JPS6353990B2 - - Google Patents
Info
- Publication number
- JPS6353990B2 JPS6353990B2 JP4906981A JP4906981A JPS6353990B2 JP S6353990 B2 JPS6353990 B2 JP S6353990B2 JP 4906981 A JP4906981 A JP 4906981A JP 4906981 A JP4906981 A JP 4906981A JP S6353990 B2 JPS6353990 B2 JP S6353990B2
- Authority
- JP
- Japan
- Prior art keywords
- acetonide
- cholestan
- diol
- cholest
- added
- 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 239000012043 crude product Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 150000002009 diols Chemical group 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- 239000012285 osmium tetroxide Substances 0.000 description 4
- 229910000489 osmium tetroxide Inorganic materials 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RTEXIPZMMDUXMR-UHFFFAOYSA-N benzene;ethyl acetate Chemical compound CCOC(C)=O.C1=CC=CC=C1 RTEXIPZMMDUXMR-UHFFFAOYSA-N 0.000 description 3
- MDHYEMXUFSJLGV-UHFFFAOYSA-N beta-phenethyl acetate Natural products CC(=O)OCCC1=CC=CC=C1 MDHYEMXUFSJLGV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UPGTYLFCVNHBTN-DPAQBDIFSA-N (+)-22-dehydrocholesterol Natural products C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)C=CCC(C)C)[C@@]1(C)CC2 UPGTYLFCVNHBTN-DPAQBDIFSA-N 0.000 description 2
- XYPISWUKQGWYGX-UHFFFAOYSA-N 2,2,2-trifluoroethaneperoxoic acid Chemical compound OOC(=O)C(F)(F)F XYPISWUKQGWYGX-UHFFFAOYSA-N 0.000 description 2
- IXVMHGVQKLDRKH-VRESXRICSA-N Brassinolide Natural products O=C1OC[C@@H]2[C@@H]3[C@@](C)([C@H]([C@@H]([C@@H](O)[C@H](O)[C@H](C(C)C)C)C)CC3)CC[C@@H]2[C@]2(C)[C@@H]1C[C@H](O)[C@H](O)C2 IXVMHGVQKLDRKH-VRESXRICSA-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
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- -1 [22R,23R]-22,23-dihydroxycholesterol Chemical compound 0.000 description 2
- IXVMHGVQKLDRKH-KNBKMWSGSA-N brassinolide Chemical compound C1OC(=O)[C@H]2C[C@H](O)[C@H](O)C[C@]2(C)[C@H]2CC[C@]3(C)[C@@H]([C@H](C)[C@@H](O)[C@H](O)[C@@H](C)C(C)C)CC[C@H]3[C@@H]21 IXVMHGVQKLDRKH-KNBKMWSGSA-N 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 description 2
- 235000019800 disodium phosphate Nutrition 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- ZIXHWHMARYZKSX-UHFFFAOYSA-N 2-methylpropan-2-ol;oxolane;hydrate Chemical compound O.CC(C)(C)O.C1CCOC1 ZIXHWHMARYZKSX-UHFFFAOYSA-N 0.000 description 1
- 229930192334 Auxin Natural products 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- SUZLCBGCNKHSMK-NXNYVBGXSA-N CC(C)C[C@H]([C@@H]([C@@H](C)[C@H]1CC[C@H]2[C@@H]3CC([C@H]4CC=CC[C@]4(C)[C@H]3CC[C@]12C)=O)O)O Chemical compound CC(C)C[C@H]([C@@H]([C@@H](C)[C@H]1CC[C@H]2[C@@H]3CC([C@H]4CC=CC[C@]4(C)[C@H]3CC[C@]12C)=O)O)O SUZLCBGCNKHSMK-NXNYVBGXSA-N 0.000 description 1
