JP2002128763A - Method for purifying 1,3-dialkylpyrazole-4-carboxylic acid - Google Patents
Method for purifying 1,3-dialkylpyrazole-4-carboxylic acidInfo
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- JP2002128763A JP2002128763A JP2000328203A JP2000328203A JP2002128763A JP 2002128763 A JP2002128763 A JP 2002128763A JP 2000328203 A JP2000328203 A JP 2000328203A JP 2000328203 A JP2000328203 A JP 2000328203A JP 2002128763 A JP2002128763 A JP 2002128763A
- Authority
- JP
- Japan
- Prior art keywords
- dialkylpyrazole
- carboxylic acid
- group
- purifying
- general 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は１，３−ジアルキル
ピラゾール−４−カルボン酸の新規な精製法に関する。
１，３−ジアルキルピラゾール−４−カルボン酸は医
薬、農薬等の中間体として有用である。TECHNICAL FIELD The present invention relates to a novel method for purifying 1,3-dialkylpyrazole-4-carboxylic acid.
1,3-Dialkylpyrazole-4-carboxylic acid is useful as an intermediate for pharmaceuticals, agricultural chemicals and the like.
【０００２】[0002]
【従来の技術】１，３−ジアルキルピラゾール−４−カ
ルボン酸の製造方法としては、β−ケト酸エステルを出
発原料として、ヒドラジン類との環化反応で１，３−ジ
アルキルピラゾール−４−カルボン酸エステルを製造し
(Aust.J.Chem.,36.135.1983)、更にそれをアルカリ加水
分解することによって得る方法(特公表 7-501549号公
報)が一般的に知られている。しかしこの製造法によっ
て製造された１，３−ジアルキルピラゾール−４−カル
ボン酸には、不純物として目的物の異性体で、主に環化
の際に生じる１，５−ジアルキルピラゾール−４−カル
ボン酸が含まれている。そしてその精製方法としては現
在シリカゲルカラムクロマトグラフィーによる精製が主
として知られているが、その操作は工業的に煩雑であ
り、大量の溶媒を使用するという問題点がある。2. Description of the Related Art As a method for producing 1,3-dialkylpyrazole-4-carboxylic acid, a β-keto acid ester is used as a starting material and a 1,3-dialkylpyrazole-4-carboxylic acid is produced by a cyclization reaction with hydrazines. To produce acid esters
(Aust. J. Chem., 36.135.1983), and a method of further obtaining it by alkali hydrolysis (Japanese Patent Publication No. 7-501549) is generally known. However, the 1,3-dialkylpyrazole-4-carboxylic acid produced by this production method is an isomer of the target product as an impurity, and is mainly a 1,5-dialkylpyrazole-4-carboxylic acid produced during cyclization. It is included. As a purification method, purification by silica gel column chromatography is mainly known at present, but the operation is industrially complicated and there is a problem that a large amount of solvent is used.
【０００３】[0003]
【発明が解決しようとする課題】前述のように、現在知
られている１，３−ジアルキルピラゾール−４−カルボ
ン酸の精製法は、工業的には不向きな方法である。そこ
で本発明の目的は、１，３−ジアルキルピラゾール−４
−カルボン酸の精製法として、主にその異性体である
１，５−ジアルキルピラゾール−４−カルボン酸との単
離法を提供することにある。As described above, the currently known method for purifying 1,3-dialkylpyrazole-4-carboxylic acid is industrially unsuitable. Therefore, an object of the present invention is to provide 1,3-dialkylpyrazole-4.
Another object of the present invention is to provide a method for purifying a carboxylic acid, which is mainly an isomer thereof, which is isolated from 1,5-dialkylpyrazole-4-carboxylic acid.
【０００４】[0004]
【課題を解決するための手段】本発明者らは１，３−ジ
アルキルピラゾール−４−カルボン酸の精製法を鋭意検
討した結果、水溶液中のｐＨ管理による晶析法で精製す
ることにより、上記課題を解決可能であることを見出
し、更に工業的にも操作可能であることを見出し、本発
明を完成させた。Means for Solving the Problems The inventors of the present invention have conducted intensive studies on a method for purifying 1,3-dialkylpyrazole-4-carboxylic acid. The inventors have found that the problem can be solved, and have found that they can be operated industrially, and have completed the present invention.
