JPS6351157B2 - - Google Patents

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Publication number
JPS6351157B2
JPS6351157B2 JP55129121A JP12912180A JPS6351157B2 JP S6351157 B2 JPS6351157 B2 JP S6351157B2 JP 55129121 A JP55129121 A JP 55129121A JP 12912180 A JP12912180 A JP 12912180A JP S6351157 B2 JPS6351157 B2 JP S6351157B2
Authority
JP
Japan
Prior art keywords
add
hydroxyl group
phenyl
chloroform
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
Application number
JP55129121A
Other languages
Japanese (ja)
Other versions
JPS5754200A (en
Inventor
Kyoshige Ochi
Isao Matsunaga
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chugai Pharmaceutical Co Ltd
Original Assignee
Chugai Pharmaceutical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Chugai Pharmaceutical Co Ltd filed Critical Chugai Pharmaceutical Co Ltd
Priority to JP55129121A priority Critical patent/JPS5754200A/en
Publication of JPS5754200A publication Critical patent/JPS5754200A/en
Publication of JPS6351157B2 publication Critical patent/JPS6351157B2/ja
Granted legal-status Critical Current

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Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/55Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

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  • Steroid Compounds (AREA)

Description

【発明の詳細な説明】 本発明は、1α位に水酸基を有する種々ビタミ
ンD3類、例えば1α―ヒドロキシビタミンD3
1α,24―ジヒドロキシビタミンD3,1α,25―ジ
ヒドロキシビタミンD3,1α,24,25―トリヒド
ロキシビタミンD3等の合成中間体の製法に関す
る。
DETAILED DESCRIPTION OF THE INVENTION The present invention provides various types of vitamin D3 having a hydroxyl group at the 1α position, such as 1α-hydroxyvitamin D3 ,
This invention relates to a method for producing synthetic intermediates such as 1α,24-dihydroxyvitamin D 3 , 1α,25-dihydroxyvitamin D 3 , and 1α,24,25-trihydroxyvitamin D 3 .

更に詳しくは、本発明は一般式で示される1
―エンステロイド誘導体の製法に関する。
More specifically, the present invention is directed to the general formula 1
- Concerning the production method of entosteroid derivatives.

(式中Rは有機残基を意味し、R1,R2は同一
又は異なつて各々水素原子、水酸基および保護さ
れた水酸基を意味し、R3は水素原子又は水酸基
の保護基を意味する。) 従来、1α―ヒドロキシビタミンD3類の製法と
して、金子等の方法(特開昭50−84555号公報、
同51−100056号公報)が知られている。この方法
には前記一般式で示される1―エンステロイド
類を酸化反応に付し対応する1α,2α―エポキシ
ド体を得る工程が含まれている。しかしながら、
この酸化反応においては1α―ヒドロキシル基の
導入が可能な1α,2α―エポキシド体の収率が約
30%と低く、本来不必要な1β,2β―エポキシド
体(一般式)が約60%副生しており工業生産上
不利な工程である。
(In the formula, R means an organic residue, R 1 and R 2 are the same or different and each means a hydrogen atom, a hydroxyl group, or a protected hydroxyl group, and R 3 means a hydrogen atom or a protecting group for the hydroxyl group. ) Conventionally, as a method for producing 1α-hydroxyvitamin D type 3 , the method of Kaneko et al.
51-100056) is known. This method includes the step of subjecting the 1-ene steroid represented by the above general formula to an oxidation reaction to obtain the corresponding 1α,2α-epoxide. however,
In this oxidation reaction, the yield of 1α,2α-epoxide, into which a 1α-hydroxyl group can be introduced, is approximately
This is a disadvantageous process for industrial production, as it produces about 60% of the 1β,2β-epoxide (general formula) as a by-product, which is as low as 30%.

