JP2518350B2 - Method for producing benzothiazolones - Google Patents
Method for producing benzothiazolonesInfo
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- JP2518350B2 JP2518350B2 JP63127287A JP12728788A JP2518350B2 JP 2518350 B2 JP2518350 B2 JP 2518350B2 JP 63127287 A JP63127287 A JP 63127287A JP 12728788 A JP12728788 A JP 12728788A JP 2518350 B2 JP2518350 B2 JP 2518350B2
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- formula
- group
- general formula
- benzothiazolones
- chloromethyl
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- Thiazole And Isothizaole Compounds (AREA)
Description
【発明の詳細な説明】 〈産業上の利用分野〉 本発明は一般式（II） 〔式中、R1,R2はそれぞれ水素原子、ハロゲン原子、ア
ルキル基、アルコキシ基、アシル基、アルコキシカルボ
ニル基もしくはシアノ基を表わす。〕 で示される３−クロロメチル−２（3H）−ベンゾチアゾ
ロン類の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention has the general formula (II) [In the formula, R 1 and R 2 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group or a cyano group. ] It is related with the manufacturing method of 3-chloromethyl-2 (3H) -benzothiazolones shown by these.
〈従来の技術〉 ３−クロロメチル−２（3H）−ベンゾチアゾロンは植
物生長調節剤の重要な中間体として知られており（例え
ば、特開昭44-151966号公報）、その製造方法としては
２（3H）−ベンゾチアゾロンの３位にヒドロキシメチル
基を導入し、しかる後ヒドロキシメチル基をクロルメチ
ル基に変換する方法が知られている（例えば米国特許第
3050526号）。<Prior Art> 3-chloromethyl-2 (3H) -benzothiazolone is known as an important intermediate for plant growth regulators (for example, JP-A-44-151966), and its production method is 2 A method is known in which a hydroxymethyl group is introduced at the 3-position of (3H) -benzothiazolone, and then the hydroxymethyl group is converted to a chloromethyl group (for example, US Pat.
No. 3050526).
〈発明が解決しようとする課題〉 しかしながら、２（3H）−ベンゾチアゾロンを用いる
公知方法では、アニリンから２（3H）−ベンゾチアゾロ
ンを製造するのに３〜４つの反応工程を必要とする（例
えば、Heterocyclic Compounds Vol.5,P.484（John Wil
ey ＆ Sons,1957））のみならず該化合物から目的化合
物（II）を製造するのに上述のように更に２つの反応工
程を必要し、公知方法は工程が複雑で操作も極めて繁雑
であるという工業上の大きな問題点を有していた。<Problems to be Solved by the Invention> However, the known method using 2 (3H) -benzothiazolone requires 3 to 4 reaction steps to produce 2 (3H) -benzothiazolone from aniline (for example, Heterocyclic Compounds Vol.5, P.484 (John Wil
ey & Sons, 1957)) as well as the production of the target compound (II) from the compound, requires two additional reaction steps as described above, and the known method is complicated in process and extremely complicated in operation. It had a big industrial problem.
本発明者らは公知方法のかかる問題点を解決すべく鋭
意検討を重ねた結果、トリアジン誘導体を用いることに
よる工業的に極めて優れた３−クロロメチル−２（3H）
−ベンゾチアゾロン類の製造方法を見出すとともに、更
に種々の検討を加えて本発明を完成した。As a result of intensive studies to solve the problems of the known method, the present inventors have found that industrially excellent 3-chloromethyl-2 (3H) by using a triazine derivative.
The present invention has been completed by finding a method for producing benzothiazolones and further conducting various studies.
