JPS596309B2 - Furanosesquiterpene derivatives and their production method - Google Patents
Furanosesquiterpene derivatives and their production methodInfo
- Publication number
- JPS596309B2 JPS596309B2 JP11035778A JP11035778A JPS596309B2 JP S596309 B2 JPS596309 B2 JP S596309B2 JP 11035778 A JP11035778 A JP 11035778A JP 11035778 A JP11035778 A JP 11035778A JP S596309 B2 JPS596309 B2 JP S596309B2
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- JP
- Japan
- Prior art keywords
- furanosesquiterpene
- tables
- derivatives
- formulas
- production method
- 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.)
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- Furan Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明、構造式：
メＵＶ゜゜゜゜一
Ｈ３ＣＣＨ３
で表わされる新規なフラノセスキテルペン誘導体及びそ
の製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel furanosesquiterpene derivative represented by the structural formula: UV゜゜゜゜-H3CCH3 and a method for producing the same.
本発明の目的化合物は、その類似骨格から、例えば天然
物として単離されているコンフエルテイフオリン（ＣＯ
ｎｉｅｒｔｉｆＯｌｉｎ）、ポリゴジアール（ＰＯｌｙ
ｇＯｄｉａｌ）〔別名タデオナール（ＴａｄｅＯｎａｌ
）：等〔Ｈ．Ｈ．Ａｐｐｃｌ．Ｊ．Ｄ．ＣＯｎｎＯｌｌ
ｙ．Ｋ．Ｈ．ＯｖｅｒｔＯｎａｎｄ（Ｉｎｐａｒｔ）Ｒ
．Ｍ．ＢＯｎｄＪ．Ｃｈｅｍ．ＳＯｃ．、１９６０、４
６８５；１．ＫｕｂＯ，．Ｙｕｅ−Ｗｅｉｌｅｅ，．Ｍ
ｅｔｔｅｌ、Ｆ．ＰｉｌｋｉｅｗｉｃｚａｎｄＫ．Ｎａ
ｋａｎｉｓｈｉ．Ｃｈｅｍ．ＣＯｍｍ．、 １９７６、
１０１３参照〕へ変換する際の重要な中間体としして有
用と考えられる。The object compound of the present invention has a similar skeleton, for example, conferteiforin (CO), which is isolated as a natural product.
niertifOlin), Polygodial (POly)
gOdial) [Also known as TadeOnal
): etc. [H. H. Appcl. J. D. ConnOll
y. K. H. OvertOnand(Inpart)R
．． M. BOndJ. Chem. SOc. , 1960, 4
685;1. KubO,. Yue-Weilee,. M
ettel, F. PilkiewiczandK. Na
Kanishi. Chem. COmm. , 1976,
It is considered to be useful as an important intermediate in the conversion to [see 1013].
トリマツ型セスキテルペン化合物は、次に述べるような
如く、特異な構造を有する種々の化合物が存在し、上記
コンフエルテイフオリンから、容易に誘導可能と考えら
れる化合物としては、例えば、夜盗蟻（Ａｆｒｉｃａｎ
ａｒｍｙｗＯｒｍ′ＸＣ対する強力な摂食阻止物質（Ａ
ｎｔｉｆｅｅｄａｎｔ）作用を示すバ＊例えば、本発明
の化合物（７）から、コンフエルテイフオリン、イソド
リメニンを経由して、バ◆１Ｌｒ′−＼１＊−バカナー
ル（Ｗａｒｂｕｒｇａｎａｌ）〔Ａ〕、アガンデンシジ
アール（Ａｐｎｄｅｎｃｉｄｉａｌ）〔別名シンナモジ
アール（ＣｉｎｎａｍＯｄｉａｌ）〕〔Ｂ〕、ポリゴジ
アール（ＰＯｌｙｇＯｄｉａｌ）別名タデオナール（Ｔ
ａｄｅＯｎａｌ）〕〔Ｃ〕、〔１．Ｋｕｂ０，．Ｙｕｅ
Ｗｅｉ１ｅｅ，．Ｍ．Ｐｅｔｔｅｉ，．Ｆ．Ｐｉ１ｋｉ
ｅｗｉｃｚａｎｄＫ．Ｎａｋａｎｉｓｈｉ，．ＣｈｅＭ
．ＣＯｍｌｎ］．、１９７６、１０１３参照〕又皮ふ生
菌類（例えば、ＴｒｙｃＯｐｈｙｔＯｎ、ＭｉｃｒＯｓ
ｐＯｒｕｍ）に対して抗カビ活性を示すシンナモライド
（Ｃｉｎｎ＆ＭＯｌｉｄｅ）〔Ｄ〕、〔Ｌ．ＣａｎＯｎ
ｉｃａ，．Ａ．ＣＯｒｂｅｌｌａ，．Ｐ．ＧａｒｉｂＯ
ｌｄｉ，．Ｇ．ＴＯｍｍｉａｎｄＪ．Ｋｒｅｐｉｎｓｋ
ｉａｎＤＧ．ＦｅｒｒａｒｉｌＣ．Ｃａｓａｇｒａｎｄ
ｅ，．ＴｅｔｒａｈｅｄｒＯｎ，ｇ』−、３８９５（１
９６９）参照）〕等がある。As described below, there are various types of Tori-type sesquiterpene compounds with unique structures, and compounds that are considered to be easily derived from the above-mentioned conferteiforin include, for example, the African
A strong feeding inhibitor against armywOrm'XC (A
For example, from the compound (7) of the present invention, via conferteiforin and isodorimenine, 1Lr'-\1*-Warburganal [A] and agandensidial (Apndencidial) [also known as CinnamOdial] [B], Polygodial (POlygOdial) also known as Tadeonal (T
adeOnal)] [C], [1. Kub0,. Yue
Wei1ee,. M. Pettei,. F. Pi1ki
ewickzandK. Nakanishi,. CheM
．． COmln]. , 1976, 1013] and skin fungi (e.g., TrycOphytOn, MicroOs
Cinnamolide (Cinn & MOlide) [D], [L. CanOn
ica,. A. Corbella,. P. GaribO
ldi,. G. TommiandJ. Krepinsk
ianDG. Ferrari C. Casagrand
e,. TetrahedrOn, g''-, 3895 (1
969)] etc.
を合成する経路としては、次の工程を挙げることができ
る。As a route for synthesizing , the following steps can be mentioned.
本願発明者らは、先に１−アビエチン酸から、コンフエ
ルテイフオリン、インドリメニン（ＩｓＯｄｒｉｍｃｎ
ｉｎ）等のセスキテルペン化合物の合成法を開発したが
、（日本薬学会第９６年会（１９７６年）講演要旨集第
分冊第１９７頁、同第９７年会（１９７７年）講演要旨
集第分冊第１９７頁、特願昭５２−３８６２８号明細書
、特開昭５３−３４７６８号公報参照）、別途に上記セ
スキテルペン化合物を合成する方法について鋭意研究の
結果、入手の容易なβ−ヨノン（β一１０ｎｅｎｅ）（
１）から極めて短工程でコンフエルティフォリン、イソ
ドリメニン等のセスキテルペン化合物を合成し得る知見
を得て本発明を完成したものである。The inventors of the present application previously discovered that 1-abietic acid was converted into conferteiforin, indolimenin (IsOdrimcn), and 1-abietic acid.
We have developed a method for synthesizing sesquiterpene compounds such as (in) (Page 197 of the 96th Annual Meeting of the Pharmaceutical Society of Japan (1976), Volume 197 of the Abstracts of Lectures, Volume 1 of the Proceedings of the 97th Annual Meeting of the Pharmaceutical Society of Japan (1977)). (see page 197, Japanese Patent Application No. 52-38628, Japanese Unexamined Patent Publication No. 53-34768), as a result of intensive research on methods for synthesizing the above sesquiterpene compounds, we found that easily available β-ionone (β-ionone) 110ne)(
The present invention was completed by obtaining the knowledge that sesquiterpene compounds such as confertifolin and isodorimenine can be synthesized from 1) in an extremely short process.
まづ、本発明の出発物質であるケトン体（５）は、本願
発明者らによつて初めて合成された新規物質であり例え
ば前記β−ヨノン（１）から次の如くにして得られる。First, the ketone body (5), which is the starting material of the present invention, is a new substance synthesized for the first time by the inventors of the present application, and can be obtained, for example, from the aforementioned β-ionone (1) in the following manner.
