JPS6048977A - 1-(3-hydroxyphenyl)-3-methyl-4-difluoromethyl-delta2-1,2,4- triazolin-5-one and its preparation - Google Patents
1-(3-hydroxyphenyl)-3-methyl-4-difluoromethyl-delta2-1,2,4- triazolin-5-one and its preparationInfo
- Publication number
- JPS6048977A JPS6048977A JP15761683A JP15761683A JPS6048977A JP S6048977 A JPS6048977 A JP S6048977A JP 15761683 A JP15761683 A JP 15761683A JP 15761683 A JP15761683 A JP 15761683A JP S6048977 A JPS6048977 A JP S6048977A
- Authority
- JP
- Japan
- Prior art keywords
- difluoromethyl
- methyl
- triazolin
- hydroxyphenyl
- preparation
- 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
- 238000002360 preparation method Methods 0.000 title abstract 2
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 8
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 239000004009 herbicide Substances 0.000 abstract description 2
- 238000002955 isolation Methods 0.000 abstract description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 abstract 2
- 239000000463 material Substances 0.000 abstract 1
- 235000010265 sodium sulphite Nutrition 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000006193 diazotization reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- ZHZYGIQVBQWOJJ-UHFFFAOYSA-N 3,4-dihydro-1,2,4-triazol-5-one Chemical compound O=C1NCN=N1 ZHZYGIQVBQWOJJ-UHFFFAOYSA-N 0.000 description 1
- ZURLOZJIDLZAOI-UHFFFAOYSA-N 3,4-dihydropyrazol-5-one Chemical class O=C1CCN=N1 ZURLOZJIDLZAOI-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- -1 useful as herbicides Chemical class 0.000 description 1
Abstract
Description
【発明の詳細な説明】
本発明はトリアゾリン誘導体およびその製造方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to triazoline derivatives and methods for producing the same.
本発明のトリアゾリン誘導体は、構造式（Ｉ）：で表わ
される。The triazoline derivative of the present invention is represented by structural formula (I):
そして、このトリアゾ１Ｊン誘導体は、構造式（■）
で表わされる１−（３−アミノフェニル）−３−メチル
−４−ジフルオロメチル−Δ２−１．２゜４−トリアゾ
リン−５−オンをジアゾ化し、次いで熱分解することに
よって製造される。This triazo-1J derivative is a diazolin-5-one derivative of 1-(3-aminophenyl)-3-methyl-4-difluoromethyl-Δ2-1.2°4-triazolin-5-one represented by the structural formula (■). It is produced by oxidation followed by pyrolysis.
本発明化合物は文献未記載の新規化合物であシ、農薬、
特に除草剤として有用な化合物を製造するための重要な
中間体であシ、本発明はその製造方法をも提供するもの
である。The compound of the present invention is a new compound that has not been described in any literature, agrochemicals,
It is an important intermediate for producing compounds particularly useful as herbicides, and the present invention also provides a method for producing it.
本発明製法を例えば図式的に示すと下記の如く表わされ
る。For example, the production method of the present invention can be diagrammatically expressed as follows.
（Ｉ）
即ち、構造式（ＩＩ）で表わされる１−（５−アミノフ
ェニル）−３−メチル−４−ジフルオロメチル−Δ”−
１，２，４−トリアゾリン−５−オンを常法に従い例え
ば硫酸水溶液中亜硝酸す） ＩＪウムでジアゾ化して構
造式ｑ′）の化合物とし、次いで単離することなく加熱
分解することによシ構造式（１）で表わされる１−（５
−ヒドロキシフェニル）−３−メチル−４−ジフルオロ
メチル−Δ”−１，２，４−）リアゾリン−５−オンを
得ることができる。(I) That is, 1-(5-aminophenyl)-3-methyl-4-difluoromethyl-Δ"- represented by structural formula (II)
1,2,4-triazolin-5-one is diazotized with nitrous acid in an aqueous sulfuric acid solution to give a compound of structural formula q') according to a conventional method, and then thermally decomposed without isolation. 1-(5
-hydroxyphenyl)-3-methyl-4-difluoromethyl-Δ"-1,2,4-) riazolin-5-one can be obtained.
本反応の反応温度はジアゾ化工程の場合、冷却下５℃以
下で行なうのが良い。又熱分解工程は室温乃至１５０℃
の範囲から適宜選択されるが、好ましくは６０乃至９０
℃の範囲で行なうのが良い。In the case of the diazotization step, the reaction temperature of this reaction is preferably 5° C. or lower under cooling. Also, the thermal decomposition process is performed at room temperature to 150℃.
60 to 90, preferably from 60 to 90.
It is best to do this within a range of ℃.
反応時間は１乃至６時間の範囲から適宜選択すれば良い
。The reaction time may be appropriately selected from the range of 1 to 6 hours.
反応モル数は構造式（１）で表わされる１−（３−アミ
ノフェニル）−３−メチル−４−ジフルオロメチル−Δ
”−１，２，４−トリアゾリン−５−オン１モルに対し
て亜硝酸ナトリウムは１．０乃至２．０モルの範囲から
、硫酸は１．５乃至１５モルの範囲から適宜選択すれば
良い。ジアゾ化反応を例えば硫酸水溶液中で行なわせた
場合、後続の分解反応時、改めて水を添加することもな
いが、高純度の目的物を得るためには適宜添加すると良
い。The number of moles of reaction is 1-(3-aminophenyl)-3-methyl-4-difluoromethyl-Δ represented by structural formula (1).
``Sodium nitrite may be appropriately selected from the range of 1.0 to 2.0 mol and sulfuric acid may be selected from the range of 1.5 to 15 mol per mol of -1,2,4-triazolin-5-one. For example, when the diazotization reaction is carried out in an aqueous sulfuric acid solution, there is no need to add water again during the subsequent decomposition reaction, but it is recommended to add water as appropriate in order to obtain a highly pure target product.
反応終了後、析出する結晶をろ過採取し、インプロパツ
ールから再結晶することＫより１−（３−ヒドロキシフ
ェニル）−３−、ｌ’ｆ−ルー４−ジフルオロメチル−
Δ２−１．２．４− ）リアゾリン−５−オンを得るこ
とができる。After the reaction is completed, the precipitated crystals are collected by filtration and recrystallized from inpropatool.
Δ2-1.2.4-) riazolin-5-one can be obtained.
構造式（ＩＩ）で表わされる１−（３−アミノフェニル
）−５−メｆルー４−ジフルオロメチル−Δ２−１．２
．４− ）リアゾリン−５−オンは例えば下記に図示す
る方法で合成することができる二〇
（ＩＩ）
（但し、式中Ｒは低級アルキル基を示し、２はハロゲン
原子を示す。）。1-(3-aminophenyl)-5-meth-4-difluoromethyl-Δ2-1.2 represented by structural formula (II)
．． 4-) Ryazolin-5-one can be synthesized, for example, by the method illustrated below (20(II)) (wherein R represents a lower alkyl group and 2 represents a halogen atom).
構造式（■）で表わされるヒドラジンと一般式（Ｍ）で
表わされる化合物とを不活性溶媒中、加熱下で閉環反応
させることによシ一般式（Ｖ）で表わされる１−（５−
ニトロフェニル）−５−メチル−Δ２−１．２．４−
）リアゾリン−５−オンとし、この化合物（■を不活性
溶媒中、一般式（ｍＶ）で表わされる化合物と反応させ
ることＫＪ：、り構造式（ＩＩＩ）で表わされる１−（
５−ニトロフェニル）−５−１＋ルー４−ジフルオロメ
チル−Δ２−１．２．４〜トリアゾリン−５−オンとし
、この化合物（ＩＩＩ）を還元剤の存在下、還元するこ
とによシ構造式（ＩＩ）で表わされる１−（５−アミノ
フェニル）−３−メチル−４−ジフルオロメチル−Δ”
−１，２，４−）リアゾリン−５−オンを得ることがで
きる。1-(5-
Nitrophenyl)-5-methyl-Δ2-1.2.4-
) liazolin-5-one, and this compound (■) is reacted with a compound represented by the general formula (mV) in an inert solvent.
By reducing this compound (III) in the presence of a reducing agent, the structural formula 1-(5-aminophenyl)-3-methyl-4-difluoromethyl-Δ” represented by (II)
-1,2,4-) riazolin-5-one can be obtained.
以下に本発明の若干の実施例を挙げる。Some examples of the present invention are listed below.
