JPS62175457A - Production of phenyl chlorothioformate - Google Patents
Production of phenyl chlorothioformateInfo
- Publication number
- JPS62175457A JPS62175457A JP1472886A JP1472886A JPS62175457A JP S62175457 A JPS62175457 A JP S62175457A JP 1472886 A JP1472886 A JP 1472886A JP 1472886 A JP1472886 A JP 1472886A JP S62175457 A JPS62175457 A JP S62175457A
- Authority
- JP
- Japan
- Prior art keywords
- solution
- mercaptan
- iodide
- water
- compound
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- HBEFYGYBMKPNSZ-UHFFFAOYSA-N s-phenyl chloromethanethioate Chemical compound ClC(=O)SC1=CC=CC=C1 HBEFYGYBMKPNSZ-UHFFFAOYSA-N 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- RYFZYYUIAZYQLC-UHFFFAOYSA-N perchloromethyl mercaptan Chemical compound ClSC(Cl)(Cl)Cl RYFZYYUIAZYQLC-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000002989 phenols Chemical class 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 8
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- -1 phenyl compound Chemical class 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims 1
- KTRFZWJCHOQHMN-UHFFFAOYSA-N chloromethanethioic s-acid Chemical class SC(Cl)=O KTRFZWJCHOQHMN-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 8
- 239000012044 organic layer Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 238000007664 blowing Methods 0.000 abstract description 4
- ZWZVWGITAAIFPS-UHFFFAOYSA-N thiophosgene Chemical compound ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000012046 mixed solvent Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 3
- 229940079593 drug Drugs 0.000 abstract 1
- 239000011369 resultant mixture Substances 0.000 abstract 1
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 150000002085 enols Chemical class 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- GQZLUBQHOLNJIL-UHFFFAOYSA-N diphenoxymethanethione Chemical class C=1C=CC=CC=1OC(=S)OC1=CC=CC=C1 GQZLUBQHOLNJIL-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、フェニル クロロチオネルメイト類の製造法
に関する。フェニル クロロチオネルメイト類は医薬、
農薬の中間体として非常に有用である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing phenyl chlorothionermates. Phenyl chlorothionermates are used as pharmaceuticals,
Very useful as an intermediate for agricultural chemicals.
フェニル クロロチオネルメイト類は、脱ハロゲン化水
素試剤存在下フェノール類とチオホスゲンの反応により
製造できることは公知である。It is known that phenyl chlorothionermates can be produced by the reaction of phenols and thiophosgene in the presence of a dehydrohalogenation agent.
また、本発明者らは、既にパークロルメチルメルカプタ
ン、有機溶媒及び水の混合溶液に二酸化イオウを吹き込
み後、反応液より水層を除去し、有機層にフエ〉−ル類
、次いで脱ハロゲン化水素試剤を添加することにより製
造できることを提案した。In addition, the present inventors have already blown sulfur dioxide into a mixed solution of perchloromethyl mercaptan, an organic solvent, and water, removed the aqueous layer from the reaction solution, added phenols to the organic layer, and then dehalogenated the solution. We proposed that it could be produced by adding a hydrogen reagent.
チオホスゲンは、毒性が高いため、取り扱いＫは非常に
注意を要する。漏洩等の異常事態を考えると天竜の貯蔵
或いは、移動は出来るだけ回避することが望ましい。そ
のため本発明者らは、パークロルメチルメルカプタン、
有機溶媒及び水の混合溶液に二酸化イオウを吹き込み後
、反応液より水層を除去し、有機１１にフェノール類、
次いで脱ハロゲン化水素試剤を添加することによりフェ
ニル クロロチオネルメイト類を高収率で製造できる方
法を提案した。Thiophosgene is highly toxic and must be handled with great care. Considering abnormal situations such as leaks, it is desirable to avoid storing or moving Tenryu as much as possible. Therefore, the present inventors investigated perchloromethyl mercaptan,
After blowing sulfur dioxide into the mixed solution of organic solvent and water, the aqueous layer was removed from the reaction solution, and phenols,
Next, we proposed a method for producing phenyl chlorothionermates in high yield by adding a dehydrohalogenation reagent.