【０００５】即ち、本発明は一般式（１）That is, the present invention provides a compound represented by the general formula (1):
【化３】 (式中、Ｒ１は炭素数１から１０の鎖状または環状のア
ルキル基を示し、Ｒ２は水素原子、ハロゲン原子、炭素
数１から１０のアルキル基、またはハロアルキル基を示
す。)で表される１，３−ジアルキルピラゾール−４−
カルボン酸と、一般式（２）Embedded image (Wherein, R1 represents a chain or cyclic alkyl group having 1 to 10 carbon atoms, and R2 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group). 1,3-dialkylpyrazole-4-
Carboxylic acid and the general formula (2)
【０００６】[0006]
【化４】 (式中、Ｒ１、Ｒ２は前記と同じ意味を示す。)で表され
る１，５−ジアルキルピラゾール−４−カルボン酸を含
む水溶液を、ｐＨ１．５〜ｐＨ４．５に調整して晶析す
ることを特徴とする１，３−ジアルキルピラゾール−４
−カルボン酸の精製法を提供するものである。Embedded image (Wherein, R1 and R2 have the same meaning as described above), and the aqueous solution containing 1,5-dialkylpyrazole-4-carboxylic acid is adjusted to pH 1.5 to pH 4.5 and crystallized. 1,3-dialkylpyrazole-4 characterized by the following:
A method for purifying carboxylic acids.
【０００７】[0007]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明に用いられる一般式（１）及び（２）の化合物に
おける置換基Ｒ１は、炭素数１から１０の鎖状または環
状のアルキル基であり、その典型的な例としては、メチ
ル基、エチル基、n-プロピル基、イソプロピル基、n-ブ
チル基、イソブチル基、sec-ブチル基、t-ブチル基、n-
ペンチル基、n-ヘキシル基、n-ヘプチル基、n-オクチル
基、シクロアルキル基等が挙げられる。好ましくはメチ
ル基である。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The substituent R1 in the compounds of the general formulas (1) and (2) used in the present invention is a linear or cyclic alkyl group having 1 to 10 carbon atoms, and typical examples thereof include a methyl group and an ethyl group. Group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-
Examples include a pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and cycloalkyl group. Preferably it is a methyl group.
【０００８】本発明に用いられる一般式（１）及び
（２）の化合物における置換基Ｒ２は、水素原子、ハロ
ゲン原子、炭素数１から１０のアルキル基、またはハロ
アルキル基であり、その典型的な例としては、フッ素原
子、塩素原子、臭素原子、メチル基、モノフルオロメチ
ル基、ジフルオロメチル基、トリフルオロメチル基、モ
ノクロロメチル基、ジクロロメチル基、トリクロロメチ
ル基、モノブロモメチル基、ジブロモメチル基、トリブ
ロモメチル基等が挙げられる。好ましくはトリフルオロ
メチル基である。The substituent R2 in the compounds of the general formulas (1) and (2) used in the present invention is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group. Examples include fluorine, chlorine, bromine, methyl, monofluoromethyl, difluoromethyl, trifluoromethyl, monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl And a tribromomethyl group. Preferably it is a trifluoromethyl group.
【０００９】晶析時の温度は好ましくは５〜９５℃であ
り、更に好ましくは１５〜２５℃である。晶析時間は一
般的に３０分乃至７日間であるが、好ましくは１乃至２
４時間である。The temperature at the time of crystallization is preferably from 5 to 95 ° C, more preferably from 15 to 25 ° C. The crystallization time is generally from 30 minutes to 7 days, preferably from 1 to 2 days.
4 hours.
