JP2513655B2 - Novel diterpenes and method for producing the same - Google Patents
Novel diterpenes and method for producing the sameInfo
- Publication number
- JP2513655B2 JP2513655B2 JP61309877A JP30987786A JP2513655B2 JP 2513655 B2 JP2513655 B2 JP 2513655B2 JP 61309877 A JP61309877 A JP 61309877A JP 30987786 A JP30987786 A JP 30987786A JP 2513655 B2 JP2513655 B2 JP 2513655B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- data
- represented
- diterpenes
- general formula
- 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
- 229930004069 diterpene Natural products 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 125000000567 diterpene group Chemical group 0.000 title description 8
- 240000002768 Alpinia galanga Species 0.000 claims description 7
- 235000006887 Alpinia galanga Nutrition 0.000 claims description 7
- 150000004141 diterpene derivatives Chemical class 0.000 claims description 7
- 241000234299 Zingiberaceae Species 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 description 33
- 238000001819 mass spectrum Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- UDKRLAJJSYRYRU-VYMYIBDJSA-N Galanal A Chemical compound O=C[C@]1([C@H](CC(=CC2)C=O)O)[C@H]2[C@@]2(C)CCCC(C)(C)[C@@H]2CC1 UDKRLAJJSYRYRU-VYMYIBDJSA-N 0.000 description 6
- UDKRLAJJSYRYRU-UHFFFAOYSA-N Galanal B Natural products C1C=C(C=O)CC(O)C2(C=O)C1C1(C)CCCC(C)(C)C1CC2 UDKRLAJJSYRYRU-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- UDKRLAJJSYRYRU-NIMBFUQJSA-N (4as,6as,7r,11ar,11bs)-7-hydroxy-4,4,11b-trimethyl-1,2,3,4a,5,6,7,8,11,11a-decahydrocyclohepta[a]naphthalene-6a,9-dicarbaldehyde Chemical compound O=C[C@]1([C@@H](CC(=CC2)C=O)O)[C@H]2[C@@]2(C)CCCC(C)(C)[C@@H]2CC1 UDKRLAJJSYRYRU-NIMBFUQJSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- LEWJAHURGICVRE-AISVETHESA-N labdane Chemical compound CC1(C)CCC[C@]2(C)[C@@H](CC[C@H](C)CC)[C@@H](C)CC[C@H]21 LEWJAHURGICVRE-AISVETHESA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 2
- 235000013411 Alpinia speciosa Nutrition 0.000 description 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 2
- 244000041517 Etlingera elatior Species 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000000259 anti-tumor effect Effects 0.000 description 2
- 125000001865 labdane diterpenoid group Chemical group 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 241000013298 Alpinia <beetle> Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000234314 Zingiber Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 230000001851 biosynthetic effect Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001142 circular dichroism spectrum Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 235000021438 curry Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000000401 methanolic extract Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000012587 nuclear overhauser effect experiment Methods 0.000 description 1
- 235000017807 phytochemicals Nutrition 0.000 description 1
- 229930000223 plant secondary metabolite Natural products 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は新規ジテルペン類及びその製造方法に関す
る。更に詳しくは、野性のアルピニアガランガ（ショウ
ガ科）の種子から２種類の新規な骨格ジテルペン（ガラ
ナルＡ及びＢと称する）を、１種類のラブダン型ジテル
ペン及び（Ｅ）−8,17−エポキシ−ラブド−12−エン−
15,16−ジアールと共に単離する方法に関する。TECHNICAL FIELD The present invention relates to novel diterpenes and a method for producing the same. More specifically, two kinds of novel skeleton diterpenes (referred to as guaranal A and B) from wild Alpinia galanga (Ginger family) seeds are converted into one labdane type diterpene and (E) -8,17-epoxy- Loved-12-En-
It relates to a method of isolating with 15,16-Dial.
ショウガ科植物からのジテルペン類の単離に関して
は、数例が報告されているにすぎない（J.Chem.Soc.,Pe
rkin Trans.1,1979,1303;Phytochemistry,14,1059（197
5）;ibid.,15,827（1976））。Only a few cases have been reported regarding the isolation of diterpenes from ginger plants (J. Chem. Soc., Pe.
rkin Trans.1, 1979 , 1303; Phytochemistry, 14 , 1059 (197
5); ibid., 15 , 827 (1976)).
