JPH0142264B2 - - Google Patents
Info
- Publication number
- JPH0142264B2 JPH0142264B2 JP19625281A JP19625281A JPH0142264B2 JP H0142264 B2 JPH0142264 B2 JP H0142264B2 JP 19625281 A JP19625281 A JP 19625281A JP 19625281 A JP19625281 A JP 19625281A JP H0142264 B2 JPH0142264 B2 JP H0142264B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- solvent
- ethanol
- spectrum
- present
- 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
Links
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は下式（）で示される23，25，26−ト
リヒドロキシビタミンD3に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to 23,25,26-trihydroxyvitamin D 3 represented by the following formula ().
本発明の式（）で示される化合物は新規化合
物であり、その分子中の23位および25位の不斉炭
素原子に由来する４種の光学異性体がある。 The compound represented by the formula () of the present invention is a new compound, and there are four types of optical isomers derived from the asymmetric carbon atoms at the 23rd and 25th positions in the molecule.
本発明の式（）で示される化合物を製造する
には種々の方法があるが、例えば25−ヒドロキシ
プロビタミンD326，23−ラクトンと４−フエニ
ル−１，２，４−トリアゾリン−３，５−ジオン
との１，４−環化付加体（）を出発物質とし以
下式示する方法によつて得られる。 There are various methods for producing the compound represented by the formula () of the present invention, for example, 25-hydroxyprovitamin D 3 26,23-lactone and 4-phenyl-1,2,4-triazoline-3, It can be obtained by the method shown below using a 1,4-cycloadduct () with 5-dione as a starting material.
この反応式において化合物（）は化合物
（）をエーテル、テトラヒドロフラン等の溶媒
中アルカリ金属水素化類、例えばリチウム水素化
アルミニウム、カリウム水素化アルミニウム等で
環元することによつて製造される。次いで化合物
（）をビタミンＤ骨格を製造する際の常套手段
である紫外線の照射−異性化という一連の手段に
付すと本発明の化合物（）が得られる。 In this reaction formula, the compound () is produced by ring-forming the compound () with an alkali metal hydride such as lithium aluminum hydride, potassium aluminum hydride, etc. in a solvent such as ether or tetrahydrofuran. Next, the compound () of the present invention is obtained by subjecting the compound () to a series of steps of ultraviolet irradiation and isomerization, which are conventional methods for producing a vitamin D skeleton.
このようにして得られた本発明の化合物（）
はビタミンＤ様の生物活性を有し医薬として有用
である。 Compound of the present invention thus obtained ()
has biological activity similar to vitamin D and is useful as a medicine.
実施例
(a) リチウム水酸化アルミニウム10mgを１mlのテ
トラヒドロフラン中で１時間加熱還流後、室温
に戻し、この中に化合物（′）28mgのテトラ
ヒドロフラン１ml溶液を加える。混合物を50分
間加熱還流後室温に戻し、水性テトラヒドロフ
ランで過剰のリチウム水酸化アルミニウムを分
解する。無機物を過し液は溶媒を留去後残
渣をセフアデツクスLH−20（10ｇ）（溶媒ヘキ
サン、クロロホルム、メタノール、25：75：
２）のカラムクロマトグラフイーに付し精製し
化合物（′）18mgを得る。Example (a) 10 mg of lithium aluminum hydroxide is heated under reflux in 1 ml of tetrahydrofuran for 1 hour, then returned to room temperature, and a solution of 28 mg of compound (') in 1 ml of tetrahydrofuran is added thereto. The mixture is heated to reflux for 50 minutes, then returned to room temperature and the excess lithium aluminum hydroxide is destroyed with aqueous tetrahydrofuran. After filtering the inorganic matter and distilling off the solvent, the residue was separated into Sephadex LH-20 (10 g) (solvent: hexane, chloroform, methanol, 25:75:
The product was purified by column chromatography as described in 2) to obtain 18 mg of compound (').
融点 225〜228℃
マススペクトルｍ／ｅ：432（M+）、414、
399、383
NMRスペクトル（DMSO−d6）δ：0.60
（3H、ｓ）、0.88（3H、ｓ）、1.10（3H、ｓ）、
5.42（2H、ABq）
UVスペクトルλmax（95％エタノール）：
293、282、272nｍ
(b) 化合物（′）６mgを局方エタノール200mlに
溶解しバイコール（Vycor）フイルターを通し
て高圧水銀灯（200W）にて５分間照射する。
溶媒を留去後残渣をセフアデツクスLH−20
（25ｇ）（溶媒クロロホルム、ヘキサン、メタノ
ール、75：25：2.5）を用いたカラムクロマト
グラフイーに付し精製し化合物（′）〔UVス
ペクトルλmax（95％エタノール）：260nｍ〕1.9
mgを得る。 Melting point 225-228℃ Mass spectrum m/e: 432 (M + ), 414,
399, 383 NMR spectrum (DMSO- d6 ) δ: 0.60
(3H, s), 0.88 (3H, s), 1.10 (3H, s),
5.42 (2H, ABq) UV spectrum λmax (95% ethanol):
293, 282, 272 nm (b) 6 mg of compound (') was dissolved in 200 ml of pharmacopoeial ethanol and irradiated for 5 minutes with a high pressure mercury lamp (200 W) through a Vycor filter.
