound such as methyl acrylate is used, its odor becomes a problem. In order to overcome these drawbacks, the present inventors researched a method for producing an organic germanium compound represented by the above general formula [], and as a result, they arrived at the present invention. That is, the present invention is based on the following general formula [] (However, in the formula, X is a halogen atom, R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) A halocyclic germanium compound represented by PH
The following general formula [] is characterized by being hydrolyzed in the range of 1.5 to 6.5 (However, R in the formula is the same as defined above.) This is a method for producing an organic germanium compound represented by the following formula. According to the method of the present invention, the general formula []
By hydrolyzing the halocyclic germanium compound with an acidity in the pH range of 0.5 to 6.5, preferably in the pH range of 1 to 6, the organic germanium compound of the general formula [] can be easily obtained in good yield. Further, according to the research of the present inventors, the above general formula [] is a germanium halide represented by the following general formula [] [] (However, in the formula, R is the same as defined above, and M represents an alkali metal.) It was found that it can be obtained by reacting with an acrylic acid derivative represented by the following. The present invention provides the following general formula [] obtained by the reaction of the general formula [] and [] as described above. (However, in the formula, X and R are the same as defined above.) The halocyclic germanium compound represented by the following can also be hydrolyzed by setting the pH of the reaction mixture containing it to the acidic state, but the particularly characteristic feature is that the reaction The halocyclic germanium compound of the formula [] can be isolated from a mixture by distillation,
In this way, a highly pure halocyclic germanium of the formula [] is obtained, which is then hydrolyzed under the acidic conditions to obtain the target formula [] with good purity.
It becomes possible to obtain an organic germanium compound of. The germanium halide represented by the general formula [] used in the present invention can be prepared by the method of obtaining trichlorogermanium hydride by reacting metal germanium with hydrogen chloride gas, for example, as described in (i) Chemical Abstracts 536996i (1959). (ii) Germanium tetrachloride is heated to a high temperature as described in Gmelin Handbutzha der Anorganizichem Chemie System, No. 45, p. 520. There is a method for producing trichlorogermanium hydride by reacting with molecular hydrogen in a gas phase, and a method for reacting tetrahalogermanium with molecular hydrogen. formula〔〕
The halogen for X is preferably chlorine. However, it is possible to use products produced by any other method, and the production method is not particularly limited. Further, the acrylic acid derivative reacted with the germanium halide of the above formula [] is represented by the following formula []. In this formula, R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group. Further, M represents an alkali metal, and metals from group A of the periodic table are particularly preferred. In particular, lithium, sodium, potassium, etc. are preferred from an industrial standpoint. This acrylic acid derivative [] can be obtained by contacting and reacting an aqueous solution of acrylic acid corresponding to the alkali salt of [] with an aqueous solution of an alkali metal in the presence of a polymerization inhibitor. As described in Japanese Publication No. 48-31085, it can also be produced by reacting an ester of an unsaturated acid with an aqueous alkaline solution in the presence of a polymerization inhibitor. However, the manufacturing method is not particularly limited as long as it corresponds to the general formula []. As described above, the compound [ ] is produced by the reaction of the raw materials [ ] and [ ], and although this reaction may be carried out without a solvent, a solvent is generally used. Such solvents include alcohols, ketones,
Examples of such solvents include ethers, hydrocarbons, halogenated hydrocarbons, and carboxylic acids. Among these solvents, for example, ethanol, methanol, propyl alcohol, acetone, ethyl ether, propyl ether, carbon tetrachloride, and the like are preferably used. The reaction is generally carried out in such a solvent and using approximately stoichiometric amounts of the reactants. The reaction temperature in the present invention is not particularly limited, but is, for example, 0°C or higher, preferably room temperature to
A range of 200℃ is recommended. The thus obtained halocyclic germanium []
The reaction mixture containing [] obtained as described above can be hydrolyzed, or [] can be isolated from the reaction mixture and hydrolyzed. You can also do it.
This isolation can be carried out by distillation. For example, in the formula [], X is a chlorine atom and R
is a hydrogen atom at 85°C at a pressure of 2 mmHg.
It has a boiling point of In the hydrolysis reaction of formula [] in the present invention, the pH of the hydrolysis solution is particularly important, and the hydrolysis must be carried out within a certain range of pH. That is, hydrolysis is performed at a pH of 0.5 or higher and 6.5 or lower, preferably PH1 or higher,
Hydrolysis is carried out within a pH range of 6 or below; at other pH's, the desired product cannot be obtained by hydrolysis, or only a very small amount of the product can be obtained. The present invention will be described in detail below with reference to Examples. Example 1 (Synthesis of trichlorogermanium hydride) A quartz tube with an inner diameter of 10 mmφ and a length of 250 mm is filled with quartz wool, and the temperature inside the tube is maintained at 900°C. H2 to this
A mixture of gas and germanium tetrachloride is supplied, and the reaction solution is collected in a dry ice-methanol trap. After the reaction is completed, the trap is heated to 60-70°C for single evaporation and transferred to another trap for purification. A colorless and transparent liquid is obtained. Boiling point 75℃. Example 2 A flask with an internal capacity of 50 c.c. was charged with 1.0 gr of sodium acrylate, 10 mg of hydroquinone, and 20 c.c. of ethyl alcohol, and while cooling on ice, 1.26 cc of GeHCl 3 obtained in Example 1 was added to the flask. Drip in minutes. After stirring at room temperature for 1 hour, the reaction was continued at 60°C for another 1 hour. After the reaction is complete, ethanol is expelled and the chlorogermanium cyclic compound is
【式】を得る。
これをPH５で加水分解すると白沈がでる。冷蔵
庫内に一夜放置し沈澱を過する。1.82ｇのヒド
ロキシエチルゲルマニウムセスキオキシドを得
た。収率は90％であつた。
実施例 ３
内容量50c.c.のフラスコにアクリル酸ナトリウム
1.0ｇｒ、ハイドロキノン10mg、エチルアルコー
ル20c.c.を仕込み外側から氷冷しつつ実施例〔〕
で得られたGeHCl31.26c.c.を５分間で滴下する。
一時間常温で撹拌したのち60℃で更に１時間反応
さす。反応終了後エタノールを追い出し、しかる
のち10c.c.の水を加え70％NaoHを４にし一時間反
応させ冷蔵庫内で一夜放置すると白沈が出る。沈
澱を過する。
1.96ｇｒのヒドロキシエチルゲルマニウムセス
オキシドを得た。収率は98％であつた。
実施例 ４
内容量50c.c.のフラスコに、アクリル酸ナトリウ
ム２ｇ、ハイドロキノン10mg、エチルアルコール
30c.c.を仕込み、氷冷しつつ、前記実施例１で得た
GeHCl32.52c.c.を５分で滴下する。一時間常温で
撹拌したのち、60℃で更に１時間反応さす。反応
後エタノールから白沈を除く。しかるのち、エタ
ノールを追い出した。残液を２mmHgで減圧蒸留
した所、86℃の主溜分が得られた。これをマスペ
クトルおよび赤外線スペクトル、脱離食塩のモル
数、塩素分析、および元素分析より
Obtain [formula]. When this is hydrolyzed at pH5, a white precipitate appears. Leave in the refrigerator overnight to allow precipitation. 1.82 g of hydroxyethyl germanium sesquioxide was obtained. The yield was 90%. Example 3 Sodium acrylate in a flask with an internal capacity of 50 c.c.
Example: Prepare 1.0 gr, 10 mg of hydroquinone, and 20 c.c. of ethyl alcohol and cool on ice from the outside.
1.26 cc of GeHCl 3 obtained in step 1 was added dropwise over 5 minutes.
After stirring at room temperature for 1 hour, the reaction was continued at 60°C for another 1 hour. After the reaction is complete, ethanol is expelled, then 10 c.c. of water is added and 70% NaoH is added to 4, reacted for 1 hour and left in the refrigerator overnight to form a white precipitate. Allow precipitation. 1.96 gr of hydroxyethyl germanium sessoxide was obtained. The yield was 98%. Example 4 In a flask with an internal capacity of 50 c.c., 2 g of sodium acrylate, 10 mg of hydroquinone, and ethyl alcohol were added.
30c.c. was prepared and cooled on ice, obtained in Example 1 above.
Add 2.52 cc of GeHCl 3 dropwise over 5 minutes. After stirring at room temperature for 1 hour, the reaction was continued at 60°C for another 1 hour. After the reaction, remove the white precipitate from the ethanol. Afterwards, the ethanol was expelled. When the residual liquid was distilled under reduced pressure at 2 mmHg, a main fraction with a temperature of 86°C was obtained. This was determined from the mass spectrum and infrared spectrum, the number of moles of eliminated salt, chlorine analysis, and elemental analysis.
【式】であることをを確認し
た。この化合物をPH２で加水分解した所定量的に
（Ge−CH2−CH2−COOH）2O3が得られた。It was confirmed that [Formula]. This compound was hydrolyzed at PH2 to obtain (Ge- CH2 - CH2 -COOH) 2O3 in a predetermined amount.
Claims (1)
は炭素数１〜３のアルキル基を示す） で表わされるハロ環状ゲルマニウム化合物をPH
0.5〜6.5の範囲で加水分解することを特徴とする
下記一般式〔〕 （但し式中Ｒは前記定義と同じ） で表わされる有機ゲルマニウム化合物の製造法。 ２ 下記一般式〔〕 X3GeH ……〔〕 （但し式中Ｘは前記定義と同じ） で表わされるハロゲン化ゲルマニウムと下記一般
式〔〕 （但し式中Ｒは前記定義と同じであり、Ｍはアル
カリ金属を示す。） で表わされるアクリル酸誘導体とを反応せしめ、
下記一般式〔〕 （但し式中ＸおよびＲは前記定義と同じ） で表わされるハロ環状ゲルマニウム化合物を得、
次いでこれをPH0.5〜6.5の範囲で加水分解するこ
とを特徴とする下記一般式〔〕 （但し式中Ｒは前記定義と同じ） で表わされる有機ゲルマニウム化合物の製造法。[Claims] 1. The following general formula [] (However, in the formula, X is a halogen atom and R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
The following general formula [] is characterized by being hydrolyzed in the range of 0.5 to 6.5 (However, R in the formula is the same as defined above.) A method for producing an organic germanium compound represented by: 2 Germanium halide represented by the following general formula [] (However, in the formula, R is the same as the above definition, and M represents an alkali metal.)
General formula below [] (wherein X and R are the same as defined above) to obtain a halocyclic germanium compound represented by
The following general formula [] is then hydrolyzed at a pH of 0.5 to 6.5. (However, R in the formula is the same as defined above.) A method for producing an organic germanium compound represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8802781A JPS57203091A (en) | 1981-06-10 | 1981-06-10 | Production of organogermanium compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8802781A JPS57203091A (en) | 1981-06-10 | 1981-06-10 | Production of organogermanium compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57203091A JPS57203091A (en) | 1982-12-13 |
| JPS637192B2 true JPS637192B2 (en) | 1988-02-15 |
Family
ID=13931336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8802781A Granted JPS57203091A (en) | 1981-06-10 | 1981-06-10 | Production of organogermanium compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57203091A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019142569A1 (en) | 2018-01-18 | 2019-07-25 | Ｊｆｅスチール株式会社 | Spectroscopic analysis device, spectroscopic analysis method, method for manufacturing steel strip, and steel strip quality assurance method |
-
1981
- 1981-06-10 JP JP8802781A patent/JPS57203091A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019142569A1 (en) | 2018-01-18 | 2019-07-25 | Ｊｆｅスチール株式会社 | Spectroscopic analysis device, spectroscopic analysis method, method for manufacturing steel strip, and steel strip quality assurance method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57203091A (en) | 1982-12-13 |
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