JPH0452274B2 - - Google Patents
Info
- Publication number
- JPH0452274B2 JPH0452274B2 JP58141884A JP14188483A JPH0452274B2 JP H0452274 B2 JPH0452274 B2 JP H0452274B2 JP 58141884 A JP58141884 A JP 58141884A JP 14188483 A JP14188483 A JP 14188483A JP H0452274 B2 JPH0452274 B2 JP H0452274B2
- Authority
- JP
- Japan
- Prior art keywords
- dehydroyohimbone
- yohimbone
- dehydroyohimbanone
- reaction
- alkaloids
- 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
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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 本発明はヨヒンボン類の新規な製法に関する。[Detailed description of the invention] The present invention relates to a novel method for producing yohimbones.
デヒドロヨヒンボンはヨヒンビノン合成の中間
体として、ヨヒンビンの全合成に有用な化合物で
ある。本発明者は先に次式
で表わされるインドロピリジン類のハルマランか
ら、ヨヒンバン骨格を有する19，20−デヒドロヨ
ヒンバノンの立体選択的合成に成功した。そして
さらに研究を進めた結果、本発明を完成した。 Dehydroyohimbone is a compound useful in the total synthesis of yohimbine as an intermediate in the synthesis of yohimbinone. The inventor previously proposed the following formula We succeeded in stereoselectively synthesizing 19,20-dehydroyohimbanone having a yohimbane skeleton from harmalan, an indropyridine represented by As a result of further research, the present invention was completed.
本発明は、19，20−デヒドロヨヒンバノンを有
機酸と40〜100℃で加熱することを特徴とする、
次式
で表されるデヒドロヨヒンボンの製法である。 The present invention is characterized by heating 19,20-dehydroyohimbanone with an organic acid at 40 to 100°C.
The following formula This is a method for producing dehydroyohimbone expressed as follows.
出発物質である19，20−デヒドロヨヒンバノン
は、「ヘテロサイクルズ」18巻1982年213頁に記載
の方法により製造できる。 The starting material, 19,20-dehydroyohimbanone, can be produced by the method described in Heterocycles, Vol. 18, 1982, p. 213.
有機酸としては、pKaが３程度の酸基を１個以
上有するもの、例えば酒石酸、くえん酸、オキザ
ロ酢酸などが好ましい。 Preferred organic acids include those having one or more acid groups with a pKa of about 3, such as tartaric acid, citric acid, and oxaloacetic acid.
本発明を実施するに際しては、19，20−デヒド
ロヨヒンバノンを有機酸と反応させる。本反応は
溶媒の存在下に行うことが好ましい。溶媒として
は例えばエーテル、炭化水素、ケトン、好ましく
はジオキサン、ハロゲン化炭化水素などが用いら
れる。反応温度は30〜120℃、好ましくは40〜100
℃であり、反応は数分ないし十数時間で終了す
る。生成物は常法により単離される。 In practicing the invention, 19,20-dehydroyohimbanone is reacted with an organic acid. This reaction is preferably carried out in the presence of a solvent. As the solvent, for example, ether, hydrocarbon, ketone, preferably dioxane, halogenated hydrocarbon, etc. are used. Reaction temperature is 30-120℃, preferably 40-100℃
℃, and the reaction is completed in several minutes to more than ten hours. The product is isolated using conventional methods.
このデヒドロヨヒンボンを還元してヨヒンボン
を製造するには、パラジウムー炭素、酸化白金な
どの触媒の存在下に接触還元することが好まし
い。還元反応は、通常は常温、常圧下に行われ、
１時間ないし数時間で終了する。生成物は常法に
より単離される。 In order to reduce this dehydroyohimbone to produce yohimbone, catalytic reduction is preferably carried out in the presence of a catalyst such as palladium-carbon or platinum oxide. The reduction reaction is usually carried out at room temperature and pressure.
It will be finished in one to several hours. The product is isolated using conventional methods.
こうして得られたヨヒンボンは、ヨヒンバン骨
格を有するので、ヨヒンビンアルカロイド類、レ
セルピンアルカロイド類、デセルピンアルカロイ
ド類などのアドレナリン遮断剤、血圧降下剤、ト
ランキライザーなどに有用なアルカイロド類の合
成に用いることができる。 Since the yohimbone thus obtained has a yohimbane skeleton, it can be used for the synthesis of alkylodes useful as adrenaline blockers, antihypertensive agents, tranquilizers, etc., such as yohimbine alkaloids, reserpine alkaloids, and deserpine alkaloids.