しかし、更に工業的に有利にクロロチオポルメイト類を
製造する方法が求められていた。However, there has been a need for a more industrially advantageous method for producing chlorothiopolmates.
本発明の目的は、大量のチオホスゲンの貯蔵或いは、移
動を回避し、簡便かつ安全にさらに高収率でフェニル
クロロチオポルメイト類を製造することにある。The object of the present invention is to avoid the storage or transfer of large amounts of thiophosgene, and to easily and safely produce phenyl in higher yields.
The purpose is to produce chlorothiopolmates.
〔発明が解決するための手段及び作用〕本発明者らは、
種々の試験をし鋭意検討した結果、パークロルメチルメ
ルカプタン、ヨウ化物。[Means and effects to be solved by the invention] The present inventors,
As a result of various tests and careful consideration, perchlormethyl mercaptan, iodide.
有機溶媒及び水の混合溶液に二酸化イオウ及び硫化水素
を吹き込み、次いで反応液より水層を除去し、有機層に
７エノール類、脱ハロゲン化水素試剤を添加することＫ
より高収率でフェニル クロロチオポルメイト類を製造
できることを見い出し本発明を完成した。Blow sulfur dioxide and hydrogen sulfide into a mixed solution of an organic solvent and water, then remove the water layer from the reaction solution, and add 7 enols and a dehydrohalogenation reagent to the organic layer.
The present invention was completed by discovering that phenyl chlorothiopolmates can be produced in higher yields.
次に本発明の実施方法について詳しく述べる。Next, a method of implementing the present invention will be described in detail.
フェノール類に対して等モル以上好ましくは、１．１倍
モル以上のパークロルメチルメルカプタン。Perchlormethyl mercaptan in an amount equal to or more than 1 mole, preferably 1.1 times or more in mole relative to the phenol.
及びヨウ化物を有機溶媒及び水の混合溶媒に添加する。and iodide are added to a mixed solvent of organic solvent and water.
有機溶媒としては、クロロホルム、ジクロルメタン、四
塩化炭素等の塩素化炭化水素、ベンゼン。Examples of organic solvents include chloroform, dichloromethane, chlorinated hydrocarbons such as carbon tetrachloride, and benzene.
トルエン、キシレン等の芳香族炭化水素等が挙げられる
。水は、パークロルメチルメルカプタンの約２倍モル以
上用いることが１ましい。Examples include aromatic hydrocarbons such as toluene and xylene. It is preferable to use water at least about twice the mole of perchloromethyl mercaptan.
あまりにも少量の硫化水素の使用は、効果を示さず、反
対に大量の添加も特別の利益をもたらさない。結局パー
クロルメチルメルカプタンに対して１〜３ ｗｔｌの硫
化水素の使用が好ましい。The use of hydrogen sulfide in too small a quantity has no effect, and conversely the addition of large quantities does not bring any particular benefit. Consequently, it is preferred to use 1 to 3 wtl of hydrogen sulfide per perchloromethyl mercaptan.
硫化水素は、二酸化イオウを吹き込む前でも、二酸化イ
オウと同時に吹き込んでも本発明の効果には何ら影響を
及ぼさない。Hydrogen sulfide has no effect on the effects of the present invention even if it is blown in before or simultaneously with sulfur dioxide.
また、反応を円滑に進めるために用いるヨウ化物として
は、ヨウ素、ヨウ化カリウム、ヨウ化カリウム、ヨウ化
水素酸等挙げることができる。In addition, examples of the iodide used to facilitate the reaction include iodine, potassium iodide, potassium iodide, and hydroiodic acid.
