JPH1087690A - Deprotection of steroid derivative - Google Patents
Deprotection of steroid derivativeInfo
- Publication number
- JPH1087690A JPH1087690A JP8239389A JP23938996A JPH1087690A JP H1087690 A JPH1087690 A JP H1087690A JP 8239389 A JP8239389 A JP 8239389A JP 23938996 A JP23938996 A JP 23938996A JP H1087690 A JPH1087690 A JP H1087690A
- Authority
- JP
- Japan
- Prior art keywords
- steroid
- phenyl
- ptad
- diene
- triazoline
- 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.)
- Pending
Links
Landscapes
- Steroid Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ステロイド−（４
−フェニル−１,２,４−トリアゾリン−３,５−ジオ
ン）付加体（以下、ステロイド−ＰＴＡＤ付加体と略記
する）から選択的に４−フェニル−１,２,４−トリアゾ
リン−３,５−ジオン（以下、ＰＴＡＤと略記する）を
脱離してステロイドの５,７−ジエン体を脱保護する方
法に関する。TECHNICAL FIELD The present invention relates to a steroid- (4
-Phenyl-1,2,4-triazoline-3,5-dione) adduct (hereinafter abbreviated as steroid-PTAD adduct) and selectively 4-phenyl-1,2,4-triazoline-3,5. A method of deprotecting a 5,7-diene derivative of a steroid by removing dione (hereinafter abbreviated as PTAD).
【０００２】[0002]
【従来の技術】ＰＴＡＤはビタミンＤ化合物のプロ体で
ある不安定な５,７−ジエン誘導体の５,７−ジエンにデ
ィールス・アルダー型の付加を行うことによってステロ
イド−ＰＴＡＤ付加体を生成させ、もって５,７−ジエ
ンを保護するための試薬としてしばしば用いられる化合
物である（有機合成化学協会誌、53,791(1995）参
照）。一方、このようにして付加されたＰＴＡＤはこれ
を脱離して５,７−ジエン体を再生しなければならない
ことから、ＰＴＡＤを選択的かつ効率良く脱離して５，
７−ジエンを再生する脱保護工程が必然的にこの保護、
脱保護の一連の工程において重要である。2. Description of the Related Art PTAD forms a steroid-PTAD adduct by performing a Diels-Alder-type addition to an unstable 5,7-diene derivative, which is a pro-form of a vitamin D compound. Thus, it is a compound often used as a reagent for protecting 5,7-diene (refer to Journal of the Society of Synthetic Organic Chemistry, 53, 791 (1995)). On the other hand, the PTAD thus added must be desorbed to regenerate the 5,7-diene derivative.
A deprotection step to regenerate the 7-diene necessarily entails this protection,
It is important in a series of steps of deprotection.
【０００３】従来、ＰＴＡＤの脱離方法としては、Ｌｉ
ＡｌＨ4、ジイソブチルアルミニウムハイドライド（Ｄ
ＩＢＡＬ）等の還元剤を用いてステロイド−ＰＴＡＤ付
加体を処理する方法やＫ2ＣＯ3−ＤＭＳＯ等のアルカリ
性条件下にステロイド−ＰＴＡＤ付加体を処理する方法
などが知られている。しかし、これらの方法はステロイ
ド内に、エポキシド、エステル等の官能基が存在する場
合には使用することが出来ない制約がある。Conventionally, PTAD desorption methods include Li
AlH 4 , diisobutylaluminum hydride (D
A method of treating a steroid-PTAD adduct with a reducing agent such as IBAL) and a method of treating a steroid-PTAD adduct under alkaline conditions such as K 2 CO 3 -DMSO are known. However, these methods have a limitation that they cannot be used when a functional group such as an epoxide or an ester is present in the steroid.
【０００４】また１,３−ジメチル−２−イミダゾリジ
ノン（ＤＭＩ）、γ−コリジン等の有機塩基を用いるス
テロイド−ＰＴＡＤ付加体を処理してＰＴＡＤを離脱す
る方法も知られているが、これらは溶媒として用いる場
合のみに有効で、しかして分離精製を含む後処理にも困
難があり、経済的な方法とは言えない欠点がある（J.Ch
em.Soc., Perkin Trans1,1995,2679 参照）。There is also known a method of removing PTAD by treating a steroid-PTAD adduct using an organic base such as 1,3-dimethyl-2-imidazolidinone (DMI) or γ-collidine. Is effective only when it is used as a solvent. However, it is difficult to carry out post-treatment including separation and purification, and has a disadvantage that it cannot be said to be an economical method (J. Ch.
em. Soc., Perkin Trans1, 1995, 2679).
【０００５】[0005]
【発明が解決しようとする課題】従って、ステロイド−
ＰＴＡＤ付加体のＰＴＡＤを選択的にかつ効率良く脱離
して付加体からのＰＴＡＤの脱保護によって５,７−ジ
エンステロイドを再生する方法の開発が望まれていた。SUMMARY OF THE INVENTION Accordingly, steroids
It has been desired to develop a method for selectively and efficiently removing PTAD of a PTAD adduct to regenerate a 5,7-diene steroid by deprotecting PTAD from the adduct.
【０００６】[0006]
【課題を解決するための手段】本発明者は、上記した課
題を解決するために鋭意研究した結果、ステロイドの
５,７−ジエンにＰＴＡＤが付加された、ステロイド−
ＰＴＡＤ付加体から、ＰＴＡＤを選択的にかつ効率良く
脱離し、５,７−ジエンステロイドを再生する方法を見
出し本発明を完成した。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, it has been found that steroids obtained by adding PTAD to 5,7-diene of steroids.
The present inventors have found a method for selectively and efficiently removing PTAD from a PTAD adduct and regenerating a 5,7-diene steroid, and completed the present invention.
【０００７】すなわち、本発明は、ステロイドの５,７
−ジエン体にＰＴＡＤを付加することにより、この５,
７−ジエンが保護されたステロイド−ＰＴＡＤ付加体
を、ジアザビシクロウンデセン（以下、ＤＢＵと略記す
る）で処理してＰＴＤＡを脱離することからなる、ステ
ロイドの５,７−ジエン体の脱保護方法に関する。That is, the present invention relates to 5,7
-By adding PTAD to the diene, this 5,
Deprotection of a steroidal 5,7-diene derivative comprising treating a 7-diene protected steroid-PTAD adduct with diazabicycloundecene (hereinafter abbreviated as DBU) to release PTDA. Regarding protection methods.
【０００８】本発明によれば、次の反応スキームに示さ
れるように一般式(Ｉ)又は(II)で表されるステロイド−
ＰＴＡＤ付加体をＤＢＵで処理することにより、ステロ
イド−ＰＴＡＤ付加体から選択的にＰＴＡＤが脱離して
それぞれ一般式(III)又は(IV)で表されるステロイド−
５,７−ジエン誘導体を効率よく再生することが出来る
のである。According to the present invention, a steroid represented by the general formula (I) or (II) is represented by the following reaction scheme:
By treating the PTAD adduct with DBU, PTAD is selectively eliminated from the PTAD adduct and the steroid represented by the general formula (III) or (IV), respectively.
The 5,7-diene derivative can be efficiently regenerated.
【０００９】[0009]
【化１】 Embedded image
【００１０】このステロイド−ＰＴＡＤ付加体からのＰ
ＴＡＤの離脱反応に用いるＤＢＵは、ステロイド−ＰＴ
ＡＤ付加体に対して０.１〜１００当量、好ましくは０.
２５〜１０.０当量の量で用いることができる。The P from the steroid-PTAD adduct
DBU used for TAD withdrawal reaction is steroid-PT
0.1 to 100 equivalents, preferably 0.1 equivalent, based on the AD adduct.
It can be used in an amount of 25 to 10.0 equivalents.
【００１１】この離脱反応は好ましくは溶媒中で行われ
る。用いる溶媒には特に限定はなく、広範囲の不活性溶
媒を用いることができるが、一般には炭化水素溶媒、具
体的にはキシレンが好ましく使用される。反応温度には
特に限定はないが、より高められた温度での反応によっ
てより速やかに反応が進行するところから、一般には使
用した溶媒の沸点付近で反応を行うことが反応温度と反
応速度の制御の観点から好ましい。This elimination reaction is preferably carried out in a solvent. The solvent to be used is not particularly limited, and a wide range of inert solvents can be used. Generally, a hydrocarbon solvent, specifically, xylene is preferably used. The reaction temperature is not particularly limited, but since the reaction proceeds more rapidly by the reaction at a higher temperature, it is generally necessary to perform the reaction near the boiling point of the solvent used to control the reaction temperature and the reaction rate. It is preferable from the viewpoint of.