すなわち本発明は、（１）一般式（Ｉ） 〔式中、R1,R2はそれぞれ水素原子、ハロゲン原子、ア
ルキル基、アルコキシ基、アシル基、アルコキシカルボ
ニル基もしくはシアノ基を表わす。〕 で示されるトリアジン誘導体にクロルカルボニルスルフ
エニルクロリドを作用させ、しかる後にルイス酸を作用
させることを特徴とする一般式（II） 〔式中、R1,R2は前記と同じ意味を表わす。〕 で示されるベンゾチアゾロン類の製造方法。That is, the present invention relates to (1) a compound represented by the general formula (I): [In the formula, R 1 and R 2 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group or a cyano group. ] The general formula (II) characterized in that chlorocarbonylsulfenyl chloride is allowed to act on the triazine derivative represented by [In the formula, R 1 and R 2 have the same meanings as described above. ] The manufacturing method of the benzothiazolones shown by these.
および（２）一般式（III） 〔式中、R1,R2は前記と同じ意味を表わす。〕 で示されるアニリン類にホルムアルデヒドを反応させ
て、一般式（Ｉ） 〔式中、R1,R2は前記と同じ意味を表わす。〕 で示されるトリアジン誘導体を得、次いで、クロルカル
ボニルスルフエニルクロリドを作用させ、しかる後にル
イス酸を作用させることを特徴とする一般式（II） 〔式中、R1,R2は前記と同じ意味を表わす。〕 で示されるベンゾチアゾロン類の製造方法を提供するも
のである。And (2) general formula (III) [In the formula, R 1 and R 2 have the same meanings as described above. ] The aniline represented by the general formula (I) [In the formula, R 1 and R 2 have the same meanings as described above. ] The triazine derivative represented by the following formula is obtained, and then chlorocarbonylsulfenyl chloride is allowed to act, and then a Lewis acid is allowed to act, then the general formula (II) [In the formula, R 1 and R 2 have the same meanings as described above. ] The manufacturing method of the benzothiazolone shown by these is provided.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
一般式（Ｉ）で示されるトリアジン誘導体は一般式
（III）で示されるアニリン類とホルムアルデヒドとの
既知の方法（例えばR.C.Elderfield著Heterocyclic Com
pounds,Vol 7,p.627（John Wiley ＆ Sons,1961））に
準拠して製造することができる。The triazine derivative represented by the general formula (I) can be obtained by a known method using an aniline represented by the general formula (III) and formaldehyde (eg, Heterocyclic Com by RC Elderfield).
pounds, Vol 7, p.627 (John Wiley & Sons, 1961)).
アニリン類（III）としては置換基R1,R2が例えば水素
原子、クロル、ブロム、ヨウ素などのハロゲン原子、メ
チル、エチル、プロピル、ブチルなどのアルキル基、メ
トキシ、エトキシ、プロポキシ、ブトキシなどのアルコ
キシ基、アシル基、メトキシカルボニル、エトキシカル
ボニル、プロポキシカルボニル、ブトキシカルボニルな
どのアルコキシカルボニル基、シアノ基などであるアニ
リン類が挙げられる。As the aniline (III), the substituents R 1 and R 2 are, for example, a hydrogen atom, a halogen atom such as chlorine, bromine and iodine, an alkyl group such as methyl, ethyl, propyl and butyl, methoxy, ethoxy, propoxy and butoxy. Examples thereof include anilines such as an alkoxy group, an acyl group, an alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, and a cyano group.
またホルムアルデヒドとしては例えばパラホルムアル
デヒド、ホルマリン等が用いられ、その使用量はアニリ
ン類に対し通常１〜10当量、好ましくは１〜３当量であ
る。As formaldehyde, for example, paraformaldehyde, formalin and the like are used, and the use amount thereof is usually 1 to 10 equivalents, preferably 1 to 3 equivalents relative to aniline.
反応溶媒としては通常メタノール、エタノール等のア
ルコール類が用いられるが、必要に応じてヘキサン、ベ
ンゼン、トルエン等の炭化水素系溶媒、クロルベンゼ
ン、ジクロルメタン、クロロホルム、ジクロルエタン等
のハロゲン系溶媒もしくは混合溶媒も用いることができ
る。Alcohols such as methanol and ethanol are usually used as a reaction solvent, but if necessary, a hydrocarbon solvent such as hexane, benzene and toluene, a halogen solvent such as chlorobenzene, dichloromethane, chloroform and dichloroethane, or a mixed solvent. Can be used.
