JPH0725849A - 2-trifluoromethylpyprole derivative and its production - Google Patents
2-trifluoromethylpyprole derivative and its productionInfo
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- JPH0725849A JPH0725849A JP19321393A JP19321393A JPH0725849A JP H0725849 A JPH0725849 A JP H0725849A JP 19321393 A JP19321393 A JP 19321393A JP 19321393 A JP19321393 A JP 19321393A JP H0725849 A JPH0725849 A JP H0725849A
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- Pyrrole Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、農薬、農医薬中間体と
して有用な２−トリフルオロメチルピロール誘導体およ
びその工業的に有利な製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a 2-trifluoromethylpyrrole derivative useful as an intermediate for agricultural chemicals and agricultural drugs, and an industrially advantageous production method thereof.
【０００２】[0002]
【従来の技術】２−アリール−５−トリフルオロメチル
ピロール類については、特開平１−１０４０４２、特開
平２−１６７２０３、特開平４−２７０２６３において
殺昆虫剤、殺ダニ剤、殺線虫剤、殺菌剤として有用なこ
とが記載されている。しかしながら、これらの中で実際
に製造されているのは、２−アリール−３−シアノ−
（またはアルコキシカルボニル）−５−トリフルオロメ
チルピロール類または２−アリール−３，４−ジシアノ
−５−トリフルオロメチルピロール類であり、５−アリ
ール−３−シアノ（またはアルコキシカルボニル）−２
−トリフルオロメチルピロール類または２−アリール−
３−アルキル−４−シアノ（またはアルコキシカルボニ
ル）−５−トリフルオロメチルピロール類については、
３−シアノ−５−（３−ジフルオロメトキシフェニル）
−２−トリフルオロメチルピロールおよび４−クロロ−
３−シアノ−２−トリフルオロメチル−５−（β−ナフ
チル）ピロールのみが例示されているが、製造方法につ
いては何ら記載されてなく製造することができない。す
なわち、特開平１−１０４０４２ではアザラクトン化合
物とα−ハロ−α，β−不飽和ニトリルをニトロメタン
などの有機溶媒中で加熱することにより２−アリール−
３−シアノ−５−トリフルオロメチルピロール類が製造
されることが記載されており、特開平４−２７０２６３
では、この反応を極性溶媒中塩基の存在下反応させるこ
とにより２−アリール−３−シアノ（またはアルコキシ
カルボニル）−５−トリフルオロメチルピロール類が製
造されることが記載されているのみである。それ以外の
文献においても５−アリール−３−シアノ（またはアル
コキシカルボニル）−２−トリフルオロメチルピロール
または２−アリール−３−アルキル−４−シアノ（また
はアルコキシカルボニル）−５−トリフルオロメチルピ
ロールが製造されたという報告はない。2. Description of the Related Art Regarding 2-aryl-5-trifluoromethylpyrroles, insecticides, acaricides and nematicides are disclosed in JP-A-1-104042, JP-A-2-167203 and JP-A-4-270263. It is described to be useful as a fungicide. However, among these, what is actually produced is 2-aryl-3-cyano-
(Or alkoxycarbonyl) -5-trifluoromethylpyrroles or 2-aryl-3,4-dicyano-5-trifluoromethylpyrroles, 5-aryl-3-cyano (or alkoxycarbonyl) -2
-Trifluoromethylpyrroles or 2-aryl-
For 3-alkyl-4-cyano (or alkoxycarbonyl) -5-trifluoromethylpyrroles,
3-cyano-5- (3-difluoromethoxyphenyl)
-2-Trifluoromethylpyrrole and 4-chloro-
Only 3-cyano-2-trifluoromethyl-5- (β-naphthyl) pyrrole is exemplified, but no production method is described and it cannot be produced. That is, in Japanese Unexamined Patent Publication (Kokai) No. 1-104042, 2-aryl-is obtained by heating an azalactone compound and an α-halo-α, β-unsaturated nitrile in an organic solvent such as nitromethane.
It is described that 3-cyano-5-trifluoromethylpyrroles are produced, and it is described in JP-A-4-270263.
Then, it is only described that 2-aryl-3-cyano (or alkoxycarbonyl) -5-trifluoromethylpyrroles are produced by reacting this reaction in the presence of a base in a polar solvent. In other documents as well, 5-aryl-3-cyano (or alkoxycarbonyl) -2-trifluoromethylpyrrole or 2-aryl-3-alkyl-4-cyano (or alkoxycarbonyl) -5-trifluoromethylpyrrole is There is no report that it was manufactured.
