JPH04134075A - Triazoles and production thereof - Google Patents
Triazoles and production thereofInfo
- Publication number
- JPH04134075A JPH04134075A JP25331290A JP25331290A JPH04134075A JP H04134075 A JPH04134075 A JP H04134075A JP 25331290 A JP25331290 A JP 25331290A JP 25331290 A JP25331290 A JP 25331290A JP H04134075 A JPH04134075 A JP H04134075A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- triazoles
- present
- formulas
- 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
- 150000003852 triazoles Chemical class 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 150000002576 ketones Chemical class 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 3
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 230000002070 germicidal effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- WQWMYQCMTRPXSJ-UHFFFAOYSA-N pentane-1,4-diol Chemical compound CC(O)CCCO.CC(O)CCCO WQWMYQCMTRPXSJ-UHFFFAOYSA-N 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- -1 sodium trimethoxyborohydride Chemical compound 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000003626 1,2,4-triazol-1-yl group Chemical group [*]N1N=C([H])N=C1[H] 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 150000000190 1,4-diols Chemical class 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- 239000012448 Lithium borohydride Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 125000005283 haloketone group Chemical group 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は農薬用途として重要なトリアゾール類およびそ
の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to triazoles which are important for agrochemical use and a method for producing the same.
〈従来の技術および発明が解決しようとする課題〉本発
明は、新規なトリアゾール類およびその製造法を提供す
るものである。<Prior art and problems to be solved by the invention> The present invention provides novel triazoles and a method for producing the same.
〈発明が解決するための手段〉
本発明は、新規なトリアゾール類およびその製造法に関
する。<Means for Solving the Invention> The present invention relates to novel triazoles and a method for producing the same.
すなわち１、本発明は、−綴代［ｌ］
（式中、Ｘは水素原子または塩素原子を示す。）で示さ
れるトリアゾール類およびその製造法に関する。That is, 1. the present invention relates to triazoles represented by -tsuzuriyoshi [l] (in the formula, X represents a hydrogen atom or a chlorine atom) and a method for producing the same.
上記トリアゾール類〔１〕は、本発明者らにより初めて
見出されたものであり、このもの自体、農薬として利用
されるが、脱水し、下記の化合物〔３］に導くことによ
って、殺菌剤、植物調節剤として利用することもできる
。The above triazole [1] was discovered for the first time by the present inventors, and is used as a pesticide in itself, but by dehydrating it and leading to the following compound [3], it can be used as a fungicide, It can also be used as a plant regulator.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明のトリアゾール類〔１〕は以下に示す一般式〔２
〕
（式中、Ｘは前記と同じ意味を有する。）で示されるケ
トン類を還元剤を用いて還元することによって得られる
。The triazole [1] of the present invention has the general formula [2] shown below.
] (In the formula, X has the same meaning as above.) It is obtained by reducing the ketones shown by using a reducing agent.
本発明の原料である一般式〔２〕で示されるケトン類は
特開昭６３−８３０７６に記載されている方法により合
成できる。The ketones represented by the general formula [2], which are the raw materials of the present invention, can be synthesized by the method described in JP-A-63-83076.
ケトン類〔２〕を還元し、トリアゾール類（１〕を得る
ための還元剤としては、通常のケトン類を還元しアルコ
ール類とすることのできるものであれば特にさしつかえ
なく使用でき、かかる還元剤としては以下のものが例示
される。As the reducing agent for reducing ketones [2] to obtain triazoles (1), any reducing agent that can reduce ordinary ketones to alcohols can be used without any restriction; Examples include the following:
水素化ホウ素ナトリウム、水素化ホウ素リチウム、水素
化ホウ素カリウム、水素化ホウ素亜鉛、水素化シアノホ
ウ素ナトリウム、水素化トリメトキシホウ素ナトリウム
、Ｌ−ブトキシリチウムアルミニウムハイドライド、リ
チウムアルミニウムハイドライド等の金属水素化物。Metal hydrides such as sodium borohydride, lithium borohydride, potassium borohydride, zinc borohydride, sodium cyanoborohydride, sodium trimethoxyborohydride, L-butoxylithium aluminum hydride, lithium aluminum hydride.
この反応における溶媒としては、水、ジエチルエーテル
、テトラヒドロフラン、ジオキサン、１２−ジメトキシ
エタン、ジクロルメタン、クロロホルム、メタノール、
エタノール、イソプロピルアルコールのような反応に不
活性なアルコールやエーテルが好ましく用いられる。Solvents for this reaction include water, diethyl ether, tetrahydrofuran, dioxane, 12-dimethoxyethane, dichloromethane, chloroform, methanol,
Alcohols and ethers that are inert to the reaction, such as ethanol and isopropyl alcohol, are preferably used.
反応温度は一２０°Ｃ〜８０°Ｃの範囲で任意であるが
、好ましくは一１５°Ｃ〜５０°Ｃの範囲である反応時
間は特に制限なく、原料ケトン類〔２〕が消失する時点
を終点とすればよい。The reaction temperature is arbitrary in the range of -20°C to 80°C, but preferably in the range of -15°C to 50°C.The reaction time is not particularly limited, and is the time at which the raw material ketones [2] disappears. should be the end point.
このような還元反応により得られる反応混合物から、過
剰の未反応還元剤を処理したのち、抽出、分液、濃縮等
の操作により、−綴代〔１〕で示されるトリアゾール類
が収率よく得られ、必要によりカラムクロマトグラフィ
ーにて精製することができる。After removing excess unreacted reducing agent from the reaction mixture obtained by such a reduction reaction, the triazoles represented by - Tsuzuriyo [1] can be obtained in good yield by extraction, separation, concentration, etc. If necessary, it can be purified by column chromatography.
〈発明の効果〉
本発明のトリアゾール類〔１〕はこのもの自体、農薬と
して有用であるばかりでなく、別途脱水反応によって前
記−綴代〔３〕で示される化合物へと有利に誘導できる
。<Effects of the Invention> The triazole [1] of the present invention is not only useful as an agrochemical in itself, but can also be advantageously induced into the compound represented by the above-mentioned -Tsuriyo [3] through a separate dehydration reaction.
なお、本発明の原料であるケトン類〔２〕は以下に示す
ようにアルカリ中、アルデヒド〔４〕とハロケトン〔５
］および１．２．４−トリアゾールとを縮合して合成さ
れるが、本発明ではこの反応液を後処理せずそのまま還
元し、ケトン類〔２〕を単離することなくトリアゾール
類〔１〕へと誘導できる優位性もある。Note that ketones [2], which are the raw materials of the present invention, are prepared by combining aldehyde [4] and haloketone [5] in an alkali as shown below.
] and 1.2.4-triazole, but in the present invention, this reaction solution is reduced as it is without post-treatment, and triazoles [1] are synthesized without isolating ketones [2]. It also has the advantage of being able to lead to.
〈実施例〉 以下、実施例により本発明を説明する。<Example> The present invention will be explained below with reference to Examples.
実施例１
ｌ−（４−１０ロフエニル）−１−４ドロキシ−２−（
１，２，４−トリアゾール−１−イル）４．４−ジメチ
ル−ペンクン−３−オン５ｇ（０゜０１６２モル）をエ
タノール１５ｄに溶解し、０°Ｃに冷却下、水素化ホウ
素ナトリウム０．２３ ｇ （０，００６１モル）を添
加後、０°Ｃで３時間攪拌した。Example 1 l-(4-10lophenyl)-1-4 droxy-2-(
5 g (0°0162 mol) of 4,4-dimethyl-pencun-3-one (1,2,4-triazol-1-yl) was dissolved in 15 d of ethanol, and while cooling to 0°C, 0.0 g of sodium borohydride was added. After adding 23 g (0,0061 mol), the mixture was stirred at 0°C for 3 hours.