- QWOJMRHUQHTCJG-UHFFFAOYSA-N CC([CH2-])=O Chemical compound CC([CH2-])=O QWOJMRHUQHTCJG-UHFFFAOYSA-N 0.000 description 1
- 150000001204 N-oxides Chemical class 0.000 description 1
- BUIQRTDBPCHRIR-UHFFFAOYSA-L O[Cr](Cl)(=O)=O Chemical compound O[Cr](Cl)(=O)=O BUIQRTDBPCHRIR-UHFFFAOYSA-L 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- QPFYXYFORQJZEC-FOCLMDBBSA-N Phenazopyridine Chemical compound NC1=NC(N)=CC=C1\N=N\C1=CC=CC=C1 QPFYXYFORQJZEC-FOCLMDBBSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002363 auxin Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001646 brassinolides Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- UREBWPXBXRYXRJ-UHFFFAOYSA-N ethyl acetate;methanol Chemical compound OC.CCOC(C)=O UREBWPXBXRYXRJ-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 description 1
- 230000009916 joint effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- CJNLSQRTIXIHGW-BNYRCUELSA-N norbrassinolide Chemical compound C1OC(=O)[C@H]2C[C@H](O)[C@H](O)C[C@]2(C)[C@H]2CC[C@]3(C)[C@@H]([C@H](C)[C@@H](O)[C@H](O)CC(C)C)CC[C@H]3[C@@H]21 CJNLSQRTIXIHGW-BNYRCUELSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000003375 plant hormone Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229940070891 pyridium Drugs 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003338 secosteroids Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Pyrane Compounds (AREA)
- Steroid Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
【発明の詳細な説明】
セイヨウアブラナ（Brassia napus L.）の花
粉から単離されたブラシノリド（22R，23R，
24S−2α，3α，22，23−テトラヒドロキシ−Ｂ−
ホモ−７−オキサ−5α−エルゴスタン−６−オ
ン）は植物生長促進作用をもつセコステロイド
で、側鎖部にビシナルジオール基を有する特徴的
な構造を示すことが知られている。[Detailed Description of the Invention] Brassinolides (22R, 23R,
24S-2α,3α,22,23-tetrahydroxy-B-
Homo-7-oxa-5α-ergostan-6-one) is a secosteroid with a plant growth-promoting effect and is known to exhibit a characteristic structure with a vicinal diol group in the side chain.
本発明者らはブラシノリドの関連化合物合成に
ついて研究を重ねた結果、文献未載の〔22R，
23R〕−2α，3α−ジアシルオキシ−5α−コレスタ
ン−６−オン−22，23−ジオール22，23−アセト
ニリド（）を製造することができ、この化合物
を経由して新規化合物〔22R，23R〕−Ｂ−ホモ
−７−オキサ−5α−コレスタン−６−オン−2α，
3α，22，23−テトラオール（XI）〔24−デメチル
ブラシノリド〕合成することに成功し、これがブ
ラシノリドと同様に植物生長促進作用を有するこ
とを知つた。 As a result of repeated research on the synthesis of related compounds of brassinolide, the present inventors found that [22R,
23R]-2α,3α-diacyloxy-5α-cholestan-6-one-22,23-diol 22,23-acetonilide () can be produced, and via this compound, a new compound [22R, 23R] -B-homo-7-oxa-5α-cholestan-6-one-2α,
We succeeded in synthesizing 3α,22,23-tetraol (XI) [24-demethylbrassinolide] and learned that it has plant growth promoting effects similar to brassinolide.
化合物（XI）は次のようにして製造することが
できる。以下、後記の反応式を参照しながら説明
する。 Compound (XI) can be produced as follows. The reaction will be explained below with reference to the reaction formula described below.
