JPS58213763A - Preparation of triazolylvinyl ketone compound - Google Patents
Preparation of triazolylvinyl ketone compoundInfo
- Publication number
- JPS58213763A JPS58213763A JP9798882A JP9798882A JPS58213763A JP S58213763 A JPS58213763 A JP S58213763A JP 9798882 A JP9798882 A JP 9798882A JP 9798882 A JP9798882 A JP 9798882A JP S58213763 A JPS58213763 A JP S58213763A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- compound
- formula
- purity
- solvent
- 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
【発明の詳細な説明】
本発明け、一般式(1)
〔式中、Xは水素原子またけ塩素原子を表わす◎〕
で示されるビストリ7ゾリルビニルケトン未化合物を酸
で処理することを%修とする一般式(1)〔式中、Xは
前述と同じ意味を有する。〕で示されるドリアゾリルビ
ニルケトン系化合物の製造法に関するものである@
一般式(II)で示される本発明の対象化合物は。DETAILED DESCRIPTION OF THE INVENTION According to the present invention, the uncompounded bistri-7zolyl vinyl ketone represented by the general formula (1) [wherein X represents a hydrogen atom and a chlorine atom] is treated with an acid. General formula (1) [wherein, X has the same meaning as above]. This relates to a method for producing a doriazolyl vinyl ketone compound represented by the formula (II).
特開昭33−/Jθ66/号公報で農園芸用殺劇剤とし
て公知であシ、さらに一般式(釦
〔式中、Xは前述と同じ意味を表わす。〕で示される特
開昭jクーq7に75号公報に記載されてい7)農園共
用殺菌剤として有用なトリ7ゾリルビニルアルコール系
化合物の製造中間体としても聾要々化合物であシ、核化
合物の有利な製造法を提供する本発明けきわめて意義の
大きいものである。It is known as a pesticide for agricultural and horticultural use in JP-A No. 33-/Jθ66/, and is further expressed by the general formula (wherein, X has the same meaning as above). Q7 is described in Publication No. 75, and 7) It is also an important compound as an intermediate for the production of a tri-7zolylvinyl alcohol compound useful as a fungicide for common use in farms, and provides an advantageous method for producing the core compound. This invention is extremely significant.
さて、一般式(II)のトリアゾリルビニルケトン系化
合物の製造法としては、一般式(1)のビストリ7ゾリ
ルとニルケトン系化合物をそのまま加熱分解擾たけ追歯
な姑媒中で加熱分解する方法が知られている(特開昭j
7−1θグ26号公軸)0しかし、この熱分解による方
法においては、比較的高温下での反応操作が必要と々す
、工業的見地からは菖泗反応に伴なう装置、設備上の制
約等、必ずしも満足できるものではない。Now, as a method for producing the triazolyl vinyl ketone compound of the general formula (II), the bistrizolyl and nylketone compound of the general formula (1) are thermally decomposed as they are in a solid medium. The method is known (Japanese Patent Publication No.
However, this thermal decomposition method requires reaction operations at relatively high temperatures. constraints, etc., are not necessarily satisfactory.
このような状況の下に本発明者らは、工業的にもよシ容
易で軽済的なトリアゾリルビニルケトン系化合物の製法
を探索すべく鋭意棟討した結果、意外にも前記一般式(
1)で示されるビストリアゾリルビニルケトン系化合物
を酸で処理することによシ、コケのトリ7ゾリル基の一
方のみが選択的に脱離し、高純度の一般式(II)で示
され!、 トリフゾリルビニルケトン弗化合物が高収率
で、且つ容易に得られることfM、出し、これに種々の
検討を加え1本発明を完成するに至った0
本発明によれば、力11湖処理という混和が条件下で高
純度で目的物が得られ、偶別な設備も要しないことから
、特に工業的規模での製造上極めて有利となる。Under these circumstances, the inventors of the present invention conducted extensive research to find a process for manufacturing triazolyl vinyl ketone compounds that is industrially easy and inexpensive, and unexpectedly found that the general formula (
By treating the bistriazolyl vinyl ketone compound represented by 1) with an acid, only one of the tri7zolyl groups of the moss is selectively eliminated, resulting in a highly pure general formula (II)! , it was found that the trifuzolyl vinyl ketone fluoride compound can be easily obtained in high yield, and after various studies were carried out, the present invention was completed.According to the present invention, the present invention has been completed. Since the desired product can be obtained with high purity under the mixing conditions and no special equipment is required, it is extremely advantageous especially in production on an industrial scale.
さらに本発明方法に於ては従来の加熱分解法では、その
回収が困難であった反応によシ生ずる脱離/、2.41
−1す7ゾールが容易に回収できる。Furthermore, in the method of the present invention, the desorption caused by the reaction, which was difficult to recover by the conventional thermal decomposition method, is
-1su7sol can be easily recovered.