【０００３】[0003]
【発明が解決しようとする課題】本発明は農薬、農医薬
中間体として有用な３−シアノ−２−トリフルオロメチ
ルピロール誘導体、３−アルコキシカルボニル−２−ト
リフルオロメチルピロール誘導体およびその工業的に有
利な製造方法を提供することを目的とする。DISCLOSURE OF THE INVENTION The present invention provides 3-cyano-2-trifluoromethylpyrrole derivatives, 3-alkoxycarbonyl-2-trifluoromethylpyrrole derivatives, which are useful as agricultural chemicals and agricultural drug intermediates, and their industrial applications. An object is to provide an advantageous manufacturing method.
【０００４】[0004]
【課題を解決するための手段】本発明は、式〔Ｉ〕The present invention provides a compound of formula [I]
【化６】 〔式中、Ｒはアリール基またはヘテロ環基を表し、これ
らは置換基を有していてもよい。Ｙは水素原子またはア
ルキル基を表す。Ｚはシアノ基またはアルコキシカルボ
ニル基を表す。〕で表される２−トリフルオロメチルピ
ロール誘導体およびその製造方法である。[Chemical 6] [In the formula, R represents an aryl group or a heterocyclic group, and these may have a substituent. Y represents a hydrogen atom or an alkyl group. Z represents a cyano group or an alkoxycarbonyl group. ] The 2-trifluoromethyl pyrrole derivative represented by these, and its manufacturing method.
【０００５】Ｒのアリール基としては、例えばフェニル
基、ナフチル基などが挙げられ、ヘテロ環基としては、
例えばピリジル基、チアゾリル基などが挙げられ、これ
らの置換基としては、例えばハロゲン、置換基を有して
もよいアルキル、置換基を有してもよいアルコキシ、置
換基を有してもよいアルキルチオ、置換基を有してもよ
いアルキルスルフォニル、ニトロ、シアノ、置換基を有
してもよいアルコキシカルボニル、置換基を有してもよ
いフェノキシなどが挙げられる。Examples of the aryl group of R include a phenyl group and a naphthyl group, and examples of the heterocyclic group include:
Examples thereof include a pyridyl group and a thiazolyl group. Examples of these substituents include halogen, alkyl which may have a substituent, alkoxy which may have a substituent, and alkylthio which may have a substituent. , Alkylsulfonyl optionally having substituent (s), nitro, cyano, alkoxycarbonyl optionally having substituent (s), phenoxy optionally having substituent (s) and the like.
【０００６】次に製造方法について述べる。 （ａ法）式〔II〕Next, a manufacturing method will be described. (Method a) Formula [II]
【化７】 〔式中、Ｒは前記と同じ意味を表す。〕で表されるアザ
ラクトン化合物と、式〔III 〕 ＨＹＣ＝ＣＸＺ 〔III 〕 〔式中、Ｘはハロゲン原子を表す。ＹおよびＺは前記と
同じ意味を表す。〕で表される化合物とを、３価のリン
化合物触媒存在下に反応させて、式〔Ｉ〕[Chemical 7] [In the formula, R represents the same meaning as described above. ] The azalactone compound represented by these, and a formula [III] HYC = CXZ [III] [In formula, X represents a halogen atom. Y and Z have the same meanings as described above. ] The compound represented by the formula [I] is reacted in the presence of a trivalent phosphorus compound catalyst.
【化８】 〔式中、Ｒ、ＹおよびＺは前記と同じ意味を表す。〕で
表される２−トリフルオロメチルピロール誘導体を製造
する。[Chemical 8] IN FORMULA, R, Y, AND Z REPRESENT A SAID MEANING. ] The 2-trifluoromethyl pyrrole derivative represented by these is manufactured.
【０００７】（ｂ法）式〔II〕(B method) Formula [II]
【化９】 〔式中、Ｒは前記と同じ意味を表す。〕で表されるアザ
ラクトン化合物と、式〔III'〕 ＹＣ≡ＣＺ’ 〔III'〕 〔式中、Ｙは前記と同じ意味を表し、Ｚ’はアルコキシ
カルボニル基を表す。〕で表される化合物とを、３価の
リン化合物触媒存在下に反応させて、式〔I'〕[Chemical 9] [In the formula, R represents the same meaning as described above. And an azalactone compound represented by the formula [III ′] YC≡CZ ′ [III ′] [wherein Y represents the same meaning as described above and Z ′ represents an alkoxycarbonyl group. ] The compound represented by the formula [I '] is reacted in the presence of a trivalent phosphorus compound catalyst.