反応温度は通常０℃〜溶媒の沸点であり、好ましくは
０〜50℃である。反応時間は通常１〜10時間で十分であ
る。The reaction temperature is usually 0 ° C to the boiling point of the solvent, preferably 0 to 50 ° C. A reaction time of 1 to 10 hours is usually sufficient.
かくしてトリアジン誘導体（Ｉ）が生成するが、この
ものは反応マスから通常の方法により単離して次工程の
原料とすることもできるし、単離することなしに次工程
に供することもできる。Thus, the triazine derivative (I) is produced, which can be isolated from the reaction mass by a conventional method as a raw material for the next step, or can be used for the next step without isolation.
トリアジン誘導体（Ｉ）にクロルカルボニルスルフェ
ニルクロリドを作用させ、しかる後にルイス酸を作用さ
せる工程における溶媒としては、通常ジクロルメタン、
クロロホルム、四塩化炭素、ジクロルエタン、トリクレ
ン等のハロゲン系溶媒が用いられるが、必要に応じエー
テル系溶媒、炭化水素系溶媒、アセトニトリル、ニトロ
メタン、二硫化炭素等も用いることができる。The solvent used in the step of reacting the triazine derivative (I) with chlorocarbonylsulfenyl chloride and then with the Lewis acid is usually dichloromethane,
Halogen-based solvents such as chloroform, carbon tetrachloride, dichloroethane and trichlene are used, but if necessary, ether-based solvents, hydrocarbon-based solvents, acetonitrile, nitromethane, carbon disulfide and the like can also be used.
クロルカルボニルスルフェニルクロリドを作用させる
に当り該クロリドはトリアジン誘導体（Ｉ）に対し３〜
５当量通常使用される。温度は通常−20℃〜溶媒の沸点
の範囲から選定されるが、０℃〜室温が好ましい。時間
は温度にも依るが通常１〜10時間程度である。In the action of chlorocarbonylsulfenyl chloride, the chloride is 3 to 3 parts with respect to the triazine derivative (I).
5 equivalents are usually used. The temperature is usually selected in the range of -20 ° C to the boiling point of the solvent, but 0 ° C to room temperature is preferable. The time depends on the temperature, but it is usually about 1 to 10 hours.
次いで作用せしめるルイス酸としては、例えば塩化ア
ルミニウム、塩化鉄、塩化スズ、塩化チタン等が挙げら
れるが、塩化アルミニウムが通常使用される。その使用
量はトリアジン誘導体（Ｉ）に対し通常３〜５当量であ
る。Examples of the Lewis acid to be acted on next include aluminum chloride, iron chloride, tin chloride, titanium chloride and the like, and aluminum chloride is usually used. The amount used is usually 3 to 5 equivalents relative to the triazine derivative (I).
温度は通常−20℃〜溶媒の沸点の範囲から選定される
が、０℃〜室温が好ましい。反応は温度にも依るが通常
２〜10時間程度で完結する。The temperature is usually selected in the range of -20 ° C to the boiling point of the solvent, but 0 ° C to room temperature is preferable. The reaction is usually completed in about 2 to 10 hours depending on the temperature.
この様にしてベンゾチアゾロン類（II）が生成する
が、このものは通常反応マスより無機物を除去後、ジク
ロロメタン、クロロホルム等の有機溶媒で抽出、水洗
し、次いで溶媒を留去することにより得ることができ
る。In this way, benzothiazolones (II) are produced, which can usually be obtained by removing inorganic substances from the reaction mass, extracting with an organic solvent such as dichloromethane or chloroform, washing with water, and then distilling off the solvent. it can.
また得られたベンゾチアゾロン類（II）は、例えば再
結晶、カラムクロマトグラフィーまたは蒸留等によって
精製することも可能である。The obtained benzothiazolones (II) can also be purified by, for example, recrystallization, column chromatography or distillation.
