JPS6129340B2 - - Google Patents
Info
- Publication number
- JPS6129340B2 JPS6129340B2 JP12547478A JP12547478A JPS6129340B2 JP S6129340 B2 JPS6129340 B2 JP S6129340B2 JP 12547478 A JP12547478 A JP 12547478A JP 12547478 A JP12547478 A JP 12547478A JP S6129340 B2 JPS6129340 B2 JP S6129340B2
- Authority
- JP
- Japan
- Prior art keywords
- tri
- aminopyrrole
- trithiocyclopropenium
- salt
- reaction
- 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
- QLSWIGRIBOSFMV-UHFFFAOYSA-N 1h-pyrrol-2-amine Chemical class NC1=CC=CN1 QLSWIGRIBOSFMV-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- -1 2-amino-3,4,5-tri-ethylthiopyrrole Chemical compound 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- SPAGBMPUXGPEOP-UHFFFAOYSA-N 2-butylsulfanyl-1h-pyrrole Chemical compound CCCCSC1=CC=CN1 SPAGBMPUXGPEOP-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006049 ring expansion reaction Methods 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- FTBBGQKRYUTLMP-UHFFFAOYSA-N 2-nitro-1h-pyrrole Chemical compound [O-][N+](=O)C1=CC=CN1 FTBBGQKRYUTLMP-UHFFFAOYSA-N 0.000 description 1
- QDHZMNOYFINVEC-UHFFFAOYSA-N 2-nitroso-1h-pyrrole Chemical compound O=NC1=CC=CN1 QDHZMNOYFINVEC-UHFFFAOYSA-N 0.000 description 1
- RRBTYEQMRJIVGU-UHFFFAOYSA-N 3,4,5-tris(tert-butylsulfanyl)-1h-pyrrol-2-amine Chemical compound CC(C)(C)SC=1NC(N)=C(SC(C)(C)C)C=1SC(C)(C)C RRBTYEQMRJIVGU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- NMVVJCLUYUWBSZ-UHFFFAOYSA-N aminomethylideneazanium;chloride Chemical compound Cl.NC=N NMVVJCLUYUWBSZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- WYOGYWFSXNDUCT-UHFFFAOYSA-N chloroform;1,2-dimethoxyethane Chemical compound ClC(Cl)Cl.COCCOC WYOGYWFSXNDUCT-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910001023 sodium amalgam Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
【発明の詳細な説明】
本発明は新規なアミノピロール誘導体に関する
ものである。詳しくは、トリチオシクロプロペニ
ウム塩の環拡大反応により製造できる新規なアミ
ノピロール誘導体に関するものである。
従来、アミノピロールはニトロピロールまたは
ニトロソピロールをナトリウムアマルガムで還元
することにより製造できることが知られている
が、α−アミノピロール類は一般に不安定で、よ
い合成法がなかつた。
一方、本発明者は、先にトリチオシクロプロペ
ニウム塩の環拡大反応により、各種の複素環化合
物を製造する方法を報告した。
これらの知見をもとに新規なアミノピロール誘
導体を製造する方法を開発すべく鋭意研究した結
果、トリチオシクロプロペニウム塩とホルムアミ
ジンを反応させれば生成するアミノピロールも安
定で、目的を達しうることも知り、本発明に到達
した。
すなわち、本発明の要旨は一般式（）
〔式中、R1は低級アルキル基を表わす。〕
で示される２−アミノピロール誘導体に存する。
以下に本発明を詳細に説明する。
このようなアミノピロール誘導体としては、例
えば２−アミノ−３・４・５−トリ−エチルチオ
ピロール、２−アミノ−３・４・５−トリ−ｎ−
プロピルチオピロール、２−アミノ−３・４・５
−トリ−イソプロピルチオピロール、２−アミノ
−３・４・５−トリ−ｔ−ブチルチオピロール等
が挙げられる。
一般式（）で示されるアミノピロール誘導体
は、例えば一般式（）
（式中、R1は低級アルキル基を表わし、Ｚは陰
イオンを表わす。）
で示されるトリチオシクロプロペニウム塩と、ホ
ルムアミジンを反応させることにより製造でき
る。原料である前記一般式（）で示されるトリ
チオシクロプロペニウム塩においてR1は、メチ
ル、エチル、ｎ−プロピル、iso−プロピル、ｎ
−ブチル、iso−ブチル、sec−ブチル、ｔ−ブチ
ル等の低級アルキル基である。
また、Ｚは任意の陰イオンである。
例えばハロゲンイオン、過塩素酸イオン、フル
オロホウ酸イオン、六フツ化アンチモンイオン、
六塩化アンチモンイオン、塩化アルミニウムイオ
ン等である。
このようなシクロプロペニウム塩としては、例
えばトリエチルチオシクロプロペニウムパークロ
レート、トリ−ｎ−プロピルチオシクロプロペニ
ウムパークロレート、トリ−iso−プロピルチオ
シクロプロペニウムパークロレート、トリ−ｔ−
ブチルチオシクロプロペニウムパークロレート、
トリ−ｔ−ブチルチオシクロプロペニウムテトラ
フルオロボレート等が挙げられる。
トリチオシクロプロペニウム塩は、例えば特開
昭48−96564号公報に記載された方法により、製
造すれば良い。
ホルムアミジンとトリチオシクロプロペニウム
塩の反応は、通常、適当な溶剤中で行なわれる。
溶剤としては、塩化メチレン、クロロホルムジ
メトキシエタン、ジメチルホルムアミド、メタノ
