JPH0283385A - 9,10-seco-cycloartane derivative - Google Patents
9,10-seco-cycloartane derivativeInfo
- Publication number
- JPH0283385A JPH0283385A JP63235948A JP23594888A JPH0283385A JP H0283385 A JPH0283385 A JP H0283385A JP 63235948 A JP63235948 A JP 63235948A JP 23594888 A JP23594888 A JP 23594888A JP H0283385 A JPH0283385 A JP H0283385A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- seco
- acid
- group
- derivative
- 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
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 5
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 claims abstract description 3
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000006239 protecting group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 9
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 abstract description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 125000001118 alkylidene group Chemical group 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 125000001188 haloalkyl group Chemical group 0.000 abstract description 2
- 230000012447 hatching Effects 0.000 abstract description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 abstract description 2
- 229940098779 methanesulfonic acid Drugs 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 241000482313 Globodera ellingtonae Species 0.000 abstract 1
- 229930193596 glycinoeclepin Natural products 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 241000416162 Astragalus gummifer Species 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 206010011732 Cyst Diseases 0.000 description 1
- 241001473456 Eutrochium purpureum Species 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000019774 Rice Bran oil Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920001615 Tragacanth Polymers 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- RTEXIPZMMDUXMR-UHFFFAOYSA-N benzene;ethyl acetate Chemical compound CCOC(C)=O.C1=CC=CC=C1 RTEXIPZMMDUXMR-UHFFFAOYSA-N 0.000 description 1
- MDHYEMXUFSJLGV-UHFFFAOYSA-N beta-phenethyl acetate Natural products CC(=O)OCCC1=CC=CC=C1 MDHYEMXUFSJLGV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 208000031513 cyst Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000005489 dwarf bean Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000008165 rice bran oil Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940116362 tragacanth Drugs 0.000 description 1
- 235000010487 tragacanth Nutrition 0.000 description 1
- 239000000196 tragacanth Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (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〉
本発明は農薬として殊にマメ科植物の成長に重大な影響
を与えるシスト線中のふ化促進物質として知られるグリ
シノエクレビン類の合成中間体として、更にはそれ自体
農薬としても有望視できる有用な新規化合物並びにその
製造法に関する。[Detailed Description of the Invention] <Industrial Application Field> The present invention is an intermediate for the synthesis of glycinoecrebins, which are known as pesticides and are known as hatching promoting substances in cyst wires that have a significant influence on the growth of leguminous plants. The present invention relates to a useful new compound that is promising both as a chemical compound and as an agrochemical in itself, and to a method for producing the same.
更に詳しくは、本発明は一般式 （Ｉ）（式中Ｘは直鎮
又は分岐鎖の低級アルキル基、アルキリデン基、ハロア
ルキル基、ヒドロキシアルキル基、カルボキシル基又は
アルコキシカルボニル基を示す、）で示される３、１０
−エポキシ−５α−９１０−セコ−シクロアルタ−８（
９）−エン−７−オン誘導体並びにその製造法に関する
。More specifically, the present invention is represented by the general formula (I) (wherein X represents a straight or branched lower alkyl group, an alkylidene group, a haloalkyl group, a hydroxyalkyl group, a carboxyl group, or an alkoxycarbonyl group) 3, 10
-Epoxy-5α-910-Seco-cycloalta-8 (
9) -En-7-one derivative and its production method.
〈従来の技術〉
グリシノエクレビン類は、植物（インゲン根）からの抽
出（現代化学１９８５年１６頁）あるいは全合成 （Ｊ
、 Ａｌｌ１． ＣｈｅＩＩｌ、 Ｓｏｃ、、 １１０
巻、 １９８５頁１９８８年）により製されているが、
前者の場合は単離収率が低く （インゲン乾燥根１トン
から１ミリグラム）、後者の場合は工程数が長く（３５
工程）実用的価値は少い。<Prior art> Glycinoeclevins are extracted from plants (kidney root) (Gendai Kagaku 1985, p. 16) or totally synthesized (J
, All1. CheIIl, Soc,, 110
Vol. 1985, p. 1988).
In the former case, the isolation yield is low (1 milligram from 1 ton of dried French bean roots), and in the latter case the number of steps is long (35
Process) has little practical value.
一方、天然物の抽出物であるシフロアステラガロールを
原料にグリシノエクレビン類の合成も試みられているが
（日本化学会１９８６年春季年会講演要旨集ｌＮ４７．
１００６頁：同１９８８年春季年会講演要旨集４１ＸＢ
Ｏ５，１１８５頁）、該原料は生薬（トラガント）から
抽出している為経済的合成法とは言い難い。On the other hand, attempts have been made to synthesize glycinoeclebins using the natural product extract ciflora stelagallol as a raw material (Chemical Society of Japan 1986 Spring Annual Meeting Abstracts 1N47).
1006 pages: 1988 Spring Annual Meeting Lecture Abstracts 41XB
O5, p. 1185), the raw material is extracted from a crude drug (tragacanth), so it cannot be called an economical synthesis method.
そこで、経済的に有利なグリシノエクレピン類の合成法
の探索が望まれていた。Therefore, it has been desired to search for an economically advantageous method for synthesizing glycinoecrepines.
〈発明が解決した問題点〉
斯る現状に於て、本発明者らは米ヌカ油から工業的規模
で抽出されるシクロアルテノール類を原料に用いれば安
価にグリシノエクレピン類が製造できると考え、鋭意研
究の結果シクロアルテノール類を酸化して得られる一般
式 （Ｉｆ）（式中Ｘは前記と同じ意味を示し、Ｒは水
素原子又はピラニル基、メトキシメチル基、エトキシエ
チル基等水酸基の保護基を示す。）で示されるシクロア
ルテノール−７−オン類を酸存在下で転位させれば、・
グリシノエクレビン類の重要中間体である新規な一般式
（Ｉ）で示される３、１０−エポキシ−５α−９，１０
−セコ−シクロアルタ−８（９）−エン−７−オン誘導
体を製しうることを見い出し本発明を完成するに至った
。<Problems Solved by the Invention> Under the current circumstances, the present inventors have discovered that glycinoecrepines can be produced at low cost by using cycloartenols extracted from rice bran oil on an industrial scale as raw materials. As a result of intensive research, the general formula (If) obtained by oxidizing cycloartenols (wherein X has the same meaning as above, and R is a hydrogen atom or a pyranyl group, a methoxymethyl group, an ethoxyethyl group, etc. If the cycloartenol-7-one represented by (representing a hydroxyl group protecting group) is rearranged in the presence of an acid,
3,10-epoxy-5α-9,10 represented by the novel general formula (I), which is an important intermediate of glycinoecrebins
The present inventors have discovered that -seco-cycloalter-8(9)-en-7-one derivatives can be produced and have completed the present invention.
なお、式 （Ｉ）の化合物を酸化等によりＢ環を開裂す
ればグリシソエクレピン頚に導くこと力く出来る。Incidentally, if the B ring of the compound of formula (I) is cleaved by oxidation or the like, it is possible to easily lead to the glycisoecrepine neck.
〈発明の構成〉
本発明の式 （１）の化合物は、シクロアルテノール類
を酸化して得られる下記式 （１口の化合物（特願昭８
２−３１７９２８号； Ｊ、 Ｏｒｇ、 Ｃｈｅｍ、、
５３巻２６２２頁１９８８年）を酸存在下で転位する
ことにより製造される。<Structure of the Invention> The compound of formula (1) of the present invention is a compound of the following formula (one mouth compound (patent application filed in 1983) obtained by oxidizing cycloartenols).
No. 2-317928; J, Org, Chem,
53, p. 2622, 1988) in the presence of an acid.