公知の化合物22，23−デヒドロコレステロール
（）をＮ−メチルモルホリン−Ｎ−オキシドの
存在下、触媒量の四酸化オスミウムで酸化すると
〔22R，23R〕−22，23−ジヒドロキシコレステロ
ール（）と〔22S，23S）−22，23−ジヒドロキ
シコレステロール（）が２：５の比率で得られ
る。これらの化合物はシリカゲルカラムクロマト
グラフイーにより容易に分離できる。〔22R，
23R〕−体（）を次いでアセトン中触媒量のｐ
−トルエンスルホン酸と反応させると、〔22R，
23R〕−コレスト−５−エン−3β，22，23−トリ
オール22，23−アセトニド（）が得られ、これ
をさらにピリジン中メタンスルホニルクロリドと
反応させると〔22R，23R〕−3β−メタンスルホ
ニルオキシ−コレスト−５−エン−22，23−ジオ
ール22，23−アセトニド（）が得られる。 Oxidation of the known compound 22,23-dehydrocholesterol () with a catalytic amount of osmium tetroxide in the presence of N-methylmorpholine-N-oxide produces [22R,23R]-22,23-dihydroxycholesterol () and [22S , 23S)-22,23-dihydroxycholesterol () is obtained in a ratio of 2:5. These compounds can be easily separated by silica gel column chromatography. [22R,
23R]-isomer () was then dissolved in a catalytic amount of p in acetone.
-When reacted with toluenesulfonic acid, [22R,
23R]-Cholest-5-ene-3β,22,23-triol 22,23-acetonide () is obtained which is further reacted with methanesulfonyl chloride in pyridine to give [22R,23R]-3β-methanesulfonyloxy. -Cholest-5-ene-22,23-diol 22,23-acetonide () is obtained.
次に化合物（）にテトラヒドロフラン中ジボ
ランを作用させてハイドロボレーシヨンを行い、
アルカリ性下過酸化水素を作用させることによつ
て水酸化を行い、さらにこの粗生成物を塩化メチ
レン中ピリジニウムクロロクロメートで酸化して
〔22R，23R〕−3β−メタンスルホニルオキシ−5α
−コレスタン−６−オン−22，23−ジオール22，
23−アセトニド（）を得ることができる。 Next, compound () is subjected to hydroboration by acting with diborane in tetrahydrofuran,
Hydroxylation was carried out by the action of hydrogen peroxide under alkaline conditions, and the crude product was further oxidized with pyridinium chlorochromate in methylene chloride to give [22R,23R]-3β-methanesulfonyloxy-5α.
-cholestan-6-one-22,23-diol 22,
23-acetonide () can be obtained.
得られた化合物（）はジメチルホルムアミド
中臭化リチウムと作用させて３位のスルホニルオ
キシ基をスルホン酸として離脱させ〔22R，
23R〕−5α−コレスト−２−エン−６−オン−22，
23−ジオール22，23−アセトニド（）を得るこ
とができる。 The obtained compound () was reacted with lithium bromide in dimethylformamide to remove the sulfonyloxy group at the 3-position as a sulfonic acid [22R,
23R〕-5α-cholest-2-en-6-one-22,
23-diol 22,23-acetonide () can be obtained.
次いで化合物（）をＮ−メチルモルホリン−
Ｎ−オキシドの存在下、触媒量の四酸化オスミウ
ムを用いて酸化すると2α、3α位に水酸基が導入
された〔22R，23R〕−5α−コレスタン−６−オ
ン−2α，3α，22，23−テトラオール22，23−ア
セトニド（）を得られ、この化合物（）をピ
リジン中無水酢酸でアセチル化して〔22R，
23R〕−2α，3α−ジアセトキシ−5α−コレスタン
−６−オン−22，23−ジオール22，23−アセトニ
ド（XI）を得ることができる。 Then compound () was converted into N-methylmorpholine-
Oxidation with a catalytic amount of osmium tetroxide in the presence of N-oxide introduced hydroxyl groups at the 2α and 3α positions [22R,23R]-5α-cholestan-6-one-2α,3α,22,23- Tetraol 22,23-acetonide () was obtained, and this compound () was acetylated with acetic anhydride in pyridine [22R,
23R]-2α,3α-diacetoxy-5α-cholestan-6-one-22,23-diol 22,23-acetonide (XI) can be obtained.