【００１０】晶析方法は、一例を挙げると、まず１，３
−ジアルキルピラゾール−４−カルボン酸と、１，５−
ジアルキルピラゾール−４−カルボン酸の混合粗結晶を
溶解させるために、一旦水溶液をｐＨ６以上に調整す
る。ｐＨの調整には、例えば水酸化ナトリウム、水酸化
カリウム等を使用し、精製する１，３−ジアルキルピラ
ゾール−４−カルボン酸と、１，５−ジアルキルピラゾ
ール−４−カルボン酸の約１．１当量分を蒸留水に溶解
する。The crystallization method is, for example, first, 1, 3
-Dialkylpyrazole-4-carboxylic acid and 1,5-
The aqueous solution is once adjusted to pH 6 or higher to dissolve the mixed crude crystals of dialkylpyrazole-4-carboxylic acid. To adjust the pH, for example, sodium hydroxide, potassium hydroxide, or the like is used, and the purified 1,3-dialkylpyrazole-4-carboxylic acid and about 1,1-dialkylpyrazole-4-carboxylic acid of about 1.1 Dissolve an equivalent amount in distilled water.
【００１１】その後に、３５％塩酸により晶析マスのｐ
Ｈを下げながら晶析させる。その際のｐＨ値について
は、１，３−ジアルキルピラゾール−４−カルボン酸の
晶析収率を上げるために、ｐＨ４．５より低いｐＨ値で
あることが望ましい。しかしここで、除去させる１，５
−ジアルキルピラゾール−４−カルボン酸が、晶析し始
めるｐＨ３．０以上に好ましくは調節することによっ
て、目的の１，３−ジアルキルピラゾール−４−カルボ
ン酸を精製することができる。Then, the p of the crystallization mass is added with 35% hydrochloric acid.
Crystallize while lowering H. The pH value at that time is desirably a pH value lower than 4.5 to increase the crystallization yield of 1,3-dialkylpyrazole-4-carboxylic acid. But here, 1,5
The target 1,3-dialkylpyrazole-4-carboxylic acid can be purified by preferably adjusting the pH of the -dialkylpyrazole-4-carboxylic acid to start to crystallize to 3.0 or more.
【００１２】晶析時のｐＨ調整に使用する試薬として
は、塩酸、硫酸等が挙げられるが、好ましくは塩酸であ
る。使用する塩酸の濃度は、いずれの濃度でも問題ない
が、好ましくは１〜３５．５％であり、更に好ましくは
３５．５％のものである。硫酸を使用する場合の濃度も
特に限定はないが、好ましくは１〜９８％であり、更に
好ましくは９８％のものである。濃度の高いものの方が
好ましい。As a reagent used for pH adjustment during crystallization, hydrochloric acid, sulfuric acid and the like can be mentioned, but hydrochloric acid is preferred. There is no problem with the concentration of the hydrochloric acid used, but it is preferably 1 to 5.5%, and more preferably 35.5%. The concentration when sulfuric acid is used is not particularly limited, but is preferably 1 to 98%, and more preferably 98%. Higher concentrations are preferred.
【００１３】晶析時のｐＨ値は１．５〜４．５であり、
好ましくは２．５〜４．０、更に好ましくは３．０〜
３．５である。The pH value during crystallization is 1.5 to 4.5,
Preferably 2.5-4.0, more preferably 3.0-4.0.
3.5.
【００１４】精製後の目的物の取り出しについては、通
常の方法で実施可能であり、例えば晶析後にろ過、及び
洗浄することで目的の結晶が得られる。The target product after purification can be taken out by a usual method. For example, the target crystal can be obtained by filtering and washing after crystallization.
【００１５】[0015]
【実施例】以下に実施例を挙げて本発明の内容を具体的
に説明する。 参考例 ２−エトキシメチリデン−３−オキソ−４，４，４−ト
リフルオロブタン酸エチルエステル 26g(0.11mol)を酢
酸エチル100ｇに溶解し、0℃条件下でモノメチルヒドラ
ジン 5g(0.11mol)を滴下し、４時間反応させた。その後
８５gの希塩酸と水で洗浄後濃縮して29.2gのオイル成分
を得、このオイル成分に含まれる１−メチル−３−トリ
フルオロメチルピラゾール−４−カルボン酸エチルは2
0.2g(0.09mol、収率83.9%)であった。EXAMPLES The contents of the present invention will be specifically described below with reference to examples. Reference Example 2-Ethoxymethylidene-3-oxo-4,4,4-trifluorobutanoic acid ethyl ester (26 g, 0.11 mol) was dissolved in ethyl acetate (100 g), and monomethylhydrazine (5 g, 0.11 mol) was added at 0 ° C. The mixture was dropped and reacted for 4 hours. Thereafter, the mixture was washed with 85 g of dilute hydrochloric acid and water and then concentrated to obtain 29.2 g of an oil component. The oil component contained ethyl 1-methyl-3-trifluoromethylpyrazole-4-carboxylate as 2
The amount was 0.2 g (0.09 mol, yield: 83.9%).