(式中、R,R1,R2,R3は前記と同じものを
意味する。) この点を解決すべく、本発明者等が鋭意研究し
た結果、1α―ヒドロキシビタミンD3類の合成に
は使用し得ない一般式で示される1β,2β―エ
ポキシド体を容易な手段により、もとの一般式
で示される1―エンステロイド類に変換する方法
を見い出し本発明を完成した。すなわち本発明は
一般式で示される1β,2β―エポキシコレスタ
―3β―オールステロイド誘導体を不活性溶媒中
ハロゲン化水素酸と反応させ一般式 (式中、R,R1,R2,R3は前記と同じものを
意味し、Xはハロゲン原子を意味する。) で示されるハロヒドリンステロイド誘導体を製造
し、次いで不活性溶媒中金属粉を反応させること
を特徴とする一般式で示される1―エンステロ
イド誘導体の製造方法に関する。
(In the formula, R, R 1 , R 2 and R 3 have the same meanings as above.) In order to solve this problem, the present inventors conducted intensive research and found that the synthesis of 1α-hydroxyvitamin D 3 The present invention has been completed by discovering a method for converting the 1β,2β-epoxide compound represented by the general formula, which cannot be used in the following, into the 1-ene steroid represented by the original general formula by a simple means. That is, the present invention involves reacting a 1β,2β-epoxy cholester-3β-allsteroid derivative represented by the general formula with hydrohalic acid in an inert solvent to obtain the general formula (In the formula, R, R 1 , R 2 , R 3 have the same meanings as above, and X means a halogen atom.) The halohydrin steroid derivative represented by The present invention relates to a method for producing a 1-ene steroid derivative represented by the general formula, which is characterized by reacting powder.

本発明により従来不必要とされていた副生成物
が、再び製造工程で使用することが可能となり、
1α―ヒドロキシビタミンD3類の工業生産を有利
に又効果的に行うことが可能となつた。
With the present invention, by-products that were previously considered unnecessary can be used again in the manufacturing process,
It has become possible to advantageously and effectively carry out industrial production of 1α-hydroxyvitamin D type 3 .

本発明の方法における一般式,およびで
示される化合物において、Rは有機残基であり、
具体的には例えばメチル,エチル基等の低級アル
キル基、置換又は非置換のフエニル基等のアリー
ル基である。R1,R2は同一又は異なつて、各々
水素原子、水酸基又は保護された水酸基を意味
し、R3は水素原子又は水酸基の保護基を意味す
る。この際、保護基としては使用するハロゲン化
水素酸に安定な基であればよく、アセチル基、ベ
ンゾイル基、プロパノイル基等のアシル基が好ま
しい例として挙げられる。
In the compound represented by the general formula and in the method of the present invention, R is an organic residue,
Specifically, they include lower alkyl groups such as methyl and ethyl groups, and substituted or unsubstituted aryl groups such as phenyl groups. R 1 and R 2 are the same or different and each means a hydrogen atom, a hydroxyl group or a protected hydroxyl group, and R 3 means a hydrogen atom or a protecting group for the hydroxyl group. In this case, the protecting group may be any group as long as it is stable to the hydrohalic acid used, and preferred examples include acyl groups such as acetyl group, benzoyl group, and propanoyl group.

本発明の方法で化合物からを製造する段階
で1β,2β―エポキシド基を開環し1α―ハロゲン
―2β―ヒドロキシ基に導く工程に使用するハロ
ゲン化水素としては、塩化水素、臭化水素、ヨウ
化水素およびフツ化水素であり、これらは単独あ
るいは例えばヨウ化ナトリウム―酢酸というハロ
ゲン化水素類を発生する形で反応系に加えること
もできる。又、反応溶媒として水を溶解する系で
あればハロゲン化水素類を水溶液の形で用いるこ
ともできる。なお入手し易く反応性がすぐれてい
る点および危険性が少ない点から臭化水素酸水溶
液が好ましく用いられる。反応溶媒としてはハロ
ゲン化水素類に安定でしかもハロゲン化水素類お
よび化合物を溶解し、安定性を保持するもので
あれば使用可能である。このような溶媒の好まし
い例としては氷酢酸がある。氷酢酸は単独あるい
はクロロホルム、ジクロルメタン、酢酸エチル等
との混合物としても用いることができる。反応温
度、反応時間は適宜選択されるが、本反応は比較
的短時間に終了する。副反応を避け収率よく行わ
しめるには短時間で処理することが必要である。
好ましくは室温下で約10分、氷冷下では数10分で
行われる。
Hydrogen halides used in the process of ring-opening a 1β,2β-epoxide group to form a 1α-halogen-2β-hydroxy group in the step of manufacturing a compound according to the method of the present invention include hydrogen chloride, hydrogen bromide, and iodine. These are hydrogen hydride and hydrogen fluoride, and these can be added to the reaction system alone or in a form that generates hydrogen halides, such as sodium iodide-acetic acid. Further, hydrogen halides can be used in the form of an aqueous solution as long as the system dissolves water as the reaction solvent. Note that an aqueous solution of hydrobromic acid is preferably used because it is easily available, has excellent reactivity, and is less dangerous. As the reaction solvent, any solvent that is stable to hydrogen halides, dissolves the hydrogen halides and the compound, and maintains stability can be used. A preferred example of such a solvent is glacial acetic acid. Glacial acetic acid can be used alone or in a mixture with chloroform, dichloromethane, ethyl acetate, etc. Although the reaction temperature and reaction time are appropriately selected, this reaction is completed in a relatively short time. In order to avoid side reactions and achieve good yield, it is necessary to perform the treatment in a short time.
Preferably, it is carried out for about 10 minutes at room temperature, and for several tens of minutes under ice cooling.