この化合物を次いで塩化メチレン中トリフルオ
ロ過酢酸でリン酸二ナトリウムの存在下酸化する
と〔22R，23R〕−Ｂ−ホモ−７−オキサ−5α−
コレスタン−６−オン−2α，3α，22，23−テト
ラオール22，23−ジアセテート（）を得られ
る。 This compound was then oxidized with trifluoroperacetic acid in methylene chloride in the presence of disodium phosphate to yield [22R,23R]-B-homo-7-oxa-5α-
Cholestan-6-one-2α,3α,22,23-tetraol 22,23-diacetate () is obtained.
続いてこの化合物（）をメタノール性水酸化
カリウムで加水分解して、塩で酸性とすると
〔22R，23R〕−Ｂ−ホモ−７−オキサ−5α−コレ
スタン−６−オン−2α，3α，22，23−テトラオ
ール（XI）を得られる。 Subsequently, this compound () is hydrolyzed with methanolic potassium hydroxide and acidified with a salt to give [22R,23R]-B-homo-7-oxa-5α-cholestan-6-one-2α,3α,22 , 23-tetraol (XI) can be obtained.
次に上記の反応工程を図示する。 Next, the above reaction steps will be illustrated.
かくして得られるデメチルブラシノリド（XI）
はオーキシン（植物ホルモン）様の作用を有し、
文献〔E.Maedaら、Phisiol.Plant 18 813
（1965）〕記載の方法によりイネのラミナジヨイン
ト活性を測定したところ、有意な活性濃度範囲は
0.01〜0.005μｇ／mlであつた。 Demethylbrassinolide (XI) thus obtained
has an auxin (plant hormone)-like effect,
Literature [E. Maeda et al., Philiol. Plant 18 813
(1965)] measured the laminar joint activity in rice using the method described, and found that the range of significant activity concentrations was
It was 0.01-0.005 μg/ml.
実施例
(1) 22，23−デヒドロコレステロール（）1.5
ｇをｔ−ブタノール−テトラヒドロフラン−水
（10：３：１）25mlとテトラヒドロフラン５ml
の混合溶媒に溶かし、これにＮ−メチルモルホ
リン−Ｎ−オキシド0.5ｇと触媒量の四酸化オ
スミウムを加えて室温にて四日間撹拌した。溶
媒を留去後生成する残渣をシリカゲルカラムク
ロマトグラフイーによりベンゼン−酢酸エチル
（20：１）の溶出画分より〔22S，23S〕−コレ
スト−５−エン−3β，22，23−トリオール
〔〕0.78ｇを得た。Example (1) 22,23-dehydrocholesterol () 1.5
g to 25 ml of t-butanol-tetrahydrofuran-water (10:3:1) and 5 ml of tetrahydrofuran.
0.5 g of N-methylmorpholine-N-oxide and a catalytic amount of osmium tetroxide were added thereto, and the mixture was stirred at room temperature for four days. After evaporating the solvent, the resulting residue was subjected to silica gel column chromatography to obtain [22S,23S]-cholest-5-ene-3β,22,23-triol [22S,23S]-cholest-5-ene-3β,22,23-triol [22S,23S] from the elution fraction of benzene-ethyl acetate (20:1). 0.78g was obtained.
融点 182−183.5゜
NMR（CDCl3）：δ（ppm）0.72（3H、ｓ）1.02
（3H、ｓ）0.95（6H、ｄ、Ｊ＝７Hz）1.04
（3H、ｄ、Ｊ＝６Hz）3.30−3.62（2H、ｍ）
3.78（1H、ｍ）5.36（1H、ｍ）
さらに、ベンゼン−酢酸エチル（５：１）の
溶出画分より〔22R，23R〕−コレスト−５−
エン−3β，22，23−トリオール（）0.32ｇを
得た。Melting point 182-183.5゜ NMR (CDCl 3 ): δ (ppm) 0.72 (3H, s) 1.02
(3H, s) 0.95 (6H, d, J=7Hz) 1.04
(3H, d, J=6Hz) 3.30−3.62 (2H, m)
3.78 (1H, m) 5.36 (1H, m) Furthermore, from the elution fraction of benzene-ethyl acetate (5:1), [22R,23R]-Cholest-5-
0.32 g of ene-3β,22,23-triol () was obtained.