【００１６】m.p. 62.6〜63.7℃1 H-NMR(CDCl3/TMS;δppm):1.35(3H,t,J=7.0Hz),3.97(3
H,s),4.30(2H,q,J=7.0Hz),7.95(1H,s) 異性体１−メチル−５−トリフルオロメチルピラゾール
−４−カルボン酸エチルは3.7g(0.02mol、収率15.2%)で
あり、異性対比は18.3%であった。Mp 62.6-63.7 ° C. 1 H-NMR (CDCl 3 / TMS; δ ppm): 1.35 (3 H, t, J = 7.0 Hz), 3.97 (3
H, s), 4.30 (2H, q, J = 7.0 Hz), 7.95 (1H, s) 3.7 g (0.02 mol, yield) of ethyl isomer 1-methyl-5-trifluoromethylpyrazole-4-carboxylate 15.2%), and the isomer ratio was 18.3%.
【００１７】1H-NMR(CDCl3;δppm):1.35(3H,t J=7.3H
z),4.07(3H,q,J=2.0Hz),4.33(3H,q,J=7.3Hz),7.91(1H,
s) 1 H-NMR (CDCl 3; δ ppm): 1.35 (3 H, t J = 7.3 H
z), 4.07 (3H, q, J = 2.0Hz), 4.33 (3H, q, J = 7.3Hz), 7.91 (1H,
s)
【００１８】実施例1 １−メチル−３−トリフルオロメチルピラゾール−４−
カルボン酸エチル20.2g(0.09mol)、その異性体１−メチ
ル−５−トリフルオロメチルピラゾール−４−カルボン
酸エチルが３．７g(０．０２mol)含まれた(異性対比１
８．３%)オイル成分29.2gを、１５％苛性水５０ｇに溶
解し、６０℃に昇温し、６０℃で１時間熟成した。この
熟成後の反応マス中、１−メチル−５−トリフルオロメ
チルピラゾール−４−カルボン酸の１−メチル−３−ト
リフルオロメチルピラゾール−４−カルボン酸に対する
異性対比は14.2%であった。その後135gの水で反応マス
を希釈した後、35.5%塩酸を滴下し、pH値3.0に調整し、
２０℃で１時間晶析、ろ過することで白色結晶を得た。
その場合の結晶中の異性体比及び、晶析収率はそれぞれ
0.3%、96.3%であった。Example 1 1-methyl-3-trifluoromethylpyrazole-4-
It contained 20.2 g (0.09 mol) of ethyl carboxylate and 3.7 g (0.02 mol) of its isomer ethyl 1-methyl-5-trifluoromethylpyrazole-4-carboxylate (1 isomer ratio).
(8.3%) 29.2 g of an oil component was dissolved in 50 g of 15% caustic water, heated to 60 ° C., and aged at 60 ° C. for 1 hour. In the reaction mass after this aging, the isomer ratio of 1-methyl-5-trifluoromethylpyrazole-4-carboxylic acid to 1-methyl-3-trifluoromethylpyrazole-4-carboxylic acid was 14.2%. After diluting the reaction mass with 135 g of water, 35.5% hydrochloric acid was added dropwise to adjust the pH value to 3.0,
Crystallization at 20 ° C. for 1 hour and filtration yielded white crystals.
In that case, the isomer ratio in the crystal and the crystallization yield are respectively
0.3% and 96.3%.