次に本発明方法につき絆しく説明する〇本発明において
はビストリアゾリルビニルケトン系化合物を溶媒を用い
たいでそのまま、または適当々溶媒に溶解させた佳、酸
で処理することにより目的を達成出来るOこの時、溶媒
類としては7セトン、メチルエチルケトンなどのケトン
類、四塩化炭素、クロロホルム、ジクロロエタン、モノ
クロルベンゼンなどのハロゲン孔版化水素類、ペンセン
、トルエン、キレしンなどの芳香族炭化水素類、アセト
ニトリル、プロピオニトリルなどのニトリル類、ジオキ
サン。Next, the method of the present invention will be explained in detail. In the present invention, the bistriazolyl vinyl ketone compound can be used as it is in a solvent, or it can be dissolved in an appropriate solvent, or the object can be achieved by treating it with an acid. At this time, the solvents include ketones such as 7cetone and methyl ethyl ketone, hydrogen halogen stencils such as carbon tetrachloride, chloroform, dichloroethane, and monochlorobenzene, aromatic hydrocarbons such as pensene, toluene, and xylene, Nitriles such as acetonitrile and propionitrile, and dioxane.
テ:・ラヒドロフラン、ジエチレングリコールジメチル
エーテルなどのエーテル類などが挙ケラれる。Ethers such as hydrofuran and diethylene glycol dimethyl ether are listed.
甘か酬としては塩酸、@酸、硝酸、リン酸、スルホン酸
などが1適である。Suitable sweeteners include hydrochloric acid, @acid, nitric acid, phosphoric acid, and sulfonic acid.
これらの酸の使用量は、特に限定されるものでは々いか
、遇常旅料のビストリ7ゾリルビニルケトン未化合物に
対してj〜70倍モル程度が好ましい0また、その水溶
液としての濃度も特に限定されるものではなく、種々の
濃度の酸性水溶液として使用することが出来るO反応濁
度は通常30〜700°C1好壕しくはりθ〜/θθ°
Cの範囲であるO上記のようにして反応させた彼、生成
物を堆シ出すには生成物の性状によシ適宜濾過、分液、
抽出などの操作によシ。The amount of these acids to be used is not particularly limited, but it is preferably about j to 70 times the molar amount of uncompounded bistri-7zolyl vinyl ketone commonly used. There is no particular limitation, and the O reaction turbidity that can be used as an acidic aqueous solution of various concentrations is usually 30 to 700°C1, or θ~/θθ°
In order to deposit the product after reacting as described above, depending on the properties of the product, filtration, liquid separation, or
For operations such as extraction.
容易に生成物を取得することが出来、得られる生成物は
そのままでも高純度のため、結晶状の物質として取得さ
れるが、必要に応じ再結晶などの操作によりさらに純度
を高めることができるO
また脱離して住じた/、J、9−1す7ゾールは使用し
た酸との塩として容易に水層から回収される◇
以下に実施例で本発明をさらに詳しく説明するが本発明
はこれらに限定されるものではないO尚、以下の実施例
で生成物の純度は、液体クロマトグラフィーによシ分析
した値である。O In addition, the desorbed /,J,9-1su7sol is easily recovered from the aqueous layer as a salt with the acid used. However, the purity of the products in the following examples is the value analyzed by liquid chromatography.
実施例/ /−(,2,グージクロロフェニル)−4t。Example/ /-(,2,goodichlorophenyl)-4t.
グージメチル−/、−−ビス(/、、2.4t−トリア
ゾール−/−イル)ペンタン−3−オンJ、9JP(0
,01モル)に3%−塩酸水溶液36.SP(0,05
モル)を加え、内温9S〜10θ°Cで2時間攪拌を行
Aう。Goodimethyl-/,--bis(/,,2.4t-triazol-/-yl)pentan-3-one J, 9JP(0
, 01 mol) to 3% aqueous hydrochloric acid solution 36. SP(0,05
mol) and stirred for 2 hours at an internal temperature of 9S to 10θ°C.
次いで該反応液をコθ゛Cまで冷却し、クロロホルム/
θθmlを加えよく振シ混ぜた援分液し、有機層を水/
θθdで洗浄したのち濃縮して白色結晶として/−(,
2,lI−ジクロロフェニル)−ヶ、l−ジメチル−2
−(/、2゜ダートリフゾール−7−イル)−/−ペン
テン−3−オン3..2/11を得た。Then, the reaction solution was cooled to θ゛C and diluted with chloroform/
Add θθml, shake well, and divide into portions. Dilute the organic layer with water/
After washing with θθd, it was concentrated to give white crystals /-(,
2,lI-dichlorophenyl)-l-dimethyl-2
-(/,2゜dartrifsol-7-yl)-/-penten-3-one3. .. Got 2/11.