融点 187〜191°
NMR（CDCl3）：δ（ppm）0.72（3H、ｓ）1.03
（3H、ｓ）0.96（6H、ｄ、Ｊ＝７Hz）0.94
（3H、ｄ、Ｊ＝７Hz）3.53（3H、ｍ）5.36
（1H、ｍ）
(2) 〔22R，23R〕−コレスト−５−エン−3β，
22，23−トリオール（）0.47ｇをアセトン20
mlに懸濁させ、これにｐ−トルエンスルホン酸
を触媒量加え、一夜室温で撹拌した。溶媒を留
去し粗生成物の〔22R，23R〕−コレスト−５
−エン−3β，22，23−トリオール22，23−ア
セトニド（）0.51ｇを得た。この粗生成物を
ピリジン３mlに溶かし、メタンスルホニルクロ
リド0.4mlを加えて室温にて一夜放置した。溶
媒を留去し、残渣をエチルエーテルで抽出し溶
媒を留去すると〔22R，23R〕−3β−メタンス
ルホニルオキシ−コレスト−５−エン22，23−
ジオール22，23−アセトニド（）の粗生成物
0.59ｇを得た。Melting point 187-191° NMR ( CDCl3 ): δ (ppm) 0.72 (3H, s) 1.03
(3H, s) 0.96 (6H, d, J=7Hz) 0.94
(3H, d, J=7Hz) 3.53 (3H, m) 5.36
(1H, m) (2) [22R, 23R]-Cholest-5-ene-3β,
0.47 g of 22,23-triol () in acetone 20
ml, a catalytic amount of p-toluenesulfonic acid was added thereto, and the mixture was stirred overnight at room temperature. The solvent was distilled off and the crude product [22R, 23R]-Cholest-5
0.51 g of -ene-3β,22,23-triol 22,23-acetonide () was obtained. This crude product was dissolved in 3 ml of pyridine, 0.4 ml of methanesulfonyl chloride was added, and the mixture was left at room temperature overnight. The solvent was distilled off, the residue was extracted with ethyl ether, and the solvent was distilled off to give [22R,23R]-3β-methanesulfonyloxy-cholest-5-ene22,23-
Crude product of diol 22,23-acetonide ()
0.59g was obtained.
NMR（CDCl3）：δ（ppm）0.70（3H、ｓ）1.03
（3H、ｓ）0.95（3H、ｄ、Ｊ＝６Hz）0.98
（6H、ｄ、Ｊ＝７Hz）3.00（3H、ｓ）3.75
（2H、ｍ）4.48（1H、ｍ）5.40（1H、ｍ）
この粗生成物を更に精製することなく次の工
程に使用した。 NMR (CDCl 3 ): δ (ppm) 0.70 (3H, s) 1.03
(3H, s) 0.95 (3H, d, J=6Hz) 0.98
(6H, d, J=7Hz) 3.00 (3H, s) 3.75
(2H, m) 4.48 (1H, m) 5.40 (1H, m) This crude product was used in the next step without further purification.
