JPS6383088A - Benzopyranopyrazolene derivative - Google Patents
Benzopyranopyrazolene derivativeInfo
- Publication number
- JPS6383088A JPS6383088A JP23089586A JP23089586A JPS6383088A JP S6383088 A JPS6383088 A JP S6383088A JP 23089586 A JP23089586 A JP 23089586A JP 23089586 A JP23089586 A JP 23089586A JP S6383088 A JPS6383088 A JP S6383088A
- Authority
- JP
- Japan
- Prior art keywords
- derivative
- formula
- present
- benzopyranopyrazolene
- hydrazine
- 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.)
- Granted
Links
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 125000003944 tolyl group Chemical group 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000002917 insecticide Substances 0.000 abstract description 3
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 abstract description 3
- SCZGZDLUGUYLRV-UHFFFAOYSA-N (2-methylphenyl)hydrazine Chemical compound CC1=CC=CC=C1NN SCZGZDLUGUYLRV-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000202 analgesic effect Effects 0.000 abstract description 2
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 abstract description 2
- 229940067157 phenylhydrazine Drugs 0.000 abstract description 2
- FORFENXCODBHOO-UHFFFAOYSA-N 2-hydrazinylethanol;methylhydrazine Chemical compound CNN.NNCCO FORFENXCODBHOO-UHFFFAOYSA-N 0.000 abstract 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 229940080817 rotenone Drugs 0.000 abstract 1
- 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 abstract 1
- 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
- 239000003905 agrochemical Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- GBHCABUWWQUMAJ-UHFFFAOYSA-N 2-hydrazinoethanol Chemical compound NNCCO GBHCABUWWQUMAJ-UHFFFAOYSA-N 0.000 description 2
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 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
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940079593 drug Drugs 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は新規なペンゾピラノビ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
される新規なペンゾビラノピラゾレン誘導体に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to novel penzopyranobirazolene derivatives. More specifically, the present invention relates to a novel penzobyranopyrazolene derivative that is expected to be used as an insecticide or analgesic.
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。Therefore, the present invention can be effectively utilized in the field of agricultural chemicals or medicine.
ロチノンは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、ロチ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。Rotinone is a component widely distributed in the roots of tropical plants of the Leguminosae family, and is known as a useful insecticide. However, rotinone has not been studied in a sufficiently systematic manner, and only the studies shown in the following documents have been conducted.
（ａ） エイ・ブチナンド、ダプリュ・マヵートニー
、ユスタス リービフヒス アンナーレンケミ、、
１９３２．４９４．１７ （Ａ、Ｂｕｔｅｎａｎｄｔ
、 Ｗ、Ｍｃｃ−ａｒｔｎｅｙ、 Ｊｕｓｔｕｓ Ｌｉ
ｅｂｉｇｓ Ａｎｎ、 Ｃｈｅｍ、１９３２＋甘ム１７
）。(a) A. Boutinand, Daplu McCartney, Justus Liebifhis Annarenchemi,...
1932.494.17 (A, Butenandt
, W., McC-artney, Justus Li
ebigs Ann, Chem, 1932 + Sweet 17
).
（ｂ） エル・クロムビー、ピー・ジエー・ゴーディ
ン、ディー・エイ・ウィティング、ケイ・ニス・シダリ
ンガイア、ジェー・ケミ・ソサ、。(b) L. Crombie, P.G. Godin, D.A. Whiting, K. Niss Sidalingaia, J. Kemi Sosa.
１９６Ｌ ２８７６ （Ｌ、Ｃｒｏｍｂｉｅ、
Ｐ、Ｊ、Ｇｏｄｉｎ、 Ｄ、八。196L 2876 (L, Crombie,
P., J., Godin, D., 8.
Ｗｈｉｔｉｎｇ、 Ｋ、Ｓ、Ｓｉｄｄａｌｉｎｇａｉａ
ｈ、 Ｊ、Ｃｈｅｍ、 Ｓｏｃ、。Whiting, K., S., Siddalingaia.
h, J,Chem,Soc,.
１９６１、２８７６）。1961, 2876).
本発明者はロチ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。The present inventor systematically investigated the chemical derivatives of rotinone,
Research was conducted with the aim of providing new derivatives useful as agricultural chemicals or medicines.
特にロチノンのへ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
のベンゾピラノと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。In particular, since the only heteroatom in rotinone is oxygen, we attempted to change it to a nitrogen-containing heterocycle. As a result, we succeeded in obtaining several new benzopyrano and lazolene derivatives.
The present invention has now been completed.
即ち、本発明は、式（１）
（式中、ＲはＨ，ＣＨｓ、ＣＨｇＣＨｚＯＨ，フェニル
又はトリル基を表す）
で示されるペンゾビ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 provides a penzobyranopyrazolene derivative represented by the formula (1) (wherein R represents H, CHs, CHgCHzOH, phenyl or tolyl group).
本発明のペンゾピラノピラゾレン誘導体は、次式（ＩＩ
）
で表されるロチノンをエタノール−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）で示されるロチノンのＣ
−１２ａと０−１３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。The penzopyranopyrazolene derivative of the present invention has the following formula (II
) in the presence of ethanol-potassium hydroxide to hydrazine, methylhydrazine, hydroxyethylhydrazine, phenylhydra, that is, as shown in the reaction formula below, first the C of rotinone represented by the above formula (II)
The bond between -12a and 0-13 is cleaved, and then the ring is closed via an intermediate represented by the following formula (III) to obtain the target compound.
・・・ （ＯＩ）
１体
〔発明の効果〕
本発明の新規ペンゾビラノピラゾレン誘専体は農薬或い
は医薬の分野において有用である。... (OI) 1 [Effects of the Invention] The novel penzobyranopyrazolene 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。EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples.
実施例１
７．６ｍＭのロチノンと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５０ｒＬ１に懸濁させ、３〜５時間還流し
た後、溶媒を蒸発させた。残渣を５％酢酸水溶液で洗い
、クロロホルムで抽出した。Example 1 7.6 mM rotinone and 76 mM hydrazine (or hydrazine hydrochloride) were suspended in 50 rL of an 8.5% potassium hydroxide ethanol solution, refluxed for 3 to 5 hours, and then the solvent was evaporated. Ta. The residue was washed with 5% acetic acid aqueous solution and extracted with chloroform.
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。After removing chloroform, the residue was separated by silica gel column chromatography and recrystallized from methylene chloride to obtain colorless columnar crystals.
収率８７％、ｍｐ ２４２〜２４４℃であった。Yield was 87%, 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、’Ｈ−ＮＭＲスペクトルの結果を表２に示す
。The results of the specific rotation and mass spectrum of the obtained compound are shown in Table 1, and the results of the '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−メチルエチニル−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 1-(2-methylethynyl-4-hydroxy-2,3-
dihydrobenzofuran-5-yl)-7,8-dimethoxy-1,9b,2,3.3a,4-hexahydro-[
1] Benzopyrano (3,4-c)pyrazole-1-
It turns out that it is en.
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、各種ペンゾピラノピラゾレン誘導体を得た。Examples 2 to 5 Various penzopyranopyrazole derivatives were prepared in the same manner as in Example 1 except that methylhydrazine, hydroxyethylhydrazine, phenylhydrazine, or tolylhydrazine was used instead of hydrazine. Obtained.
その結果を表１及び２に示す。The results are shown in Tables 1 and 2.
Claims (1)
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。[Claims] 1. A benzopyranopyrazolene derivative represented by the formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (wherein R represents H, CH_3, CH_2CH_2OH, 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 true JPS6383088A (en) | 1988-04-13 |
| JPH072746B2 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) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63193325U (en) * | 1988-06-22 | 1988-12-13 | ||
| CN102295650A (en) * | 2011-06-30 | 2011-12-28 | 湖南大学 | Rotenone oxime allyl / propargyl ether and application of the same as insecticide |
| CN103288810A (en) * | 2013-06-20 | 2013-09-11 | 湖南大学 | Cyclopropyl derris hydrazide, and preparation method and application thereof |
| CN103304553A (en) * | 2013-06-20 | 2013-09-18 | 湖南大学 | 2-(propylene-2-yl)-2,3-dihydro-4-benzofuranol as well as preparation method and application thereof |
| CN114920753A (en) * | 2022-05-24 | 2022-08-19 | 华南理工大学 | 6-fluoro-dihydropyrano [2,3-c ] pyrazole derivative and synthetic method and application thereof |
-
1986
- 1986-09-29 JP JP23089586A patent/JPH072746B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63193325U (en) * | 1988-06-22 | 1988-12-13 | ||
| CN102295650A (en) * | 2011-06-30 | 2011-12-28 | 湖南大学 | Rotenone oxime allyl / propargyl ether and application of the same as insecticide |
| CN103288810A (en) * | 2013-06-20 | 2013-09-11 | 湖南大学 | Cyclopropyl derris hydrazide, and preparation method and application thereof |
| CN103304553A (en) * | 2013-06-20 | 2013-09-18 | 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 |
| CN114920753A (en) * | 2022-05-24 | 2022-08-19 | 华南理工大学 | 6-fluoro-dihydropyrano [2,3-c ] pyrazole derivative and synthetic method and application thereof |
| CN114920753B (en) * | 2022-05-24 | 2023-06-20 | 华南理工大学 | 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and synthetic method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH072746B2 (en) | 1995-01-18 |
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