該混合溶液にパークロルメチルメルカプタンに対して約
等モル〜５倍モルの二酸化イオウな吹き込み、次いで反
応液より水層を除去し、有機層に７エノール類次いで脱
ハロゲン化水素試剤を添加する。Sulfur dioxide is blown into the mixed solution in an amount of approximately equal to 5 times the mole relative to perchloromethyl mercaptan, then the aqueous layer is removed from the reaction solution, and the 7 enols and then a dehydrohalogenation reagent are added to the organic layer.
フェノール類としては、無置換のフェノール。Unsubstituted phenol is a phenol.
メチルフェノール、エチルフェノール、 ｔｅｒｔ−７
’チルフエノール等のアルキル置換フェノール、β−ナ
フトール、＆４７．８−テトラヒトｃ１−２−ナフトー
ル等の縮合フェノールを用いることができる。Methylphenol, ethylphenol, tert-7
'Alkyl-substituted phenols such as tilphenol, condensed phenols such as β-naphthol, &47.8-tetrahydroc1-2-naphthol can be used.
脱ハロゲン化水素試剤としては、アルカリ金属水酸化物
、アルカリ土類金属水酸化物、そしてアルカリ金稿炭酸
塩等の無機塩基、トリエチルアミン、ピリジン、キノリ
ン、イソキノリン等の有機塩基が挙げられ、フェノール
に対して約等モル使用する。Examples of dehydrohalogenation reagents include alkali metal hydroxides, alkaline earth metal hydroxides, inorganic bases such as alkali metal carbonates, and organic bases such as triethylamine, pyridine, quinoline, and isoquinoline. Use approximately equal moles.
これらの脱ハロゲン化水素試剤は、通常溶液の形態で用
いることができ、溶液中の脱ハロゲン化水素試剤の濃度
とフェニル クロロチオポルメイト類の収率は、密接な
関係にある。These dehydrohalogenating reagents can usually be used in the form of a solution, and the concentration of the dehydrohalogenating reagent in the solution and the yield of phenyl chlorothiopolmates are closely related.
即ち、高濃度の脱ハロゲン化水素試剤溶液を用いるとジ
フェニルチオ炭酸エステル類の副生によりフェニル ク
ロロチオポルメイト類の収率が低下する。必要以上に低
濃度の脱ハロゲン化水素試剤溶液を用いる場合は、大容
量の反応器を使用しなければならないので不利である。That is, when a highly concentrated dehydrohalogenating reagent solution is used, the yield of phenylchlorothiopolmates decreases due to the by-product of diphenylthiocarbonate esters. When using a dehydrohalogenation reagent solution with a lower concentration than necessary, it is disadvantageous because a large-capacity reactor must be used.
したがって脱ノ・ロゲン化水素試剤溶液の濃度は、約５
〜２０俤が好ましい。反応温度は通常約−４１０”Ｃ〜
室温が好ましい。反応時間は通常約１０時間以内に完結
さ騒ることかできる。Therefore, the concentration of the dehydrogenation reagent solution is approximately 5
~20 yen is preferable. The reaction temperature is usually about -410"C~
Room temperature is preferred. The reaction time can usually be completed within about 10 hours.
パークロルメチルメルカプタン、ヨウ化物、有機溶媒及
び水の混合溶液に二酸化イオウ及び硫化水素を吹き込み
後反応液より水層を除去し、フェノール類次いで脱ハロ
ゲン化水素試剤を添加することにより簡便かつ安全に高
収率でフェニル クロロチオポルメイト類を製造できる
。After blowing sulfur dioxide and hydrogen sulfide into a mixed solution of perchloromethyl mercaptan, iodide, an organic solvent, and water, remove the aqueous layer from the reaction solution, and then add phenols and then a dehydrohalogenation agent to easily and safely. Phenyl chlorothiopolmates can be produced in high yield.
次に実施例でもって本発明を具体的に説明するが本発明
は、これら実施例のみに限定されるものではない。Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited only to these Examples.