本発明方法によれば、ヨヒンビノン、ヨヒンビ
ンなどのヨヒンバンアルカロイドの立体選択的合
成の中間体として有用なデヒドロヨヒンボン及び
ヨヒンボンが、簡易かつ高収率で得られる。 According to the method of the present invention, dehydroyohimbone and yohimbone, which are useful as intermediates for the stereoselective synthesis of yohimbane alkaloids such as yohimbinone and yohimbine, can be obtained easily and in high yields.
実施例１ デヒドロヨヒンボンの製造
19，20−デヒドロヨヒンバノン200mgをジオキ
サン15mlに溶解し、溶液に酒石酸200mgを加えて、
80℃で８時間加熱する。次いで反応液を水で希釈
し、炭酸水素ナトリウムでアルカリ性にし、塩化
メチレンで抽出する。抽出液を水洗し、乾燥した
のち、溶媒を留去し、残留物に少量のエチルエー
テルを加えて結晶化させると、融点218〜220℃の
デヒドロヨヒンボンの黄色結晶が150mg得られる。
収率75％。Example 1 Production of dehydroyohimbone Dissolve 200 mg of 19,20-dehydroyohimbanone in 15 ml of dioxane, add 200 mg of tartaric acid to the solution,
Heat at 80℃ for 8 hours. The reaction solution is then diluted with water, made alkaline with sodium bicarbonate, and extracted with methylene chloride. After washing the extract with water and drying, the solvent is distilled off and the residue is crystallized by adding a small amount of ethyl ether to obtain 150 mg of yellow crystals of dehydroyohimbone with a melting point of 218-220°C.
Yield 75%.
NMR（δ）：7.80（1H，ｓ，NH）
6.80（1H，dd，Ｊ＝10，1.5，
19−Ｈ）
6.08（1H，dd，Ｊ＝10，３，18
−Ｈ）
IR ν CHCl3 nax cm-1：3480，1680
参考例１ ヨヒンボンの製法
実施例１により得られたデヒドロヨヒンボン50
mgを無水メタノール10mlに溶解し、溶液にパラジ
ウム−炭素50mgを加え、常温常圧下に水素ガスを
通じて２時間接触還元する。次いで触媒を別
し、液を濃縮し、残留物に少量のエチルエーテ
ルを加えて結晶化させると、ヨヒンボンの白色結
晶が45mg得られる。収率95％。得られたヨヒンボ
ンは、公知方法により得られたヨヒンボンと各種
スペクトルが一致することにより同定された。 NMR (δ): 7.80 (1H, s, NH) 6.80 (1H, dd, J=10, 1.5,
19-H) 6.08 (1H, dd, J=10, 3, 18
-H) IR ν CHCl3 nax cm -1 : 3480, 1680 Reference example 1 Yohimbone production method Dehydroyohimbone 50 obtained according to Example 1
mg was dissolved in 10 ml of anhydrous methanol, 50 mg of palladium-carbon was added to the solution, and hydrogen gas was passed through the solution at room temperature and pressure for catalytic reduction for 2 hours. Then, the catalyst is separated, the liquid is concentrated, and the residue is crystallized by adding a small amount of ethyl ether to obtain 45 mg of white crystals of yohimbone. Yield 95%. The obtained yohimbone was identified because its various spectra matched with yohimbone obtained by a known method.
Claims (1)
〜100℃で加熱することを特徴とする、次式 で表されるデヒドロヨヒンボンの製法。[Claims] 1 19,20-dehydroyohimbanone with an organic acid and 40
Characterized by heating at ~100°C, the following formula The manufacturing method of dehydroyohimbone expressed as
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58141884A JPS6032789A (en) | 1983-08-04 | 1983-08-04 | Preparation of yohimbones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58141884A JPS6032789A (en) | 1983-08-04 | 1983-08-04 | Preparation of yohimbones |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6032789A JPS6032789A (en) | 1985-02-19 |
| JPH0452274B2 true JPH0452274B2 (en) | 1992-08-21 |
Family
ID=15302399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58141884A Granted JPS6032789A (en) | 1983-08-04 | 1983-08-04 | Preparation of yohimbones |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6032789A (en) |
-
1983
- 1983-08-04 JP JP58141884A patent/JPS6032789A/en active Granted
Non-Patent Citations (1)
| Title |
|---|
| HETEROCYCLES=1892 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6032789A (en) | 1985-02-19 |
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