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 preparation

Info

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
Application number
JP15761683A
Other languages
Japanese (ja)
Inventor
Hisanori Matsui
久典 松井
Keiji Sudo
須藤 啓司
Moriharu Yamamoto
山本 守治
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Kayaku Co Ltd
Nihon Nohyaku Co Ltd
Original Assignee
Nippon Kayaku Co Ltd
Nihon Nohyaku Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Kayaku Co Ltd, Nihon Nohyaku Co Ltd filed Critical Nippon Kayaku Co Ltd
Priority to JP15761683A priority Critical patent/JPS6048977A/en
Publication of JPS6048977A publication Critical patent/JPS6048977A/en
Pending legal-status Critical Current

Links

Abstract

NEW MATERIAL:A compound shown by the formula I . USE:An intermediate for preparing herbicides. PREPARATION:1-( 3-Aminophenyl )-3-methyl-4-difluoromethyl-DELTA<2>-1, 2,4-triazolin-5- one shown by the formula II, for example, is diazotized which sodium sulfite in an aqueous solution of sulfuric acid at <=5 deg.C, without isolation, it is thermally discomposed at 60-90 deg.C to give a compound shown by the formula I .

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)

【特許請求の範囲】[Claims] (1)構造式(■): で表わされる1−(3−ヒドロキシフェニル)−5−メ
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.
(2)構造式(■): で表わされるj−(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.
JP15761683A 1983-08-29 1983-08-29 1-(3-hydroxyphenyl)-3-methyl-4-difluoromethyl-delta2-1,2,4- triazolin-5-one and its preparation Pending JPS6048977A (en)

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)

* Cited by examiner, † Cited by third party
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

Cited By (1)

* Cited by examiner, † Cited by third party
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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