JPH072746B2 - Benzopyranopyrazolene derivative - Google Patents
Benzopyranopyrazolene derivativeInfo
- Publication number
- JPH072746B2 JPH072746B2 JP23089586A JP23089586A JPH072746B2 JP H072746 B2 JPH072746 B2 JP H072746B2 JP 23089586 A JP23089586 A JP 23089586A JP 23089586 A JP23089586 A JP 23089586A JP H072746 B2 JPH072746 B2 JP H072746B2
- Authority
- JP
- Japan
- Prior art keywords
- benzopyranopyrazolene
- derivative
- present
- rotenone
- novel
- 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.)
- Expired - Lifetime
Links
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 229940080817 rotenone Drugs 0.000 description 7
- JUVIOZPCNVVQFO-UHFFFAOYSA-N rotenone Natural products O1C2=C3CC(C(C)=C)OC3=CC=C2C(=O)C2C1COC1=C2C=C(OC)C(OC)=C1 JUVIOZPCNVVQFO-UHFFFAOYSA-N 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- SCZGZDLUGUYLRV-UHFFFAOYSA-N (2-methylphenyl)hydrazine Chemical compound CC1=CC=CC=C1NN SCZGZDLUGUYLRV-UHFFFAOYSA-N 0.000 description 2
- GBHCABUWWQUMAJ-UHFFFAOYSA-N 2-hydrazinoethanol Chemical compound NNCCO GBHCABUWWQUMAJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 2
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 2
- 229940067157 phenylhydrazine Drugs 0.000 description 2
- -1 2-methylethenyl-4-hydroxy-2,3-dihydrobenzofuran-5-yl Chemical group 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000220485 Fabaceae Species 0.000 description 1
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 1
- 230000000202 analgesic effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は新規なベンゾピラノピラゾレン誘導体に関す
る。更に詳しくは殺虫剤或いは鎮痛剤としての使用が期
待される新規なベンゾピラノピラゾレン誘導体に関す
る。従って、本発明は農薬或いは医薬の分野において有
効に利用される。TECHNICAL FIELD The present invention relates to a novel benzopyranopyrazolene derivative. More specifically, it relates to a novel benzopyranopyrazolene derivative expected to be used as an insecticide or analgesic. Therefore, the present invention is effectively used in the field of agricultural chemicals or medicine.
ロテノンはLeguminosae科の熱帯植物の根に広く分布す
る成分であり、有用な殺虫剤として知られている。しか
し、ロテノンについては従来から十分に体系的な研究が
なされておらず、例えば、下記の文献に示されるような
研究がなされているにすぎない。Rotenone is a component widely distributed in the roots of tropical plants of the Leguminosae family and is known as a useful insecticide. However, rotenone has not been sufficiently systematically studied so far, for example, only the studies shown in the following documents have been made.
（ａ）エイ・ブテナント，ダブリュ・マカートニー，ユ
スタス，リービッヒス アンナーレンケミ,1932,494,17
（A.Butenandt,W.Mccartney,Justus Liebigs Ann.Che
m.,1932,494,17）。(A) A. Bouten, W. McCartney, Justus, Liebigs Anna Renchemy, 1932, 494 , 17
(A.Butenandt, W.Mccartney, Justus Liebigs Ann.Che
m., 1932, 494 , 17).
（ｂ）エル・クロムビー，ピー・ジェー・ゴーディン，
ディー・エイ・ウイティング，ケイ・エス・シダリンガ
イア，ジェー・ケミ・ソサ.,1961,2876（L.Crombie,P.
J.Godin,D.A.Whiting,K.S.Siddalingaiah,J.Chem.Soc.,
1961,2876）。(B) El Cromby, PJ Gaudin,
D. A. Witting, K.S. Sedallingaia, J. Kemi Sosa., 1961, 2876 (L.Crombie, P.
J.Godin, DAWhiting, KSSiddalingaiah, J.Chem.Soc.,
1961, 2876).
本発明者はロテノンの化学的誘導体を体系的に究明し、
農薬或いは医薬として有用な新規誘導体を提供すること
を目的として研究を行った。特にロテノンのヘテロ原子
は酸素だけであるので、含窒素複素環に変える試みを行
った。その結果、数種の新規のベンゾピラノピラゾレン
誘導体を得ることに成功し、本発明を完成するに到っ
た。The present inventors systematically investigated chemical derivatives of rotenone,
Research was conducted for the purpose of providing a novel derivative useful as an agricultural chemical or a medicine. In particular, since the only heteroatom of rotenone is oxygen, we tried to convert it to a nitrogen-containing heterocycle. As a result, they succeeded in obtaining several kinds of novel benzopyranopyrazolene derivatives, and completed the present invention.
即ち、本発明は、式（１） （式中、ＲはH,CH3，CH2CH2OH，フェニル又はトリル基
を表す） で示されるベンゾピラノピラゾレン誘導体を提供するも
のである。That is, the present invention uses the formula (1) (Wherein R represents H, CH 3 , CH 2 CH 2 OH, phenyl or tolyl group).
本発明のベンゾピラノピラゾレン誘導体は、 次式（II） で表されるロテノンをエタノール−水酸化カリウム存在
下でヒドラジン、メチルヒドラジン、ヒドロキシエチル
ヒドラジン、フェニルヒドラジン或いはトリルヒドラジ
ンと反応させることにより得られる。The benzopyranopyrazolene derivative of the present invention has the following formula (II) It can be obtained by reacting rotenone represented by with hydrazine, methylhydrazine, hydroxyethylhydrazine, phenylhydrazine or tolylhydrazine in the presence of ethanol-potassium hydroxide.
即ち、下記の反応式に示すように、最初に上記式（II）
で示されるロテノンのＣ−12aとＯ−13との間の結合が
開裂し、その後下記式（III）で示される中間体を経由
して閉環して目的とする化合物が得られる。That is, as shown in the following reaction formula, first, the above formula (II)
The bond between C-12a and O-13 of rotenone represented by is cleaved, and then the ring is closed via an intermediate represented by the following formula (III) to obtain the desired compound.
〔発明の効果〕 本発明の新規ベンゾピラノピラゾレン誘導体は農薬或い
は医薬の分野において有用である。 [Effects of the Invention] The novel benzopyranopyrazolene derivative of the present invention is useful in the field of agricultural chemicals or medicine.
以下、本発明を実施例により詳細に説明するが、本発明
はこれらの実施例に限定されるものではない。Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.
実施例１ 7.6mMのロテノンと76mMのヒドラジン（又はヒドラジン
の塩酸塩）とを8.5％の水酸化カリウムのエタノール溶
液50mlに懸濁させ、３〜５時間還流した後、溶媒を蒸発
させてた。残渣を５％酢酸水溶液で洗い、クロロホルム
で抽出した。クロロホルムを除去後、シリカゲルカラム
クロマトグラフィーで分離し、塩化メチレンで再結晶し
て、無色、柱状の結晶を得た。Example 1 7.6 mM rotenone and 76 mM hydrazine (or hydrazine hydrochloride) were suspended in 50 ml of 8.5% potassium hydroxide in ethanol, refluxed for 3 to 5 hours, and the solvent was evaporated. The residue was washed with a 5% aqueous acetic acid solution and extracted with chloroform. After removing chloroform, the residue was separated by silica gel column chromatography and recrystallized with methylene chloride to obtain colorless columnar crystals.
収率87％、mp242〜244℃であった。The yield was 87% and mp 242-244 ° C.
得られた化合物の比旋光度、質量スペクトルの結果を表
１に、又、1Ｈ−NMRスペクトルの結果を表２に示す。The results of the specific optical rotation and the mass spectrum of the obtained compound are shown in Table 1, and the results of the 1 H-NMR spectrum are shown in Table 2.
これらの結果から、得られた化合物は下記式で示される
１−（２−メチルエテニル−４−ヒドロキシ−2,3−ジ
ヒドロベンゾフラン−５−イル）−7,8−ジメトキシ−
1,9b,2,3,3a,4−ヘキサヒドロ−〔１〕ベンゾピラノ
〔3,4−ｃ〕ピラゾール−１−エンであることがわか
る。From these results, the obtained compound is represented by the following formula: 1- (2-methylethenyl-4-hydroxy-2,3-dihydrobenzofuran-5-yl) -7,8-dimethoxy-
It can be seen that it is 1,9b, 2,3,3a, 4-hexahydro- [1] benzopyrano [3,4-c] pyrazol-1-ene.
実施例２〜５ 実施例１に於いて、ヒドラジンの代わりにメチルヒドラ
ジン、ヒドロキシエチルヒドラジン、フェニルヒドラジ
ン又はトリルヒドラジンを用いる以外は実施例１と同様
にして、各種ベンゾピラノピラゾレン誘導体を得た。 Examples 2 to 5 Various benzopyranopyrazolene derivatives were obtained in the same manner as in Example 1 except that methylhydrazine, hydroxyethylhydrazine, phenylhydrazine or tolylhydrazine were used instead of hydrazine. It was
その結果を表１及び２に示す。The results are shown in Tables 1 and 2.
Claims (1)
を表す） で示されるベンゾピラノピラゾレン誘導体。1. A formula (In the formula, R represents H, CH 3 , CH 2 CH 2 OH, phenyl or tolyl group).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23089586A JPH072746B2 (en) | 1986-09-29 | 1986-09-29 | Benzopyranopyrazolene derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23089586A JPH072746B2 (en) | 1986-09-29 | 1986-09-29 | Benzopyranopyrazolene derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6383088A JPS6383088A (en) | 1988-04-13 |
| JPH072746B2 true JPH072746B2 (en) | 1995-01-18 |
Family
ID=16914979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23089586A Expired - Lifetime JPH072746B2 (en) | 1986-09-29 | 1986-09-29 | Benzopyranopyrazolene derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH072746B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63193325U (en) * | 1988-06-22 | 1988-12-13 | ||
| CN102295650B (en) * | 2011-06-30 | 2013-08-21 | 湖南大学 | Rotenone oxime allyl / propargyl ether and application of the same as insecticide |
| CN103304553B (en) * | 2013-06-20 | 2015-03-11 | 湖南大学 | 2-(propylene-2-yl)-2,3-dihydro-4-benzofuranol as well as preparation method and application thereof |
| CN103288810B (en) * | 2013-06-20 | 2015-03-25 | 湖南大学 | Cyclopropyl derris hydrazide, and preparation method and application thereof |
| CN114920753B (en) * | 2022-05-24 | 2023-06-20 | 华南理工大学 | 6-Fluoro-dihydropyrano[2,3-c]pyrazole derivatives and their synthesis methods and applications |
-
1986
- 1986-09-29 JP JP23089586A patent/JPH072746B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6383088A (en) | 1988-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0289380A1 (en) | Aryl-heteroaryl-carbinol derivatives having an analgesic activity | |
| HU191960B (en) | Process for preparing substituted 2-mercapto-imidazoles | |
| FR2679555A1 (en) | NOVEL DERIVATIVES OF UREA, THEIR PREPARATION AND THEIR USE IN THERAPEUTICS. | |
| EP4504191A1 (en) | Inhibiting histone deacetylase 6 (hdac6) | |
| JPH072746B2 (en) | Benzopyranopyrazolene derivative | |
| JPS5951537B2 (en) | Method for producing novel α-aminooxycarboxylic acid hydrazide derivative | |
| CS219943B2 (en) | Method of making the racemic and optically unite derivatives of the 1-phenyl-2-cyclohexene-1-alcylamine | |
| Bender et al. | Synthetic quinine analogs. I. Synthesis and some chemical transformations of 6'-methoxy-7-oxo-8-rubene | |
| Burakevich et al. | Phenylfurazan oxide. Chemistry | |
| JPH04234367A (en) | Process for producing 1-hydroxymethylpyrazoles | |
| Martell et al. | The 6-Deoxytetracyclines. IX. Imidomethylation | |
| CA2166032A1 (en) | 1-oxo-2-(phenylsulfonylamino)pentylpiperidine; process for preparing them and their use as therapeutic agents | |
| US2970159A (en) | Hydrazine derivatives | |
| NO137727B (en) | ANALOGICAL PROCEDURE FOR THE PREPARATION OF THERAPEUTIC ACTIVE 1-PHENYL-3-HYDROXY-3-METHYLTRIAZENES | |
| US3936460A (en) | 1',4'-Dihydro-1-methyl-spiro[piperidine and pyrolidine-2,3'(2'H)quinoline]c | |
| US4163856A (en) | Azetidine compounds and process for production | |
| JPH061776A (en) | Production of substituted pyrazinecarbonitrile | |
| US3108045A (en) | Metal chelates of oxazolidinones as central nervous system stimulants | |
| JP2631668B2 (en) | New urocanic acid derivatives | |
| JPS6019911B2 (en) | 1-Azaerythrinane derivative | |
| JPH0324077A (en) | Production of imidazole derivative | |
| Samet et al. | Synthesis of heterocyclic systems with a carbohydrate fragment: 1. Stereoselective synthesis of azoloanhydrosugars via the addition of azoles to levoglucosenone | |
| RU2584692C2 (en) | Method of producing 3-(1-adamantyl)-1,5,3-ditiazepane and use thereof as fungicidally active agent | |
| JP3538630B2 (en) | Method for producing quinoline compound | |
| JPS6144868A (en) | Novel frediricamycin a derivative |