JPS6216939B2 - - Google Patents
Info
- Publication number
- JPS6216939B2 JPS6216939B2 JP53136761A JP13676178A JPS6216939B2 JP S6216939 B2 JPS6216939 B2 JP S6216939B2 JP 53136761 A JP53136761 A JP 53136761A JP 13676178 A JP13676178 A JP 13676178A JP S6216939 B2 JPS6216939 B2 JP S6216939B2
- Authority
- JP
- Japan
- Prior art keywords
- methyl
- dimethoxy
- benzoquinone
- reaction
- water
- 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
- UIXPTCZPFCVOQF-UHFFFAOYSA-N ubiquinone-0 Chemical compound COC1=C(OC)C(=O)C(C)=CC1=O UIXPTCZPFCVOQF-UHFFFAOYSA-N 0.000 claims description 16
- OMDNFMOQYYDECR-UHFFFAOYSA-N 2,3,4-trimethoxy-6-methylbenzaldehyde Chemical compound COC1=CC(C)=C(C=O)C(OC)=C1OC OMDNFMOQYYDECR-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229940005561 1,4-benzoquinone Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000012141 vanillin Nutrition 0.000 description 2
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 2
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 2
- DIVNUTGTTIRPQA-UHFFFAOYSA-N (3,4-dimethoxyphenyl)methanamine Chemical compound COC1=CC=C(CN)C=C1OC DIVNUTGTTIRPQA-UHFFFAOYSA-N 0.000 description 1
- WMXFNCKPYCAIQW-UHFFFAOYSA-N 1,2-dimethoxy-3-methylbenzene Chemical compound COC1=CC=CC(C)=C1OC WMXFNCKPYCAIQW-UHFFFAOYSA-N 0.000 description 1
- KCIZTNZGSBSSRM-UHFFFAOYSA-N 3,4,5-Trimethoxytoluene Chemical compound COC1=CC(C)=CC(OC)=C1OC KCIZTNZGSBSSRM-UHFFFAOYSA-N 0.000 description 1
- -1 3,6-diamino-4,5-dimethoxytoluene Chemical compound 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- PMTPMXFVLDRETJ-UHFFFAOYSA-N 4-amino-2,3-dimethoxy-6-methylphenol Chemical compound COC1=C(N)C=C(C)C(O)=C1OC PMTPMXFVLDRETJ-UHFFFAOYSA-N 0.000 description 1
- 238000007013 Reimer-Tiemann formylation reaction Methods 0.000 description 1
- 238000005874 Vilsmeier-Haack formylation reaction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- ACTIUHUUMQJHFO-UPTCCGCDSA-N coenzyme Q10 Chemical compound COC1=C(OC)C(=O)C(C\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CCC=C(C)C)=C(C)C1=O ACTIUHUUMQJHFO-UPTCCGCDSA-N 0.000 description 1
- 235000017471 coenzyme Q10 Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DGQOCLATAPFASR-UHFFFAOYSA-N tetrahydroxy-1,4-benzoquinone Chemical compound OC1=C(O)C(=O)C(O)=C(O)C1=O DGQOCLATAPFASR-UHFFFAOYSA-N 0.000 description 1
- IECKAVQTURBPON-UHFFFAOYSA-N trimethoxymethylbenzene Chemical compound COC(OC)(OC)C1=CC=CC=C1 IECKAVQTURBPON-UHFFFAOYSA-N 0.000 description 1
- TZPKFPYZCMHDHL-UHFFFAOYSA-N trimethoxytoluene Natural products COC1=CC(OC)=C(C)C(OC)=C1 TZPKFPYZCMHDHL-UHFFFAOYSA-N 0.000 description 1
Description
【発明の詳細な説明】
本発明は下記化学式で示される２・３−ジメト
キシ−５−メチル−１・４−ベンゾキノンの製造
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 2,3-dimethoxy-5-methyl-1,4-benzoquinone represented by the following chemical formula.