実施例１
攪拌機、温度計、５００ｍの滴下漏斗を付した１ｔの３
０フラスコにパークロルメチルメルカプタン１８６９．
ジクロルメタン３００＋＋ｔ／、水５００ｄ、ヨウ化カ
リウム１．８２を取りフラスコを氷冷した。次いで硫化
水素５ｇｒそして二酸化イオウ１７０りを上記溶液に攪
拌しつつ吹き込んだ。Example 1 1 ton 3 with stirrer, thermometer and 500 m dropping funnel
Perchloromethyl mercaptan 1869.
300++ tons of dichloromethane, 500 d of water, and 1.82 g of potassium iodide were taken, and the flask was cooled on ice. 5 grams of hydrogen sulfide and 170 grams of sulfur dioxide were then bubbled into the solution with stirring.
フラスコ内の温度は０〜１０℃に保った。The temperature inside the flask was maintained at 0-10°C.
二酸化イオウ吹き込み後、反応液より水層を除去し残っ
た有機層にフェノール８０２次いで１０チ水酸化ナトリ
ウム水溶液５７５ｄ滴下した。滴下後さらに２時間攪拌
した。反応終了後、反応液より有機層を分取し、蒸留し
、フェニル クロロチオホルメイ） １４１．５９を得
た。フェニル クロロチオホルメイトの収率は、フェノ
ール基準で９６、．５１ｓであった。After blowing in sulfur dioxide, the aqueous layer was removed from the reaction solution, and phenol 802 and then 575 d of a 10-thiodium hydroxide aqueous solution were added dropwise to the remaining organic layer. After the dropwise addition, the mixture was further stirred for 2 hours. After the reaction was completed, the organic layer was separated from the reaction solution and distilled to obtain 141.59 phenylchlorothioformei. The yield of phenyl chlorothioformate was 96% based on phenol. It was 51s.
比較例１
実施例１と同一の反応装置に、硫化水素を用いることな
〈実施例１と同一の反応条件９反応操作によりフェニル
クロロチオホルメイト１５２ ｇｒを得た。フェニル
クロロチオホルメイトの収率は、フェノール基準で９
０％であった。Comparative Example 1 Phenyl chlorothioformate 152 gr was obtained in the same reaction apparatus as in Example 1 under the same reaction conditions as in Example 1 but without using hydrogen sulfide. The yield of phenyl chlorothioformate is 9% based on phenol.
It was 0%.
実施例２〜４
実施例１と同様の方法において、溶媒、原料２反応温度
および反応時間等を変えて反応を行った。Examples 2 to 4 Reactions were carried out in the same manner as in Example 1 by changing the solvent, reaction temperature of the raw material 2, reaction time, etc.
ヨウ化カリウムは実施例２〜４において２ｇ用いた。結
果を表１に示す。2 g of potassium iodide was used in Examples 2-4. The results are shown in Table 1.
Claims (1)
び水の混合溶液に二酸化イオウ及び硫化水素を吹き込み
後反応液より水層を除去し、フェノール類次いで脱ハロ
ゲン化水素試剤を添加することを特徴とするフェニル
クロロチオホルメイト類の製造法。A phenyl compound characterized by bubbling sulfur dioxide and hydrogen sulfide into a mixed solution of perchloromethyl mercaptan, iodide, an organic solvent and water, removing the aqueous layer from the reaction solution, and adding phenols and then a dehydrohalogenating agent.
Method for producing chlorothioformates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1472886A JPS62175457A (en) | 1986-01-28 | 1986-01-28 | Production of phenyl chlorothioformate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1472886A JPS62175457A (en) | 1986-01-28 | 1986-01-28 | Production of phenyl chlorothioformate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62175457A true JPS62175457A (en) | 1987-08-01 |
| JPH0552304B2 JPH0552304B2 (en) | 1993-08-05 |
Family
ID=11869191
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1472886A Granted JPS62175457A (en) | 1986-01-28 | 1986-01-28 | Production of phenyl chlorothioformate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62175457A (en) |
-
1986
- 1986-01-28 JP JP1472886A patent/JPS62175457A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0552304B2 (en) | 1993-08-05 |
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