（式中Ｒ，Ｘは前記と同じ意味を示す。）反応は、反応
に関与しない溶媒に式 （ＩＩ）の化合物を溶解し、こ
れに触媒量の酸を加え加温することにより行われる。溶
媒としては、クロロホルム、ベンゼン、四塩化炭素、ジ
クルロロエタン、酢酸エチルエステル、アセトン、メタ
ノール等が好ましい。酸触媒としては、メタンスルホン
酸、トリフロロ酢酸、酢酸、Ｐ−トルエンスルホン酸等
の有機酸、塩酸、硫酸、ポリリン酸、三沸化ホウ素等の
無機酸やシリカゲル等の担体が用いられる。反応温度は
室温〜２００℃、好ましくは４０〜１００℃で行われ、
反応時間は通常１０分間〜２４時間である。(In the formula, R and X have the same meanings as above.) The reaction is carried out by dissolving the compound of formula (II) in a solvent that does not participate in the reaction, adding a catalytic amount of acid to the solution, and heating it. Preferred solvents include chloroform, benzene, carbon tetrachloride, dichloroethane, ethyl acetate, acetone, and methanol. As the acid catalyst, organic acids such as methanesulfonic acid, trifluoroacetic acid, acetic acid, and P-toluenesulfonic acid, inorganic acids such as hydrochloric acid, sulfuric acid, polyphosphoric acid, and boron trifluoride, and carriers such as silica gel are used. The reaction temperature is room temperature to 200°C, preferably 40 to 100°C,
The reaction time is usually 10 minutes to 24 hours.
〈発明の効果〉
本発明の化合物を使用することにより、従来の合成法に
比べより経済的にグリシノエクレピン類の製造が可能と
なる。<Effects of the Invention> By using the compound of the present invention, glycinoecrepines can be produced more economically than conventional synthesis methods.
実施例１
３．８−ジハイドロキシー５α−シクロアルタ−７−オ
ン５０１！１ｇを無水ベンゼン１０ｍρに溶解し、この
混合溶液にＰ−トルエンスルホン酸２滴を加え６０℃で
１時間反応を行った。反応終了後、５％炭酸水素ナトリ
ウム水溶液を加えた後ベンゼン層を分取した。ベンゼン
溶液は、水洗後、無水硫酸ナトリウムを加え脱水し、つ
いで溶媒を留去した。Example 1 501!1 g of 3.8-dihydroxy-5α-cycloalt-7-one was dissolved in 10 mρ of anhydrous benzene, and 2 drops of P-toluenesulfonic acid were added to this mixed solution, and the reaction was carried out at 60°C for 1 hour. . After the reaction was completed, a 5% aqueous sodium hydrogen carbonate solution was added and the benzene layer was separated. The benzene solution was washed with water, dehydrated by adding anhydrous sodium sulfate, and then the solvent was distilled off.
粗反応生成物をシリカゲルカラムに付し、ベンゼン−酢
酸エチル （２０：１）で溶出し、溶出部を濃縮し、３
．１０−エポキシ−５α−９，ｌＯ−セコ−シクロアル
タ−８（９）−エン−７−オンが得られた。The crude reaction product was applied to a silica gel column, eluted with benzene-ethyl acetate (20:1), and the eluate was concentrated.
．． 10-Epoxy-5α-9,1O-seco-cycloalt-8(9)-en-7-one was obtained.
このものの物理的化学的性状は下記の通りであった。The physical and chemical properties of this product were as follows.
融 点：非結晶個体
ＩＲ（にＢ ｒ ） ： ｖ １６４５ （Ｃ−０）
、 １６０５ｃｍ−’ （Ｃ−Ｃ）ＮＭＲ（ＣＤＪ３
） ： δ ３，８５ （１１（、ｄ、 Ｊ−５，４Ｈ
ｚＣＯ−（Ｏ−））
３．０７ （ＩＨ，ｄ、 Ｊ−１３Ｈｚ。Melting point: Amorphous solid IR (Br): v 1645 (C-0)
, 1605 cm-' (C-C) NMR (CDJ3
): δ 3,85 (11(,d, J-5,4H
zCO-(O-)) 3.07 (IH, d, J-13Hz.
−（ニーＣＨＨ−Ｃ−） ２．１５ （ＩＨ，ｄ、Ｊ−１３Ｈｚ。-(knee CHH-C-) 2.15 (IH, d, J-13Hz.