２・３−ジメトキシ−５−メチル−１・４−ベ
ンゾキノンは補酵素Ｑ合成の中間体として極めて
有用な化合物で、その従来公知の製造法として
は、ワニリンを出発原料とし４工程を経て、３−
アミノ−４・５−ジメトキシトルエンとして、こ
れを酸化する方法。（J.Chem.Soc.、1938年439
頁）同じくワニリンから数工程で、３・６−ジア
ミノ−４・５−ジメトキシトルエンとし、これを
酸化する方法、（特公昭39−23397号、昭39−
10118号）あるいは数工程で２−アミノ−３・４
−ジメトキシトルエンとして酸化する方法。
（Chem.Rev.、71巻229頁1971年）
没食子酸を出発原料として３・４・５−トリメ
トキシトルエンを経て、２−アミノ−３・４・５
−トリメトキシトルエンとし、これを酸化する方
法、（特公昭38−11981号）あるいは、２・３−ジ
メトキシ−４−アミノ−６−メチルフエノールに
導いて、これを酸化する方法（特公昭38−22574
号）などが提出されている。 2,3-dimethoxy-5-methyl-1,4-benzoquinone is an extremely useful compound as an intermediate for coenzyme Q synthesis.The conventionally known method for producing it is to use vanillin as a starting material through four steps. −
A method of oxidizing this as amino-4,5-dimethoxytoluene. (J.Chem.Soc., 1938, 439
Page) Similarly, a method of converting vanillin into 3,6-diamino-4,5-dimethoxytoluene in several steps and oxidizing this (Japanese Patent Publication No. 39-23397, 1983-
10118) or 2-amino-3/4 in several steps.
- Method of oxidation as dimethoxytoluene.
(Chem.Rev., Vol. 71, p. 229, 1971) Using gallic acid as a starting material, 2-amino-3,4,5 was produced through 3,4,5-trimethoxytoluene.
-trimethoxytoluene and oxidizing it (Japanese Patent Publication No. 11981/1989), or 2,3-dimethoxy-4-amino-6-methylphenol and oxidizing it (Japanese Patent Publication No. 11981/1986). 22574
No.) etc. have been submitted.
しかしながら、これら公知の方法は反応工程が
長く、出発原料から２・３−ジメトキシ−５−メ
チル−１・４−ベンゾキノンまでの通算収率が低
いとか、中間体が不安定な化合物であつたりし
て、工業的に有利な方法とは云い難い。そこで本
発明者等は、工業的に有利な２・３−ジメトキシ
−５−メチル−１・４−ベンゾキノンの製造法に
ついて種々検討した結果、工業的に安価に入手で
きる、３・４・５−トリメトキシトルエンを原料
とし、このものからガツターマン
（Gattermann）のアルデヒド合成法、リーマー・
テイマン（Reimer Tiemann）反応あるいはビル
スマイアー（Vilsmeier）反応等で容易に製造で
きる、２−メチル−４・５・６−トリメトキシベ
ンツアルデヒドを酸性条件下で過酸化物で酸化す
ると、緩和な反応条件で、かなり選択的に２・３
−ジメトキシ−５−メチル−１・４−ベンゾキノ
ンが生成することを知見として本発明を完成し
た。 However, these known methods involve long reaction steps, the total yield of 2,3-dimethoxy-5-methyl-1,4-benzoquinone from the starting material is low, and the intermediate is an unstable compound. Therefore, it is difficult to say that it is an industrially advantageous method. Therefore, the present inventors investigated various methods for manufacturing 2,3-dimethoxy-5-methyl-1,4-benzoquinone, which are industrially advantageous, and found that 3,4,5- Using trimethoxytoluene as a raw material, Gattermann's aldehyde synthesis method, Reamer
When 2-methyl-4,5,6-trimethoxybenzaldehyde, which can be easily produced by Reimer Tiemann reaction or Vilsmeier reaction, is oxidized with peroxide under acidic conditions, mild reaction conditions can be obtained. So, quite selectively 2.3
The present invention was completed based on the finding that -dimethoxy-5-methyl-1,4-benzoquinone is produced.
本発明を化学式を以て示せば、下記のとおりで
ある。 The present invention is illustrated by a chemical formula as follows.
