JPH01226838A - Cembrene type diterpene compound - Google Patents
Cembrene type diterpene compoundInfo
- Publication number
- JPH01226838A JPH01226838A JP63052687A JP5268788A JPH01226838A JP H01226838 A JPH01226838 A JP H01226838A JP 63052687 A JP63052687 A JP 63052687A JP 5268788 A JP5268788 A JP 5268788A JP H01226838 A JPH01226838 A JP H01226838A
- Authority
- JP
- Japan
- Prior art keywords
- type diterpene
- cembrene
- compounds
- formula
- chromatography
- 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
- 229930004069 diterpene Natural products 0.000 title claims abstract description 9
- -1 diterpene compound Chemical class 0.000 title claims description 9
- DMHADBQKVWXPPM-PDDCSNRZSA-N (1e,3z,6e,10z,14s)-3,7,11-trimethyl-14-propan-2-ylcyclotetradeca-1,3,6,10-tetraene Chemical compound CC(C)[C@@H]\1CC\C(C)=C/CC\C(C)=C\C\C=C(\C)/C=C/1 DMHADBQKVWXPPM-PDDCSNRZSA-N 0.000 title abstract 2
- DMHADBQKVWXPPM-SBHJBAJOSA-N cembrene Natural products CC(C)C1CCC(=C/CCC(=CCC=C(C)/C=C/1)C)C DMHADBQKVWXPPM-SBHJBAJOSA-N 0.000 title abstract 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 9
- 238000004587 chromatography analysis Methods 0.000 abstract description 6
- 206010028980 Neoplasm Diseases 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 230000002265 prevention Effects 0.000 abstract description 3
- 238000010898 silica gel chromatography Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 230000000711 cancerogenic effect Effects 0.000 abstract description 2
- 231100000315 carcinogenic Toxicity 0.000 abstract description 2
- 239000000284 extract Substances 0.000 abstract description 2
- YVPDVEMKKLARPZ-JTSWHKSPSA-N 2-[(1r,3e,7e,11e)-4,8,12-trimethylcyclotetradeca-3,7,11-trien-1-yl]prop-2-enal Chemical compound C\C1=C/CC\C(C)=C\C[C@H](C(=C)C=O)CC\C(C)=C\CC1 YVPDVEMKKLARPZ-JTSWHKSPSA-N 0.000 abstract 1
- HUQBQHDAVDLYEP-YGNYIHPWSA-N 2-[(1r,3z,7z,11z)-4,8,12-trimethylcyclotetradeca-3,7,11-trien-1-yl]prop-2-enoic acid Chemical compound C\C1=C\CC\C(C)=C/C[C@H](C(=C)C(O)=O)CC\C(C)=C/CC1 HUQBQHDAVDLYEP-YGNYIHPWSA-N 0.000 abstract 1
- JLLBBBITYJIESU-OPFQSLALSA-N C1C\C(C(C)C)=C/C=C(C)/CC\C=C(CO)\CC[C@@H]2O[C@]21C Chemical compound C1C\C(C(C)C)=C/C=C(C)/CC\C=C(CO)\CC[C@@H]2O[C@]21C JLLBBBITYJIESU-OPFQSLALSA-N 0.000 abstract 1
- YADVRLOQIWILGX-MIWLTHJTSA-N Sarcophytol A Chemical compound CC(C)C/1=C/C=C(C)/CC\C=C(C)\CC\C=C(C)\C[C@@H]\1O YADVRLOQIWILGX-MIWLTHJTSA-N 0.000 abstract 1
- 241000512742 Sinularia Species 0.000 abstract 1
- YVPDVEMKKLARPZ-UHFFFAOYSA-N Sinularial A Natural products CC1=CCCC(C)=CCC(C(=C)C=O)CCC(C)=CCC1 YVPDVEMKKLARPZ-UHFFFAOYSA-N 0.000 abstract 1
- HUQBQHDAVDLYEP-UHFFFAOYSA-N Sinularic acid A Natural products CC1=CCCC(C)=CCC(C(=C)C(O)=O)CCC(C)=CCC1 HUQBQHDAVDLYEP-UHFFFAOYSA-N 0.000 abstract 1
- 150000004141 diterpene derivatives Chemical class 0.000 abstract 1