【００１９】１−メチル−３−トリフルオロメチルピラ
ゾール−４−カルボン酸 m.p. 201〜203℃1 H-NMR(CDCl3;δppm):3.97(3H,s),8.01(1H,s) １−メチル−５−トリフルオロメチルピラゾール−４−
カルボン酸1 H-NMR(DMSO;δppm):4.03(3h,q,J=2.0Hz),7.95(1H,s) m.p. 200〜201℃1-methyl-3-trifluoromethylpyrazole-4-carboxylic acid mp 201-203 ° C. 1 H-NMR (CDCl3; δ ppm): 3.97 (3H, s), 8.01 (1H, s) 1-methyl- 5-trifluoromethylpyrazole-4-
Carboxylic acid 1 H-NMR (DMSO; δ ppm): 4.03 (3 h, q, J = 2.0 Hz), 7.95 (1 H, s) mp 200-201 ° C.
【００２０】実施例2 異性体である１−メチル−５−トリフルオロメチルピラ
ゾール−４−カルボン酸が、約10.57%の割合で含まれて
いる１−メチル−３−トリフルオロメチルピラゾール−
４−カルボン酸の混合粗結晶１０ｇを、水１００ｇにＮ
ａＯＨ２．４ｇを溶解させたアルカリ溶液に溶解させ
た。そしてそこに塩酸を滴下し各ｐＨ値に調整し、２０
℃で１時間晶析、ろ過することで各種白色結晶を得た。
それらの分析結果から、各pH値で得られた結晶中の異性
対比及び、１−メチル−３−トリフルオロメチルピラゾ
ール−４−カルボン酸の晶析収率は以下の表１に示すよ
うになった。Example 2 1-methyl-3-trifluoromethylpyrazole containing the isomer 1-methyl-5-trifluoromethylpyrazole-4-carboxylic acid in a proportion of about 10.57%
10 g of the mixed crude crystals of 4-carboxylic acid was added to 100 g of water with N
The solution was dissolved in an alkaline solution in which 2.4 g of aOH was dissolved. Then, hydrochloric acid was added dropwise to the mixture to adjust each pH value.
Crystallization at 1 ° C. for 1 hour and filtration yielded various white crystals.
From the analysis results, the isomer ratio in the crystals obtained at each pH value and the crystallization yield of 1-methyl-3-trifluoromethylpyrazole-4-carboxylic acid are as shown in Table 1 below. Was.
【００２１】[0021]
【表１】 [Table 1]
【００２２】[0022]
【発明の効果】以上で述べたように、本発明によれば、
医薬、農薬等の中間体として有用な１，３−ジアルキル
ピラゾール−４−カルボン酸を効率よく精製することが
可能であり、工業的に優れているものである。As described above, according to the present invention,
It is possible to efficiently purify 1,3-dialkylpyrazole-4-carboxylic acid, which is useful as an intermediate for pharmaceuticals, agricultural chemicals, etc., and it is industrially excellent.
Claims (4)
ルキル基を示し、Ｒ２は水素原子、ハロゲン原子、炭素
数１から１０のアルキル基、またはハロアルキル基を示
す。)で表される１，３−ジアルキルピラゾール−４−
カルボン酸と、一般式（２） 【化２】 (式中、Ｒ１、Ｒ２は前記と同じ意味を示す。)で表され
る１，５−ジアルキルピラゾール−４−カルボン酸を含
む水溶液を、ｐＨ１．５〜ｐＨ４．５に調整して晶析す
ることを特徴とする１，３−ジアルキルピラゾール−４
−カルボン酸の精製法。1. A compound of the general formula (1) (Wherein, R1 represents a chain or cyclic alkyl group having 1 to 10 carbon atoms, and R2 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group). 1,3-dialkylpyrazole-4-
A carboxylic acid and a compound represented by the general formula (2): (Wherein, R1 and R2 have the same meaning as described above), and the aqueous solution containing 1,5-dialkylpyrazole-4-carboxylic acid is adjusted to pH 1.5 to pH 4.5 and crystallized. 1,3-dialkylpyrazole-4 characterized by the following:
A method for purifying carboxylic acids.
求項1記載の方法。2. The method according to claim 1, wherein the pH of the aqueous solution is 2.5 to 4.0.
求項1記載の方法。3. The method according to claim 1, wherein the pH of the aqueous solution is 3.0 to 3.5.