【００１２】本発明に従って、ステロイド−ＰＴＡＤ付
加体とＤＢＵとを溶媒中で加熱してＰＴＡＤの脱離反応
を行った後で、溶媒を留去し、残留物を常法により結晶
化するか、またはクロマトグラフィーで精製することに
より脱保護された５,７−ジエンが得られる。According to the present invention, after the steroid-PTAD adduct and DBU are heated in a solvent to carry out the elimination reaction of PTAD, the solvent is distilled off, and the residue is crystallized by a conventional method. Alternatively, purification by chromatography yields the deprotected 5,7-diene.
【００１３】[0013]
【実施例】次に本発明を実施例をあげて説明するが、本
発明はこれらに限定されるものではない。Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
【００１４】実施例１ １α,２α−エポキシ−５,７−コレスタジエン−３β,
２５−ジオ−ルの合成 １α,２α−エポキシ−５α,８α−（４−フェニル−
３,５−ジオキソ−１,２,４−トリアゾリジン）−６−
コレステン−３β,２５−ジオール３００mg、ＤＢＵ１
５０mgにキシレン５mlを加え１時間加熱還流した。次い
で、キシレンを留去し、残留物をシリカゲルクロマトグ
ラフィーで精製し、５,７−ジエン体を１９０mg得た。1 Ｈ−ＮＭＲ（ＣＤＣl3）：０.６３（３Ｈ,ｓ），０.９
５（３Ｈ,ｄ），１.０２（３Ｈ,ｓ），１.０８，１.１
０（各３Ｈ,６Ｈ），３.０５（１Ｈ,ｍ），３.３２（１
Ｈ,ｍ）３.８８（１Ｈ,ｍ），５.３９（１Ｈ,ｍ），５.
７２（１Ｈ,ｍ）．Example 1 1α, 2α-Epoxy-5,7-cholestadiene-3β,
Synthesis of 25-diol: 1α, 2α-epoxy-5α, 8α- (4-phenyl-
3,5-dioxo-1,2,4-triazolidine) -6
Cholesten-3β, 25-diol 300 mg, DBU1
5 ml of xylene was added to 50 mg, and the mixture was heated under reflux for 1 hour. Then, xylene was distilled off, and the residue was purified by silica gel chromatography to obtain 190 mg of a 5,7-diene compound. 1 H-NMR (CDCl3): 0.63 (3H, s), 0.9
5 (3H, d), 1.02 (3H, s), 1.08, 1.1
0 (3H, 6H each), 3.05 (1H, m), 3.32 (1
H, m) 3.88 (1H, m), 5.39 (1H, m), 5.
72 (1H, m).
【００１５】実施例２ １α,３β−ジアセトキシ−５,７−コレスタジエンの合
成 １α,３β−ジアセトキシ−５α,８α−（４−フェニル
−３,５−ジオキソ−１,２,４−トリアゾリジン）−６
−コレステン２００mg、ＤＢＵ５０mgにキシレン４mlを
加え、２時間加熱還流した。次いで、キシレンを留去
し、残留物をシリカクロマトグラフィーで精製した。
５,７−ジエン体を１２０mg得た。1 Ｈ−ＮＭＲ（ＣＤＣl3）：０.６２（３Ｈ,ｓ），０.８
８（６Ｈ,ｄ），０.９５（３Ｈ,ｄ），１.０２（３Ｈ,
ｓ），２.０３，２.０８（各３Ｈ,ｓ），５.０２（２
Ｈ,ｍ），５.４１（１Ｈ,ｍ），５.７２（１Ｈ,ｍ）．Example 2 Synthesis of 1α, 3β-diacetoxy-5,7-cholestadiene 1α, 3β-diacetoxy-5α, 8α- (4-phenyl-3,5-dioxo-1,2,4-triazolidine) -6
4 ml of xylene was added to 200 mg of cholestene and 50 mg of DBU, and the mixture was heated under reflux for 2 hours. Then xylene was distilled off and the residue was purified by silica chromatography.
120 mg of the 5,7-diene compound was obtained. 1 H-NMR (CDCl3): 0.62 (3H, s), 0.8
8 (6H, d), 0.95 (3H, d), 1.02 (3H,
s), 2.03, 2.08 (each 3H, s), 5.02 (2
H, m), 5.41 (1H, m), 5.72 (1H, m).