【化１０】 〔式中、Ｒ、ＹおよびＺ’は前記と同じ意味を表す。〕
で表される２−トリフルオロメチルピロール誘導体を製
造する。[Chemical 10] [In the formula, R, Y and Z ′ represent the same meaning as described above. ]
A 2-trifluoromethylpyrrole derivative represented by
【０００８】ここで、Ｘのハロゲン原子としては、例え
ば塩素原子、臭素原子などが挙げられる。３価のリン化
合物としては、例えば（Ｒ3 ）3 Ｐ（式中、Ｒ3 はアル
キルなどで置換されてもよいフェニル基、アルキル基、
アラルキル基などを表す。）などが挙げられる。Here, examples of the halogen atom of X include a chlorine atom and a bromine atom. Examples of the trivalent phosphorus compound include (R 3 ) 3 P (wherein R 3 is a phenyl group which may be substituted with alkyl, an alkyl group,
Represents an aralkyl group. ) And the like.
【０００９】反応（ａ法、ｂ法）は、式〔II〕のアザラ
クトン化合物と、少なくとも１モル当量、好適には約１
〜５モル当量の式〔III 〕または式〔III'〕で表される
化合物、および０．０１〜５モル当量の３価リン化合物
を有機溶媒の存在下好適には約２０〜１８０℃の温度の
範囲で反応させることにより行なう。有機溶媒としては
ベンゼントルエンなどの芳香族類、酢酸エチル、アセト
ニトリル、ニトロメタン、ＤＭＦなどの非プロトン性極
性溶媒、ＴＨＦ、ジオキサンなどのエーテル類、クロロ
ホルム、四塩化炭素などのハロゲン化炭化水素類が使用
される。生成物の式〔Ｉ〕の化合物は通常溶媒を減圧濃
縮後シリカゲルカラムクロマトグラフィーにより単離精
製するが、有機溶媒に対し溶解度が低く副生物の分離操
作に困難をともなう場合については反応混合物をそのま
まハロゲン化アルキルと反応させ１−位アルキル誘導体
にしたのち、シリカゲルカラムクロマトグラフィーによ
り分離精製を行なうこともできる。The reaction (method a, method b) is carried out with the azalactone compound of the formula [II] at least 1 molar equivalent, preferably about 1
To 5 molar equivalents of the compound represented by the formula [III] or the formula [III '] and 0.01 to 5 molar equivalents of the trivalent phosphorus compound in the presence of an organic solvent, preferably at a temperature of about 20 to 180 ° C. It is carried out by reacting within the range. As the organic solvent, aromatics such as benzenetoluene, aprotic polar solvents such as ethyl acetate, acetonitrile, nitromethane and DMF, ethers such as THF and dioxane, halogenated hydrocarbons such as chloroform and carbon tetrachloride are used. To be done. The product of the formula [I], which is a product, is usually isolated and purified by silica gel column chromatography after concentration of the solvent under reduced pressure. However, in the case of low solubility in organic solvent and difficulty in separating by-products, the reaction mixture is left as it is After reacting with an alkyl halide to form a 1-position alkyl derivative, it can be separated and purified by silica gel column chromatography.
【００１０】式〔II〕で表される化合物は、以下のよう
にして得られる。すなわち式〔IV〕The compound represented by the formula [II] is obtained as follows. That is, the formula [IV]
【化１１】 〔式中、Ｒは前記と同じ意味を表す。〕で表わされるグ
リシン誘導体と２当量の無水トリフルオロ酢酸を無溶媒
もしくは非プロトン性有機溶媒の存在下５０〜８０℃、
１〜５時間反応させる。非プロトン性有機溶媒としては
ベンゼントルエンなどの芳香族類、酢酸エチル、アセト
ニトリル、ニトロメタン、ＤＭＦなどの非プロトン性極
性溶媒、ＴＨＦ、ジオキサンなどのエーテル類、クロロ
ホルム、四塩化炭素などのハロゲン化炭化水素類が使用
される。この反応液は濃縮して次の反応に用いてもよ
い。合成した化合物は、ＮＭＲ、ＩＲ、ＭＳ等により同
定できる。[Chemical 11] [In the formula, R represents the same meaning as described above. ] The glycine derivative represented by and 2 equivalents of trifluoroacetic anhydride in the presence of a solvent-free or aprotic organic solvent at 50 to 80 ° C,
Allow to react for 1-5 hours. As the aprotic organic solvent, aromatics such as benzenetoluene, aprotic polar solvents such as ethyl acetate, acetonitrile, nitromethane and DMF, ethers such as THF and dioxane, halogenated hydrocarbons such as chloroform and carbon tetrachloride. Kind is used. This reaction liquid may be concentrated and used in the next reaction. The synthesized compound can be identified by NMR, IR, MS and the like.