反応混合物から化合物の単離・精製は常法に
より容易に行われるが、特に精製することなく次
の工程に付すことも可能である。
Isolation and purification of the compound from the reaction mixture can be easily carried out by conventional methods, but it is also possible to subject it to the next step without any particular purification.

化合物を金属粉で処理し化合物を得る工程
で、金属粉としてはアエン末、銅粉、スズ末等脱
ハロゲン化能を有するものであればよく、これら
の単独あるいは混合物として使用し得る。なお、
これらの金属は表面のみで反応が起るため微粉末
であることが好ましい。溶媒としては化合物を分
解させることなく金属粉に対して安定なものであ
れば使用可能であり、好ましくはエタノール、プ
ロパノール、酢酸等のプロトン系溶媒又はこれら
と他の溶媒との混合物である。反応温度は室温乃
至加熱還流の間で適宜選択される。
In the step of obtaining a compound by treating a compound with a metal powder, the metal powder may be any powder having a dehalogenation ability, such as aene powder, copper powder, or tin powder, and these may be used alone or as a mixture. In addition,
Since the reaction occurs only on the surface of these metals, it is preferable that they be in the form of fine powder. As the solvent, any solvent can be used as long as it does not decompose the compound and is stable against the metal powder, preferably protic solvents such as ethanol, propanol, acetic acid, or mixtures of these and other solvents. The reaction temperature is appropriately selected between room temperature and heating to reflux.

反応混合物から化合物の単離は常法により、
例えば抽出、再結晶等の手段により容易に行うこ
とができる。
The compound is isolated from the reaction mixture by a conventional method.
For example, this can be easily carried out by means such as extraction and recrystallization.

実施例 1 1β,2β―エポキシコレスタ―5,7―ジエン
―3β―オールと4―フエニル―1,2,4―ト
リアゾリン―3,5―ジオンとの1,4―付加体
1.0gを氷酢酸5mlに懸濁し、激しく撹拌しなが
ら室温下47%臭化水素水0.5mlを氷酢酸1mlに溶
解した液を加える。5分後白色結晶が析出する。
クロロホルム1mlを加え更に5分間撹拌を続け、
10mlのクロロホルムを加える。反応混合物を2回
水洗した後クロロホルム層を硫酸マグネシウムで
乾燥し、溶媒を留去する。残渣にエタノールを加
え、析出した針状晶を過する。0.95gの1α―ブ
ロモコレスタ―5,7―ジエン―2β,3β―ジオ
ールと4―フエニル―1,2,4―トリアゾリン
―3,5―ジオンとの1,4―付加体を得た。
Example 1 1β,2β-epoxy cholesta-5,7-dien-3β-ol and 1,4-adduct of 4-phenyl-1,2,4-triazoline-3,5-dione
Suspend 1.0 g in 5 ml of glacial acetic acid, and add a solution prepared by dissolving 0.5 ml of 47% hydrogen bromide in 1 ml of glacial acetic acid at room temperature while stirring vigorously. After 5 minutes, white crystals precipitate.
Add 1 ml of chloroform and continue stirring for another 5 minutes.
Add 10ml chloroform. After washing the reaction mixture twice with water, the chloroform layer was dried over magnesium sulfate, and the solvent was distilled off. Add ethanol to the residue and filter out the precipitated needle crystals. 0.95 g of a 1,4-adduct of 1α-bromocholester-5,7-diene-2β,3β-diol and 4-phenyl-1,2,4-triazoline-3,5-dione was obtained.