ール等が用いられる。
また、反応を円滑に進行させるため、ホルムア
ミジンとトリチオシクロプロペニウム塩の反応の
際、塩基を反応系に加えてもよい。塩基として
は、例えば水素化ナトリウムなどのアルカリ金属
水素化物やｔ−ブトキシカリウムなどの金属アル
コキシドがあげられ、その好適な量は、トリチオ
シクロプロペニウム塩に対して２倍モル程度用い
るのがよい。
反応系に塩基を加えない場合、ホルムアミジン
は、トリチオシクロプロペニウム塩に対し２倍モ
ル程度、塩基を加える場合、ホルムアミジンは、
トリチオシクロプロペニウム塩に対し等モル程度
加えるのが望ましい。
反応温度は−100〜０℃、通常−40〜−20℃付
近が選ばれる。
反応時間は0.5〜５時間、通常１〜２時間程度
である。
生成したアミノピロール誘導体は有機化学合成
の常法に従いろ過、抽出、溶媒留去等の方法によ
つて反応液より粗生成物を分離し、カラムクロマ
トグラフイー、昇華、再結晶等の方法により単
離、精製することができる。
本発明に係わるアミノピロール誘導体は農薬、
医薬等に利用され、またその反応性を利用して各
種合成化学原料としての用途が期待される。さら
に、本発明に係るアミノピロール誘導体をラネー
ニツケル等の金属触媒の存在下水素で処理すると
−SR1基を脱離させることができ、アミノピロー
ルに導くことも出来るので、アミノピロールの製
造方法としても有用である。
以下に実施例を挙げて、本発明を更に具体的に
説明するが、本発明はその要旨を越えない限り、
実施例により限定を受けるものではない。
実施例 １
窒素置換下、０℃に冷却した100mlの二口フラ
スコに、ジメチルホルムアミド（以下DMFと略
す）15ml、水素化ナトリウム50mg（２ミリモル）
（油中の50％懸濁液として100mg）を加えて、よく
撹拌しながら、DMF7mlに溶かしたホルムアミジ
ン塩酸塩160mg（２ミリモル）をゆつくり滴下し
た。30分撹拌後、さらに反応容器を−40℃に冷却
させ、DMF10mlに溶解させたトリ−ｔ−ブチル
チオシクロプロペニウムパークロレート403mg
（１ミリモル）を徐々に滴下し、その後１時間撹
拌を続けた後、水200mlを加えてよくふり、石油
エーテルで抽出を行い、その石油エーテル層を無
水硫酸ナトリウムを用いて乾燥させ、濃縮後、エ
チルエーテル：石油エーテル１：１（容積比）の
混合溶媒を用いてシリカゲルカラムクロマトグラ
フイー処理することにより、２−アミノ−３・
４・５−トリ−ｔ−ブチルチオピロールを32％の
収率で得た。
赤色結晶 m.p.84℃
irスペクトル（KBr）．3400〜3300cm-1（Ｎ−Ｈ）
nmrスペクトル（CCl3）δ．1.18（Ｓ、9H、ｔ−
ブチル）
1.21（Ｓ、9H、ｔ−ブチル）
1.23（Ｓ、9H、ｔ−ブチル）
4.10（2H、broad Ｓ、−NH2）
8.62（1H、broad Ｓ、−NH）
マススペクトル ｍ／ｅ M+346
得られた２−アミノ−３・４・５−トリ−ｔ−
ブチルチオピロールを常法によりアセチル化した
２−アセチルアミノ−３・４・５−トリ−ｔ−ブ
チルチオピロール（m.p.138℃）の元素分析結果
は次の通り。（何れも重量％）
Ｃ Ｈ Ｎ Ｓ
計算値 55.63 8.30 7.21 24.35
分析値 55.86 8.53 7.11 24.65
なお、この２−アミノ−３・４・５−トリ−ｔ
−ブチルチオピロールの製造の際には、４・５−
ジ−ｔ−ブチルチオピリミジンが８％、２−
（１・２・３−トリ−ｔ−ブチルチオ−２−プロ
ペン−１−イレンアミノ）−３・４・５−トリ−
ｔ−ブチルチオピロールが28％の収率でそれぞれ
副生した。
実施例 ２−４
実施例１において、反応温度を表１に示した様
に変えた他は全く同様にして、表１の通りの結果
を得た。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel aminopyrrole derivatives. Specifically, the present invention relates to a novel aminopyrrole derivative that can be produced by a ring expansion reaction of a trithiocyclopropenium salt. Conventionally, it has been known that aminopyrrole can be produced by reducing nitropyrrole or nitrosopyrrole with sodium amalgam, but α-aminopyrroles are generally unstable and there has been no good synthesis method. On the other hand, the present inventor previously reported a method for producing various heterocyclic compounds by a ring expansion reaction of a trithiocyclopropenium salt. Based on these findings, we conducted intensive research to develop a new method for producing aminopyrrole derivatives, and found that the aminopyrrole produced by reacting trithiocyclopropenium salt with formamidine is stable and achieves our goal. This led to the discovery of the present invention. That is, the gist of the present invention is the general formula () [In the formula, R 1 represents a lower alkyl group. ] It exists in the 2-aminopyrrole derivative shown by these. The present invention will be explained in detail below. Such aminopyrrole derivatives include, for example, 2-amino-3,4,5-tri-ethylthiopyrrole, 2-amino-3,4,5-tri-n-
Propylthiopyrrole, 2-amino-3, 4, 5