収率:?9%
糸1度 二 26 %
一方、分液された水層を濃縮することによ#)/、θ/
iの/、、2.ダートリアゾール塩酸塩を回収した。yield:? 9% Thread 1 degree 2 26% On the other hand, by concentrating the separated aqueous layer, #)/, θ/
i's/,,2. Dartriazole hydrochloride was recovered.
回収率:96.コチ 実施例コ /、−(+2.グージクロロフェニル)−4t。Recovery rate: 96. flathead Example /, -(+2.goodichlorophenyl)-4t.
タージメチル−/、コーピス(/1.2.ダートリアゾ
ール−7−イル)ペンタン−3−オニ/ J、?J P
(0,07モル)をトルエンjoWLl!ニ溶解させ
た後1.2θ係−塩酸水溶液igxP(0,1モル)を
加え、内温9j〜10θ°Cにて6時間攪拌を行なう。terdimethyl-/, corpis(/1.2.dartriazol-7-yl)pentan-3-oni/J,? J.P.
(0.07 mol) toluene joWLl! After dissolving, a 1.2θ-hydrochloric acid aqueous solution igxP (0.1 mol) was added and stirred at an internal temperature of 9j to 10θ°C for 6 hours.
次いで該反応液を4θ°Cまで冷却し分液を行ない有機
層を水30yslで洗浄したのち濃縮して、白色結晶と
して/ −(,2゜q−ジクロロフェニル)−y、t−
ジメチル−3−(/、J、41−トリアゾール−/−イ
ル)−7−ペンテン−3−オン3.7IIを得た。The reaction solution was then cooled to 4θ°C and separated, and the organic layer was washed with 30ysl of water and concentrated to give white crystals / -(,2°q-dichlorophenyl)-y,t-
Dimethyl-3-(/,J,41-triazol-/-yl)-7-penten-3-one 3.7II was obtained.
収率:tg%
純度:?4t%
実施例3
実施例−において、−〇係−地酸水溶液に代え、SO嗟
−硫酸水溶液/9.tf(0,1モル)を用いた以外は
、全く同様の操作を行ない白色結晶として/−(J、l
−ジクロロフェニル)−ダ、クージメチル−,2−(/
、コ、4t−トリアゾールー/−イル)−/−ペンテン
−3−オン3./4tp、を得た。Yield: tg% Purity: ? 4t% Example 3 In Example 1, instead of the base acid aqueous solution, SO-sulfuric acid aqueous solution/9. Exactly the same operation was carried out except that tf (0.1 mol) was used, and white crystals were obtained as /-(J, l
-dichlorophenyl)-da, kudimethyl-,2-(/
, co, 4t-triazol-/-yl)-/-penten-3-one3. /4tp was obtained.
収率:り7%
純度:9I%
実施例亭
実施例−において1.2θ係−塩酸水溶液に代え、j
O% !J ン酸水#tei、241.A4tfCO,
1% 7L )を用いた以外は全く同様の操作を行ない
、白色結晶として/−(J、1II−ジクロロフェニル
)−9,41−ジメチル−2−(/、、2,4t−トリ
7ゾールー/−イル)−/−ペンテン−3−オン3J6
1を得た。Yield: 7% Purity: 9I%
O%! J acid water #tei, 241. A4tfCO,
Exactly the same operation was performed except that 1% 7L) was used, and white crystals were obtained as /-(J,1II-dichlorophenyl)-9,41-dimethyl-2-(/,,2,4t-tri7zole-/- )-/-penten-3-one 3J6
I got 1.
収率:97.ダ%
純度:9I%
実施例!
実施例−において1.20係−塩酸水溶液に代え、30
%−バラ−トルエンスルホン酸〃1gF(0,05モル
)を用いた以外は全く゛同様の操作を性力゛い白色結a
として/−(,2,4I−ジクロロフェニル)−ダ、+
−ジメチルーーー(/、2.II−トリ7ゾールー/−
イル)−7−ベンチシル3−オン3.iiyを4@た〇
収率:φ6%
純度: 94t、j係
実施例6
/−(グークロロフェニル)−4t、グージメチルー/
9.2〜ビス(/1+21グートリ7ゾールー/−イル
)ペンタン−3−オン3.3ざF(0,01モル)II
C5%−塩酸水溶液31hJP(0,05モル)を加え
、内温95−/θθ’C−C2時間攪拌を行なう◇
/θθ耐で洗浄したのち、濃縮して白色結晶として1−
(4I−クロロフェニル)−q、グージメチルーj−(
/、、2.4を一トリ7ゾールー/−イル)−/−ペン
テン−3−オン−0評!を得た。Yield: 97. DA% Purity: 9I% Example! Example - In place of 1.20 - hydrochloric acid aqueous solution, 30
The same procedure was repeated except that 1 gF (0.05 mol) of %-bala-toluenesulfonic acid was used to produce a white crystal.