【００１１】[0011]
【実施例】次に実施例を挙げ、本発明を更に具体的に説
明する。EXAMPLES Next, the present invention will be described more specifically with reference to examples.
【００１２】実施例１ ３−シアノ−２−トリフルオロ
メチル−５−フェニルピロール（化合物番号１）の合成
〔ａ法〕Example 1 Synthesis of 3-cyano-2-trifluoromethyl-5-phenylpyrrole (Compound No. 1) [method a]
【化１２】 ４−フェニル−２−トリフルオロメチル−２Ｈ−オキサ
ゾリン−５−オン １．６０ｇ（０．００７モル）、２
−クロロアクリロニトリル ０．７９ｇ（０．００９モ
ル）、トリフェニルホスフィン ２．３６ｇ（０．００
９モル）をトルエン３０ｍｌに溶解し、撹拌下徐々に加
熱昇温した。９０〜１００℃で２時間保ち得られた反応
混合物を減圧濃縮し、残渣をシリカゲルカラムクロマト
グラフィー（クロロホルム）にて精製した。 収量 １．１２ｇ（６８％） ｍ．ｐ １６４−１６６℃ 得られた３−シアノ−２−トリフルオロメチル−５−フ
ェニルピロールはプロトンＮＭＲでピロール環の４位の
プロトンが６．７ｐｐｍにピークを示し、このプロトン
を照射することによりベンゼン環２位及び６位のプロト
ンにＮＯＥが観測された。一方特開平１−１０４０４２
及び特開平４−２７０２６３に記載されている、３−シ
アノ−２−フェニル−５−トリフルオロメチルピロール
はプロトンＮＭＲでピロール環４位のプロトンが６．８
６ｐｐｍにピークを示し、このプロトンを照射してもベ
ンゼン環２位及び６位プロトンにＮＯＥが観測されなか
った。以上のことより、本発明化合物の構造が確認され
た。[Chemical 12] 4-phenyl-2-trifluoromethyl-2H-oxazolin-5-one 1.60 g (0.007 mol), 2
-Chloroacrylonitrile 0.79 g (0.009 mol), triphenylphosphine 2.36 g (0.00
9 mol) was dissolved in 30 ml of toluene, and the temperature was gradually raised with heating under stirring. The reaction mixture obtained was kept at 90 to 100 ° C. for 2 hours, concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (chloroform). Yield 1.12 g (68%) m.p. p 164 to 166 ° C. The obtained 3-cyano-2-trifluoromethyl-5-phenylpyrrole showed a peak at 6.7 ppm in the 4-position of the pyrrole ring in proton NMR, and benzene was irradiated with this proton. NOEs were observed on the protons at the ring 2 and 6 positions. On the other hand, Japanese Patent Laid-Open No. 1-104042
In 3-cyano-2-phenyl-5-trifluoromethylpyrrole described in JP-A-4-270263, the proton at the 4-position of the pyrrole ring is 6.8 in proton NMR.
A peak was shown at 6 ppm, and no NOE was observed at the 2- and 6-position protons of the benzene ring even when irradiated with this proton. From the above, the structure of the compound of the present invention was confirmed.
【００１３】実施例２ ３−エトキシカルボニル−２−
トリフルオロメチル−５−（３−クロロフェニル）ピロ
ール（化合物番号６）の合成〔ｂ法〕Example 2 3-Ethoxycarbonyl-2-
Synthesis of trifluoromethyl-5- (3-chlorophenyl) pyrrole (Compound No. 6) [Method b]
【化１３】 ４−（３−クロロフェニル）−２−トリフルオロメチル
−２Ｈ−オキサゾリン−５−オン ５．２７ｇ（０．０
２モル）、プロピオル酸エチル １．９６ｇ（０．０２
モル）をベンゼン２０ｍｌに溶解し、撹拌しながら室温
でトリブチルホスフィン、４．２４ｇ（０．０２モル）
を滴下した。徐々に発熱が起り内温６０℃付近で激しく
炭酸ガスを発生した。３０分還流したのち反応混合物を
減圧濃縮し残留をシリカゲルカラムクロマトグラフィー
（溶媒 ヘキサン／酢酸エチル＝１０／１）にて精製し
目的物４．６２ｇを得た。（収率７３％） ｍ．ｐ １４１−１４２℃ 得られた化合物は実施例１と同様にプロトンＮＭＲでＮ
ＯＥが観測され構造が確認された。[Chemical 13] 4- (3-chlorophenyl) -2-trifluoromethyl-2H-oxazolin-5-one 5.27 g (0.0
2 mol), 1.96 g (0.02 g) of ethyl propiolate.