(3) 上記で得た〔22R，23R〕−3β−メタンスル
ホニルオキシ−コレスト−５−エン−22，23−
ジオール22，23−アセトニド0.59ｇをテトラヒ
ドロフランに溶かし、これにジボラン−テトラ
ヒドロフラン溶液（1M溶液）４mlを０℃で加
え室温とした後四時間撹拌した。この混合溶液
に水を加え、さらに０℃で2N水酸化ナトリウ
ム水溶液10mlと30％過酸化水素水6.5mlを加え
て室温とした後一時間撹拌した。エチルエーテ
ルで抽出し、無水硫酸マグネシウムで乾燥後、
溶媒を減圧留去した。残渣を塩化メチレン25ml
に溶かしこれにピリジウムクロロクロメート
0.6ｇを加え、室温で三時間撹拌した。エーテ
ル100mlを加えて希釈し、クロリジルカラムに
て溶出する画分を留去して〔22R，23R〕−3β
−メタンスルホニルオキシ−5α−コレスタン
−６−オン−22，23−ジオール22，23−アセト
ニド（）0.28ｇを得た。(3) [22R,23R]-3β-methanesulfonyloxy-cholest-5-ene-22,23- obtained above
0.59 g of diol 22,23-acetonide was dissolved in tetrahydrofuran, and 4 ml of diborane-tetrahydrofuran solution (1M solution) was added thereto at 0°C, and the mixture was heated to room temperature and stirred for 4 hours. Water was added to this mixed solution, and 10 ml of a 2N aqueous sodium hydroxide solution and 6.5 ml of 30% hydrogen peroxide were added at 0°C to bring the mixture to room temperature, followed by stirring for 1 hour. After extraction with ethyl ether and drying with anhydrous magnesium sulfate,
The solvent was removed under reduced pressure. Pour the residue into 25 ml of methylene chloride.
Pyridium chlorochromate dissolved in this
0.6 g was added and stirred at room temperature for 3 hours. Dilute with 100 ml of ether, distill off the eluted fraction on a chloridyl column, and collect [22R, 23R]-3β.
-Methanesulfonyloxy-5α-cholestan-6-one-22,23-diol 0.28 g of 22,23-acetonide () was obtained.
NMR（CDCl3）：δ（ppm）0.68（3H、ｓ）0.90
（3H、ｄ、Ｊ＝６Hz）0.94（6H、ｄ、Ｊ＝７
Hz）1.38（6H、ｓ）3.02（3H、ｓ）3.75（2H、
ｍ）4.63（1H、ｍ）
この生成物を更に精製することなく次の工程
に使用した。 NMR (CDCl 3 ): δ (ppm) 0.68 (3H, s) 0.90
(3H, d, J=6Hz) 0.94 (6H, d, J=7
Hz) 1.38 (6H, s) 3.02 (3H, s) 3.75 (2H,
m) 4.63 (1H, m) This product was used in the next step without further purification.
(4) 上記で得た〔22R，23R〕−3β−メタンスル
ホニルオキシ−5α−コレスタン−６−オン−
22，23−ジオール22，23−アセトニド40mgをジ
メチルホルムアミド２mlに溶かし臭化リチウム
40mgを加えて一時間加熱還流した。室温まで冷
却した後、水を加え、エチルエーテルで抽出
し、無水硫酸マグネシウムで乾燥後、減圧留去
し粗生成物を得た。これをメタノールより再結
晶し〔22R，23R〕−5α−コレスト−２−エン
−６−オン−22，23−ジオール22，23−アセト
ニド（）28mgを得た。(4) [22R,23R]-3β-methanesulfonyloxy-5α-cholestan-6-one- obtained above
Dissolve 40 mg of 22,23-diol 22,23-acetonide in 2 ml of dimethylformamide and add lithium bromide.
40 mg was added and heated under reflux for 1 hour. After cooling to room temperature, water was added, extracted with ethyl ether, dried over anhydrous magnesium sulfate, and evaporated under reduced pressure to obtain a crude product. This was recrystallized from methanol to obtain 28 mg of [22R,23R]-5α-cholest-2-en-6-one-22,23-diol 22,23-acetonide ().