実施例１
ｌ−（５−アミノフェニル）−５−メチル−４−ジフル
オロメチル−ΔＺ−１，２，４−）リアゾリン−５−オ
ン５８ｆ（０，１６モル）を５０％（ｖｏｌ）硫ｆｉ１
３４Ｍｌに溶解し、０℃以下に冷却する。この溶液に亜
硝酸ナトリウム１（３，９？ （（Ｊ、１６モル）を溶
解した水溶液６５ｍ１を反応温度を０℃以下に保持しな
がら滴下する。Example 1 l-(5-aminophenyl)-5-methyl-4-difluoromethyl-ΔZ-1,2,4-) riazolin-5-one 58f (0.16 mol) in 50% (vol) sulfur fi1
Dissolve in 34 ml and cool to below 0°C. To this solution, 65 ml of an aqueous solution in which sodium nitrite 1 (3,9? (J, 16 mol)) was dissolved was added dropwise while maintaining the reaction temperature below 0°C.
滴下終了後３０分間攪拌し、次いで水５５０ｍＪを加え
、７０℃で２時間反応を行う。反応終了後、反応液を冷
却し析出する結晶をｒ過採取し、得られた結晶をインプ
ロパツールから再結晶することにより５５．９ｆの１−
（３−ヒドロキシフェニル）−３−メチル−４−ジフル
オロメチル−Δ２−１．２．４−トリアゾリン−５−オ
ンを得る。After the dropwise addition was completed, the mixture was stirred for 30 minutes, then 550 mJ of water was added, and the reaction was carried out at 70°C for 2 hours. After the reaction is completed, the reaction solution is cooled, the precipitated crystals are collected by filtration, and the obtained crystals are recrystallized from an impropat tool to obtain 55.9f of 1-
(3-Hydroxyphenyl)-3-methyl-4-difluoromethyl-Δ2-1.2.4-triazolin-5-one is obtained.
融点 １２９〜１３２℃ 収率 ８９．３％特許出願人
日本農薬株式会社Melting point: 129-132℃ Yield: 89.3% Patent applicant: Nippon Nohyaku Co., Ltd.
Claims (2)
チル−４−ジフルオロメチル−Δ２−１、２．４ −
）リアゾリン−５−オン。(1) Structural formula (■): 1-(3-hydroxyphenyl)-5-methyl-4-difluoromethyl-Δ2-1,2.4-
) Riazolin-5-one.
ー４−ジフルオロメチル−Δ２−１゜２．４−）リアゾ
リン−５−オンをジアゾ化し、次いで熱分解することを
特徴とする構造式（Ｉ）：で表わされる１−（３−ヒド
ロキシフェニル）−３−メチル−４−ジフルオロメチル
−Δ２−１、２．４− ）リアゾリン−５−オンの製造
方法。(2) Structural formula (■): j-(3-aminophenyl)-5-mef-4-difluoromethyl-Δ2-1゜2.4-) riazolin-5-one is diazotized, and then 1-(3-hydroxyphenyl)-3-methyl-4-difluoromethyl-Δ2-1,2.4-) liazolin-5-one represented by the structural formula (I), which is characterized by thermal decomposition. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15761683A JPS6048977A (en) | 1983-08-29 | 1983-08-29 | 1-(3-hydroxyphenyl)-3-methyl-4-difluoromethyl-delta2-1,2,4- triazolin-5-one and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15761683A JPS6048977A (en) | 1983-08-29 | 1983-08-29 | 1-(3-hydroxyphenyl)-3-methyl-4-difluoromethyl-delta2-1,2,4- triazolin-5-one and its preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6048977A true JPS6048977A (en) | 1985-03-16 |
Family
ID=15653617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15761683A Pending JPS6048977A (en) | 1983-08-29 | 1983-08-29 | 1-(3-hydroxyphenyl)-3-methyl-4-difluoromethyl-delta2-1,2,4- triazolin-5-one and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6048977A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4845232A (en) * | 1985-10-26 | 1989-07-04 | Nihon Nohyaku Co., Ltd. | Process for producing 1,2,4-triazolin-5-one derivatives, and intermediates therefor |
-
1983
- 1983-08-29 JP JP15761683A patent/JPS6048977A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4845232A (en) * | 1985-10-26 | 1989-07-04 | Nihon Nohyaku Co., Ltd. | Process for producing 1,2,4-triazolin-5-one derivatives, and intermediates therefor |
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