原料が消失したのを確認後、減圧下エタノールを留去し
、酢酸エチル８０ｄおよび冷水１０ｄを加え、酢酸エチ
ルで抽出後、硫酸マグネシウムで乾燥した。After confirming that the raw materials had disappeared, ethanol was distilled off under reduced pressure, 80 d of ethyl acetate and 10 d of cold water were added, and the mixture was extracted with ethyl acetate and dried over magnesium sulfate.
溶媒を濃縮後、シリカゲルカラムクロマトにより精製し
、１−（４−クロロフェニル）−２−（１，２，４−）
リアゾール−■−イル）−４，４−ジメチル−ペンクン
−１，４−ジオール３．８１ ｇ（収率７６％）を得た
。After concentrating the solvent, it was purified by silica gel column chromatography to obtain 1-(4-chlorophenyl)-2-(1,2,4-)
3.81 g (yield: 76%) of riazol-■-yl)-4,4-dimethyl-pencune-1,4-diol were obtained.
白色結晶 ｍｐ、 １６６−１６７°Ｃ実施例２
ｌ−（２，４−ジクロロフェニル）−１−ヒドロキシ−
２−（１２４−）リアゾール−１イル）’−４．４−ジ
メチルーペンクンー３−オン１０ ｇ （０，０２９２
モル）を無水テトラヒドロフラン３０−に溶解し、０°
Ｃに冷却下、水素化ホウ素ナトリウム０．４１ ｇ （
０，０１１モル）を添加後、０°Ｃで４時間攪拌した。White crystals mp, 166-167°C Example 2 l-(2,4-dichlorophenyl)-1-hydroxy-
2-(124-)riazol-1yl)'-4,4-dimethylpencun-3-one 10 g (0,0292
mol) in anhydrous tetrahydrofuran and heated to 0°
0.41 g of sodium borohydride (
After adding 0.011 mol), the mixture was stirred at 0°C for 4 hours.
原料が消失したのを確認後、実施例１と同様に後処理を
行い、１−（２，４−ジクロロフェニル）−２−（１，
２，４−トリアゾール−１−イル）−４，４−ジメチル
−ペンクン１．４−ジオール８．３４ｇ （収率８３％
）を得た。After confirming that the raw material had disappeared, post-treatment was carried out in the same manner as in Example 1, and 1-(2,4-dichlorophenyl)-2-(1,
2,4-triazol-1-yl)-4,4-dimethyl-penkune 1,4-diol 8.34 g (yield 83%)
) was obtained.
白色結晶 ｍｐ、 １９１−１９２°Ｃ（以下、
余白）White crystal mp, 191-192°C (hereinafter referred to as
margin)
Claims (3)
れるトリアゾール類。(1) Triazoles represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, X represents a hydrogen atom or a chlorine atom.)
れるケトン類を還元剤を用いて還元することを特徴とす
る一般式 ▲数式、化学式、表等があります▼ （式中、Ｘは前記と同じ意味を有する。） で示されるトリアゾール類の製造法。(2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A general formula characterized by reducing a ketone represented by (in the formula, X represents a hydrogen atom or a chlorine atom) using a reducing agent. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X has the same meaning as above.) A method for producing triazoles shown by.
の化合物。(3) The compound according to claim 1, wherein the triazole is an optically active compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25331290A JPH04134075A (en) | 1990-09-21 | 1990-09-21 | Triazoles and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25331290A JPH04134075A (en) | 1990-09-21 | 1990-09-21 | Triazoles and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04134075A true JPH04134075A (en) | 1992-05-07 |
Family
ID=17249546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25331290A Pending JPH04134075A (en) | 1990-09-21 | 1990-09-21 | Triazoles and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04134075A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6496377B1 (en) | 1994-08-08 | 2002-12-17 | Coopertechnologies Company | Vehicle electric power distribution system |
-
1990
- 1990-09-21 JP JP25331290A patent/JPH04134075A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6496377B1 (en) | 1994-08-08 | 2002-12-17 | Coopertechnologies Company | Vehicle electric power distribution system |
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