- 239000012530 fluid Substances 0.000 abstract 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 abstract 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical group O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- YADVRLOQIWILGX-UHFFFAOYSA-N sarcophytol N Natural products CC(C)C1=CC=C(C)CCC=C(C)CCC=C(C)CC1O YADVRLOQIWILGX-UHFFFAOYSA-N 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- JLLBBBITYJIESU-PMACEKPBSA-N sinulariol C Natural products CC(C)C1=CC=C(/C)CCC=C(/CO)CC[C@@H]2O[C@@]2(C)CC1 JLLBBBITYJIESU-PMACEKPBSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 201000011510 cancer Diseases 0.000 description 3
- 239000012156 elution solvent Substances 0.000 description 3
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 3
- 150000002632 lipids Chemical class 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 239000000287 crude extract Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 210000003918 fraction a Anatomy 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 244000175448 Citrus madurensis Species 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical class CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 235000017317 Fortunella Nutrition 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000013040 bath agent Substances 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- SLUNEGLMXGHOLY-UHFFFAOYSA-N benzene;hexane Chemical compound CCCCCC.C1=CC=CC=C1 SLUNEGLMXGHOLY-UHFFFAOYSA-N 0.000 description 1
- BFAKENXZKHGIGE-UHFFFAOYSA-N bis(2,3,5,6-tetrafluoro-4-iodophenyl)diazene Chemical compound FC1=C(C(=C(C(=C1F)I)F)F)N=NC1=C(C(=C(C(=C1F)F)I)F)F BFAKENXZKHGIGE-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- QSKWJTXWJJOJFP-UHFFFAOYSA-N chloroform;ethoxyethane Chemical compound ClC(Cl)Cl.CCOCC QSKWJTXWJJOJFP-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930192242 sarcophytol Natural products 0.000 description 1
- 230000000276 sedentary effect Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
Landscapes
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（座業上の利用分野）
本発明はｖｒ現なセンプラン型ジテルペン化合物に関す
るものでるる。DETAILED DESCRIPTION OF THE INVENTION (Field of Sedentary Use) The present invention relates to a senpuran type diterpene compound.
（従来の技＊）
センプラン型ジテルペン化合物の１櫨でおるザルコツイ
トールＡお工ひＢは癌化の過程を抑制することが知られ
、がんの予防お工び治療に有用な化合物でおる（符公昭
６２−６１００７号、ｉ４６回癌学会飴会 予桶東 第
１３頁、１９８７年９月）０
本発明者は、ザルコツイトールＡお↓びＢ周辺化合物は
同様な効果が期待できることから、ウミトサカ目ハケカ
タトサ力（５ｉｎｕｌａｒｉａ ｍａｙｉ）ｚ＃）新規
なセンプラン型ジテルペン化合物の探索を行い、下記一
般式（Ｉ）
（式中ＲはＣＨ，ＯＨ、ＣＨＯｌＣＯＯＨを辰わす。）
で示嘔れるセンプラン型ジテルペン化合物を見い出し本
発明を完成するに至った。(Conventional technique*) Sarcotuitol A and B, which are one of the senpuran-type diterpene compounds, are known to inhibit the process of canceration, and are useful compounds for the prevention and treatment of cancer. Publication No. 62-61007, i46th Cancer Society Candy Party Yooke Higashi, page 13, September 1987) 0 The present inventors believe that compounds around Sarcotuitol A↓ and B can be expected to have similar effects, and therefore We searched for a new senpuran-type diterpene compound, which has the following general formula (I) (wherein R represents CH, OH, or CHOlCOOH).
The inventors have discovered a senpuran-type diterpene compound that exhibits the following properties and completed the present invention.
（発明の構成）
本発明に係わる新規なセンプラン型ジテルペン化合物は
前記一般式（Ｉ）で表わ石れる化合物である。式中、Ｒ
がＣ）１１．ＯＨのものｔシヌラリオ−ルＣ（５１ｎｕ
１ａｒｉｏＩＣ） と称し、ＲがＣＨＯｏものをシス
２リアールＡ （５ｉｎｕｌａｒｉａｌ Ａ ） Ｒ
がＣ０ＯＨのものをシヌラリツクアシドＡ （５ｉｎｕ
−１ａｒｉｃ ａｃｉｄ Ａ ） と称す。(Structure of the Invention) The novel senpuran type diterpene compound according to the present invention is a compound represented by the above general formula (I). In the formula, R
isC)11. OH one Cinulariol C (51nu
1arioIC), and the one where R is CHOo is called cis2realA (5inural A) R
is C0OH.
-1aric acid A).
本発明に係わる化合物は、列えばウミトサカ目 ハケカ
タトサカ（８１ｎｕｌａｒｉａ ｍａｙｉ ） ｋｂ
好ましくは狭面の粘稠法がなくなる程度に脱水し＃ｔＩ
ｌ断した恢、溶剤抽出で抽出し、それをシリカゲルカラ
ムクロマトグラフィー等のクロマトグラフィーにより分
離梢製することによって得られる。The compounds according to the present invention include 81nularia mayi kb
Preferably, it is dehydrated to the extent that the narrow viscosity method disappears #tI
It can be obtained by cutting it, extracting it by solvent extraction, and separating it by chromatography such as silica gel column chromatography.
抽出＃剤としては、例えばメタノール、エタノール、イ
ングロバノール等の低級アルコール類、クロロホルム寺
のハロゲン化炭化水系類、トルエン、ベンゼン、ヘキサ
／、ヘプタン等の炭化水素類、エチルエーテル、イソプ
ルピルエーテル、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寺のケト／訓、酢酸エチル寺のエ
ステル類の有機浴剤ま九はこれらの混合浴剤が挙げられ
る。Examples of the extraction agent include lower alcohols such as methanol, ethanol, and inglobinol, halogenated hydrocarbons such as chloroform, hydrocarbons such as toluene, benzene, hexa/heptane, ethyl ether, isopropyl ether, Examples of organic bath agents include ethers such as dioxane, acetone, methyl ethyl ketone, and ethyl acetate esters.
抽出操作中は＠；ｕＪＪ５ｔ、分の分解を避けるため、
なるべく空気との慣触面稙が小さくなる工うにするか、
不活性ガス存囲気下で行うことが望でしい０
佃出はＮ偏でもａＴ＊″′Ｃδるが゛抽出を早めるため
には、加温下に行っても工い。During the extraction operation, to avoid decomposition of @;uJJ5t,
Try to make the contact surface with the air as small as possible.
It is preferable to carry out the process in the presence of an inert gas.Although the extraction may be N-biased, aT*'''Cδ may be carried out, but in order to speed up the extraction, the process may be carried out under heating.
常法に工す浅漬と分離して得られた抽出ａに、常法に工
り溶媒を留去して、粗抽出智を得ることができる。A crude extract can be obtained by distilling off the solvent in a conventional manner to the extraction a obtained by separating it from shallow pickling in a conventional manner.
粗抽出物はＮ法〔ψ１」えはフォルシュ（Ｊ、Ｆｏｌｃ
ｈ）の方法−フォルシュら、ジャーナル オプ バイオ
ロジカル ケミストリー（Ｊ、 Ｂ１１１． Ｃｈｅｍ
、 ）２２６＠、４９７貞、１９５７年、アメリカ画参
照〕により、脂質画分に分画することがでさる０
かくして得られたハケカタトサ力の抽出物の脂質画分の
性状は、粘＠恍の茶褐色の油状である０
史に梢喪するには、クロマトグラフィーに工れば工い。The crude extract was obtained using the N method [ψ1].
Method h) - Forsch et al., Journal op Biological Chemistry (J, B111. Chem
, ) 226@, 497 Sada, 1957, American painting], the properties of the lipid fraction of the thus obtained Hakekatosa Chikara extract are as follows: It is a brownish oily substance that can be removed by chromatography.
クロマトグラフィーは、カラムクロマトグラフィーお工
ひ調表出薄増クロマトグラフィーの何れでもよい。The chromatography may be either column chromatography or exposure chromatography.
カラムクロマトグラフィーの充填剤としては、シリカゲ
ル、アルミナ、セルロースパウダー、活性炭等が用いら
れる。溶出溶剤としては、充填剤に応じて適宜選沢決定
すれば良いが、充填剤としてシリカゲルを用いた場合に
は、ヘキサン−ベンゼンの混合溶媒が好適でろる。ヘキ
サンとベンゼンの混合比は、３：１〜１：１（容積比）
程度が好適である。ま九、得られた粗分画は、充填剤や
溶出溶媒を変えて、更にカラムクロマトグラフィーによ
り精製・単離することもできる。Silica gel, alumina, cellulose powder, activated carbon, etc. are used as packing materials for column chromatography. The elution solvent may be appropriately selected depending on the filler, but when silica gel is used as the filler, a mixed solvent of hexane-benzene is suitable. The mixing ratio of hexane and benzene is 3:1 to 1:1 (volume ratio)
degree is suitable. (9) The obtained crude fraction can be further purified and isolated by column chromatography by changing the packing material and elution solvent.
調製用薄増クロマトグラフィーのゲルトシては、シリカ
ゲル、アルミナ、セルロースパウダー寺が用いられる。Silica gel, alumina, and cellulose powder are used as gels for preparative thickening chromatography.
展開溶媒としては、クロロホルムまたはクロロホルム−
エーテル混合溶媒が好適である。As a developing solvent, chloroform or chloroform-
Ether mixed solvents are preferred.
本発明に係わる化合物は空気酸化を受けやすいので、浴
剤抽出の際と同様、取扱い、保存等には注意が必要であ
る。Since the compounds related to the present invention are susceptible to air oxidation, care must be taken when handling and storing them, as in the case of bath additive extraction.
かくして、本発明の前記一般式（Ｉ）で示される新規な
センプラン型ジテルペン化合物を得ることかでさる。In this way, a novel senpuran-type diterpene compound represented by the general formula (I) of the present invention can be obtained.
（発明の効果）
本発明の化合物は、発癌プロモーション過程を抑制する
ザルコツイトールＡ、Ｂと同様、癌の治療お工ひ予防に
使用し得る。また、ザルコフイトールＡｉ？工びＢの合
成中間体としてもＭ用である。(Effects of the Invention) The compounds of the present invention can be used for the treatment and prevention of cancer, similar to sarcotuitol A and B, which suppress the carcinogenic promotion process. Also, sarcophytol Ai? It is also used as a synthetic intermediate for process B.
（実施汐ＩＪ）
以下に実施ｒｌＪを挙げて、本発明？更に詳細に説明す
るが、本発明はその要旨を超えない限り、以下の災ｈガ
Ｖｃニジ制限金受けるものでにない。(Implementation IJ) Is the present invention listed below? As will be explained in more detail, the present invention is not intended to be subject to the following limitations unless it goes beyond its gist.
実施例１
沖縄石垣島にて昭和５８年６月に採駿し友ハケカタトサ
力１５．８ゆをおシーむね脱水し、＃ｌかく刻み、最初
に５０ｔのメタノール、次いで５０ｔのクロロホルム−
メタノール（容積比２：１）で、充分に室−にて佃出し
友。佃出Ｍｋ、ｍ圧下浴媒を留去した０佃出残の乾燥嵐
址は、豹５ゆ（但し塩分を営む）でめった。次いでフォ
ルシュらの万ｆｆｚ ［Ｊ、 Ｆｏｌｃｈら、ジャーナ
ル オプバイオロジカル ケミストリー（Ｊ、 Ｂｉｏ
ｌ、 Ｃｈｅｍ）２２６巻、４９７頁、１９５７年、ア
メリカ国参照〕に工す、脂質画分に分画した。かくして
、粘梱の茶褐色の旧状の脂買部２．０７ｋｐ金得た〇脂
質画分のうち１７５ｆ’ｉｉヘキサンに浴かし、シリカ
ゲル（ワコーグルＣ−３００和光紬薬［）１．５ｋｌｉ
Ｉのカラムクロマトグラフィーで分離した。Example 1 A 15.8 yen (15.8 yu) fish harvested in Ishigaki Island, Okinawa in June 1980 was dehydrated, chopped into #l pieces, and first mixed with 50 tons of methanol and then 50 tons of chloroform.
Dispense the mixture thoroughly with methanol (volume ratio 2:1) at room temperature. The dried residue of Tsukuda Mk, m after the bath medium was distilled off under 0.0 Tsukuda pressure was dried in a 5-year-old tank (however, it handles salt production). Next, Folch et al.'s [J, Folch et al., Journal Opbiological Chemistry (J, Bio
1, Chem), Vol. 226, p. 497, 1957, USA], and fractionated into a lipid fraction. In this way, we obtained 2.07 kl of the brownish old fat part of the sticky bag. Of the lipid fraction obtained, 175 f'ii was soaked in hexane, and 1.5 kli of silica gel (Wako Glu C-300 Wako Tsumugi [)] was obtained.
It was separated by column chromatography.
溶出溶媒と、各号−の関係は表−１の通りでるる。The relationship between the elution solvent and each item is shown in Table 1.
表−１
骨 Ｒ＝ ＣＨ２０Ｈ
軸 Ｒ＝ＣＨＯ
Ｈ４＃ Ｒ＝Ｃ００Ｈ
次−１中、浴出温媒の混合比は、容積で示した。（以下
同様ン
かくして得られた分画Ａのｍ分金シリカゲル金柑いたカ
ラムクロマトグラフィーＶ′Ｃ工り精製した。Table-1 Bone R= CH20H Axis R=CHO H4# R=C00H In the following-1, the mixing ratio of the bathing heating medium was expressed by volume. (Hereinafter, fraction A of the thus obtained fraction A was purified by column chromatography using gold silica gel kumquat.
即ち、サンプルの５０＋Ｆ！電のシリカゲル金柑い、分
画Ａを最小皺のへキサンに浴鱗し、ヘキサン−酢酸エチ
ル（９７，５： ２．５ ）でシヌラリアールＡを含む
分画を得、ついで１０％硝酸銀処理したシリカゲルカラ
ムクロマトグラフィーでヘキサン−酢酸エチル（９５：
５）に工って、シヌラリアールＡを梢装し友。That is, 50+F of the sample! The silica gel containing Cinular Real A was immersed in minimally wrinkled hexane to obtain the fraction containing Cinular Real A with hexane-ethyl acetate (97,5:2.5), and the silica gel was then treated with 10% silver nitrate. Column chromatography using hexane-ethyl acetate (95:
5), and installed Cinular Real A in the treetops.
分画ＢＩ７）部分を、同様の方法にてヘキサン−酸ハエ
チル（７３：１７）でシヌラリオールＣお工ひシヌラリ
ツクアシドＡを含む分画を得、ついで、１０％硝酸銀処
理し次シリカゲルカラムクロマトグラフィーでヘキサン
−酢酸エチル（９０： １０ ）でシヌラリオールＣを
、（８０：２０）でシヌラリツクアシドＡｉ得た。Fraction BI7) was treated with hexane-ethyl acid (73:17) to obtain a fraction containing Cinulariol C and Cinulariol C acid A in the same manner, treated with 10% silver nitrate, and then subjected to silica gel column chromatography. Cinulariol C was obtained using hexane-ethyl acetate (90:10) and Cinulariol acid Ai was obtained using (80:20).
以下に、上記で得られ九本発明化合物の物江徨を示す。The properties of the nine compounds of the present invention obtained above are shown below.
■ シヌラリオールＣ
無色細状
〔α〕。＋１４°（ｃｍα８４ ＣＨＣ２ｓ ）ｅａ
ｔ
赤外スペクトル ν ｃｍ−” ３３５０．１
６４５゜ａｘ
ＮＭＲスペクトル ＣＤＣｌ３中でＴＭ８’ｉ内部標
準としＩＨ−ＮＭＲｉ、２７０ＭＨｚ。■ Cinulariol C Colorless thin shape [α]. +14° (cmα84 CHC2s)ea
t Infrared spectrum ν cm-” 3350.1
645° ax NMR spectrum IH-NMRi with TM8'i internal standard in CDCl3, 270 MHz.
１３Ｃ−ＮＭＲは、２２．５ＭＨｚで 抑」定した。13C-NMR at 22.5MHz suppressed.
ＩＨ−ＮＭＲｉ： １．５６（６Ｈ，ａ）、１．５９（
ｊＨ，ｒｓ）。IH-NMRi: 1.56 (6H, a), 1.59 (
jH,rs).
ａ、０９（２Ｈ，ｓ、 １６−Ｈ）、 ４．９０ ａｎ
ｄ ５．０９（ｅａｃｈ ＩＨ，ｓ、１７−Ｈ）、４．
９７（ＩＨ，ｂｒ ｔ、Ｊ：＆６Ｈ２）。a, 09 (2H, s, 16-H), 4.90 an
d 5.09 (each IH, s, 17-H), 4.
97 (IH, br t, J:&6H2).
ＳＯ６（Ｉ Ｈ，ｏｖｅｒｌａｐｐｅｄ ｂｒ ｔ、
Ｊ＝＆２Ｈｚ ）、 ５．１７（Ｉ Ｈ，ｂｒ ｔ、
Ｊ ＝ＥＬ５Ｈ２）、 １３Ｃ−ＮＭＲｉ： １５−３
（ｑ）。SO6 (I H, overlapped br t,
J=&2Hz), 5.17(I H, br t,
J = EL5H2), 13C-NMRi: 15-3
(q).
１ ！ａ６ （ｑ）、 １７．９ （ｑ九２５８（ｔ）
、 ２４．９（ｔ）、 ２９．２（を九６Ｓ１（す、
３４．２（ｔ）、 ３９．０（ｔ）、 ３９．５（ｔ）
。1! a6 (q), 17.9 (q9258(t)
, 24.9(t), 29.2(96S1(su,
34.2(t), 39.0(t), 39.5(t)
.
４２．２ （ｄ入６５．０（ｔ、ｌ、 １０＆６（ｔ）
、 １２２．５（ｄ）。42.2 (d included 65.0 (t, l, 10 & 6 (t)
, 122.5(d).
１２Ａ９（ｄ）、１２＆０（ｄ）、１３五５（ａ）、１
３ｉ８（ｓ）。12A9(d), 12&0(d), 1355(a), 1
3i8(s).
１５ｃＬ２（ａ）、１５Ａ１（す。15cL2(a), 15A1(su.
烏分購舵マススペクトル
Ｃ２，）Ｈ３２０Ｍ ｍ／ｚ 分析７１ ２８８．
２３５７８計算１直 ２８８． ２４５２８
■ シス２リアールＡ
無色油状
（ａ）、 ＋ １２．５°（ｃｍα６４ ＣＨＣｌ３
）ｅａｔ
赤外スヘ／ トルνｃｒｈ−” ２７００．１６９５
゜ａｘ
１６２０．９４０
紫外スペクトル λＥ″ｏＨｎｍ末端吸収のみａｘ
ＮＭＲスペクトル
ＩＨ−ＮＭＲδ： １．５３．１．５８．１．６０（
ｅａｃｈ ３Ｈ，ｓ）。Karasubun steering mass spectrum C2,) H320M m/z analysis 71 288.
23578 Calculation 1 shift 288. 24528 ■ Cis 2 Real A Colorless oil (a), + 12.5° (cmα64 CHCl3
) eat infrared suhe/torvcrh-” 2700.1695
゜ax 1620.940 Ultraviolet spectrum λE″oHnm terminal absorption only ax NMR spectrum IH-NMRδ: 1.53.1.58.1.60 (
each 3H,s).
２．６２（ＩＨ，ｍ、 １−Ｈ）、 ４．９７（ＩＨ，
ｂｒ、 ｄｄ、 Ｊ＝４５゜ａ５Ｈ２）、ＡＯ７（ＩＨ
，ｍ）、！１１５（ＩＨ，ｂｒ ｄａ、Ｊ＝７．７．７
．０Ｈｙｔ）、 ＆ｏ２ ａｎｄ ＆２４（ｅａｃｈ
ＩＨ，ｓ、 １７−Ｈ）、９．５５（ＩＨ，８，１６
−Ｈ）、１３Ｃ−ＮＭＲδ：１ ’ｔ５ （ｑ）、 Ｉ
Ｓ、６ （ｑ）、 １７．７ （ｑ、ｌ、 ２五８（
ｔ）、 ２４．９（ｔ、ｌ、 ２９．１ （ｔ）、 ３
２．４（ｔ、ｌ、 ５４．３（ｔ）、 ３＆６（ｄ）。2.62 (IH, m, 1-H), 4.97 (IH,
br, dd, J=45°a5H2), AO7(IH
,m),! 115 (IH, br da, J=7.7.7
．． 0Hyt), &o2 and &24(each
IH, s, 17-H), 9.55 (IH, 8, 16
-H), 13C-NMRδ: 1 't5 (q), I
S, 6 (q), 17.7 (q, l, 258 (
t), 24.9 (t, l, 29.1 (t), 3
2.4(t, l, 54.3(t), 3&6(d).
３９．０ （ｔ）、 ５９．５ （ｔ）、 １２２．６
（ｄ）、 １２五３ （ｄＪ。39.0 (t), 59.5 (t), 122.6
(d), 1253 (dJ.
１２５．９（ｄ）、１３Ａ５（ｔ）、１３１８（ｓ）、
１３５．７（ａ）。125.9(d), 13A5(t), 1318(s),
135.7(a).
１５４．５（ａ）、１９４．８（ｄ）。154.5(a), 194.8(d).
高分子ｈＮ１５マススペクトル
Ｃ２０Ｈ３Ｏ０Ｍ ｍ／ ｚ 分析値 ２８６．２
３０２０計１−−Ｌイ１自Ｌ ２８６，２２５２０■
シヌラリツクアシドＡ
無色油状
〔α）Ｄ＋１９．７（Ｃ＝（Ｉ７１ＣＨＣｌ３）ｎθａ
ｔ
赤外スペクトル ｙ ｃｍ−” ２７００〜
３６００（ｂｒ、）ａｘ
１６９Ｂ、 １６２５．９５Ｏ
ＮＭＲスペクトル
ＩＨ−ＮＭＲδ： １５５，１．５８，１．５９（ｅ
ａｃｈ ３Ｈ，ａ）。Polymer hN15 mass spectrum C20H3O0M m/z analysis value 286.2
3020 total 1--L 1 own L 286,22520 ■
Cinularic acid A Colorless oil [α)D+19.7(C=(I71CHCl3)nθa
t Infrared spectrum y cm-” 2700~
3600 (br,) ax 169B, 1625.95O NMR spectrum IH-NMR δ: 155, 1.58, 1.59 (e
ach 3H, a).
２．５８（ＩＨ，ｍ、 １−Ｈ）、 ４．９７（Ｉ Ｈ
，ｂｒ ｄｄ、 Ｊ ＝＆２゜５．５Ｈｚ方５．０７（
Ｉ Ｈ，ｂｒ ｄａ、Ｊ＝４４５．’ｘ５Ｈｚ）、Ｓ、
１７（ＩＨ，ｂｒ ｄｄ、Ｊ＝７．７，７．３Ｈｚル５
．６Ｓ ａｎｄ ＆３５（ｅａｃｈ ＩＨ，ａ、１７
−Ｈ）、１３Ｃ−ＮＭＲδ： １５．．５＜ｑ）。2.58 (IH, m, 1-H), 4.97 (IH
,br dd, J =&2゜5.5Hz side 5.07(
I H, br da, J=445. 'x5Hz), S,
17 (IH, br dd, J=7.7, 7.3Hz le 5
．． 6S and &35 (each IH, a, 17
-H), 13C-NMRδ: 15. ．． 5<q).
１５．６（ｑル１７．７ （（Ｉ）、 ２３９ （す、
２４．９（す、２９．３（す。15.6 (qle 17.7 ((I), 239 (su,
24.9(su), 29.3(su.
３２．９ （を九３４．３（ｔ）、 ３９．１ （す、
３９７（す、 ３９．７ （ｄ）。32.9 (934.3(t), 39.1 (su,
397 (su, 39.7 (d).
１２２．５（ｄ）、１２五５（ａ）、１２５．９（ａ）
、１２６ｔ）（ｔ）。122.5(d), 125.5(a), 125.9(a)
, 126t) (t).
１６五５（８人 １３４．０（ｓ）、１１ａ６（ｓ）、
１４４．３（８）。1655 (8 people 134.0(s), 11a6(s),
144.3(8).
１７２．９（ａ）。172.9(a).
局分肩龍マススペクトル
Ｃ２＠Ｈ３Ｏ０１Ｍ ｍ／ ｚ 分析ｆｉｊＬ ３
０２．２２６５６討Ｘ１直 ３０２．２２４５６Kyobun Shoulderyu mass spectrum C2@H3O01M m/z analysis fijL 3
02.22656 Raid X1 shift 302.22456
Claims (1)
ペン化合物 ▲数式、化学式、表等があります▼（ I ） （式中ＲはＣＨ＿２ＯＨ、ＣＨＯ、ＣＯＯＨを表わす。 ）[Claims] 1. A senpuran-type diterpene compound represented by the following general formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R represents CH_2OH, CHO, COOH.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63052687A JPH01226838A (en) | 1988-03-08 | 1988-03-08 | Cembrene type diterpene compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63052687A JPH01226838A (en) | 1988-03-08 | 1988-03-08 | Cembrene type diterpene compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01226838A true JPH01226838A (en) | 1989-09-11 |
Family
ID=12921800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63052687A Pending JPH01226838A (en) | 1988-03-08 | 1988-03-08 | Cembrene type diterpene compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01226838A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60253428A (en) * | 1984-05-30 | 1985-12-14 | 住友電気工業株式会社 | Fiberscope with bending mechanism |
| JPS61196702U (en) * | 1985-05-31 | 1986-12-08 | ||
| JPS63169101U (en) * | 1987-04-27 | 1988-11-02 |
-
1988
- 1988-03-08 JP JP63052687A patent/JPH01226838A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60253428A (en) * | 1984-05-30 | 1985-12-14 | 住友電気工業株式会社 | Fiberscope with bending mechanism |
| JPS61196702U (en) * | 1985-05-31 | 1986-12-08 | ||
| JPS63169101U (en) * | 1987-04-27 | 1988-11-02 |
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