−Ｃ−ＣＨＨ−Ｃ−）-C-CHH-C-)
Claims (2)
ルキリデン基、ハロアルキル基、ヒドロキシアルキル基
、カルボキシル基又はアルコキシカルボニル基を示す）
で示される３，１０−エポキシ−５α−９，１０−セコ
−シクロアルタ−８（９）−エン−７−オン誘導体(1) General formula ▲ Numerical formula, chemical formula, table, etc. )
3,10-epoxy-5α-9,10-seco-cycloalt-8(9)-en-7-one derivative represented by
ラニル基、メトキシメチル基、エトキシエチル基等水酸
基の保護基を示す。）を酸存在下で転位させることを特
徴とする一般式 ▲数式、化学式、表等があります▼ （式中Ｘは前記と同じ意味を示す。）で示される３，１
０−エポキシ−５α−９，１０−セコ−シクロアルタ−
８（９）−エン−７−オン誘導体の製造法(2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X has the same meaning as above. R represents a hydrogen atom or a protecting group for a hydroxyl group such as a pyranyl group, a methoxymethyl group, or an ethoxyethyl group. ) is rearranged in the presence of an acid ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X has the same meaning as above.) 3,1
0-epoxy-5α-9,10-seco-cycloalta-
Method for producing 8(9)-en-7-one derivative
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63235948A JP2718715B2 (en) | 1988-09-20 | 1988-09-20 | 9,10-seco-cycloartane derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63235948A JP2718715B2 (en) | 1988-09-20 | 1988-09-20 | 9,10-seco-cycloartane derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0283385A true JPH0283385A (en) | 1990-03-23 |
| JP2718715B2 JP2718715B2 (en) | 1998-02-25 |
Family
ID=16993590
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63235948A Expired - Fee Related JP2718715B2 (en) | 1988-09-20 | 1988-09-20 | 9,10-seco-cycloartane derivatives |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2718715B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9677550B2 (en) | 2005-07-28 | 2017-06-13 | Graco Minnesota Inc. | Reciprocating pump with electronically monitored air valve and piston |
-
1988
- 1988-09-20 JP JP63235948A patent/JP2718715B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9677550B2 (en) | 2005-07-28 | 2017-06-13 | Graco Minnesota Inc. | Reciprocating pump with electronically monitored air valve and piston |
| US9677549B2 (en) | 2005-07-28 | 2017-06-13 | Graco Minnesota Inc. | Reciprocating pump with electronically monitored air valve and piston |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2718715B2 (en) | 1998-02-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0418925B1 (en) | Method of producing (S)-4-hydroxymethyl-gamma-lactone | |
| FI91638B (en) | Process for the preparation of tetracyclic antidepressants | |
| US4147703A (en) | Process to produce 8-methoxypsoralen | |
| JPH0283385A (en) | 9,10-seco-cycloartane derivative | |
| JPS6024781B2 (en) | Method for producing cis-2-hydroxy-2-phenyl-r-1-cyclohexanecarboxylic acid | |
| EP0243646B1 (en) | A process for the preparation of forskolin from 9-deoxy-forskolin and intermediates used therein | |
| US3641146A (en) | Halocolchicine derivatives | |
| US3786068A (en) | Intermediate in the total synthesis of elenolic acid | |
| JP2557429B2 (en) | Cycloartenol-7-one derivative | |
| JPS59130832A (en) | 4-halogeno-2-chloro-3-phenylcrotonaldehyde | |
| JPS604835B2 (en) | Manufacturing method of neothramycin | |
| Matoba et al. | Synthetic Studies of Azaflavonoids. II. Synthesis of 6-Azaflavonoids | |
| JPS6261587A (en) | Production of optically active (r)-hydroxymandelic acid ester intermediate | |
| JPS603382B2 (en) | Novel production method for isoindoline derivatives | |
| US3413338A (en) | 2-nitrocyclopent-1-enecarboxylic acid | |
| CN116715675A (en) | Synthetic method of isopsoralen | |
| JPS6372696A (en) | Production of 1,5-anhydro-d-fructose and hydrate thereof | |
| JPS6019310B2 (en) | Benzoxepine derivatives and their production method | |
| JPS615039A (en) | Preparation of alpha-chlorodiketone compound by photochemical reaction and synthesis of brevicomin from obtained alpha-chlorodiketone | |
| JPS6032789A (en) | Preparation of yohimbones | |
| NO744184L (en) | ||
| JPS6178746A (en) | Inversion of optically active cyclopentenone | |
| JPS5838434B2 (en) | Method for producing 2,3,6-trimethylhydroquinone-1-nicotinic acid ester | |
| JPS58154563A (en) | Manufacture of novel benzoxadine | |
| JPS5949220B2 (en) | Novel cyclohexane derivative |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |