JPS6241713B2 - - Google Patents
Info
- Publication number
- JPS6241713B2 JPS6241713B2 JP59190158A JP19015884A JPS6241713B2 JP S6241713 B2 JPS6241713 B2 JP S6241713B2 JP 59190158 A JP59190158 A JP 59190158A JP 19015884 A JP19015884 A JP 19015884A JP S6241713 B2 JPS6241713 B2 JP S6241713B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- dithiazolium
- disubstituted
- compounds
- 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
- MNNJLAZJQBWSST-UHFFFAOYSA-N 1,4,2-dithiazole Chemical class C1SC=NS1 MNNJLAZJQBWSST-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- XQIJUNRYEIASNK-UHFFFAOYSA-N amino carbamodithioate Chemical class NSC(N)=S XQIJUNRYEIASNK-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 238000006210 cyclodehydration reaction Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- -1 cyclic cationic compounds Chemical class 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000009102 absorption Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XTLFOTGRJYJFTE-UHFFFAOYSA-N 3h-1,2,4-dithiazole Chemical class C1SSC=N1 XTLFOTGRJYJFTE-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- DQPBABKTKYNPMH-UHFFFAOYSA-N amino hydrogen sulfate Chemical compound NOS(O)(=O)=O DQPBABKTKYNPMH-UHFFFAOYSA-N 0.000 description 1
- JGBDWRSVCOWWAD-UHFFFAOYSA-N amino n,n-diethylcarbamodithioate Chemical compound CCN(CC)C(=S)SN JGBDWRSVCOWWAD-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は３−アリール−５−ジ置換アミノ−
１，４，２−ジチアゾリウム塩の製造法に関する
もので、より詳細にはこれらの化合物をＮ−アロ
イル−Ｓ−ジ置換チオカルバモイルスルフエンア
ミドを無機強酸の存在下で、脱水環化反応により
簡単にかつ収率よく製造する方法に関するもので
ある。
従来、含硫黄の環状カチオン化合物たとえば３
−ジチオリウム塩、１，２，４−ジチアゾリウム
塩などのように、農薬、カチオン染料、有機導電
性化合物として、あるいは、これらの合成中間体
として広く利用されていた。しかし、農薬の普及
により耐薬品性を有する害虫の出現対策として耐
薬品性を与えない新規農薬への期待は極めて強
い。また新素材としての有機電導性化合物の新た
な開発はきわせて有望視されている。そこで本発
明はかかる現状にかんがみなされたものであり、
各種の含硫黄環状カチオン化合物を合成し、これ
らの農薬としての薬理効果を検討したり、有機化
合物の導電性について鋭意検討を重ねていたとこ
ろ、新規かつ有用な各種の１，４，２−ジチアゾ
リウム塩をきわめて簡単な方法で収率よく製造で
きることを見出し、本発明を完成するに至つた。
すなわち本発明は
一般式
（式中R1，R2は不活性な置換基を有していて
もよいアルキルまたはアリール基を表わし、
R1，R2，はその末端が結合していてもよく、R3
は不活性な置換基を有していてもよいアリール基
を表わす。）で示されるＮ−アロイル−Ｓ−ジ置
換チオカルバモイルスルフエンアミドを強酸の存
在下で脱水環化反応させることを特徴とする
一般式
（式中R1，R2は前記と同一であり、Ｘは無機
強酸の酸根を表わす。）
で表わされる３−アリール−５−ジ置換アミノ−
１，４，２−ジチアゾリウム塩の製造方法を提供
するものである。
本発明の化合物は、前記一般式（）を脱水性
の強い、かつ強酸性の溶媒中で反応させることに
よつて合成されるが、原料であるＮ−アロイル−
Ｓ−ジ置換チオカルバモイルスルフエンアミドは
ジ置換ジチオカルバミン酸塩にヒドロキシルアミ
ン−Ｏ−スルホン酸を作用させるとジ置換チオカ
ルバモイルスルフエニンアミドが容易に得られ、
さらに、このものにカルボン酸無水物または酸塩
化物を反応させることによつてきわめて容易誘導
される。
従つてR1，R2についてはジチオカルバミン酸
の種類を選ぶことによつて所望の置換基を導入す
ることが可能である。またR3についてもカルボ
ン酸無水物、また酸塩化物を適当に選ぶことによ
り目的とする置換基を導入することができる。ま
た、R1，R2，R3は不活性な置換基を有すること
ができるが、この場合の不活性置換基としては、
例えば低級アルコキシやハロゲン等が挙げられ
る。
次に目的とする脱水環化反応の経路をＮ−フエ
ニル−Ｓ−ジエチルカルバモイルスルフエンアミ
ド（IA）を用い、強酸として過塩素酸を用いた
場合を例にとれば下記の式（）のように表現で
きる。
この反応は水浴上で若干加温するだけで完結す
るが、脱水性の強い溶媒、たとこば無水酢酸、塩
化ホスホリルなどの溶媒中で、濃厚状態の強酸、
たとえば、過塩素酸、四フツ化ホウ素酸、硫酸な
どの存在下で行わせると、目的とする１，４，２
−ジチアゾリウム塩が生成し、よい収率で安定な
結晶状態で多くの場合析出してくるが、必要に応
じて不活性な有機溶媒を添加して生成物の析出を
促進させることもできる。
このように得られた１，４，２−ジチアゾリウ
ム塩は必要に応じて再結晶によつてさらに精製す
ることができる。
新規物質３−アリール−５−ジ置換アミノ−
１，４，２−ジチアゾリウム塩である構造の確認
は元素分析、および赤外吸収スペクトルの特性吸
収などによつて行つた。上述したように本発明の
１，４，２−ジチアゾリウム塩はいずれも新規の
化合物であるが、５員環の含硫黄芳香族カチオン
化合物の一種として考えられ、化学的には、それ
らの既知化合物と類似している。従つて、この化
合物も、増感剤、農薬、カチオン染料、電子工業
材料などとして有効であるばかりではなく、含窒
素環状化合物の合成のための重要な中間体原料に
もなる。また、これらの１，４，２−ジチアゾリ
ウム塩はいずれも簡単ら反応で、かつよい収率で
得られるばかりでなくその原料もきわめて容易に
入手できるので、工業的にもきわめて有利であ
る。
次に本発明を実施例により更に詳細に説明す
る。
実施例 １
無水酢酸15mlに70％過塩素酸１mlを予め混合し
た溶液に2.68ｇ（0.01モル）のＮ−ベンゾイル−
Ｓ−ジエチルチオカルバモイルスルフエンアミド
を溶解させ、水溶上で２時間加温する。その後放
冷し、反応液が室温まで下つたら乾燥エーテル20
mlを反応液に加える。析出した白色の板状結晶を
別し、アセトニトリルで再結晶すると、融点
141℃の白色板状結晶３−フエニル−５−ジエチ
ルアミノ−１，４，２−ジチアゾリウム過塩素酸
塩2.79ｇ（収率80％）を得た。このものの赤外吸
収スペクトルの特性吸収は下記のとおりであつ
た。
3050cm-1，2968cm-1，1582cm-1，1571cm-1，
1538cm-1，1465cm-1，1441cm-1，1283cm-1，1068
cm-1，761cm-1，688cm-1，617cm-1。，
C12H15N2S2ClO4としての元素分析値は次のよ
うであつた。
計算値（％）Ｃ：41.08，Ｈ：4.31，Ｎ：7.98。
測定値（％）Ｃ：41.02，H4.30，Ｎ：8.07。
実施例 ２
前記と同様に無水酢酸15mlに70％過塩素酸１ml
を予め混合した溶液に下記の表に示す0.01モルの
Ｎ−アロイル−Ｓ−ジ置換チオカルバモイルスル
フエンアミドを溶解させ、水溶上で２時間加温す
る。その後放冷し、反応液が室温まで下つたら乾
燥エーテルを加えて、生成物の析出を促進させ
る。生成物を別し、アセトニトリルで再結晶す
ると白色の微結晶３−アリール−５−ジ置換アミ
ノ−１，４，２−ジチアゾリウム過塩素酸塩を得
る。このようにして得たジチアゾリウム塩の融点
収率、および元素分析の結果は表１に示す。
The present invention provides 3-aryl-5-disubstituted amino-
It relates to a method for producing 1,4,2-dithiazolium salts, and more specifically, these compounds are easily prepared by cyclodehydration reaction of N-aroyl-S-disubstituted thiocarbamoylsulfenamide in the presence of a strong inorganic acid. The present invention relates to a method for producing the same with good yield. Conventionally, sulfur-containing cyclic cationic compounds such as 3
-Dithiolium salts, 1,2,4-dithiazolium salts, etc., have been widely used as agricultural chemicals, cationic dyes, organic conductive compounds, or as intermediates for their synthesis. However, with the spread of pesticides, there are extremely high expectations for new pesticides that do not provide chemical resistance as a countermeasure against the emergence of chemically resistant pests. Furthermore, the new development of organic conductive compounds as new materials is viewed as very promising. Therefore, the present invention was conceived in view of the current situation,
After synthesizing various sulfur-containing cyclic cation compounds and studying their pharmacological effects as agricultural chemicals, and conducting intensive studies on the conductivity of organic compounds, we discovered various new and useful 1,4,2-dithiazolium compounds. The inventors discovered that salts can be produced in a very simple manner and with good yield, leading to the completion of the present invention.
That is, the present invention has the general formula (In the formula, R 1 and R 2 represent an alkyl or aryl group that may have an inert substituent,
R 1 , R 2 , may be bonded at their ends, and R 3
represents an aryl group which may have an inert substituent. ) is characterized by subjecting N-aroyl-S-disubstituted thiocarbamoylsulfenamide to a cyclodehydration reaction in the presence of a strong acid. (In the formula, R 1 and R 2 are the same as above, and X represents an acid group of a strong inorganic acid.) 3-aryl-5-disubstituted amino-
A method for producing a 1,4,2-dithiazolium salt is provided. The compound of the present invention is synthesized by reacting the general formula () in a highly dehydrating and strongly acidic solvent.
S-disubstituted thiocarbamoylsulfenamide can be easily obtained by reacting hydroxylamine-O-sulfonic acid with disubstituted dithiocarbamate to give disubstituted thiocarbamoylsulfeninamide,
Furthermore, it is very easily induced by reacting this compound with a carboxylic acid anhydride or an acid chloride. Therefore, desired substituents can be introduced into R 1 and R 2 by selecting the type of dithiocarbamic acid. Also, for R 3 , a desired substituent can be introduced by appropriately selecting a carboxylic acid anhydride or an acid chloride. In addition, R 1 , R 2 , and R 3 can have an inert substituent, and in this case, the inert substituent is
Examples include lower alkoxy and halogen. Next, if we take the case where N-phenyl-S-diethylcarbamoylsulfenamide (IA) is used and perchloric acid is used as the strong acid, the desired cyclodehydration reaction route is expressed as the following formula (). It can be expressed as This reaction can be completed by simply heating it slightly on a water bath, but in a highly dehydrating solvent such as acetic anhydride or phosphoryl chloride, a concentrated strong acid,
For example, when carried out in the presence of perchloric acid, tetrafluoroboric acid, sulfuric acid, etc., the desired 1, 4, 2
-Dithiazolium salts are produced and often precipitated in a stable crystalline state in good yields, but if necessary, an inert organic solvent can be added to promote the precipitation of the product. The 1,4,2-dithiazolium salt thus obtained can be further purified by recrystallization, if necessary. New substance 3-aryl-5-disubstituted amino-
The structure of the 1,4,2-dithiazolium salt was confirmed by elemental analysis and characteristic absorption in an infrared absorption spectrum. As mentioned above, all of the 1,4,2-dithiazolium salts of the present invention are new compounds, but they are considered as a type of 5-membered sulfur-containing aromatic cation compounds, and are chemically comparable to those known compounds. is similar to Therefore, this compound is not only effective as a sensitizer, agricultural chemical, cationic dye, electronic material, etc., but also serves as an important intermediate raw material for the synthesis of nitrogen-containing cyclic compounds. Further, all of these 1,4,2-dithiazolium salts are not only easily obtained by reaction and in good yields, but also their raw materials are very easily available, so they are extremely advantageous from an industrial standpoint. Next, the present invention will be explained in more detail with reference to Examples. Example 1 2.68 g (0.01 mol) of N-benzoyl-
Dissolve S-diethylthiocarbamoylsulfenamide and heat over water for 2 hours. After that, let it cool, and when the reaction solution drops to room temperature, add 20% of dry ether.
ml to the reaction solution. Separate the precipitated white plate-like crystals and recrystallize them with acetonitrile to find the melting point.
2.79 g (yield: 80%) of white plate-like crystals of 3-phenyl-5-diethylamino-1,4,2-dithiazolium perchlorate was obtained at 141°C. The characteristic absorption in the infrared absorption spectrum of this product was as follows. 3050cm -1 , 2968cm -1 , 1582cm -1 , 1571cm -1 ,
1538cm -1 , 1465cm -1 , 1441cm -1 , 1283cm -1 , 1068
cm -1 , 761cm -1 , 688cm -1 , 617cm -1 . , C 12 H 15 N 2 S 2 ClO 4 elemental analysis values were as follows. Calculated values (%) C: 41.08, H: 4.31, N: 7.98. Measured value (%) C: 41.02, H4.30, N: 8.07. Example 2 Same as above, add 1 ml of 70% perchloric acid to 15 ml of acetic anhydride.
0.01 mol of N-aroyl-S-disubstituted thiocarbamoylsulfenamide shown in the table below is dissolved in a pre-mixed solution, and the mixture is heated for 2 hours over an aqueous solution. Thereafter, the reaction mixture is allowed to cool, and when the reaction mixture reaches room temperature, dry ether is added to promote precipitation of the product. The product is separated and recrystallized from acetonitrile to yield white microcrystalline 3-aryl-5-disubstituted amino-1,4,2-dithiazolium perchlorate. The melting point yield and elemental analysis results of the dithiazolium salt thus obtained are shown in Table 1.
【表】
実施例 ３
無水酢酸15mlに40％四フツ化ホウ素酸1.5mlを
予め混合した溶液に2.68ｇ（0.01モル）のＮ−ベ
ンゾイル−Ｓ−ジチエルチオカルバモイルスルフ
エンアミドを溶解させ、水溶上で２時間加温す
る。その後放冷し、反応液が室温まで下つたら、
乾燥エーテルをその反応液に加え、生成物の析出
を促進させる。析出した白色の粉末を、別し、
アセトニトリルで再結晶すると、融点120℃の３
−フエニル−５−ジエチルアミノ−１，４，２−
ジチアゾリウム四フツ化ホウ素酸塩1.12ｇ（収率
33％）を得た。このものの赤外吸収スペクトルの
特性吸収は実施例１に示した３−フエニル−５−
ジエチルアミノ−１，４，２−ジチアゾリウム過
塩素酸塩の特性吸収のうち1068cm-1（過塩素酸塩
に帰属）の吸収以外はすべて一致した。
C12H15N2S2BF4としての元素分析値は次のよう
であつた。
計算値（％）Ｃ：42.62，Ｈ：4.47，Ｎ：8.28。
測定値（％）Ｃ：42.58，Ｈ：4.43，Ｎ：8.29。[Table] Example 3 2.68 g (0.01 mol) of N-benzoyl-S-dithyerthiocarbamoylsulfenamide was dissolved in a solution prepared by mixing 15 ml of acetic anhydride with 1.5 ml of 40% tetrafluoroboric acid, and the solution was dissolved in water. Warm on top for 2 hours. After that, let it cool, and when the reaction solution drops to room temperature,
Dry ether is added to the reaction to promote precipitation of the product. Separate the precipitated white powder,
Recrystallization from acetonitrile yields 3 with a melting point of 120℃.
-phenyl-5-diethylamino-1,4,2-
Dithiazolium tetrafluoroborate 1.12g (yield
33%). The characteristic absorption in the infrared absorption spectrum of this product is as shown in Example 1, 3-phenyl-5-
All of the characteristic absorptions of diethylamino-1,4,2-dithiazolium perchlorate were consistent except for the absorption at 1068 cm -1 (attributable to perchlorate). The elemental analysis value as C 12 H 15 N 2 S 2 BF 4 was as follows. Calculated values (%) C: 42.62, H: 4.47, N: 8.28. Measured values (%) C: 42.58, H: 4.43, N: 8.29.
Claims (1)
もよいアルキルまたはアリール基であり、R1，
R2はその末端が結合していてもよく、R3は不活
性な置換基を有していてもよいアリール基を表わ
す。）で示されるＮ−アロイル−Ｓ−ジ置換チオ
カルバモイルスルフエンアミドを強酸の存在下で
脱水環化反応させることを特徴とする 一般式 （式中R1，R2，R3は前記と同一であり、Ｘは
無機強酸の酸根を表わす。） で示される３−アリール−５−ジ置換アミノ−
１，４，２−ジチアゾリウム塩の製造方法。[Claims] 1. General formula (In the formula, R 1 and R 2 are alkyl or aryl groups that may have an inert substituent, and R 1 ,
R 2 may be bonded at its terminal, and R 3 represents an aryl group which may have an inert substituent. ) is characterized by subjecting N-aroyl-S-disubstituted thiocarbamoylsulfenamide to a cyclodehydration reaction in the presence of a strong acid. (In the formula, R 1 , R 2 , R 3 are the same as above, and X represents an acid group of a strong inorganic acid.)
Method for producing 1,4,2-dithiazolium salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59190158A JPS6168481A (en) | 1984-09-11 | 1984-09-11 | Production of 3-aryl-5-disubstituted-1,4,2-dithiazolium salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59190158A JPS6168481A (en) | 1984-09-11 | 1984-09-11 | Production of 3-aryl-5-disubstituted-1,4,2-dithiazolium salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6168481A JPS6168481A (en) | 1986-04-08 |
| JPS6241713B2 true JPS6241713B2 (en) | 1987-09-04 |
Family
ID=16253386
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59190158A Granted JPS6168481A (en) | 1984-09-11 | 1984-09-11 | Production of 3-aryl-5-disubstituted-1,4,2-dithiazolium salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6168481A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0558Y2 (en) * | 1987-04-30 | 1993-01-05 |
-
1984
- 1984-09-11 JP JP59190158A patent/JPS6168481A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0558Y2 (en) * | 1987-04-30 | 1993-01-05 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6168481A (en) | 1986-04-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |