JPS60136572A - Production of triazolone derivative - Google Patents
Production of triazolone derivativeInfo
- Publication number
- JPS60136572A JPS60136572A JP24719983A JP24719983A JPS60136572A JP S60136572 A JPS60136572 A JP S60136572A JP 24719983 A JP24719983 A JP 24719983A JP 24719983 A JP24719983 A JP 24719983A JP S60136572 A JPS60136572 A JP S60136572A
- Authority
- JP
- Japan
- Prior art keywords
- base
- formula
- lower alkyl
- compound expressed
- present
- 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】 本発明はトリアシロン誘導体の新規製造方法に関する。[Detailed description of the invention] The present invention relates to a novel method for producing triacylone derivatives.
本発明によって得られるトリアシロン誘導体は、医薬、
農薬の中間体として有用であり、特に除草剤の中間体と
して有用な化合物である。The triacylone derivative obtained by the present invention can be used for pharmaceuticals,
It is a compound useful as an intermediate for agricultural chemicals, particularly as an intermediate for herbicides.
従来、トリアシロン誘導体の製造方法としては、本出願
人自身の出願である特開昭５６−４６８７１号、特開昭
５６−５５６６２号、特開昭５６−５５６６４号及び特
開昭５６−５６６６５号公報痔で柚々の新規な製造方法
を提案している。しかしながらこれらの製造方法は原料
が高価でメジ、収率が低い等の欠点を有していた。本発
明者等は更に前売を重ねた結果本発明を完成させたもの
である。Conventionally, methods for producing triacylone derivatives have been disclosed in JP-A-56-46871, JP-A-56-55662, JP-A-56-55664, and JP-A-56-56665, which were filed by the present applicant. We are proposing a new manufacturing method for hemorrhoids. However, these production methods have drawbacks such as expensive raw materials and low yields. The present inventors completed the present invention as a result of further advance sales.
即ち、本発明は一般式（■）：
（）
（式中、
ｉｔは低級アルキル基、フェニル基を表わし為Ｘは水素
原子、ハロゲン原子、低級アルキル基、低級アルコキシ
基、ニトロ基又は水酸基を表わし、ｎ ｆよ−乃至乙の
整数であり、但し１１が２乃至乙の場合Ｘは同−又は相
異なっても良い。）で表わされるトリアシリジン誘導体
を塩基の存在下反応させて、一般式（Ｉ）：（式中几、
Ｘ及びｎは前記の意味を表わす。）で表わされる１、２
．４−）！ＪアゾロンＭＷ体を製造するものである。That is, the present invention has the following formula: , n is an integer from f to O, provided that when 11 is from 2 to O, X may be the same or different. ): (formula,
X and n have the meanings given above. ) represented by 1, 2
．． 4-)! This is to produce J Azolone MW body.
本発明製造方法を例えば図式的に示すと次の如く表わさ
れる。For example, the manufacturing method of the present invention can be diagrammatically expressed as follows.
（式中Ｒ２Ｘ及びｍは前記と同じ意味を表わす。）即ち
一般式（ｎ）で表わされるトリアシリジン誘導体を塩基
及び溶媒の存在下、加熱反応することにより一般式（Ｉ
）で表わされるトリアシロン誘導体を得ることができる
。(In the formula, R 2
) can be obtained.
本発明で使用できる不活性溶媒としては、この神の反応
を著しく阻害しないものであれば良く、洞見ばベンゼン
、ｌ・ルエン・キシレン等の芳香族炭化水素類；メタノ
ール、エタノール、プロパツール、グリコール等のアル
コール類；ジエチルアニリン、テトラヒドロフラン、ジ
オキサン等のエーテル類；アセトン、メチルエチルケト
ン、シクロヘキサノン等のケトン類；酢酸エチル等の低
級脂肪酸エステル類；ジメチルホルムアミド、ジメチル
アセトアミド等の低級脂肪族アミド類、水、ジメチルス
ルホキシド等を挙げることができる。Inert solvents that can be used in the present invention include aromatic hydrocarbons such as benzene, l, luene, and xylene; methanol, ethanol, propatool, and glycol. alcohols such as diethylaniline, tetrahydrofuran, dioxane, etc.; ketones such as acetone, methyl ethyl ketone, cyclohexanone; lower fatty acid esters such as ethyl acetate; lower aliphatic amides such as dimethylformamide, dimethylacetamide, water, Dimethyl sulfoxide and the like can be mentioned.
これらの溶媒は、単独で、または混合物として使用する
ことができる。These solvents can be used alone or in mixtures.
本発明の反応で使用することのできる塩基としては、例
えば炭酸ナトリウム、水素化ナトリウム、炭酸カリウム
、炭ｔｉ’ｙ水素ナトリウム、炭酸水素カリウム、水酸
化ナトリウム、水酸化カリウム及びアルカリ金九のアル
コラード等の無［１基、ピリジン、トリメチルアミン、
トリエチルアミン、ジエチルアニリン、１，８−ジアザ
ビシクロ−（５，４，Ｏ］ −７−ウ／デセン等の有機
塩基を挙けることができる。Examples of the base that can be used in the reaction of the present invention include sodium carbonate, sodium hydride, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide, alkali metal chloride, etc. No [1 group, pyridine, trimethylamine,
Organic bases such as triethylamine, diethylaniline, 1,8-diazabicyclo-(5,4,O]-7-u/decene and the like can be mentioned.
又、トリエチルベンジルアンモニウムクロライド等の相
聞移動触媒も使用することができる。Phase transfer catalysts such as triethylbenzylammonium chloride can also be used.
本発明に於ける反応温度は、室温乃至溶媒の沸点の範囲
から適宜選択すれば良いが、好丑しくは４？℃乃至９０
℃の範囲が適当である。The reaction temperature in the present invention may be appropriately selected from the range of room temperature to the boiling point of the solvent, but is preferably 4°C. °C to 90
A range of ℃ is suitable.
反応時１ｎＪは通常１乃至６時間の範囲から選択される
がこれらに限定されるものではない。The reaction time of 1 nJ is usually selected from the range of 1 to 6 hours, but is not limited thereto.
本発明に於ける塩基の使用量は等モル以上、好ましくは
３乃至５倍モルの範囲から選択すれば良い。塩基として
相間移動触媒を使用する場合、その鼠は０乃至当モルの
範囲から選択すれば良く、好ましくはＯ乃至１０重量％
の範囲が良い。The amount of the base to be used in the present invention may be selected from the range of equal molar or more, preferably 3 to 5 times the molar range. When a phase transfer catalyst is used as a base, the amount thereof may be selected from the range of 0 to equimolar, preferably 0 to 10% by weight.
Good range.
反応終了後、常法に従い処理すれば目的物とする一般式
（Ｉ）で表わされる１、２．４−トリアゾリン誘導体を
得ることができる。After completion of the reaction, the desired 1,2,4-triazoline derivative represented by the general formula (I) can be obtained by processing according to a conventional method.
一般式（ＩＩ）で示されるトリアシリジン誘導体は、例
えば特開昭５４−１５４７６９号公報記載の方法でも合
成することができる。以下に本発明製造方法の実施例の
若干を挙けるが本発明はこれらに限定されるものではな
い。The triacylidine derivative represented by the general formula (II) can also be synthesized, for example, by the method described in JP-A-54-154769. Some examples of the manufacturing method of the present invention are listed below, but the present invention is not limited thereto.
実施例１：
ｍ−ニトロフェニルヒドラジン１．５３ ｒ （０，０
１モル）、８０％アセトアルデヒド水溶液０．６１ケ酢
酸２０罰に加え、５０℃で６０分反応を行う。この反応
液を室温まで冷却後、シアン酸ナトリウム０．７７ｒ
（０，０１モル）を加え、更に１時間反応を行う。反応
終了後反応液に水を加えて析出する結晶ｔｖｉ取し１−
（６−ニトロフェニル）−６−メチル−１，２，４−ト
リアシリジン−５−オン２０１を得る。収率９０．９％
ｍ、 ｐ、１２５〜１２８℃。上記で得られた１−（６
−ニトロフェニル）−６−メチル−１，２，４−トリア
シリジン−５−オン１ ｆ （０，００４５モル）、水
酸化ナトリウム１ ｆ／ （０，［Ｊ２５モル）、テト
ラノルマルブチルアンモニウムプロミド０．１ＳＦ、水
１ｄ及びトルエン２５１の混合物を８０℃で４時間加熱
攪拌する。反応終了後反応液を放冷し、水２５ｍＪを加
えて、水層を分取する。得られた水増を塩酸で削性にし
、析出する結晶ｆｃＦ取し目的物で、ｉる１−（３−ニ
トロフェニル）−６−メチル−Δ” １．２．４− ）
リアゾロン−５−オン０．６２２を得ることができる〇
収率６２％ 融点２４７〜２５＋１１’Ｃ。Example 1: m-nitrophenylhydrazine 1.53 r (0,0
1 mol), 0.61 mol of 80% acetaldehyde aqueous solution and 20 ml of acetic acid, and reacted at 50°C for 60 minutes. After cooling this reaction solution to room temperature, 0.77r of sodium cyanate was added.
(0.01 mol) was added, and the reaction was further carried out for 1 hour. After the completion of the reaction, add water to the reaction solution and collect the precipitated crystals tvi 1-
(6-nitrophenyl)-6-methyl-1,2,4-triacylidin-5-one 201 is obtained. Yield 90.9%
m, p, 125-128°C. 1-(6
-nitrophenyl)-6-methyl-1,2,4-triacylidin-5-one 1 f (0,0045 mol), sodium hydroxide 1 f/ (0, [J25 mol), tetran-butylammonium bromide 0 A mixture of .1 SF, 1 d of water, and 251 ml of toluene is heated and stirred at 80° C. for 4 hours. After the reaction is completed, the reaction solution is allowed to cool, 25 mJ of water is added, and the aqueous layer is separated. The resulting water is made machinable with hydrochloric acid, and the precipitated crystals fcF are collected.
0.622% of riazolon-5-one can be obtained. Yield: 62%. Melting point: 247-25+11'C.
特許出勉゛Ｉ大 日本農桑林式会社 （すｆか１名ンPatent study ゛ I University Nihon Nosoubayashi Type Company (Sf or 1 person)
Claims (1)
子、ハロゲン原子、低級アルキル基、低級アルコキシ基
、ニトロ基又は水酸基な表わし、 ｎは１乃至３の核数ヶ表わし、 但しｎが２乃至３の場合Ｘは同−又は相異なっても良い
。）で表わされるトリアシリジン誘導体を地糸の存在下
反応させることを特徴とする一般式（１）； （式中Ｒ，Ｘ及びｎは口Ｕ記の意味を表わす。）で表わ
される１、２．４−）リアゾロン誘導体の製造方法。[Claims] General formula (■): (wherein, (■) represents a lower alkyl group or phenyl group, and X represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, or a hydroxyl group, A general method characterized by reacting a triacylidine derivative represented by (n represents the number of nuclei from 1 to 3; however, when n is 2 to 3, X may be the same or different) in the presence of ground yarn. A method for producing a 1,2.4-) riazolone derivative represented by formula (1);
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24719983A JPS60136572A (en) | 1983-12-26 | 1983-12-26 | Production of triazolone derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24719983A JPS60136572A (en) | 1983-12-26 | 1983-12-26 | Production of triazolone derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60136572A true JPS60136572A (en) | 1985-07-20 |
Family
ID=17159920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24719983A Pending JPS60136572A (en) | 1983-12-26 | 1983-12-26 | Production of triazolone derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60136572A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991003470A1 (en) * | 1989-09-08 | 1991-03-21 | Fmc Corporation | Production of triazolinones |
| US5256793A (en) * | 1992-05-13 | 1993-10-26 | Fmc Corporation | Triazolinone ring formation in tert-butanol |
| US5440045A (en) * | 1992-05-13 | 1995-08-08 | Fmc Corporation | Triazolinone ring formation in tert-butanol |
| LT3949B (en) | 1988-08-31 | 1996-05-27 | Fmc Corp | Herbicidal triazolinones, method for preparing thereof, herbicidal compositions and method for control of undesirable plants |
-
1983
- 1983-12-26 JP JP24719983A patent/JPS60136572A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| LT3949B (en) | 1988-08-31 | 1996-05-27 | Fmc Corp | Herbicidal triazolinones, method for preparing thereof, herbicidal compositions and method for control of undesirable plants |
| WO1991003470A1 (en) * | 1989-09-08 | 1991-03-21 | Fmc Corporation | Production of triazolinones |
| US5256793A (en) * | 1992-05-13 | 1993-10-26 | Fmc Corporation | Triazolinone ring formation in tert-butanol |
| US5440045A (en) * | 1992-05-13 | 1995-08-08 | Fmc Corporation | Triazolinone ring formation in tert-butanol |
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