融点 186−188℃
IR 1702ｍ-1
NMR（CDCl3）：δ（ppm）0.69（3H、ｓ）0.72
（3H、ｓ）0.92（3H、ｄ、Ｊ＝７Hz）0.95
（6H、ｄ、Ｊ＝７Hz）1.38（6H、ｓ）3.74
（2H、ｍ）5.60（2H、ｍ）
(5) 上記で得た〔22R，23R〕−5α−コレスト−
２−エン−６−オン−22，23−ジオール22，23
−アセトニド（）105mgをテトラヒドロフラ
ン−ｔ−ブチルアルコール−水（10：３：１）
５mlとテトラヒドロフラン３mlと混合溶媒に溶
かし、これにＮ−メチルモルホリン−Ｎ−オキ
シド150mgと触媒量の四酸化オスミウムを加え
て室温で一夜撹拌した。溶媒を留去した後、残
渣をピリジン２mlと無水酢酸１mlに溶かし室温
にて一夜放置した。溶媒を減圧留去し、粗生成
物をアセトンより再結晶し〔22R，23R〕−2α，
3α−ジアセトキシ−5α−コレスタン−６−オ
ン−22，23−ジオール22，23−アセトニド
（XI）115mgを得た。Melting point 186-188℃ IR 1702m -1 NMR (CDCl 3 ): δ (ppm) 0.69 (3H, s) 0.72
(3H, s) 0.92 (3H, d, J=7Hz) 0.95
(6H, d, J=7Hz) 1.38 (6H, s) 3.74
(2H, m)5.60 (2H, m) (5) [22R, 23R]-5α-Cholest- obtained above
2-en-6-one-22,23-diol22,23
- 105 mg of acetonide () in tetrahydrofuran-t-butyl alcohol-water (10:3:1)
5 ml of tetrahydrofuran and 3 ml of tetrahydrofuran were dissolved in a mixed solvent, 150 mg of N-methylmorpholine-N-oxide and a catalytic amount of osmium tetroxide were added thereto, and the mixture was stirred at room temperature overnight. After evaporating the solvent, the residue was dissolved in 2 ml of pyridine and 1 ml of acetic anhydride and left overnight at room temperature. The solvent was distilled off under reduced pressure, and the crude product was recrystallized from acetone to give [22R, 23R]-2α,
115 mg of 3α-diacetoxy-5α-cholestan-6-one-22,23-diol 22,23-acetonide (XI) was obtained.
融点 177−180℃
NMR（CDCl3）：δ（ppm）0.68（3H、ｓ）0.84
（3H、ｓ）1.37（6H、ｓ）1.99（3H、ｓ）2.10
（3H、ｓ）3.74（2H、ｍ）4.94（1H、ｍ）5.35
（1H、ｍ）
(6) 上記で得た〔22R，23R〕−2α，3α−ジアセ
トキシ−5α−コレスタン−６−オン−22，23
−ジオール22，23−アセトニド（）72mgを塩
化メチレン2.5mlに溶かし、これにリン酸二ナ
トリウム0.5ｇを加え、０℃とした後トリフル
オロ過酢酸の塩化メチレン溶液を加え０℃で三
時間撹拌した。水を加え有機層を無水硫酸マグ
ネシウムで乾燥後、減圧留去して粗生成物を得
た。これをシリカゲルカラムクロマトグラフイ
ーで、精製し、ベンゼン−酢酸エチル（１：
１）の溶出画分より〔22R，23R〕−Ｂ−ホモ
−７−オキサ−5α−コレスタン−６−オン−
2α，3α，22，23−テトラオール22，23−ジア
セテート（）53mgを得た。Melting point 177-180℃ NMR (CDCl 3 ): δ (ppm) 0.68 (3H, s) 0.84
(3H, s) 1.37 (6H, s) 1.99 (3H, s) 2.10
(3H, s) 3.74 (2H, m) 4.94 (1H, m) 5.35
(1H, m) (6) [22R,23R]-2α,3α-diacetoxy-5α-cholestan-6-one-22,23 obtained above
-Dissolve 72 mg of diol 22,23-acetonide () in 2.5 ml of methylene chloride, add 0.5 g of disodium phosphate to this, cool the temperature to 0°C, add a methylene chloride solution of trifluoroperacetic acid, and stir at 0°C for 3 hours. did. Water was added and the organic layer was dried over anhydrous magnesium sulfate and then evaporated under reduced pressure to obtain a crude product. This was purified by silica gel column chromatography, and benzene-ethyl acetate (1:
From the elution fraction of 1), [22R, 23R]-B-homo-7-oxa-5α-cholestan-6-one-
53 mg of 2α,3α,22,23-tetraol 22,23-diacetate () was obtained.