Ｒ２がトリフルオロメチル基である請求項１〜３記載の
方法。4. In the general formula (1), R1 is a methyl group,
4. The method according to claim 1, wherein R2 is a trifluoromethyl group.
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| JP (1) | JP2002128763A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004103975A1 (en) | 2003-05-21 | 2004-12-02 | Bayer Cropscience Aktiengesellschaft | Iodopyrazolyl carboxanilides |
| WO2008102678A1 (en) * | 2007-02-20 | 2008-08-28 | Mitsui Chemicals, Inc. | Fluorine-containing pyrazolecarbonitrile derivative and method for producing the same, and fluorine-containing pyrazolecarboxylic acid derivative obtained by using the fluorine-containing pyrazolecarbonitrile derivative and method for producing the same |
| EP1997808A1 (en) * | 2007-05-31 | 2008-12-03 | Syngeta Participations AG | Process for the production of pyrazoles |
| WO2008145257A1 (en) * | 2007-05-31 | 2008-12-04 | Syngenta Participations Ag | Process for the production of pyrazoles |
| CN101133031B (en) * | 2005-02-25 | 2010-07-21 | 财团法人相模中央化学研究所 | Method for producing 1-substituted-3-fluoroalkyl pyrazole-4-carboxylate |
| JP2013006780A (en) * | 2011-06-22 | 2013-01-10 | Central Glass Co Ltd | Method for producing pyrazole compound |
-
2000
- 2000-10-27 JP JP2000328203A patent/JP2002128763A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004103975A1 (en) | 2003-05-21 | 2004-12-02 | Bayer Cropscience Aktiengesellschaft | Iodopyrazolyl carboxanilides |
| US7906656B2 (en) | 2003-05-21 | 2011-03-15 | Bayer Cropscience Ag | Iodopyrazolyl carboxanilides |
| US8119682B2 (en) | 2003-05-21 | 2012-02-21 | Bayer Cropscience Ag | Iodopyrazolyl carboxanilides |
| CN101133031B (en) * | 2005-02-25 | 2010-07-21 | 财团法人相模中央化学研究所 | Method for producing 1-substituted-3-fluoroalkyl pyrazole-4-carboxylate |
| WO2008102678A1 (en) * | 2007-02-20 | 2008-08-28 | Mitsui Chemicals, Inc. | Fluorine-containing pyrazolecarbonitrile derivative and method for producing the same, and fluorine-containing pyrazolecarboxylic acid derivative obtained by using the fluorine-containing pyrazolecarbonitrile derivative and method for producing the same |
| US7884216B2 (en) | 2007-02-20 | 2011-02-08 | Mitsui Chemicals Agro, Inc. | Fluorine-containing pyrazolecarbonitrile derivative and method for producing the same, and fluorine-containing pyrazolecarboxylic acid derivative obtained by using the fluorine-containing pyrazolecarbonitrile derivative and method for producing the same |
| CN101627015B (en) * | 2007-02-20 | 2012-02-29 | 三井化学Agro株式会社 | Fluorine-containing pyrazolecarbonitrile derivative and method for producing the same, and fluorine-containing pyrazolecarboxylic acid derivative obtained by using the fluorine-containing pyrazolecarb and preparation method thereof |
| JP5117485B2 (en) * | 2007-02-20 | 2013-01-16 | 三井化学アグロ株式会社 | Fluorine-containing pyrazole carbonitrile derivative and method for producing the same, and fluorine-containing pyrazole carboxylic acid derivative obtained using the fluorine-containing pyrazole carbonitrile derivative and a method for producing the same. |
| EP1997808A1 (en) * | 2007-05-31 | 2008-12-03 | Syngeta Participations AG | Process for the production of pyrazoles |
| WO2008145257A1 (en) * | 2007-05-31 | 2008-12-04 | Syngenta Participations Ag | Process for the production of pyrazoles |
| US8124787B2 (en) | 2007-05-31 | 2012-02-28 | Syngenta Crop Protection, Inc. | Process for the production of pyrazoles |
| JP2013006780A (en) * | 2011-06-22 | 2013-01-10 | Central Glass Co Ltd | Method for producing pyrazole compound |
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