融点;202〜203℃(分解、エタノールから再結
晶) NMRスペクトル(CDCl3)δ;7.32(5H,s,
フエニル),6.30(2H,dd,6―7―H),
4.40(1H,b,s,1―H),3.5〜3.8
(2H,m,2―,3―H),0.90(3H,s,
CH3),0.81(3H,s,CH3) IRスペクトル(KBr)cm-1;3475(OH),
1743,1685(C=0) 実施例 2 1α―ブロモコレスタ―5,7―ジエン―2β,
3β―ジオールと4―フエニル―1,2,4―ト
リアゾリン―3,5―ジオンとの1,4―付加体
0.8gをエタノール5mlに懸濁したアエン末0.4g
を加え撹拌しながら30分加熱還流する。氷酢酸
0.1mlを加え数分加熱した後デカントにより上澄
液をとる。残渣をクロロホルムで洗滌する。上澄
液とクロロホルム洗液とを合してクロロホルム抽
出する。クロロホルム層を水洗し、乾燥し、溶媒
を留去する。残渣をメタノールから再結晶しコレ
スタ―1,5,7―トリエン―3β―オールと4
―フエニル―1,2,4―トリアゾリン―3,5
―ジオンとの1,4―付加体0.64gを得た。
Melting point: 202-203℃ (decomposition, recrystallization from ethanol) NMR spectrum (CDCl 3 ) δ: 7.32 (5H, s,
phenyl), 6.30 (2H, dd, 6-7-H),
4.40 (1H, b, s, 1-H), 3.5-3.8
(2H, m, 2-, 3-H), 0.90 (3H, s,
CH 3 ), 0.81 (3H, s, CH 3 ) IR spectrum (KBr) cm -1 ; 3475 (OH),
1743, 1685 (C=0) Example 2 1α-bromocholester-5,7-diene-2β,
1,4-adduct of 3β-diol and 4-phenyl-1,2,4-triazoline-3,5-dione
0.4g of aene powder suspended in 5ml of ethanol
Add and heat to reflux for 30 minutes while stirring. glacial acetic acid
Add 0.1ml and heat for several minutes, then remove the supernatant by decantation. Wash the residue with chloroform. The supernatant liquid and the chloroform washing liquid are combined and extracted with chloroform. The chloroform layer is washed with water, dried, and the solvent is distilled off. The residue was recrystallized from methanol to give cholesta-1,5,7-trien-3β-ol and 4
-Phenyl-1,2,4-triazoline-3,5
-0.64 g of 1,4-adduct with dione was obtained.

融点:178〜182℃ NMRスペクトル(CDCl3)δ;7.33(5H,s,
フエニル),6.31(2H,dd,6―,7―
H)、5.70(2H,s,1―,2―H),3.34
(1H,dd,3―H) IRスペクトル(KBr)cm-1;3450(OH),
1755,1700(C=0) 実施例 3 1β,2β―エポキシコレスタ―5,7―ジエン
―3β,25―ジオールと4―フエニル―1,2,
4―トリアゾリン―3,5―ジオンとの1,4―
付加体0.107gを氷酢酸1mlに溶解し、激しく撹
拌しながら47%臭化水素化0.03mlを氷酢酸0.5ml
に溶解したものを加え、室温で10分撹拌する。ク
ロロホルム20mlを加え、水洗する。硫酸マグネシ
ウムで乾燥し、溶媒を留去する。残渣をシリカゲ
ルカラムクロマトグラフイーに付し20%アセトン
含有クロロホルムで溶出し、目的物を含むフラク
シヨンを集め濃縮する。残渣をアセトン―エーテ
ルから再結晶すると1α―ブロモコレスタ―5,
7―ジエン―2β,3β,25―トリオールと4―フ
エニル―1,2,4―トリアゾリン―3,5―ジ
オンとの1,4―付加体41.4mgを得た。
Melting point: 178-182℃ NMR spectrum (CDCl 3 ) δ; 7.33 (5H, s,
phenyl), 6.31 (2H, dd, 6-, 7-
H), 5.70 (2H, s, 1-, 2-H), 3.34
(1H, dd, 3-H) IR spectrum (KBr) cm -1 ; 3450 (OH),
1755, 1700 (C=0) Example 3 1β,2β-epoxy cholester-5,7-diene-3β,25-diol and 4-phenyl-1,2,
1,4- with 4-triazoline-3,5-dione
Dissolve 0.107 g of the adduct in 1 ml of glacial acetic acid, and add 0.03 ml of 47% hydrobromide to 0.5 ml of glacial acetic acid while stirring vigorously.
Add the solution dissolved in and stir at room temperature for 10 minutes. Add 20ml of chloroform and wash with water. Dry over magnesium sulfate and evaporate the solvent. The residue is subjected to silica gel column chromatography, eluted with chloroform containing 20% acetone, and fractions containing the target product are collected and concentrated. When the residue was recrystallized from acetone-ether, 1α-bromocholester-5,
41.4 mg of a 1,4-adduct of 7-diene-2β,3β,25-triol and 4-phenyl-1,2,4-triazoline-3,5-dione was obtained.

融点;199〜201℃(分解) NMRスペクトル(CDCl3)δ;7.34(5H,s,
フエニル),6.28(2H,dd,6―,7―
H),4.34(1H,b,s,1―H),3.4〜
3.8(2H,m,2―,3―H) IRスペクトル(KBr)cm-1;3500(OH),
1740,1680(C=0) 実施例 4 1α―ブロモコレスタ―5,7―ジエン―2β,
3β,25―トリオールと4―フエニル―1,2,
4―トリアゾリン―3,5―ジオンとの1,4―
付加体41mgをエタノール2mlに懸濁させアエン末
20mgを加え撹拌しながら30分加熱還流する。氷酢
酸を0.1ml加え数分加熱し、上澄液にクロロホル
ム20mlを加える。クロロホルム層を水洗後、硫酸
マグネシウムで乾燥し、溶媒を留去する。メタノ
ールから再結晶すると30.9mgのコレスタ―1,
5,7―トリエン―3β,25―ジオールと4―フ
エニル―1,2,4―トリアゾリン―3,5―ジ
オンとの1,4―付加体を得た。
Melting point: 199-201℃ (decomposition) NMR spectrum ( CDCl3 ) δ: 7.34 (5H, s,
phenyl), 6.28 (2H, dd, 6-, 7-
H), 4.34 (1H, b, s, 1-H), 3.4~
3.8 (2H, m, 2-, 3-H) IR spectrum (KBr) cm -1 ; 3500 (OH),
1740, 1680 (C=0) Example 4 1α-bromocholester-5,7-diene-2β,
3β,25-triol and 4-phenyl-1,2,
1,4- with 4-triazoline-3,5-dione
Suspend 41 mg of adduct in 2 ml of ethanol and add aene powder.
Add 20 mg and heat to reflux for 30 minutes while stirring. Add 0.1 ml of glacial acetic acid and heat for several minutes, then add 20 ml of chloroform to the supernatant. After washing the chloroform layer with water, it is dried over magnesium sulfate, and the solvent is distilled off. When recrystallized from methanol, 30.9 mg of cholester-1,
A 1,4-adduct of 5,7-triene-3β,25-diol and 4-phenyl-1,2,4-triazoline-3,5-dione was obtained.

融点;159〜160℃ NMRスペクトル(CDCl3)δ;7.41(5H,s,
フエニル),6.50,6.27(each 1H,d,5
―,6―H),5.76(2H,s,1―,2―
H),5.02(1H,m,3―H),1.19(6H,
s),1.07,0.80(each 3H,s) IRスペクトル(KBr)cm-1;3440(0H),1750,
1688(C=0) 実施例 5 1β,2β―エポキシコレクタ―3β,24ξ―ジオー
ルと4―フエニル―1,2,4―トリアゾリン―
3,5―ジオンとの1,4―付加体1.0gを氷酢
酸5mlに溶解し47%臭化水素水0.5mlを氷酢酸1
mlに溶解したものを加え室温で10分撹拌する。ク
ロロホルム20mlを加え水洗する。硫酸マグネシウ
ムで乾燥し、溶媒を留去する。残渣を5mlのエタ
ノールに溶解しアエン末0.4gを加え30分加熱還
流する。氷酢酸0.1mlを加え数分加熱した後上澄
液をとりクロロホルム20mlに加える。水洗した後
硫酸マグネシウムで乾燥する。クロロホルムを留
去した後残渣をシリカゲルカラムクロマトグラフ
イーに付し、20%アセトン含有クロロホルムで溶
出する。目的物のフラクシヨンを集め溶媒を留去
すると0.65gのコレスター1,5,7―トリエン
―3β,24ξ―ジオールと4―フエニル―1,2,
4―トリアゾリン―3,5―ジオンを得た。
Melting point: 159-160℃ NMR spectrum (CDCl 3 ) δ: 7.41 (5H, s,
phenyl), 6.50, 6.27 (each 1H, d, 5
-, 6-H), 5.76 (2H, s, 1-, 2-
H), 5.02 (1H, m, 3-H), 1.19 (6H,
s), 1.07, 0.80 (each 3H, s) IR spectrum (KBr) cm -1 ; 3440 (0H), 1750,
1688 (C=0) Example 5 1β,2β-epoxy collector-3β,24ξ-diol and 4-phenyl-1,2,4-triazoline-
Dissolve 1.0 g of 1,4-adduct with 3,5-dione in 5 ml of glacial acetic acid, add 0.5 ml of 47% hydrogen bromide solution to 1 ml of glacial acetic acid.
ml of the solution and stir at room temperature for 10 minutes. Add 20ml of chloroform and wash with water. Dry over magnesium sulfate and evaporate the solvent. Dissolve the residue in 5 ml of ethanol, add 0.4 g of aene powder, and heat under reflux for 30 minutes. Add 0.1 ml of glacial acetic acid and heat for several minutes, then remove the supernatant and add to 20 ml of chloroform. After washing with water, dry with magnesium sulfate. After chloroform was distilled off, the residue was subjected to silica gel column chromatography and eluted with chloroform containing 20% acetone. When fractions of the target product were collected and the solvent was distilled off, 0.65 g of cholester 1,5,7-triene-3β,24ξ-diol and 4-phenyl-1,2,
4-triazoline-3,5-dione was obtained.