本発明で使用する過酸化物としては、過酸化水
素もしくは過硫酸塩などの無機過酸化物の酢酸あ
るいは希硫酸酸性水溶液、および過酢酸、過蟻
酸、過安息香酸等の有機過酸化物の酢酸溶液を用
いることができる。また本反応は通常使用される
溶媒中で実施可能で、例えばアセトン、メタノー
ル、エタノール、ジメチルホルムアミド等の有機
溶媒。あるいはこれ等の有機溶媒と水の混合物を
適宜使用することができる。 Peroxides used in the present invention include acetic acid or dilute sulfuric acid aqueous solutions of inorganic peroxides such as hydrogen peroxide or persulfates, and acetic acid of organic peroxides such as peracetic acid, performic acid, and perbenzoic acid. A solution can be used. Further, this reaction can be carried out in a commonly used solvent, such as an organic solvent such as acetone, methanol, ethanol, or dimethylformamide. Alternatively, a mixture of these organic solvents and water can be used as appropriate.
反応温度、反応時間は過酸化物の種類、使用
量、溶媒の種類等により最適条件を選択する必要
があるが、反応温度を０〜50℃の範囲、例えば常
温程度とし、反応の進行を薄層クロマトグラフイ
ーあるいはキノン−ハイドロキノンの紫外線吸収
で追跡し、２・３−ジメトキシ−５−メチル−
１・４−ベンゾキノンの生成量が最大になつたと
きに、反応を中止すれば良い。 It is necessary to select the optimum conditions for the reaction temperature and reaction time depending on the type of peroxide, amount used, type of solvent, etc., but the reaction temperature should be set in the range of 0 to 50°C, for example around room temperature, to slow the progress of the reaction. Tracked by layer chromatography or ultraviolet absorption of quinone-hydroquinone, 2,3-dimethoxy-5-methyl-
The reaction may be stopped when the amount of 1,4-benzoquinone produced reaches the maximum.
反応溶液は水で希釈し、適当な抽出溶媒、例え
ばエーテル、塩化メチレン、ベンゼン、トルエン
等で抽出し、抽出溶液を適宜濃縮して、目的の
２・３−ジメトキシ−５−メチル−１・４−ベン
ゾキノンを高収率で得ることができる。 The reaction solution is diluted with water, extracted with an appropriate extraction solvent such as ether, methylene chloride, benzene, toluene, etc., and the extracted solution is appropriately concentrated to obtain the desired 2,3-dimethoxy-5-methyl-1,4 - Benzoquinone can be obtained in high yield.
以上の様に本発明は工程が短く、簡単な操作で
収率よく２・３−ジメトキシ−５−メチル−１・
４−ベンゾキノンを製造することのできる工業的
に有利な新規方法である。以下実施例をあげて本
発明を説明する。 As described above, the process of the present invention is short, and 2,3-dimethoxy-5-methyl-1.
This is a new industrially advantageous method for producing 4-benzoquinone. The present invention will be explained below with reference to Examples.
実施例 １
２−メチル−４・５・６−トリメトキシベンツ
アルデヒド５ｇを酢酸25mlに溶解し、40％過酢酸
10ｇを徐々に加え20〜30℃で６時間反応させる。
反応溶液に水50mlを加え、二塩化メチレンで抽出
する。抽出した二塩化メチレン層を５％炭酸水素
ナトリウム溶液および水で洗浄した後、無水硫酸
ナトリウムで乾燥する。溶媒を減圧下蒸発、濃縮
すると赤色の針状晶が析出する。収量3.0ｇ、69
％
これを石油エーテルより再結晶すると融点58〜
59℃の赤色針状晶となり、そのIRは公知方法で
合成した、２・３−ジメトキシ−５−メチル−
１・４−ベンゾキノン標品のIRと完全に一致
し、また混融しても融点降下しない。Example 1 Dissolve 5 g of 2-methyl-4,5,6-trimethoxybenzaldehyde in 25 ml of acetic acid, and add 40% peracetic acid.
Gradually add 10g and react at 20-30°C for 6 hours.
Add 50 ml of water to the reaction solution and extract with methylene dichloride. The extracted methylene dichloride layer is washed with 5% sodium bicarbonate solution and water, and then dried over anhydrous sodium sulfate. When the solvent is evaporated and concentrated under reduced pressure, red needle-like crystals are precipitated. Yield 3.0g, 69
% When this is recrystallized from petroleum ether, the melting point is 58 ~
It becomes red needle-like crystals at 59℃, and its IR is 2,3-dimethoxy-5-methyl- synthesized by a known method.