〈発明の効果〉 かくして目的とする３−クロロメチルベンゾチアゾロ
ン類が製造されるが、本発明によれば目的物がトリアジ
ン誘導体から一挙に得られ、しかもトリアジン誘導体も
アニリン類から一挙に得られるので、工程、設備等の簡
素化、作業の単純化など種々の合理化を計ることができ
る。<Effects of the Invention> Thus, the desired 3-chloromethylbenzothiazolones are produced. According to the present invention, the desired product can be obtained from the triazine derivative at once, and the triazine derivative can also be obtained from the anilines at once. Therefore, various rationalizations such as simplification of processes and facilities and simplification of work can be achieved.
〈実施例〉 以下、実施例により本発明をより詳細に説明するが、
本発明はこれ等のみに限定されるものではない。<Example> Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to these.
実施例１ 1,3,5−トリフェニル−Ｓ−トリアジン1.05gを20mlの
ジクロルメタンに溶解した後、室温で攪拌しながらクロ
ルカルボニルスルフェニルクロリド1.44gを加えて同温
度で２時間攪拌を続けた。Example 1 1.05 g of 1,3,5-triphenyl-S-triazine was dissolved in 20 ml of dichloromethane, 1.44 g of chlorocarbonylsulfenyl chloride was added with stirring at room temperature, and stirring was continued at the same temperature for 2 hours. .
次いで同温度で攪拌しながら無水塩化アルミニウム1.
46gを徐々に加えて同温度で10時間攪拌を続けた。Then, while stirring at the same temperature, anhydrous aluminum chloride 1.
46 g was gradually added and stirring was continued at the same temperature for 10 hours.
反応後反応マスを氷水20gに注加した後、ジクロルメ
タンで２回（10m×２）抽出を行った。有機層を合わ
せ、これを水20ml、飽和食塩水20mlで順次洗浄後、無水
硫酸ナトリウムで乾燥、溶媒留去を行った。After the reaction, the reaction mass was poured into 20 g of ice water, and then extracted twice with dichloromethane (10 m × 2). The organic layers were combined, washed with 20 ml of water and 20 ml of saturated saline in this order, dried over anhydrous sodium sulfate, and the solvent was distilled off.
次いで得られた粗生成物をシリカゲルカラムクロマト
グラフィー（溶出液：ヘキサン／酢酸エチル＝5/1）で
精製を行い、３−クロロメチル−２（3H）−ベンゾチア
ゾロン1.17gを得た。収率59％ m.p.128 129℃ 実施例２ 実施例１において、1,3,5−トリフェニル−Ｓ−トリ
アジンの代りに1,3,5−トリ（ｐ−トリル）−Ｓ−トリ
アジン1.19gを用いる以外は実施例１と同様にして３−
クロロメチル−４−メチル−２（3H）−ベンゾチアゾロ
ン1.38gを得た。収率65％ m.p.113〜114℃ マス分析 m/e 213（M+）1 H‐NMR（▲δCDCi3 ppm▼,TMS） 2.75（s,3H）,5.95（s,2H）,6.90〜7.45（m,3H） 実施例３ 実施例１において、1,3,5−トリフェニル−Ｓ−トリ
アジンの代りに1,3,5−（Ｐ−クロルフェニル）−Ｓ−
トリアジン0.42gを用いる以外は実施例１と同様にして
３−クロロメチル−６−クロル−２（3H）−ベンゾチア
ゾロン0.36gを得た。収率51％、mp.135〜137℃ マス分析 m/e 233（M+）1 H‐NMR（▲δCDCl3 ppm▼,TMS） 5.75（s,2H）,6.95〜7.55（m,3H） 実施例４ 実施例１において、1,3,5−トリフェニル−Ｓ−トリ
アジンの代りに1,3,5−（Ｐ−ブロムフェニル）−Ｓ−
トリアジン0.55gを用いる以外は実施例１と同様にして
３−クロロメチル−６−ブロム−２（3H）−ベンゾチア
ゾロン0.34gを得た。収率41％、mp.128〜130℃ マス分析 m/e 278（M+）1 H‐NMR（▲δCDCl3 ppm▼,TMS） 5.75（s,2H）,7.00〜7.50（m,3H） 実施例５ エタノール10mlにアニリン0.93gを溶解し、室温下に
攪拌しながら40％ホルマリン溶液1.5mlを加え、0.5時間
攪拌した。Then, the obtained crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 5/1) to obtain 1.17 g of 3-chloromethyl-2 (3H) -benzothiazolone. Yield 59% mp128 129 ° C Example 2 In Example 1, 1,3,5-tri (p-tolyl) -S-triazine (1.19 g) is used in place of 1,3,5-triphenyl-S-triazine. 3 is the same as Example 1 except for
1.38 g of chloromethyl-4-methyl-2 (3H) -benzothiazolone was obtained. Yield 65% mp113-114 ℃ Mass analysis m / e 213 (M + ) 1 H-NMR (▲ δ CDCi3 ppm ▼, TMS) 2.75 (s, 3H), 5.95 (s, 2H), 6.90-7.45 (m , 3H) Example 3 In Example 1, 1,3,5- (P-chlorophenyl) -S- was used instead of 1,3,5-triphenyl-S-triazine.
0.36 g of 3-chloromethyl-6-chloro-2 (3H) -benzothiazolone was obtained in the same manner as in Example 1 except that 0.42 g of triazine was used. 51% yield, mp.135~137 ℃ Mass spectrometry m / e 233 (M +) 1 H-NMR (▲ δ CDCl3 ppm ▼, TMS) 5.75 (s, 2H), 6.95~7.55 (m, 3H) carried Example 4 In Example 1, 1,3,5-triphenyl-S-triazine was replaced by 1,3,5- (P-bromophenyl) -S-
0.34 g of 3-chloromethyl-6-bromo-2 (3H) -benzothiazolone was obtained in the same manner as in Example 1 except that 0.55 g of triazine was used. 41% yield, mp.128~130 ℃ Mass spectrometry m / e 278 (M +) 1 H-NMR (▲ δ CDCl3 ppm ▼, TMS) 5.75 (s, 2H), 7.00~7.50 (m, 3H) carried Example 5 0.93 g of aniline was dissolved in 10 ml of ethanol, 1.5 ml of 40% formalin solution was added with stirring at room temperature, and the mixture was stirred for 0.5 hours.
次いで50mlのベンゼンを加えてエタノールと水を共沸
留去した後、ベンゼンを留去し、20mlのジクロルメタン
を加えた。Then, 50 ml of benzene was added to distill off ethanol and water azeotropically, then benzene was distilled off, and 20 ml of dichloromethane was added.
これにクロルカルボニルフルフェニルクロリド1.44
g、塩化アルミニウム1.46gを実施例１と同様にして順次
反応させた後、後処理することにより３−（クロロメチ
ル）−２（3H）−ベンゾチアゾロン0.6gを得た。mp.128
〜129℃ 実施例６ エタノール50mlにＰ−トルイジン10gを溶解した後、
室温下で攪拌しながら40％のホルマリン溶液15mlを加え
た後、0.5時間攪拌を続けた。Chlorocarbonyl full phenyl chloride 1.44
g and 1.46 g of aluminum chloride were sequentially reacted in the same manner as in Example 1 and then post-treated to obtain 0.6 g of 3- (chloromethyl) -2 (3H) -benzothiazolone. mp.128
~ 129 ° C Example 6 After dissolving 10 g of P-toluidine in 50 ml of ethanol,
After adding 15 ml of 40% formalin solution with stirring at room temperature, stirring was continued for 0.5 hours.
析出した粗結晶を取し、これをヘプタン100mlでソ
ックスレー抽出を行った後、得られたヘプタン溶液を室
温まで放冷した。析出した結晶を取・乾燥して1,3,5
−トリス（Ｐ−トリル）−Ｓ−トリアジン8.5gを得た。The crude crystals precipitated were taken out and subjected to Soxhlet extraction with 100 ml of heptane, and then the obtained heptane solution was allowed to cool to room temperature. The precipitated crystals are taken and dried to 1,3,5
8.5 g of -tris (P-tolyl) -S-triazine were obtained.
無色針状晶、mp.124〜127℃ 収率67％ 次いで、1,3,5−トリフェニル−Ｓ−トリアジンの代
りに上記結晶1.19gを用いる以外は実施例１と同様に反
応、後処理を行い３−クロロメチル−６−メチル−２
（3H）−ベンゾチアゾロン456mgを得た。収率65％、mp.
122〜124℃ マス分析 m/e 213（M+）1 H‐NMR（▲δCDCl3 ppm▼,TMS） 2.35（s,3H）,5.70（s,2H）,7.10〜7.30（m,3H）Colorless needle crystals, mp.124-127 ° C Yield 67% Then, reaction and post-treatment were carried out in the same manner as in Example 1 except that 1.19 g of the above crystal was used in place of 1,3,5-triphenyl-S-triazine. Perform 3-chloromethyl-6-methyl-2
456 mg of (3H) -benzothiazolone was obtained. Yield 65%, mp.
122-124 ℃ Mass analysis m / e 213 (M + ) 1 H-NMR (▲ δ CDCl3 ppm ▼, TMS) 2.35 (s, 3H), 5.70 (s, 2H), 7.10-7.30 (m, 3H)
Claims (2)
ルキル基、アルコキシ基、アシル基、アルコキシカルボ
ニル基もしくはシアノ基を表わす。〕 で示されるトリアジン誘導体にクロルカルボニルスルフ
エニルクロリドを作用させ、しかる後にルイス酸を作用
させることを特徴とする一般式（II） 〔式中、R1,R2は前記と同じ意味を表わす。〕 で示される３−クロロメチルベンゾチアゾロン類の製造
方法。1. A general formula (I) [In the formula, R 1 and R 2 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group or a cyano group. ] The general formula (II) characterized in that chlorocarbonylsulfenyl chloride is allowed to act on the triazine derivative represented by [In the formula, R 1 and R 2 have the same meanings as described above. ] The manufacturing method of 3-chloromethyl benzothiazolones shown by these.
ルキル基、アルコキシ基、アシル基、アルコキシカルボ
ニル基もしくはシアノ基を表わす。〕 で示されるアニリン類にホルムアルデヒドを反応させ
て、一般式（Ｉ） 〔式中、R1,R2は前記と同じ意味を表わす。〕 で示されるトリアジン誘導体を得、次いで、クロルカル
ボニルスルフエニルクロリドを作用させ、しかる後にル
イス酸を作用させることを特徴とする一般式（II） 〔式中、R1,R2は前記と同じ意味を表わす。〕 で示される３−クロロメチルベンゾチアゾロン類の製造
方法。2. General formula (III) [In the formula, R 1 and R 2 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group or a cyano group. ] The aniline represented by the general formula (I) [In the formula, R 1 and R 2 have the same meanings as described above. ] The triazine derivative represented by the following formula is obtained, and then chlorocarbonylsulfenyl chloride is allowed to act, and then a Lewis acid is allowed to act, then the general formula (II) [In the formula, R 1 and R 2 have the same meanings as described above. ] The manufacturing method of 3-chloromethyl benzothiazolones shown by these.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63127287A JP2518350B2 (en) | 1988-05-25 | 1988-05-25 | Method for producing benzothiazolones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63127287A JP2518350B2 (en) | 1988-05-25 | 1988-05-25 | Method for producing benzothiazolones |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01299278A JPH01299278A (en) | 1989-12-04 |
| JP2518350B2 true JP2518350B2 (en) | 1996-07-24 |
Family
ID=14956237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63127287A Expired - Lifetime JP2518350B2 (en) | 1988-05-25 | 1988-05-25 | Method for producing benzothiazolones |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2518350B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3130924A1 (en) * | 1981-08-05 | 1983-02-17 | Röhm GmbH, 6100 Darmstadt | SURFACE-BASED SYSTEMS FOR FIXING SUBSTRATES CONTAINING NUCLEOPHILE GROUPS |
-
1988
- 1988-05-25 JP JP63127287A patent/JP2518350B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01299278A (en) | 1989-12-04 |
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