as/-(,2,4I-dichlorophenyl)-da, +
-dimethyl-(/, 2.II-tri7zole-/-
yl)-7-bentisyl-3-one3. iiy was 4@〇 Yield: φ6% Purity: 94t, Section J Example 6 /-(goochlorophenyl)-4t, goodimethyl-/
9.2~bis(/1+21gutrizol-/-yl)pentan-3-one 3.3ZF (0.01 mol) II
Add C5%-hydrochloric acid aqueous solution 31hJP (0.05 mol) and stir for 2 hours at an internal temperature of 95-/θθ' C-C. After washing with ◇ /θθ resistance, concentrate to obtain 1- as white crystals.
(4I-chlorophenyl)-q, goudimethyl-j-(
/,, 2.4 to one tri7zole/-yl)-/-penten-3-one-0 reviews! I got it.
植y 率 : タ gLfb N!度:9≦係Planting rate: gLfb N! Degree: 9≦
Claims (1)
で処理することを%命とする一般式〔式中、Xは前述と
同じ意味を有するO〕で示されるドリアゾリルビニルケ
トン系化合物の製造法[Claims] [In the formula, X represents a hydrogen atom or a chlorine atom.] A method for producing a doriazolyl vinyl ketone compound represented by O having the same meaning as above.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9798882A JPS58213763A (en) | 1982-06-07 | 1982-06-07 | Preparation of triazolylvinyl ketone compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9798882A JPS58213763A (en) | 1982-06-07 | 1982-06-07 | Preparation of triazolylvinyl ketone compound |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS58213763A true JPS58213763A (en) | 1983-12-12 |
Family
ID=14207045
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9798882A Pending JPS58213763A (en) | 1982-06-07 | 1982-06-07 | Preparation of triazolylvinyl ketone compound |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS58213763A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103664809A (en) * | 2013-12-09 | 2014-03-26 | 江苏七洲绿色化工股份有限公司 | Preparation method for paclobutrazol |
-
1982
- 1982-06-07 JP JP9798882A patent/JPS58213763A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103664809A (en) * | 2013-12-09 | 2014-03-26 | 江苏七洲绿色化工股份有限公司 | Preparation method for paclobutrazol |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU2005257478B2 (en) | Method for producing (Z)-1-phenyl-1-diethylaminocarbonyl-2-aminomethyl cyclopropane hydrochloride | |
KR930005446B1 (en) | Process for preparing 2-alkoxy-n-(1-azabicyclo |2,2,2¨ octan-3-yl)aminobenzamides | |
JP3166215B2 (en) | Method for producing 1,2-naphthoquinonediazide-5-sulfonyl chloride | |
CA2268586A1 (en) | Process for producing n-glycyltyrosine and its crystal structure | |
JPS5843939A (en) | Mandelate and manufacture | |
JP2006188449A (en) | Method for producing cyclic disulfonic acid ester | |
JPS58213763A (en) | Preparation of triazolylvinyl ketone compound | |
JPH11228540A (en) | Production of 2-(4-pyridyl)ethanethiol | |
JPH027951B2 (en) | ||
US7476760B2 (en) | Purification and production methods of 1-aminocyclopropanecarboxylic acid | |
JP3042122B2 (en) | Method for producing N-cyanoacetamidine derivative | |
JPS63145262A (en) | Production of trifluoromethylbenzonitrile | |
JPH0597782A (en) | Production of bevantolol hydrochloride | |
JPS62255456A (en) | Production of diethylformamide | |
CN111848423B (en) | Preparation method of tert-butyl 3-oxocyclobutylcarbamate | |
JPH0558985A (en) | Production of cyanoguanidine derivative | |
JP2891165B2 (en) | Method for producing metabenzenedisulfonic acid | |
JPS6122034A (en) | Preparation of tetramethylbiphenyl | |
JP3547497B2 (en) | Method for producing benzothiazolone compound | |
JPS63211280A (en) | Production of 2-(4-thiazolyl)benzimidazole | |
WO2001034588A1 (en) | Process for producing benzylamine compound | |
JP2872444B2 (en) | Method for purifying bis (4-aminophenyl) sulfone compound containing copper compound | |
JPS63174963A (en) | Production of 2-hydroxynaphthalene-6-carbonitrile compound | |
JPS6317869A (en) | Production of 2-lower alkyl-4-amino-5-formylpyrimidine | |
JPS6241501B2 (en) |