Mol) in 20 ml of benzene and stirred at room temperature with tributylphosphine, 4.24 g (0.02 mol)
Was dripped. Exothermic heat gradually occurred and carbon dioxide gas was violently generated at an internal temperature of about 60 ° C. After refluxing for 30 minutes, the reaction mixture was concentrated under reduced pressure and the residue was purified by silica gel column chromatography (solvent hexane / ethyl acetate = 10/1) to obtain 4.62 g of the desired product. (Yield 73%) m. p 141-142 ° C. The obtained compound was analyzed by proton NMR in the same manner as in Example 1 to obtain N
OE was observed and the structure was confirmed.
【００１４】上記実施例を含め、製造した化合物を第１
表に示す。またその他の代表例を第２表に示す。The compounds prepared above, including the above examples,
Shown in the table. Further, other representative examples are shown in Table 2.
【００１５】[0015]
【表１】 [Table 1]
【００１６】1Ｈ−ＮＭＲ（ＣＤＣｌ 3）, δ（ｐｐｍ）
： ＊＊１ １．４（ｔ）３Ｈ，４．３５（ｑ）２Ｈ，
７．０５（ｓ）１Ｈ，７．３５（ｍ）２Ｈ，７．５
（ｓ）１Ｈ，９．６（ｂｓ）１Ｈ ＊＊２ ６．６（ｓ）１Ｈ，７．０（ｍ）４Ｈ，７．
３（ｍ）３Ｈ，７．６（ｍ）２Ｈ，１２．５（ｂｓ）１
Ｈ ＊＊３ ６．６５（ｓ）１Ｈ，７．１（ｔ）１Ｈ，
７．５（ｍ）１Ｈ，７．９５（ｄｄ）１Ｈ，１２．６５
（ｂｓ）１Ｈ ＊＊４ ６．８５（ｂｓ）１Ｈ，７．５（ｍ）２Ｈ，
７．７５（ｄ）１Ｈ，７．８５（ｍ）３Ｈ，８．２
（ｓ）１Ｈ，１２．６５（ｂｓ）１Ｈ[0016]1H-NMR (CDCl 3),δ (ppm)
: ** 1 1.4 (t) 3H, 4.35 (q) 2H,
7.05 (s) 1H, 7.35 (m) 2H, 7.5
(S) 1H, 9.6 (bs) 1H ** 2 6.6 (s) 1H, 7.0 (m) 4H, 7.
3 (m) 3H, 7.6 (m) 2H, 12.5 (bs) 1
H ** 3 6.65 (s) 1H, 7.1 (t) 1H,
7.5 (m) 1H, 7.95 (dd) 1H, 12.65
(Bs) 1H ** 4 6.85 (bs) 1H, 7.5 (m) 2H,
7.75 (d) 1H, 7.85 (m) 3H, 8.2
(S) 1H, 12.65 (bs) 1H
【００１７】[0017]
【表２】 [Table 2]
【００１８】[0018]
【表３】 [Table 3]
【００１９】[0019]
【発明の効果】従来合成例のない３−シアノ−２−トリ
フルオロメチルピロール誘導体、３−アルコキシカルボ
ニル−２−トリフルオロメチルピロール誘導体が温和な
条件下短かい反応時間で得られ、それらは殺虫、殺ダニ
剤、殺菌剤等の農薬、農医薬中間体として有用である。EFFECTS OF THE INVENTION 3-Cyano-2-trifluoromethylpyrrole derivatives and 3-alkoxycarbonyl-2-trifluoromethylpyrrole derivatives, which have not been synthesized in the past, can be obtained under mild conditions in a short reaction time. It is also useful as an agrochemical such as an acaricide, a bactericide, and an agricultural pharmaceutical intermediate.
