CN107474096A - A kind of α of 22E alkene 3, the preparation method of the ketone of 5 ring, 5 α cholesterics 6 - Google Patents

A kind of α of 22E alkene 3, the preparation method of the ketone of 5 ring, 5 α cholesterics 6 Download PDF

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Publication number
CN107474096A
CN107474096A CN201710872138.4A CN201710872138A CN107474096A CN 107474096 A CN107474096 A CN 107474096A CN 201710872138 A CN201710872138 A CN 201710872138A CN 107474096 A CN107474096 A CN 107474096A
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alkene
ring
cholesteric
ketone
solvent
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CN107474096B (en
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肖石基
刘长生
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Jiangsu Qianyuan Biological Technology Co., Ltd.
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Jiangsu Leader Pharmaceutical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J53/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton has been modified by condensation with a carbocyclic rings or by formation of an additional ring by means of a direct link between two ring carbon atoms, including carboxyclic rings fused to the cyclopenta(a)hydrophenanthrene skeleton are included in this class

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  • Organic Chemistry (AREA)
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Abstract

The invention belongs to technical field of organic synthesis, it is related to a kind of α of 22E alkene 3, the preparation method of the ketone of 5 ring, 5 α cholesterics 6, including：By the α of 22E alkene 3, the alcohol of 5 ring, 5 α cholesterics 6 is placed in organic solvent, and catalyst is added under certain temperature, and oxidation reaction is carried out under air or oxygen atmosphere, final products are made after the crystallized suction filtration of crude product.The present invention is using catalyst system of any one in free radical catalyst, metal salt or free radical catalyst+metal salt as reaction, by the α of 22E alkene 3 under air or oxygen, the α of 22E alkene 3, the ketone of 5 ring, 5 α cholesterics 6, its yield is made in the alcohol direct oxidation of 5 ring, 5 α cholesterics 6>90%, content>98%, advantages of nontoxic raw materials or low toxicity, the catalyst that is used in reaction is cheap, source is wide, gently and in whole flow process the caused three wastes are much smaller than existing process for safe operation, simple and convenient, reaction condition simultaneously, production cost is low, without poisonous three waste discharge, and total recovery is high, is advantageous to industrialize.