アルピニアガランガの根茎は肉料理及びカレー料理の
調理の際に食物に風味をつけるために用いられている。
本発明者らは以前にアルピニアガランガの根茎と種子か
ら抗腫瘍性物質と辛味性成分とを単離し、論文に報告し
たが、更に本発明者らはアルピニアガランガの植物化学
的要素に関する研究を続けた結果、２種類の新規な骨格
ジテルペンを、１種類のラブダン型ジテルペン及び
（Ｅ）−8,17−エポキシ−ラブド−12−エン−15,16−
ジアールと共に、抗腫瘍性作用の期待される物質として
単離することができ、本発明を完成するに至った。Alpinia galanga rhizome is used to flavor foods during cooking of meat and curry dishes.
The present inventors previously isolated an antitumor substance and a pungency component from rhizomes and seeds of Alpinia galanga, and reported in a paper. Furthermore, the present inventors further studied the phytochemical elements of Alpinia galanga. As a result, two kinds of novel skeleton diterpenes were added to one kind of labdane type diterpene and (E) -8,17-epoxy-labd-12-ene-15,16-
It could be isolated as a substance expected to have an antitumor effect together with Diar, and completed the present invention.
即ち、本発明は、下記一般式（Ｉ）または（II）で表
される新規ジテルペン類、及びアルピニアガランガ（シ
ョウガ科）の種子から誘導することを特徴とする下記一
般式（Ｉ）または（II）で表される新規ジテルペン類の
製造方法に係わるものである。That is, the present invention is characterized by being derived from novel diterpenes represented by the following general formula (I) or (II) and seeds of Alpinia galanga (Ginger family), or the following general formula (I) or ( It relates to a method for producing a new diterpene represented by II).
以下、本発明の新規ジテルペン類の製造方法を具体的
に説明する。 Hereinafter, the method for producing the novel diterpenes of the present invention will be specifically described.
市販品として購入したアルピニアガランガの種子をメ
タノールで抽出し、メタノール抽出物に水を添加した
後、ｎ−ヘキサンと共に振盪する。ｎ−ヘキサンに可溶
なフラクションをクロマトグラフィー精製して一般式
（Ｉ）及び（II）で表される２種類の新規な骨格ジテル
ペン（ガラナルＡ及びＢ）と、下記一般式（III）で表
される１種類のラブダン型ジテルペン、及び下記一般式
（IV）で表される（Ｅ）−8,17−エポキシ−ラブド−12
−エン−15,16−ジアールを単離した。Seeds of Alpinia galanga purchased as a commercial product are extracted with methanol, water is added to the methanol extract, and then shaken with n-hexane. Fractions soluble in n-hexane were purified by chromatography and represented by the two new skeleton diterpenes (Galanal A and B) represented by the general formulas (I) and (II) and the general formula (III) below. One type of labdane-type diterpene, and (E) -8,17-epoxy-labd-12 represented by the following general formula (IV)
The ene-15,16-dial was isolated.
一般式（Ｉ）で表されるガラナルＡと名付けた化合物
（１）は無色針状結晶として得られ、融点は167.0〜16
9.0℃であった。高分解能マススペクトル（318.2214）
に基づく分子式はC20H30O3であった。 The compound (1) named Galanal A represented by the general formula (I) is obtained as colorless needle crystals and has a melting point of 167.0-16.
It was 9.0 ° C. High resolution mass spectrum (318.2214)
Molecular formula based on was C 20 H 30 O 3.
この化合物（１）の13C‐NMRスペクトルのデータを表
１に、1H‐NMRスペクトルのデータを表２に示す。又、
マススペクトル（MS），比旋光度，赤外線吸収スペクト
ル（IR），紫外線吸収スペクトル（UV）のデータを以下
に示す。The data of 13 C-NMR spectrum and the data of 1 H-NMR spectrum of this compound (1) are shown in Table 1 and Table 2, respectively. or,
The data of mass spectrum (MS), specific rotation, infrared absorption spectrum (IR) and ultraviolet absorption spectrum (UV) are shown below.
MS m/z（％）:318（M+,48）,300（34）,271（25）,207
（27）,194（59）,189（42）,163（46）,149（57）,137
（81）,123（94）,112（75）,95（89）,91（94）,81（9
4）,69（100） 〔α〕Ｄ−44.0°（c0.1,CHCl3） IR（CHCl3）cm-1:3620,2940,1710,1685,1640,1460,144
5,1390,1370,1165,1055 UV（EtOH）:232nm,ε7600 この化合物（１）の1H‐NMR（CDCl3）,IR（CHCl3）及
びUV（EtOH）スペクトルはジアルデヒドの存在を示し
た。即ち、１つは通常のアルデヒド（δ10.10;1710c
m-1）、他の１つは不飽和アルデヒド（δ9.38;1685c
m-1;232nm,ε7600）であった。MS m / z (%): 318 ( M + , 48), 300 (34), 271 (25), 207
(27), 194 (59), 189 (42), 163 (46), 149 (57), 137
(81), 123 (94), 112 (75), 95 (89), 91 (94), 81 (9
4), 69 (100) [α] D −44.0 ° (c0.1, CHCl 3 ) IR (CHCl 3 ) cm −1 : 3620,2940,1710,1685,1640,1460,144
5,1390,1370,1165,1055 UV (EtOH): 232nm, ε7600 1 H-NMR (CDCl 3 ), IR (CHCl 3 ) and UV (EtOH) spectra of this compound (1) show the presence of dialdehyde. It was That is, one is a normal aldehyde (δ10.10; 1710c
m -1 ), the other one is unsaturated aldehyde (δ 9.38; 1685c
m −1 ; 232 nm, ε7600).
２級水酸基の存在はIR（3620cm-1）と1H‐NMR（δ4.0
6）によって示された。３個の３級メチルの存在を示す1
H‐NMRシグナル（δ0.77,0.80,0.88）と表１に示す13C
‐NMRシグナルは容易にラブダン骨格に適合させること
ができるものであり、公開されているデーター（Tetrah
edron Lett.,1976,1897）と同じであった。The presence of secondary hydroxyl groups is due to IR (3620 cm -1 ) and 1 H-NMR (δ4.0
6) indicated by. Indicates the presence of three tertiary methyls 1
1 H-NMR signal (δ 0.77, 0.80, 0.88) and 13 C shown in Table 1
-NMR signals can be easily adapted to the labdane skeleton and published data (Tetrah
edron Lett., 1976 , 1897).
化合物（１）の２個のアルデヒド基と第二ヒドロキシ
ル基との関係は詳しい二重共鳴実験及び化合物（１）の
PCCによる酸化によって得られる下記一般式（Ｖ） で表される化合物（５）のスペクトルと比較して決定し
た。The relationship between the two aldehyde groups of compound (1) and the secondary hydroxyl group is detailed by double resonance experiments and of compound (1).
The following general formula (V) obtained by oxidation with PCC Was determined by comparison with the spectrum of the compound (5) represented by
尚、化合物（５）は無色針状結晶で、融点は193.0〜1
95.0℃であり、13C‐NMRスペクトルのデータは表１に、
1H‐NMRスペクトルのデータは表２に示す通りである。
又、分子式，マススペクトル（MS），比旋光度，赤外線
吸収スペクトル（IR），紫外線吸収スペクトル（UV）の
データは以下に示す通りである。Compound (5) is a colorless needle crystal and has a melting point of 193.0-1.
95.0 ° C., 13 C-NMR spectrum data are shown in Table 1.
The data of 1 H-NMR spectrum is as shown in Table 2.
The data of molecular formula, mass spectrum (MS), specific rotation, infrared absorption spectrum (IR), and ultraviolet absorption spectrum (UV) are as shown below.
分子式C20H28O3 MS m/z（％）:316（M+,24）,288（42）,205（23）,178
（24）,151（34）,137（70）,123（78）,110（88）,95
（62）,91（68）,81（75）,69（100） 〔α〕Ｄ−142.9°（c0.07,CHCl3） IR（CHCl3）cm-1:2950,2850,1730,1700,1645,1460,144
0,1390,1370,1285,1275,1150,1115,1060 UV（EtOH）:223nm,ε7700 化合物（１）と化合物（５）の相関スペクトルによっ
て、化合物（１）の２個のアルデヒド基と第二ヒドロキ
シル基との関係は次の部分構造 によって示す通りに確立された。Molecular formula C 20 H 28 O 3 MS m / z (%): 316 ( M + , 24), 288 (42), 205 (23), 178
(24), 151 (34), 137 (70), 123 (78), 110 (88), 95
(62), 91 (68), 81 (75), 69 (100) [α] D -142.9 ° (c0.07, CHCl 3 ) IR (CHCl 3 ) cm -1 : 2950,2850,1730,1700, 1645,1460,144
0,1390,1370,1285,1275,1150,1115,1060 UV (EtOH): 223nm, ε7700 The correlation spectrum between compound (1) and compound (5) shows that the two aldehyde groups of compound (1) and the second The relationship with the hydroxyl group is the following partial structure Established as shown by.
