JPH07109267A - Production of chromanone derivative - Google Patents
Production of chromanone derivativeInfo
- Publication number
- JPH07109267A JPH07109267A JP27735293A JP27735293A JPH07109267A JP H07109267 A JPH07109267 A JP H07109267A JP 27735293 A JP27735293 A JP 27735293A JP 27735293 A JP27735293 A JP 27735293A JP H07109267 A JPH07109267 A JP H07109267A
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- formula
- compound
- derivative
- halogen
- 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
Landscapes
- Pyrane Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はクロマノン誘導体の新規
製造法に関するものである。該クロマノン誘導体は医農
薬中間体として有用である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for producing a chromanone derivative. The chromanone derivative is useful as an intermediate for medicines and agricultural chemicals.
【０００２】[0002]
【従来の技術】クロマノン誘導体を製造する場合、３−
ｐｈｅｎｏｘｙｐｒｏｐｉｏｎｉｃ−ａｃｉｄ誘導体を
酸クロライドに変換した後、分子内Ｆｒｉｅｄｅｌ−Ｃ
ｒａｆｔｓ反応による製造法が知られている。2. Description of the Related Art In the production of chromanone derivatives, 3-
After converting the phenoxypropionic-acid derivative into acid chloride, intramolecular Friedel-C
A production method by the Rafts reaction is known.
【０００３】[0003]
【発明が解決しようとする課題】しかしその製造工程に
おいて用いるジクロロメタンなどのハロゲン系溶媒及び
塩化アルミのようなルイス酸の環境に与える影響などな
どが問題視されていることから、これらを用いない新規
製造法が望まれていた。However, the influence of halogen solvents such as dichloromethane and Lewis acids such as aluminum chloride used in the manufacturing process on the environment has been regarded as a problem. A manufacturing method was desired.
【０００４】[0004]
【課題を解決するための手段】本発明者らは工業的に有
利にクロマノン誘導体を得ることを目的に研究を進め、
その結果その新規製造法を見いだし本発明を完成した。
すなわち、本発明は一般式（２）[Means for Solving the Problems] The present inventors have conducted research aiming at obtaining a chromanone derivative industrially,
As a result, they found the new manufacturing method and completed the present invention.
That is, the present invention has the general formula (2)
【０００５】[0005]
【化３】 [Chemical 3]
【０００６】（式中、Ｒ1 ，Ｒ2 ，Ｒ3 およびＲ4 は前
記のものを示す。）で表わされるクロマノン誘導体の製
造法である。(In the formula, R 1 , R 2 , R 3 and R 4 are the same as those mentioned above).
【０００７】一般式（２）の化合物は以下のようにして
製造することができる。すなわち一般式（１）The compound of the general formula (2) can be produced as follows. That is, the general formula (1)
【０００８】[0008]
【化４】 [Chemical 4]
【０００９】（式中、Ｒ1 ，Ｒ2 ，Ｒ3 およびＲ4 は前
記のものを示す。）で表わされる化合物を有機溶媒中ま
たは無溶媒にて無水トリフルオロ酢酸にて処理すること
により製造することができる。A compound represented by the formula (wherein R 1 , R 2 , R 3 and R 4 are as described above) is treated with trifluoroacetic anhydride in an organic solvent or without solvent. can do.
【００１０】上記反応に用いる有機溶媒としては、トル
エンなどの芳香族炭化水素、ヘキサンなどの脂肪族炭化
水素、ジクロロメタンなどのハロゲン系炭化水素および
エーテル系炭化水素などが挙げられ、好ましくは芳香族
炭化水素および脂肪族炭化水素である。また、無溶媒で
行うこともできる。Examples of the organic solvent used in the above reaction include aromatic hydrocarbons such as toluene, aliphatic hydrocarbons such as hexane, halogen-based hydrocarbons such as dichloromethane and ether-based hydrocarbons, preferably aromatic hydrocarbons. Hydrogen and aliphatic hydrocarbons. It can also be carried out without solvent.
【００１１】反応温度は−２０℃〜溶媒還流温度であ
り、好ましくは０℃〜６０℃である。The reaction temperature is -20 ° C to solvent reflux temperature, preferably 0 ° C to 60 ° C.