NMR（CDCl3）：δ（ppm）0.72（3H、ｓ）0.97
（6H、ｄ、Ｊ＝７Hz）0.94（3H、ｄ、Ｊ＝６
Hz）1.00（3H、ｓ）2.00（3H、ｓ）2.12（3H、
ｓ）3.01（1H、dd、Ｊ＝10.5Hz）3.35（1H、
ｍ）3.62（1H、ｍ）4.10（2H、ｍ）4.86（1H、
ｍ）5.37（1H、ｍ）
(7) 上記で得た〔22R，23R〕−Ｂ−ホモ−７−
オキサ−5α−コレスタン−６−オン−2α，3α，
22，23−テトラオール22，23−ジアセテート
（）31mgをテトラヒドロフラン１mlに溶かし、
これに５％水酸カリウムのメタノール性水溶液
５mlを加え、室温で五時間撹拌した。2N塩酸
水溶液を加えて酸性とし、酢酸エチルで抽出
し、無水硫酸マグネシウムで乾燥後減圧留去し
た。この粗生成物をメタノール−酢酸エチルよ
り再結晶し、〔22R，23R〕−Ｂ−ホモ−７−オ
キサ−5α−コレスタン−６−オン−2α，3α，
22，23−テトラオール（24−デメチルブラシノ
リド）19mgを得た。 NMR (CDCl 3 ): δ (ppm) 0.72 (3H, s) 0.97
(6H, d, J=7Hz) 0.94 (3H, d, J=6
Hz) 1.00 (3H, s) 2.00 (3H, s) 2.12 (3H,
s) 3.01 (1H, dd, J=10.5Hz) 3.35 (1H,
m) 3.62 (1H, m) 4.10 (2H, m) 4.86 (1H,
m) 5.37 (1H, m) (7) [22R, 23R]-B-homo-7- obtained above
Oxa-5α-cholestan-6-one-2α, 3α,
Dissolve 31 mg of 22,23-tetraol 22,23-diacetate () in 1 ml of tetrahydrofuran,
To this was added 5 ml of a methanolic aqueous solution of 5% potassium hydroxide, and the mixture was stirred at room temperature for 5 hours. The mixture was made acidic by adding 2N aqueous hydrochloric acid solution, extracted with ethyl acetate, dried over anhydrous magnesium sulfate, and then evaporated under reduced pressure. This crude product was recrystallized from methanol-ethyl acetate, [22R,23R]-B-homo-7-oxa-5α-cholestan-6-one-2α,3α,
19 mg of 22,23-tetraol (24-demethylbrassinolide) was obtained.
融点 256−259゜ 〔α〕14 D＝＋32゜（３＝1.15メタノール）Melting point 256−259゜〔α〕 14 D = +32゜ (3 = 1.15 methanol)
Claims (1)
基を表わす） で示される〔22R，23R〕−Ｂ−ホモ−７−オキ
サ−5α−コレスタン−６−オン誘導体。[Claims] 1 formula (In the formula, OR represents a hydroxyl group that may or may not be acylated.) [22R,23R]-B-homo-7-oxa-5α-cholestan-6-one derivative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4906981A JPS57163400A (en) | 1981-03-31 | 1981-03-31 | 5alpha-cholestan-6-one derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4906981A JPS57163400A (en) | 1981-03-31 | 1981-03-31 | 5alpha-cholestan-6-one derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57163400A JPS57163400A (en) | 1982-10-07 |
| JPS6353990B2 true JPS6353990B2 (en) | 1988-10-26 |
Family
ID=12820786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4906981A Granted JPS57163400A (en) | 1981-03-31 | 1981-03-31 | 5alpha-cholestan-6-one derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57163400A (en) |
-
1981
- 1981-03-31 JP JP4906981A patent/JPS57163400A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57163400A (en) | 1982-10-07 |
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