【００１６】実施例３ ３β−（ｔ−ブチルジメチルシリロキシ）−２３、２４
−ジノル−５,７−コラジエン−２２−オ−ルの合成 ３β−（ｔ−ブチルジメチルシリロキシ）−５α,８α
−（４−フェニル−３、５−ジオキソ−１,２,４−トリ
アゾリジン）−２３,２４−ジノル−６−コレン−２２
−オール４００mg、ＤＢＵ４００mgにキシレン１０mlを
加え、０.５時間加熱還流した。この反応液をブライン
で洗浄した後、溶媒を留去した。得られた残留物をメタ
ノ−ルで結晶化して、２６０mgの５,７−ジエン体を得
た。1 Ｈ−ＮＭＲ（ＣＤＣl3）：０.１０（６Ｈ,ｓ），０.６
８（３Ｈ,ｓ），０.８９（９Ｈ,ｓ），０.９５（３Ｈ,
ｓ），１.０９（３Ｈ,ｄ），３.３５（１Ｈ,ｍ），３.
６０（２Ｈ,ｍ），５.３７（１Ｈ,ｍ），５.５６（１
Ｈ,ｍ）Example 3 3β- (t-Butyldimethylsilyloxy) -23,24
Synthesis of -dinor-5,7-colladien-22-ol 3β- (t-butyldimethylsilyloxy) -5α, 8α
-(4-phenyl-3,5-dioxo-1,2,4-triazolidine) -23,24-dinor-6-cholene-22
10 ml of xylene was added to 400 mg of all and 400 mg of DBU, and the mixture was refluxed for 0.5 hour. After washing the reaction solution with brine, the solvent was distilled off. The obtained residue was crystallized from methanol to obtain 260 mg of a 5,7-diene compound. 1 H-NMR (CDCl 3): 0.10 (6H, s), 0.6
8 (3H, s), 0.89 (9H, s), 0.95 (3H, s)
s), 1.09 (3H, d), 3.35 (1H, m), 3.
60 (2H, m), 5.37 (1H, m), 5.56 (1
H, m)
【００１７】実施例４ ３β−アセトキシ−５,７−エルゴスタジエン−２５−
オールの合成 ３β−アセトキシ−５α,８α−（４−フェニル−３、
５−ジオキソ−１,２,４−トリアゾリジン）−６−エル
ゴステン−２５−オール３００mg、ＤＢＵ１５０mgにキ
シレン５mlを加え、１時間加熱還流した。その後、実施
例１と同様に処理して、５,７−ジエン体を１９５mg得
た。1 Ｈ−ＮＭＲ（ＣＤＣl3）：０.６５（３Ｈ,ｓ），０.８
９（３Ｈ,ｄ），０.９５（３Ｈ,ｓ），０.９９（３Ｈ,
ｄ），１.０８，１.０９（各３Ｈ,ｓ），２.０３（３
Ｈ,ｓ），４.７１（１Ｈ,ｍ），５.４０（１Ｈ,ｍ），
５.５８（１Ｈ,ｍ）．Example 4 3β-acetoxy-5,7-ergostadiene-25
Synthesis of all 3β-acetoxy-5α, 8α- (4-phenyl-3,
5 ml of xylene was added to 300 mg of 5-dioxo-1,2,4-triazolidine) -6-ergosten-25-ol and 150 mg of DBU, and the mixture was heated under reflux for 1 hour. Thereafter, the same treatment as in Example 1 was carried out to obtain 195 mg of a 5,7-diene compound. 1 H-NMR (CDCl3): 0.65 (3H, s), 0.8
9 (3H, d), 0.95 (3H, s), 0.99 (3H,
d), 1.08, 1.09 (each 3H, s), 2.03 (3
H, s), 4.71 (1H, m), 5.40 (1H, m),
5.58 (1H, m).