It completely matches the IR of the 1,4-benzoquinone sample, and the melting point does not drop even when mixed.
実施例 ２
２−メチル−４・５・６−トリメトキシベンツ
アルデヒド10ｇをメタノール50mlに溶解し、30％
過酸化水素水20ml、次で10％硫酸５mlを加え、40
℃以下に保ちながら６時間反応させる。反応溶液
に水100mlを加え、ベンゼンで抽出する。抽出し
たベンゼン層を５％炭酸水素ナトリウム溶液およ
び水で洗浄した後、無水硫酸ナトリウムで乾燥す
る。溶媒を減圧下蒸発、濃縮すると赤色針状の
２・３−ジメトキシ−５−メチル−１・４−ベン
ゾキノン4.7ｇを得る。収率54％
実施例 ３
２−メチル−４・５・６−トリメトキシベンツ
アルデヒド５ｇをメタノール50ml、水50mlの混合
液に溶解し、次で過硫酸カリウム21ｇを加え撹拌
しながら50℃で20時間反応させる。反応溶液に水
50mlを加えてトルエンで抽出する。トルエン層を
５％炭酸水素ナトリウム溶液および水で洗浄した
後、無水硫酸ナトリウムで乾燥する。溶媒を減圧
下蒸発、濃縮すると赤色針状の２・３−ジメトキ
シ−５−メチル−１・４−ベンゾキノン1.8ｇを
得る。収率42％Example 2 10g of 2-methyl-4,5,6-trimethoxybenzaldehyde was dissolved in 50ml of methanol to give a concentration of 30%
Add 20ml of hydrogen peroxide solution, then 5ml of 10% sulfuric acid,
React for 6 hours while keeping the temperature below ℃. Add 100 ml of water to the reaction solution and extract with benzene. The extracted benzene layer is washed with 5% sodium bicarbonate solution and water, and then dried over anhydrous sodium sulfate. The solvent was evaporated and concentrated under reduced pressure to obtain 4.7 g of red needle-like 2,3-dimethoxy-5-methyl-1,4-benzoquinone. Yield 54% Example 3 5 g of 2-methyl-4,5,6-trimethoxybenzaldehyde was dissolved in a mixture of 50 ml of methanol and 50 ml of water, and then 21 g of potassium persulfate was added and the mixture was heated at 50°C for 20 minutes with stirring. Allow time to react. water to reaction solution
Add 50ml and extract with toluene. The toluene layer is washed with 5% sodium bicarbonate solution and water, and then dried over anhydrous sodium sulfate. The solvent was evaporated and concentrated under reduced pressure to obtain 1.8 g of red needle-like 2,3-dimethoxy-5-methyl-1,4-benzoquinone. Yield 42%
Claims (1)
ツアルデヒドを酸性条件下過酸化物で酸化するこ
とを特徴とする２・３−ジメトキシ−５−メチル
−１・４−ベンゾキノンの製造法。1. A method for producing 2,3-dimethoxy-5-methyl-1,4-benzoquinone, which comprises oxidizing 2-methyl-4,5,6-trimethoxybenzaldehyde with a peroxide under acidic conditions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13676178A JPS5564544A (en) | 1978-11-08 | 1978-11-08 | Preparation of 2,3-dimethoxy-5-methyl-1,4-benzoquinone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13676178A JPS5564544A (en) | 1978-11-08 | 1978-11-08 | Preparation of 2,3-dimethoxy-5-methyl-1,4-benzoquinone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5564544A JPS5564544A (en) | 1980-05-15 |
| JPS6216939B2 true JPS6216939B2 (en) | 1987-04-15 |
Family
ID=15182880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13676178A Granted JPS5564544A (en) | 1978-11-08 | 1978-11-08 | Preparation of 2,3-dimethoxy-5-methyl-1,4-benzoquinone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5564544A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01313451A (en) * | 1988-06-13 | 1989-12-18 | Agency Of Ind Science & Technol | Production of 2,3-dimethoxy-5-methylbenzoquinone |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4980031A (en) * | 1972-12-07 | 1974-08-02 |
-
1978
- 1978-11-08 JP JP13676178A patent/JPS5564544A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4980031A (en) * | 1972-12-07 | 1974-08-02 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5564544A (en) | 1980-05-15 |
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