After distilling off the solvent, the residue was transferred to Sephadex LH-20.
(25 g) (solvent chloroform, hexane, methanol, 75:25:2.5) to purify the compound (') [UV spectrum λmax (95% ethanol): 260 nm] 1.9
Get mg.
(c) 化合物（′）を局方エタノール２mlに溶解
しアルゴン気流下60〜63℃で７時間加温、室温
で８時間放置後溶媒を留去し残渣をセフアデツ
クスLH−20（25ｇ）（溶媒クロロホルム、ヘキ
サン、メタノール、75：25：７）を用いたカラ
ムクロマトグラフイーに付し精製し（23S、
25R）−23，25，26−トリヒドロキシビタミン
D3（′）1.9mgを得る。(c) Compound (') was dissolved in 2 ml of pharmacopoeial ethanol, heated at 60-63°C under an argon atmosphere for 7 hours, left at room temperature for 8 hours, the solvent was distilled off, and the residue was dissolved in Cephadex LH-20 (25 g) (solvent It was purified by column chromatography using chloroform, hexane, methanol (75:25:7) (23S,
25R)-23,25,26-trihydroxyvitamin
Obtain 1.9 mg of D 3 (′).
マススペクトルｍ／ｅ：432（M+）、414、399、
383、136、118
λmax（局方エタノール）：265nｍ
λmin：228nｍ
1HNMRスペクトル（CDCl3）δ：0.56（3H、
ｓ）、1.22（3H、ｓ）、3.57（2H、ABq、Ｊ＝11
Hz）、3.8〜4.2（2H、ｍ）、4.82（1H、bs）、5.04
（1H、bs）、6.13（2H、ABq、Ｊ＝11Hz）。 Mass spectrum m/e: 432 (M + ), 414, 399,
383, 136, 118 λmax (pharmacopoeial ethanol): 265nm λmin: 228nm 1 HNMR spectrum (CDCl 3 ) δ: 0.56 (3H,
s), 1.22 (3H, s), 3.57 (2H, ABq, J=11
Hz), 3.8-4.2 (2H, m), 4.82 (1H, bs), 5.04
(1H, bs), 6.13 (2H, ABq, J=11Hz).
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19625281A JPS5899461A (en) | 1981-12-08 | 1981-12-08 | 23,25,26-trihydroxyvitamin d3 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19625281A JPS5899461A (en) | 1981-12-08 | 1981-12-08 | 23,25,26-trihydroxyvitamin d3 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5899461A JPS5899461A (en) | 1983-06-13 |
| JPH0142264B2 true JPH0142264B2 (en) | 1989-09-11 |
Family
ID=16354711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19625281A Granted JPS5899461A (en) | 1981-12-08 | 1981-12-08 | 23,25,26-trihydroxyvitamin d3 |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5899461A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58109469A (en) * | 1981-12-23 | 1983-06-29 | Teijin Ltd | 23,25,26-trihydroxyvitamin d3 |
-
1981
- 1981-12-08 JP JP19625281A patent/JPS5899461A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5899461A (en) | 1983-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cornforth et al. | Studies of cholesterol biosynthesis. 1. A new chemical degradation of cholesterol | |
| JPS5854160B2 (en) | Method for producing 1α,3β-dihydroxysteroid-5-ene or its derivative | |
| WO1998000397A1 (en) | Crystals of vitamin d derivatives and process for the preparation thereof | |
| McMorris et al. | Synthesis of antheridiol and some observations on the chemistry of butenolides | |
| JPH0142264B2 (en) | ||
| JPS5995231A (en) | Manufacture of optically active compound | |
| JPS6148497B2 (en) | ||
| JPS643880B2 (en) | ||
| Wenkert et al. | Synthesis of Retuline | |
| KR950008970B1 (en) | Process for preparing t'butyl ergoline derivatives | |
| HU187843B (en) | Process for producing 17-alpha-hydroxy-17-beta-bracket-hydroxy-acetyl-bracket closed-steroides | |
| DOORENBOS et al. | Steroids. IV. Synthesis of Some 4-Azacholestanes1-4 | |
| Spry et al. | Azabicyclic alcohols. VI. Azabicyclo [2.2. 1] heptan-3-ol epimers | |
| Heathcock et al. | On Mukharji's “cyclodecadienone” | |
| JPS5813515A (en) | Antialdosterone active steroid derivative | |
| Yoshioka et al. | Tetraneurin-E and-F. New C-15 oxygenated pseudoguaianolides from Parthenium (Compositae) | |
| US3058976A (en) | 3, 3-dimethoxy-20-spirox-5(10)-ene-21-one and process of preparation | |
| US2534823A (en) | 1-keto-2-hydroxymethylene-7-or-1, 2, 3, 4-tetrahydrophenanthrenes | |
| Goldberg et al. | Leguminosae alkaloids. V. Chemistry and stereochemistry of multiflorine | |
| US3300501A (en) | 6-azasteroids | |
| DE1593613C3 (en) | 7 (alpha and beta) -methyl androstened derivatives and process for their preparation | |
| JPS5822450B2 (en) | Isolongiphoran-3-ol | |
| JPS6352636B2 (en) | ||
| Williams et al. | Synthesis of Δ5-Pregnene-3α, 16α, 20α-triol1 | |
| JPS5862187A (en) | Production of 6-hydroxymethyluridine |