この部分構造をラブダン骨格に結合させるために環Ｃ
が７員環として存在すると考えられた。７員環の存在は
表２に示した化合物（５）のNMRとIRスペクトル（1700c
m-1）によっても満足に説明することができる。In order to attach this partial structure to the labdane skeleton, ring C
Was considered to exist as a 7-membered ring. The presence of the 7-membered ring is shown in Table 2 by the NMR and IR spectra of compound (5) (1700c
It can be satisfactorily explained by m -1 ).
B/C環結合及びヒドロキシル基の相対的配置は、化合
物（１）と化合物（５）のNOE実験によって決定した。
化合物（５）のH-20とＨ−９を照射すると、それぞれH-
17とH-14の積分吸収強度が７％及び12％増加した。従っ
て、この環結合はトランスであると結論された。更に、
４％NOEが化合物（１）のC-15とC-17のプロトンの間で
観察されたことはヒドロキシル基の相対的配置がαであ
ることを実証した。The relative configurations of the B / C ring bond and the hydroxyl group were determined by NOE experiments of compound (1) and compound (5).
When compound (5) was irradiated with H-20 and H-9, H-
The integrated absorption intensities of 17 and H-14 increased by 7% and 12%. Therefore, it was concluded that this ring bond is trans. Furthermore,
The 4% NOE observed between the C-15 and C-17 protons of compound (1) demonstrated that the relative configuration of the hydroxyl groups was α.
一般式（II）で表されるガラナルＢと名付けた化合物
（２）は、無色針状結晶として得られ、融点は134.0〜1
34.5℃であり、高分解能マススペクトル（318.2213）に
基づく分子式はC20H30O3であった。The compound (2) named Galanal B represented by the general formula (II) is obtained as colorless needle crystals and has a melting point of 134.0 to 1
Was 34.5 ° C., molecular formula based on high resolution mass spectrum (318.2213) was C 20 H 30 O 3.
この化合物（２）の13C‐NMRスペクトルのデータを表
１に、1H‐NMRスペクトルのデータを表２に示す。又、
マススペクトル（MS），比旋光度，赤外線吸収スペクト
ル（IR），紫外線吸収スペクトル（UV）のデータを以下
に示す。The 13 C-NMR spectrum data and the 1 H-NMR spectrum data of this compound (2) are shown in Table 1 and Table 2, respectively. or,
The data of mass spectrum (MS), specific rotation, infrared absorption spectrum (IR) and ultraviolet absorption spectrum (UV) are shown below.
MS m/z（％）:318（M+,15）,300（９）,271（７）,194
（17）,189（17）,163（27）,149（29）,137（100）,12
3（56）,109（53）,95（65）,91（68）,81（72）,69（9
0） 〔α〕Ｄ−48.0°（c0.1,CHCl3） IR（CHCl3）cm-1:3610,2950,1710,1680,1650,1460,144
0,1390,1370,1160,1085,1050 UV（EtOH）:236nm,ε8000 この化合物（２）はスペクトルデータによって化合物
（１）に密接に関係した構造であると考えられた。化合
物（１）と（２）は、化合物（２）のPCCによる酸化が
あらゆる点で化合物（５）と同じ化合物を生じたことに
よって、ヒドロキシル基に関するエピマーであることが
実証された。化合物（２）のＣ−９とC-15のプロトンの
間では５％のNOEが観察され、このことはヒドロキシル
基の相対的配置がβであることを示した。MS m / z (%): 318 ( M + , 15), 300 (9), 271 (7), 194
(17), 189 (17), 163 (27), 149 (29), 137 (100), 12
3 (56), 109 (53), 95 (65), 91 (68), 81 (72), 69 (9
0) [α] D −48.0 ° (c0.1, CHCl 3 ) IR (CHCl 3 ) cm −1 : 3610,2950,1710,1680,1650,1460,144
0,1390,1370,1160,1085,1050 UV (EtOH): 236 nm, ε8000 This compound (2) was considered to have a structure closely related to compound (1) according to the spectral data. Compounds (1) and (2) were demonstrated to be epimers with respect to the hydroxyl group by oxidation of PCC of compound (2) with PCC in all respects yielding the same compound as compound (5). A NOE of 5% was observed between the C-9 and C-15 protons of compound (2), indicating the relative configuration of the hydroxyl groups was β.
一般式（III）で表される化合物（３）は不安定な無
色油状物として得られ、分子式C20H30O2（302.2238），
〔α〕Ｄ＋15.8°の主要なジテルペンであった。この化
合物（３）の13C‐NMRスペクトルのデータを表１に示
す。このスペクトルデータは本発明者らの以前の報告
（Chem.Pharm.Bull.,28,3452（1980））で他のアルピニ
ア属植物（Alpinia speciosa）から単離したラブダー８
（17）,12−ジエン−15,16−ジアール（下記一般式（V
I）で表される化合物（６）：〔α〕Ｄ−15.0°）と、
比旋光度以外は完全に同じであった。The compound (3) represented by the general formula (III) is obtained as an unstable colorless oily substance and has a molecular formula of C 20 H 30 O 2 (302.2238),
It was the major diterpene of [α] D + 15.8 °. The data of 13 C-NMR spectrum of this compound (3) are shown in Table 1. This spectral data was obtained from our previous report (Chem.Pharm.Bull., 28 , 3452 (1980)) and was isolated from other Alpinia plants (Alpinia speciosa).
(17), 12-diene-15, 16-diar (the following general formula (V
Compound (6) represented by I): [α] D -15.0 °),
Except for the specific rotation, they were exactly the same.
化合物（３）の絶対構造を決定するために、化合物
（３）のオゾン分解によって得られた下記一般式（VI
I）で表される化合物（７）にオクタントルールを適用
した。 In order to determine the absolute structure of compound (3), the following general formula (VI
The octant rule was applied to the compound (7) represented by I).
化合物（７）のCDスペクトルは負のコットン効果（28
9nm,Δε＝−2.79,c＝0.18,EtOH）を示した。従って化
合物（３）の絶対構造は上記の式（III）に示す通りに
決定された。アルピニア属植物（Alpinia speciosa）か
ら単離した化合物（６）の絶対構造も上記の式（VI）に
示す通りに決定された。 The CD spectrum of compound (7) shows a negative Cotton effect (28
9 nm, Δε = −2.79, c = 0.18, EtOH). Therefore, the absolute structure of compound (3) was determined as shown in formula (III) above. The absolute structure of compound (6) isolated from Alpinia speciosa was also determined as shown in formula (VI) above.
化合物（４）の13C‐NMRスペクトルのデータは表１に
示す通りであり、これは抗真菌性ラブダンジアルデヒド
である（Ｅ）−8,17−エポキシ−ラブド−12−エン−1
5,16−ジアールと完全に同じであった。The data of the 13 C-NMR spectrum of the compound (4) are shown in Table 1, which is an antifungal labdane dialdehyde (E) -8,17-epoxy-labd-12-ene-1.
It was exactly the same as the 5,16-Gir.
生合成的の見地から、ガラナルＡとガラナルＢは化合
物（４）のエポキシドの開裂後の閉環によって誘導され
ると考えられた。From a biosynthetic point of view, it was considered that Galanal A and Galanal B were derived by ring closure after cleavage of the epoxide of compound (4).
本発明の化合物（１）、化合物（２）及び化合物
（３）は抗腫瘍剤としての有用性が期待される。The compounds (1), (2) and (3) of the present invention are expected to be useful as antitumor agents.
Claims (2)
ジテルペン類。 1. A novel diterpene represented by the general formula (I) or (II).
から誘導することを特徴とする一般式（Ｉ）または（I
I）で表される新規ジテルペン類の製造方法。 2. A general formula (I) or (I), which is derived from seeds of Alpinia galanga (Ginger family).
A method for producing a novel diterpene represented by I).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61309877A JP2513655B2 (en) | 1986-12-26 | 1986-12-26 | Novel diterpenes and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61309877A JP2513655B2 (en) | 1986-12-26 | 1986-12-26 | Novel diterpenes and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63162644A JPS63162644A (en) | 1988-07-06 |
| JP2513655B2 true JP2513655B2 (en) | 1996-07-03 |
Family
ID=17998377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61309877A Expired - Lifetime JP2513655B2 (en) | 1986-12-26 | 1986-12-26 | Novel diterpenes and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2513655B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999053935A1 (en) * | 1998-04-16 | 1999-10-28 | Ida Development A/S | Novel synergistic compositions containing aromatic compounds and terpenoids present in alpinia galanga |
| JP4849388B2 (en) * | 2005-03-03 | 2012-01-11 | 国立大学法人名古屋大学 | Physiologically active substance and method for producing the same, tasting method of pungent physiologically active substance, and health / medical composition |
| CN103965088B (en) * | 2013-02-05 | 2016-03-16 | 中国科学院沈阳应用生态研究所 | A kind of compound and Synthesis and applications thereof deriving from China fir |
| TWI516474B (en) | 2013-05-27 | 2016-01-11 | 中央研究院 | Synthesis of galanal compounds and analogues thereof |
| TWI478902B (en) * | 2013-06-07 | 2015-04-01 | Dev Center Biotechnology | Glp-1 potentiators and their applications |
| CN104529733B (en) * | 2015-01-05 | 2016-04-06 | 海南医学院 | The monomer be separated in a kind of Rhizoma Alpiniae Officinarum and for anticancer usage |
-
1986
- 1986-12-26 JP JP61309877A patent/JP2513655B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| ＫｕｏＬｉＣｈｕｎｇ−ＫｕｏＩＹａｏＹｅｎＣｈｉｕＳｏＹｅｕＣｈｉｕＰａｎＫａｏ，（１９８２），（Ｊｕｌｙ），Ｐ．１４７−１６２ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63162644A (en) | 1988-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kashman et al. | New diterpenoids from the soft corals Xenia macrospiculata and Xenia obscuronata | |
| Bennett et al. | Triterpenoids, tocotrienols and xanthones from the bark of Cratoxylum cochinchinense | |
| Asakawa et al. | Insect antifeedant secoaromadendrane-type sesquiterpenes from Plagiochila species | |
| Bohlmann et al. | Allenic germacranolides, bourbonene derived lactones and other constituents from Vernonia species | |
| Stipanovic et al. | Pentaketide metabolites of Verticillium dahliae. 3. Identification of (-)-3, 4-dihydro-3, 8-dihydroxy-1 (2H) naphthalenone [(-)-vermelone] as a precursor to melanin | |
| Bohlmann et al. | Caryophyllene derivatives and a hydroxyisocomene from Pulicaria dysenterica | |
| Semmelhack et al. | Synthesis of racemic fomannosin and illudol using a biosynthetically patterned common intermediate | |
| Glotter et al. | Steroidal constituents of Physalis minima (Solanaceae) | |
| Asakawa et al. | New diterpenes from Porella perrottetiana | |
| JP2513655B2 (en) | Novel diterpenes and method for producing the same | |
| Ahmad et al. | Hydroxyalk-(4Z)-enoic acids and volatile components from the seeds of Zanthoxylum armatum | |
| Poss et al. | Vitamin C in organic synthesis: reaction with p-hydroxybenzyl alcohol derivatives | |
| Herz et al. | Sesquiterpene lactones of Eupatorium perfoliatum | |
| Bohlmann et al. | New germacranolides and other sesquiterpene lactones from Dicoma species | |
| Ahmed et al. | Eudesmanolides and other constituents from Artemisia herba-alba | |
| Singh et al. | 3β, 24-Dihydroxyolean-12-en-28-oic acid, a pentacyclic triterpene acid from Lantana indica | |
| Bohlmann et al. | A daucanolide further farnesene derivatives from Ageratum fastigiatum | |
| Morita et al. | New diterpenes from Alpinia galanga Wild. | |
| Snider et al. | Intramolecular Diels-Alder and ene reactions of 2, 6-dimethyl-2, 7-octadienal | |
| Herz et al. | New pseudoguaianolides from Hymenoxys species. A new type of lactone closure | |
| Herz et al. | Woodhousin, a new germacranolide from Bahia woodhousei (Gray) Gray' | |
| Huffman | Resin acids. V. Preparation and reactions of ring-A olefins from dehydroabietic acid | |
| Kimbu et al. | The structure of a labdane dialdehyde from Afromomum daniellii (Zingiberaceae) | |
| Steyn et al. | Structure and carbon-13 nuclear magnetic resonance assignments of versiconal acetate, versiconol acetate, and versiconol, metabolites from cultures of Aspergillus parasiticus treated with dichlorvos | |
| Sankaram et al. | Bharangin, a novel diterpenoid quinonemethide from pygmacopremna herbacea (Roxb.) moldenke |