-tri-isopropylthiopyrrole, 2-amino-3,4,5-tri-t-butylthiopyrrole, and the like. Aminopyrrole derivatives represented by the general formula () are, for example, (In the formula, R 1 represents a lower alkyl group and Z represents an anion.) It can be produced by reacting a trithiocyclopropenium salt represented by the following with formamidine. In the trithiocyclopropenium salt represented by the general formula () which is a raw material, R 1 is methyl, ethyl, n-propyl, iso-propyl, n
-butyl, iso-butyl, sec-butyl, t-butyl and other lower alkyl groups. Moreover, Z is an arbitrary anion. For example, halogen ions, perchlorate ions, fluoroborate ions, antimony hexafluoride ions,
These include antimony hexachloride ion and aluminum chloride ion. Examples of such cyclopropenium salts include triethylthiocyclopropenium perchlorate, tri-n-propylthiocyclopropenium perchlorate, tri-iso-propylthiocyclopropenium perchlorate, tri-t-
Butylthiocyclopropenium perchlorate,
Examples include tri-t-butylthiocyclopropenium tetrafluoroborate. The trithiocyclopropenium salt may be produced, for example, by the method described in JP-A-48-96564. The reaction between formamidine and trithiocyclopropenium salt is usually carried out in a suitable solvent. As the solvent, methylene chloride, chloroform dimethoxyethane, dimethylformamide, methanol, etc. are used. Furthermore, in order to make the reaction proceed smoothly, a base may be added to the reaction system during the reaction of formamidine and trithiocyclopropenium salt. Examples of the base include alkali metal hydrides such as sodium hydride and metal alkoxides such as potassium t-butoxy, and a suitable amount thereof is about twice the molar amount of the trithiocyclopropenium salt. . When no base is added to the reaction system, formamidine is about twice the molar amount of the trithiocyclopropenium salt, and when a base is added, formamidine is
It is desirable to add about equimolar amount to the trithiocyclopropenium salt. The reaction temperature is selected to be -100 to 0°C, usually around -40 to -20°C. The reaction time is 0.5 to 5 hours, usually about 1 to 2 hours. The produced aminopyrrole derivative is separated from the reaction solution by methods such as filtration, extraction, and solvent distillation according to conventional organic chemical synthesis methods, and then isolated by methods such as column chromatography, sublimation, and recrystallization. It can be separated and purified. The aminopyrrole derivatives according to the present invention are agricultural chemicals,
It is used in medicine, etc., and its reactivity is expected to be used as a raw material for various synthetic chemicals. Furthermore, when the aminopyrrole derivative according to the present invention is treated with hydrogen in the presence of a metal catalyst such as Raney nickel, the -SR 1 group can be eliminated and it can be led to aminopyrrole, so it can also be used as a method for producing aminopyrrole. Useful. The present invention will be explained in more detail with reference to Examples below, but the present invention does not exceed the gist thereof.