すなわち、β−ヨノン（１）を公知の方法により、ラネ
一・ニツケル等の触媒を用いて接触還元してジヒトロー
β−ヨノン（２）を得、〔Ｊ．ＫａｎｄｅｌｅｔａｌＡ
ｎｎ．Ｃｈｉｍ．、旦、７３（１９３９）、ＣＯｍｐｔ
，．ｒｅｎｄ．、２０５、９９４（１９３７）〕これを
ＨＣｌＯ４等の酸存在下ＣＨ（０ＣＨ３）３と反応させ
るとＣ１−ユニツト（Ｕｎｉｔ）の増した化合物、テト
ラメトキシ体（３）、アルデヒド体（４）、本発明の出
発物質であるケトン体（５）が得られる。That is, β-ionone (1) is catalytically reduced by a known method using a catalyst such as Raney and Nickel to obtain dihydro β-ionone (2) [J. KandeletalA
nn. Chim. , Dan, 73 (1939), Compt.
、． rend. , 205, 994 (1937)] When this is reacted with CH(0CH3)3 in the presence of an acid such as HClO4, compounds with increased C1-units, tetramethoxy form (3), aldehyde form (4), this Ketone body (5), which is the starting material of the invention, is obtained.
化合物（５）は化合物（３）をビリジン一ＨＢｒ−Ｈ２
Ｏで、又は化合物（４）をピリジン−ＨＢｒで処理して
も得られる。本発明によれば前記ケトン体（５）を出発
物質となし、これをα−ハロゲノ酸エステル、例えばＣ
ｌＣＨ２ＣＯＯＣＨ３を用いて、ＣＨ３ＯＮａｌＣ２Ｈ
，ＯＮａ．ｔ−Ｃ４Ｈ９ＯＫ等の存在下でダルツエンス
（Ｄａｒｚｅｎ８）縮合を行なつてエポキシ体（６）が
得られる。この際反応温度、反応時間はそれぞれ−２５
る〜３０℃、１〜３時間が適当である。次いで、得られ
たエポキシ体（６）を加熱処理すれば、本発明の目的物
であるフラノセスキテルペン化合物（７）を得るが、反
応温度、反応時間はそれぞれ１０）〜１５０℃と、３０
分〜１時間が適当である。これらの化合物（６）、（７
）は新規化合物である。Compound (5) converts compound (3) into pyridine-HBr-H2
or by treating compound (4) with pyridine-HBr. According to the present invention, the ketone body (5) is used as a starting material, and this is used as an α-halogenoic acid ester, for example, C
CH3ONalC2H using lCH2COOCH3
, ONa. Epoxy compound (6) is obtained by performing Darzen8 condensation in the presence of t-C4H9OK or the like. At this time, the reaction temperature and reaction time were each -25
~30°C for 1 to 3 hours is appropriate. Next, the obtained epoxy compound (6) is heat-treated to obtain the furanosesquiterpene compound (7) which is the object of the present invention, but the reaction temperature and reaction time are 10) to 150°C and 30°C, respectively.
Appropriate time is 1 minute to 1 hour. These compounds (6), (7
) is a new compound.
次に、本発明を実施例によつて説明する。実施例（５）
１３．７６６ｔ（５１ｍｍ０１）とＣｌＣＨ２ＣＯＯＭ
ｅ（ＭＷ＝１０８．５３）１６．−６０３Ｖ（５１Ｘ３
ｍｍ０１）を無水エーテル１５０ｍ１に溶解させ、寒剤
冷却下、Ｎ２ガスを通じながらナトリウムメチラート８
．２６２ｔ（５１×３ｍｍ０１）（使用直前減圧下、１
５０℃で３０分乾燥したもの）を加え、その後、Ｎ２ガ
スを止めて、２時間攪拌する。Next, the present invention will be explained with reference to examples. Example (5)
13.766t (51mm01) and ClCH2COOM
e(MW=108.53)16. -603V (51X3
mm01) was dissolved in 150 ml of anhydrous ether, and sodium methylate 8 was dissolved while passing N2 gas under cryogen cooling.
．． 262t (51 x 3mm01) (under reduced pressure just before use, 1
(dried at 50°C for 30 minutes) was added, then the N2 gas was turned off and the mixture was stirred for 2 hours.