【００１８】実施例５ （２４Ｒ）−３β−ベンゾイロキシ−１α,２α−エポ
キシ−５,７−エルゴスタジエン−２５−オールの合成 （２４Ｒ）−３β−ベンゾイロキシ−１α,２α−エポ
キシ−５α,８α−（４−フェニル−３,５−ジオキソ−
１,２,４−トリアゾリジン）−６−エルゴステン−２５
−オール３００mg、ＤＢＵ７０mgにキシレン１０mlを加
え、３時間加熱還流した。その後、実施例１と同様に処
理して、５,７−ジエン体を１９７mg得た。1 Ｈ−ＮＭＲ（ＣＤＣl3）：０.６３（３Ｈ,ｓ），０.８
５（３Ｈ,ｄ），０.９６（３Ｈ,ｓ），１.０２（３Ｈ,
ｄ），１.０９，１.１０（各３Ｈ,ｓ），３.１２（１
Ｈ,ｍ），３.４８（１Ｈ,ｍ），５.１７（１Ｈ,ｍ），
５.４０（１Ｈ,ｍ），５.７６（１Ｈ,ｍ），７.４１
（２Ｈ,ｍ），７.５７（１Ｈ,ｍ），８.０６（２Ｈ,
ｍ）Example 5 Synthesis of (24R) -3β-benzoyloxy-1α, 2α-epoxy-5,7-ergostadien-25-ol (24R) -3β-benzoyloxy-1α, 2α-epoxy-5α, 8α -(4-phenyl-3,5-dioxo-
1,2,4-triazolidine) -6-ergostene-25
10 ml of xylene was added to 300 mg of ol and 70 mg of DBU, and the mixture was refluxed for 3 hours. Thereafter, the same treatment as in Example 1 was carried out to obtain 197 mg of a 5,7-diene compound. 1 H-NMR (CDCl3): 0.63 (3H, s), 0.8
5 (3H, d), 0.96 (3H, s), 1.02 (3H,
d), 1.09, 1.10 (each 3H, s), 3.12 (1
H, m), 3.48 (1H, m), 5.17 (1H, m),
5.40 (1H, m), 5.76 (1H, m), 7.41
(2H, m), 7.57 (1H, m), 8.06 (2H,
m)
【００１９】本発明の方法によって得られた実験結果を
表１および表２にまとめた。The experimental results obtained by the method of the present invention are summarized in Tables 1 and 2.
【表１】 [Table 1]
【００２０】[0020]
【表２】 [Table 2]
Claims (1)
ェニル−１,２,４−トリアゾリン−３,５−ジオンを付
加することにより、この５,７−ジエンが保護されたス
テロイド−（４−フェニル−１,２,４−トリアゾリン−
３,５−ジオン）付加体を、ジアザビシクロウンデセン
で処理して４−フェニル−１,２,４−トリアゾリン−
３,５−ジオンを脱離することからなる、ステロイドの
５,７−ジエン体の脱保護方法。The present invention relates to a steroid wherein the 5,7-diene is protected by adding 4-phenyl-1,2,4-triazoline-3,5-dione to the 5,7-diene derivative of the steroid. 4-phenyl-1,2,4-triazoline-
The 3,5-dione) adduct is treated with diazabicycloundecene to give 4-phenyl-1,2,4-triazoline-
A method for deprotecting a 5,7-diene derivative of a steroid, comprising removing 3,5-dione.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8239389A JPH1087690A (en) | 1996-09-10 | 1996-09-10 | Deprotection of steroid derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8239389A JPH1087690A (en) | 1996-09-10 | 1996-09-10 | Deprotection of steroid derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1087690A true JPH1087690A (en) | 1998-04-07 |
Family
ID=17044064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8239389A Pending JPH1087690A (en) | 1996-09-10 | 1996-09-10 | Deprotection of steroid derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1087690A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015157262A1 (en) | 2014-04-07 | 2015-10-15 | Women & Infants Hospital Of Rhode Island | Novel 7-Dehydrocholesterol Derivatives and Methods Using Same |
| CN114685337A (en) * | 2022-04-24 | 2022-07-01 | 浙江花园生物高科股份有限公司 | Preparation method of eldecalcitol |
-
1996
- 1996-09-10 JP JP8239389A patent/JPH1087690A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015157262A1 (en) | 2014-04-07 | 2015-10-15 | Women & Infants Hospital Of Rhode Island | Novel 7-Dehydrocholesterol Derivatives and Methods Using Same |
| EP3128996A4 (en) * | 2014-04-07 | 2017-11-29 | Women and Infants Hospital of Rhode Island Inc. | Novel 7-Dehydrocholesterol Derivatives and Methods Using Same |
| CN114685337A (en) * | 2022-04-24 | 2022-07-01 | 浙江花园生物高科股份有限公司 | Preparation method of eldecalcitol |
| CN114685337B (en) * | 2022-04-24 | 2023-08-29 | 浙江花园生物高科股份有限公司 | Preparation method of idecalcitol |
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