融点:150〜156℃ NMRスペクトル(CDCl3)δ;7.38(5H,s,
フエニル),6.45,6.25( each 1H,d,
6―,7―H),5.71(2H,s,1―,2
―H),5.00(1H,m,3―H),1.07(3H,
s),0.88(6H,d),0.82(3H,s) IRスペクトル(KBr)cm-1;3430(OH),
1752,1700(C=0)
Melting point: 150-156℃ NMR spectrum (CDCl 3 ) δ; 7.38 (5H, s,
phenyl), 6.45, 6.25 ( each 1H, d,
6-, 7-H), 5.71 (2H, s, 1-, 2
-H), 5.00 (1H, m, 3-H), 1.07 (3H,
s), 0.88 (6H, d), 0.82 (3H, s) IR spectrum (KBr) cm -1 ; 3430 (OH),
1752, 1700 (C=0)

Claims (1)

【特許請求の範囲】 1 一般式 (式中Rは有機残基を意味し、R1,R2は同一
又は異なつて各々水素原子、水酸基および保護さ
れた水酸基を意味し、R3は水素原子又は水酸基
の保護基を意味する。) で示される1β,2β―エポキシコレスタ―3β―オ
ールステロイド誘導体を不活性溶媒中ハロゲン化
水素酸と反応させ一般式 (式中、R,R1,R2,R3は前記と同じものを
意味し、Xはハロゲン原子を意味する。) で示されるハロヒドリンステロイド誘導体とし、
次いで不活性溶媒中金属粉を反応させることを特
徴とする一般式 (式中、R,R1,R2,R3は前記と同じものを
意味する。) で示される1―エンステロイド誘導体の製法。
[Claims] 1. General formula (In the formula, R means an organic residue, R 1 and R 2 are the same or different and each means a hydrogen atom, a hydroxyl group, or a protected hydroxyl group, and R 3 means a hydrogen atom or a protecting group for the hydroxyl group. ) The 1β,2β-epoxy cholesta-3β-allsteroid derivative represented by (In the formula, R, R 1 , R 2 , R 3 mean the same as above, and X means a halogen atom.) A halohydrin steroid derivative represented by
General formula characterized by then reacting metal powder in an inert solvent (In the formula, R, R 1 , R 2 and R 3 have the same meanings as above.) A method for producing a 1-ene steroid derivative.
JP55129121A 1980-09-19 1980-09-19 Preparation of steroid derivative Granted JPS5754200A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP55129121A JPS5754200A (en) 1980-09-19 1980-09-19 Preparation of steroid derivative

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Application Number Priority Date Filing Date Title
JP55129121A JPS5754200A (en) 1980-09-19 1980-09-19 Preparation of steroid derivative

Publications (2)

Publication Number Publication Date
JPS5754200A JPS5754200A (en) 1982-03-31
JPS6351157B2 true JPS6351157B2 (en) 1988-10-13

Family

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Application Number Title Priority Date Filing Date
JP55129121A Granted JPS5754200A (en) 1980-09-19 1980-09-19 Preparation of steroid derivative

Country Status (1)

Country Link
JP (1) JPS5754200A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4728331B2 (en) * 2005-06-16 2011-07-20 裕 片岡 Sound absorption structure

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