The invention is not limited by the examples. Example 1 15 ml of dimethylformamide (hereinafter abbreviated as DMF) and 50 mg (2 mmol) of sodium hydride were placed in a 100 ml two-necked flask cooled to 0°C under nitrogen atmosphere.
(100 mg as a 50% suspension in oil) and, with good stirring, 160 mg (2 mmol) of formamidine hydrochloride dissolved in 7 ml of DMF was slowly added dropwise. After stirring for 30 minutes, the reaction vessel was further cooled to -40°C, and 403 mg of tri-t-butylthiocyclopropenium perchlorate dissolved in 10 ml of DMF was added.
(1 mmol) was gradually added dropwise, stirring was continued for 1 hour, 200 ml of water was added, shaken well, extracted with petroleum ether, the petroleum ether layer was dried using anhydrous sodium sulfate, and after concentration. , 2-amino-3.
4,5-tri-t-butylthiopyrrole was obtained with a yield of 32%. Red crystal mp84℃ IR spectrum (KBr). 3400-3300 cm -1 (NH) nmr spectrum (CCl 3 ) δ. 1.18 (S, 9H, t-
Butyl) 1.21 (S, 9H, t-butyl) 1.23 (S, 9H, t-butyl) 4.10 (2H, broad S, -NH 2 ) 8.62 (1H, broad S, -NH) Mass spectrum m/e M + 346 Obtained 2-amino-3,4,5-tri-t-
The elemental analysis results of 2-acetylamino-3,4,5-tri-t-butylthiopyrrole (mp 138°C) obtained by acetylating butylthiopyrrole by a conventional method are as follows. (All weight%) C H N S Calculated value 55.63 8.30 7.21 24.35 Analyzed value 55.86 8.53 7.11 24.65 In addition, this 2-amino-3,4,5-tri-t
-When producing butylthiopyrrole, 4,5-
8% di-t-butylthiopyrimidine, 2-
(1,2,3-tri-t-butylthio-2-propen-1-ylenamino)-3,4,5-tri-
t-Butylthiopyrrole was produced as a by-product at a yield of 28%. Example 2-4 The same procedure as in Example 1 was performed except that the reaction temperature was changed as shown in Table 1, and the results shown in Table 1 were obtained. 【table】
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12547478A JPS5551065A (en) | 1978-10-12 | 1978-10-12 | Aminopyrrole derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12547478A JPS5551065A (en) | 1978-10-12 | 1978-10-12 | Aminopyrrole derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5551065A JPS5551065A (en) | 1980-04-14 |
| JPS6129340B2 true JPS6129340B2 (en) | 1986-07-05 |
Family
ID=14910975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12547478A Granted JPS5551065A (en) | 1978-10-12 | 1978-10-12 | Aminopyrrole derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5551065A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6271392B1 (en) | 1994-10-07 | 2001-08-07 | Rhone-Poulenc Inc. | Intermediates useful for the synthesis of 1-arylpyrrole pesticides |
-
1978
- 1978-10-12 JP JP12547478A patent/JPS5551065A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5551065A (en) | 1980-04-14 |
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