【００１２】無水トリフルオロ酢酸は通常１当量以上必
要であるが、反応系内に無水トリフルオロ酢酸を再生す
るようなものが存在する場合は１当量以下でもよい。ま
た、生成するトリフルオロ酢酸は回収し、リサイクルす
ることができる。[0012] Trifluoroacetic anhydride is usually required in an amount of 1 equivalent or more, but if there is a substance that regenerates trifluoroacetic anhydride in the reaction system, it may be 1 equivalent or less. In addition, the trifluoroacetic acid produced can be recovered and recycled.
【００１３】本方法で得られる一般式（２）で表わされ
る化合物の例としては、８−ｔｅ−ｒｔ−ｂｕｔｙｌ−
５−ｍｅｔｈｙｌｃｒｏｍａｎｏｎｅなどが挙げられ
る。As an example of the compound represented by the general formula (2) obtained by this method, 8-te-rt-butyl-
5-methylchromone and the like can be mentioned.
【００１４】この化合物は次いでケトン基を還元し、ベ
ンゼン環の６−位にカルボニルを有する基の導入、８−
位の基の脱離を経て式（３）This compound then reduces the ketone group to introduce a group having a carbonyl at the 6-position of the benzene ring, 8-
Via the elimination of the group at position (3)
【化５】 [Chemical 5]
【００１５】で示される化合物に変換される。式（３）
の化合物はＥＰＯ４９６３４２号公報で知られるリン翅
目、半翅目などの害虫に対し高い殺虫を有するベンゾイ
ルヒドラジン系化合物の原料として用いられる。It is converted to a compound represented by Formula (3)
The above compound is used as a raw material of a benzoylhydrazine compound having a high insecticidal effect on harmful insects such as Lymoptera and Hemiptera known in EPO 496342.
【００１６】[0016]
【実施例】以下に本発明の方法を実施例により具体的に
説明する。EXAMPLES The method of the present invention will be specifically described below with reference to examples.
【００１７】実施例 ８−ｔｒｅｔ−Ｂｕｔｙｌ−５−ｍｅｔｈｙｌ−４−ｃ
ｒｏｍａｎｏｎｅの製造 ３−（２−ｔｒｅｔ−Ｂｕｔｙｌ−５−ｍｅｔｈｌｙｌ
ｐｈｅｎｏｘｙ）−ｐｒｏｐｉｏｎｉｃ ｓｃｉｄ １
ｇおよび無水トリフルオロ酢酸０．９ｍｌをトルエン１
０ｍｌに加え、室温にて４時間攪拌する。溶媒留去後得
られる残留物をシリカゲルカラムクロマトグラフィーに
付し、ｎ−ｈｅｘａｎｅ−ＡｃＯＥｔ流分より目的とす
るクロマノン誘導体０．９３ｇ（１００％）を白色結晶
（ｍ．ｐ．３９−４１℃）として得る。Example 8-tret-Butyl-5-methyl-4-c
Production of romanone 3- (2-tret-Butyl-5-methlyl
phenoxy) -proportional scid 1
g and 0.9 ml of trifluoroacetic anhydride to toluene 1
Add to 0 ml and stir at room temperature for 4 hours. The residue obtained after distilling off the solvent was subjected to silica gel column chromatography to obtain 0.93 g (100%) of the desired chromanone derivative from the n-hexane-AcOEt fraction as white crystals (mp 39-41 ° C.). Get as.
【００１８】1Ｈ−ＮＭＲ−（ＣＤＣｌ3,ｐｐｍ）δ：
１．３７（９Ｈ，ｓ）、２．６０（３Ｈ，ｓ）２．８０
（２Ｈ，ｔ，Ｊ＝６．６Ｈｚ）、４．４９（２Ｈ，ｔ，
Ｊ＝６．６Ｈｚ）、６．７１（１Ｈ，ｄ，Ｊ＝７．９Ｈ
ｚ）、７．９０（１Ｈ，ｄ，Ｊ＝７．９Ｈｚ） 1 H-NMR- (CDCl 3, ppm) δ:
1.37 (9H, s), 2.60 (3H, s) 2.80
(2H, t, J = 6.6 Hz), 4.49 (2H, t, J
J = 6.6 Hz), 6.71 (1H, d, J = 7.9H
z), 7.90 (1H, d, J = 7.9Hz)
Claims (2)
原子を、Ｒ2 はＣ2 〜Ｃ6 の第３級アルキル基またはハ
ロゲン原子を、Ｒ3 及びＲ4 はそれぞれ独立して水素原
子またはメチル基を示す。）で表わされる化合物を有機
溶媒中または無溶媒にて無水トリフルオロ酢酸にて処理
することを特徴とする一般式（２） 【化２】 （式中、Ｒ1 ，Ｒ2 ，Ｒ3 およびＲ4 は前記のものを示
す。）で表わされるクロマノン誘導体の製造法。1. A general formula (1): (In the formula, R 1 is a C 1 -C 2 alkyl group or a halogen atom, R 2 is a C 2 -C 6 tertiary alkyl group or a halogen atom, and R 3 and R 4 are independently hydrogen. An atom or a methyl group) is treated with trifluoroacetic anhydride in an organic solvent or without a solvent. (In the formula, R 1 , R 2 , R 3 and R 4 are the same as defined above.) A process for producing a chromanone derivative.
ブチル基であり、Ｒ3 およびＲ4 がそれぞれ水素原子で
ある請求項１記載の製造法。2. R 1 is a methyl group and R 2 is tert-
The process according to claim 1, wherein the process is a butyl group, and R 3 and R 4 are each a hydrogen atom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27735293A JPH07109267A (en) | 1993-10-12 | 1993-10-12 | Production of chromanone derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27735293A JPH07109267A (en) | 1993-10-12 | 1993-10-12 | Production of chromanone derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07109267A true JPH07109267A (en) | 1995-04-25 |
Family
ID=17582334
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27735293A Pending JPH07109267A (en) | 1993-10-12 | 1993-10-12 | Production of chromanone derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07109267A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0773216A1 (en) | 1995-11-09 | 1997-05-14 | Rohm And Haas Company | Process for the production of chroman carboxylates |
-
1993
- 1993-10-12 JP JP27735293A patent/JPH07109267A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0773216A1 (en) | 1995-11-09 | 1997-05-14 | Rohm And Haas Company | Process for the production of chroman carboxylates |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| HU221295B1 (en) | 4-aryl-piperidine-derivatives and process for producing them | |
| DD290188A5 (en) | CHEMICAL PROCESSES | |
| JPH07109267A (en) | Production of chromanone derivative | |
| KR100763077B1 (en) | One-pot synthesis of alkyl 3-cyclopropylamino-2-[2,4-dibromo-3-difluoromethoxybenzoyl]-2-propenoate as a useful intermediate for antibacterial quinolone medicaments | |
| JP3101012B2 (en) | Method for producing 2-aryl-5- (trifluoromethyl) pyrrole compound | |
| RU2628287C2 (en) | Production of n-substituted sulfoximine pyridine n-oxides | |
| CN113683608B (en) | N-substituted-2-amino-4-saccharin substituted methylthiazole compound with bactericidal activity, preparation method and application | |
| CA1137482A (en) | Process for the production of 5-aminoisoxazoles | |
| EP0311086A1 (en) | N-fluorinated sulfon amides, process for their preparation and their use | |
| JP3023197B2 (en) | Method for producing indole | |
| KR800000624B1 (en) | Process for preparing oxirane derivates | |
| JP3538631B2 (en) | Quinoline derivative and method for producing the same | |
| JP3257393B2 (en) | Method for producing (E) -allylsilane | |
| KR102051523B1 (en) | Synthetic method of tetrahydroisoquinoline derivatives | |
| JP3538630B2 (en) | Method for producing quinoline compound | |
| US4376871A (en) | Method for purification of cyclopentenolones | |
| JPS5888361A (en) | 3-amino-1,4-bis(alkoxycarbonyl)maleimide compound and its preparation | |
| JPS63211264A (en) | Production of indolines | |
| JPS6152133B2 (en) | ||
| JPH0813814B2 (en) | Process for producing fused heterocyclic compound | |
| JP3830995B2 (en) | Method for producing succinate derivative | |
| JPH03157345A (en) | Synthesis of carboxylic acids | |
| JPH07133270A (en) | Chroman derivative and its production | |
| JPH06263673A (en) | Production of 3-allylphenols | |
| Nitta et al. | On the reaction of tricarbonyl (4–7-η-1 H-1, 2-diazepine) iron with activated acetylenes. Preparation of 1-vinyl-1 H-1, 2-diazepine derivatives |