反応終了後含水酢酸（酢酸：Ｈ２Ｏ＝１：１５）３０１
１１を加え、エーテルから抽出する。エーテル層を飽和
ＮａＨＣＯ３溶液、飽和食塩水で順次洗浄し、Ｎａ２ｓ
Ｏ４で脱水乾燥後、溶媒を溜去すると油状物を得る。こ
れをシリカゲル１５０ｆを用いてカラムクロマトに付し
、ｎ−ヘキサン：酢酸エチル＝２０：１〜１０：１の溶
出部から単一な油状物（６）１４．６８ｒ（８４％）を
得る。〔（６）の物理的性質〕ＧＣ−ＭＳ：Ｃｌ，Ｈ３
２Ｏ５＝３４０としてＭ＋＝３４０ｍ／１：３０８＝Ｍ
＋−ＭｅＯＨ＝３４０−３２、２７６＝Ｍ＋−２Ｍｅ０
ＨＩＲ（ＣＣｌ４）：νＭ８ｘｌ７６Ｏ、１７３５ｃｍ
ＮＭＲ（６０ＭＨｚ．ＣＤＣ１３）：δ
１．００Ｓ６Ｈ（４−ＧｌｍＭｅ２）
１．５７Ｓ３Ｈ（１０−Ｍｅ）
：［：：］各Ｓ３Ｈ（１１−（０Ｍｅ）２）３．７６Ｓ
３Ｈ（ＣＯＯＭｅ）４．４８ｔ，．Ｊ＝６Ｈｚ１１Ｈ（
１１−Ｈ）実施例 ２
エポキシ体（６）３．６１４ｔを２００℃で４５分間加
熱攪拌する。After completion of the reaction, add hydrated acetic acid (acetic acid: H2O = 1:15) 301
Add 11 and extract from ether. The ether layer was washed sequentially with saturated NaHCO3 solution and saturated saline, and Na2s
After dehydration and drying with O4, the solvent is distilled off to obtain an oil. This was subjected to column chromatography using silica gel 150f, and 14.68r (84%) of a single oily substance (6) was obtained from the eluate of n-hexane:ethyl acetate=20:1 to 10:1. [Physical properties of (6)] GC-MS: Cl, H3
As 2O5=340, M+=340m/1:308=M
+-MeOH=340-32, 276=M+-2Me0
HIR (CCl4): νM8xl76O, 1735cm
NMR (60MHz.CDC13): δ 1.00S6H (4-GlmMe2) 1.57S3H (10-Me) : [::] Each S3H (11-(0Me)2) 3.76S
3H (COOMe) 4.48t,. J=6Hz11H(
11-H) Example 2 3.614 t of epoxy body (6) was heated and stirred at 200° C. for 45 minutes.
この際生成するＭｅＯＨを溜去する。反応終了後、内容
物をシリカゲル５０７を用いてカラムクロマトに付し、
ｎ−ヘキサン：酢酸エチル＝２０：１の溶出部から単一
な油状物（７）２．３５９ｔ（８０％）を得る。〔（７
）の物理的性質〕MeOH produced at this time is distilled off. After the reaction, the contents were subjected to column chromatography using silica gel 507,
2.359 t (80%) of a single oil (7) was obtained from the eluate of n-hexane:ethyl acetate=20:1. [(7
) physical properties of
Claims (1)
ゲノ酸エステルで処理してダルツエンス（Ｄａｒｚｅｎ
ｓ）縮合せしめて式：▲数式、化学式、表等があります
▼ で表わされる化合物を得、これを加熱処理して式：▲数
式、化学式、表等があります▼で表わされる化合物を得
ることを特徴とするフラノセスキテルペン誘導体の製造
法。[Claims] 1 A furanosesquiterpene derivative represented by the following structural formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 2 Structural formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ A compound represented by is used as a starting material, and this is treated with an α-halogenoic acid ester to produce Darzen.
s) Condensation is performed to obtain a compound represented by the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and this is heated to obtain a compound represented by the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ A method for producing characteristic furanosesquiterpene derivatives.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11035778A JPS596309B2 (en) | 1978-09-08 | 1978-09-08 | Furanosesquiterpene derivatives and their production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11035778A JPS596309B2 (en) | 1978-09-08 | 1978-09-08 | Furanosesquiterpene derivatives and their production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5536439A JPS5536439A (en) | 1980-03-14 |
| JPS596309B2 true JPS596309B2 (en) | 1984-02-10 |
Family
ID=14533717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11035778A Expired JPS596309B2 (en) | 1978-09-08 | 1978-09-08 | Furanosesquiterpene derivatives and their production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS596309B2 (en) |
-
1978
- 1978-09-08 JP JP11035778A patent/JPS596309B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5536439A (en) | 1980-03-14 |
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