Claims (3)
らは置換基を有していてもよい。Ｙは水素原子またはア
ルキル基を表す。Ｚはシアノ基またはアルコキシカルボ
ニル基を表す。〕で表される２−トリフルオロメチルピ
ロール誘導体。1. A compound represented by the formula [I]: [In the formula, R represents an aryl group or a heterocyclic group, and these may have a substituent. Y represents a hydrogen atom or an alkyl group. Z represents a cyano group or an alkoxycarbonyl group. ] The 2-trifluoromethyl pyrrole derivative represented by these.
ラクトン化合物と、式〔III 〕 ＨＹＣ＝ＣＸＺ 〔III 〕 〔式中、Ｘはハロゲン原子を表す。ＹおよびＺは前記と
同じ意味を表す。〕で表される化合物とを、３価のリン
化合物触媒存在下に反応させることを特徴とする、式
〔Ｉ〕 【化３】 〔式中、Ｒ、ＹおよびＺは前記と同じ意味を表す。〕で
表される２−トリフルオロメチルピロール誘導体の製造
方法。2. A formula [II]: [In the formula, R represents the same meaning as described above. ] The azalactone compound represented by these, and a formula [III] HYC = CXZ [III] [In formula, X represents a halogen atom. Y and Z have the same meanings as described above. ] The compound represented by the formula [I] embedded image characterized by reacting with a compound represented by the formula [3] in the presence of a trivalent phosphorus compound catalyst. IN FORMULA, R, Y, AND Z REPRESENT A SAID MEANING. ] The manufacturing method of the 2-trifluoromethyl pyrrole derivative represented by these.
ラクトン化合物と、式〔III'〕 ＹＣ≡ＣＺ’ 〔III'〕 〔式中、Ｙは前記と同じ意味を表し、Ｚ’はアルコキシ
カルボニル基を表す。〕で表される化合物とを、３価の
リン化合物触媒存在下に反応させることを特徴とする、
式〔I'〕 【化５】 〔式中、Ｒ、ＹおよびＺ’は前記と同じ意味を表す。〕
で表される２−トリフルロオメチルピロール誘導体の製
造方法。3. The formula [II]: [In the formula, R represents the same meaning as described above. And an azalactone compound represented by the formula [III ′] YC≡CZ ′ [III ′] [wherein Y represents the same meaning as described above and Z ′ represents an alkoxycarbonyl group. ] The compound represented by the above is reacted in the presence of a trivalent phosphorus compound catalyst,
Formula [I '] [In the formula, R, Y and Z ′ represent the same meaning as described above. ]
A method for producing a 2-trifluoromethylpyrrole derivative represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19321393A JPH0725849A (en) | 1993-07-08 | 1993-07-08 | 2-trifluoromethylpyprole derivative and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19321393A JPH0725849A (en) | 1993-07-08 | 1993-07-08 | 2-trifluoromethylpyprole derivative and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0725849A true JPH0725849A (en) | 1995-01-27 |
Family
ID=16304190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19321393A Pending JPH0725849A (en) | 1993-07-08 | 1993-07-08 | 2-trifluoromethylpyprole derivative and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0725849A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000057877A1 (en) * | 1999-03-26 | 2000-10-05 | Euro-Celtique S.A. | Aryl substituted pyrazoles, imidazoles, oxazoles, thiazoles and pyrroles, and the use thereof |
-
1993
- 1993-07-08 JP JP19321393A patent/JPH0725849A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000057877A1 (en) * | 1999-03-26 | 2000-10-05 | Euro-Celtique S.A. | Aryl substituted pyrazoles, imidazoles, oxazoles, thiazoles and pyrroles, and the use thereof |
| US6414011B1 (en) | 1999-03-26 | 2002-07-02 | Euro-Celtique S.A. | Aryl substituted pyrazoles, and pyrroles, and the use thereof |
| US6737418B2 (en) | 1999-03-26 | 2004-05-18 | Euro-Celtique S.A. | Aryl substituted pyrazoles, imidazoles, oxazoles, thiazoles and pyrroles, and the use thereof |
| EP2266960A2 (en) | 1999-03-26 | 2010-12-29 | Euro-Celtique S.A. | Aryl-substituted pyrazoles, imidazoles, oxazoles, thiazoles and pyrroles as anticonvulsants |
| EP2266960A3 (en) * | 1999-03-26 | 2011-11-09 | Euro-Celtique S.A. | Aryl-substituted pyrazoles, imidazoles, oxazoles, thiazoles and pyrroles as anticonvulsants |
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