Description

A kind of preparation method of -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone
Technical field
The invention belongs to technical field of organic synthesis, is related to a kind of preparation of -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone Method.
Background technology
Brassin lactones are a kind of new green environment protection plant growth regulator, 1970, and American scientist Grove is from oil Cauliflower powder is isolated, and by the research to its crystalline texture, it is a kind of phytosterin compound to find this, is referred to as in brassin Ester.This is one of plant growth regulator of nature latest find, referred to as the 6th class plant hormone, and its bioactivity is much super Cross existing five big hormones.Most plants hormone only has Physiological effect effect to some or certain several periods of plant, such as：It is red mould Element can promote the division and elongation of plant cell；Abscisic acid can suppress plant growth, accelerate fruit abscission.But in brassin Ester has great role in terms of production estimation is promoted, suitable for any stage of the growth cycle of various plants, according to plant The demand in each period acts on each physiological periods of plant.- 5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone is as brassin The key intermediate of lactone, its chemical synthesis cause the concern of many chemists.
Synthetic method reported in the literature mainly has following four kinds：The first is aoxidized using chromium trioxide (J.AM.Chem.Soc.,1980,102,6580；J.Org.Chem.1993,58,2338；Pesticides 1996,35,8； J.Org.Chem.1979,44,5002；Synthesis Chem.1986,181；Chem.Pharm.Bull.1987,35, 3006), the chromium trioxide of this method high poison, pollution is very big, larger potential safety hazard be present, produces a large amount of wastewater with chromium；The Two kinds are to use manganese dioxide (Agric.Biol.Chem.1980,44,1211), and the reaction system is although nontoxic, but are produced Substantial amounts of Mn-bearing waste water, easily causes environmental pollution；The third method is aoxidized (CN1217227A) using DMSO, and the method produces A large amount of DMSO waste water and smell are very big, cause environmental pollution；4th kind is to use periodate oxidation (Organic Chemistry Synthesis Division, National chemical Laboratory, pune-11008, India), A large amount of waste water containing iodine are equally existed, cause environmental pollution.
The content of the invention
For above-mentioned the deficiencies in the prior art, the present invention discloses a kind of -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- The preparation method of ketone.
The preparation method of -5 α of a kind of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone, by -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- Alcohol is placed in organic solvent, and catalyst is added under certain temperature, oxidation reaction is carried out under air or oxygen atmosphere, crude product is through knot Final products are made after filtering in crystalline substance, and reaction equation is：
In formula, it can be H atom or methyl that R, which is represented,.
Specifically preparation method is：
(1) organic solvent, catalyst and the α of 22E- alkene -3 are sequentially added into reaction vessel under air or oxygen atmosphere, - 5 α of 5- rings-cholesteric -6- alcohol, the stirring reaction at 0-100 DEG C, be incubated at this temperature into total material 22E- alkene -3 α, 5- ring - 5 α-cholesteric -6- alcohol gas spectrum normalizing content ＜ 1%；Total material pH is adjusted to carry out liquid separation after 7, precipitation obtain 22E- alkene -3 α, 5- ring - 5 α-cholesteric -6- ketone crude products；
(2) in another reaction vessel, organic solvent and prepared 22E- alkene -3 α, 5- ring -5 α-cholesterics-are sequentially added 6- ketone crude products, at 0-100 DEG C stirring insulation 1h, slow cooling to 0 DEG C, be incubated 2h, crystallization filter 22E- alkene -3 α, 5- ring - 5 α-cholesteric -6- ketone sterlings.
The more excellent disclosed example of the present invention, in step (1), -5 α of 22E- alkene -3 α, the 5- ring-cholesteric -6- alcohol and catalyst Mol ratio is 1:0.01-0.2；The α of organic solvent and 22E- alkene -3, the mol ratio of -5 α of 5- rings-cholesteric -6- alcohol is 1-10:1； The mol ratio of the dosage of organic solvent described in step (2) and 22E- alkene -3 α, 5- ring -5 α-cholesteric -6- ketone is 1-10:1.
The more excellent disclosed example of the present invention, step (1) are 0-100 DEG C with the reaction temperature described in (2).
The more excellent disclosed example of the present invention, catalyst described in step (1) are that free radical catalyst, metal salt or free radical are urged Any one in agent+metal salt.
The more excellent disclosed example of the present invention, step (1) described free radical catalyst are TEMPO, NHPI, NDHPI, AIBN, peroxide Any one in benzoyl；The metal salt is Co (OAc)2、Co(acac)2、MnO2、Mn(acac)2、FeCl2、FeCl3、 PdCl2、Pd(OAc)2, any one in CuCl, CuO.
The more excellent disclosed example of the present invention, organic solvent described in step (1) and step (2) are halogenated hydrocarbon solvent, aromatic series Any one in class solvent, ether solvent, esters solvent or alcohols solvent.
Preferably, the halogenated hydrocarbon solvent is dichloromethane, dichloroethanes, chloroform etc., and fragrant same clan's solvent is Chlorine benzene,toluene,xylene etc., the ether solvent are tetrahydrofuran etc., and the esters solvent is methyl acetate, ethyl acetate It is methanol, ethanol, isopropanol etc. Deng, the alcohols solvent.
Beneficial effect
The present invention uses new catalyst system, by -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- alcohol under air or oxygen - 5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone, its yield is made in direct oxidation>90%, content>98%, advantages of nontoxic raw materials or low toxicity, The catalyst that is used in reaction is cheap, source is wide, at the same safe operation, simple and convenient, reaction condition be gentle and whole flow process in The caused three wastes are much smaller than already known processes, and production cost is low, without poisonous three waste discharge, and total recovery is high, is advantageous to industrialize.
Embodiment
With reference to embodiment, the present invention is described in detail, so that those skilled in the art more fully understand this hair It is bright, but the invention is not limited in following examples.
Tradition or existing process prepare 22E- alkene -3 α, -5 α of 5- rings-cholesteric -6- ketone
In the 500ml four-hole boiling flasks equipped with condenser, 33.8g22E- alkene -3 α, 5- ring -5 is sequentially added under 1atm air α-cholesteric -6- alcohol, 200mL acetone, after being down to less than 5 DEG C, start that 38.5mL Jones reagents are added dropwise, drop finishes, reaction 3h or so；Protect The gas spectrum normalizing content of temperature -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- alcohol into material<1%, 250mLNaCl is added into flask Solution, stirring, stratification separate organic phase, and organic phase uses 25mL NaHCO successively3Solution, 75mLNaCl solution washing three It is secondary.Organic phase anhydrous Na SO4Dry, filter, vacuum is spin-dried for.Crude product carries out column chromatography for separation, obtains 22E- alkene -3,5- rings -5- Cholesteric -6- ketone, yield 80%, produce 400mL and contain Cr and salt waste water.
Embodiment 1
A kind of preparation method of -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone：
(1) 22E- alkene -3 α, -5 α of 5- rings-cholesteric -6- ketone crude products are prepared
In the 500ml four-hole boiling flasks equipped with condenser, 200mL dichloroethanes, 0.5mol are sequentially added under 1atm air - 5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- alcohol and 0.01mol TEMPO, are warming up to 50 DEG C, are incubated into material the α of 22E- alkene -3, The gas spectrum normalizing content of -5 α of 5- rings-cholesteric -6- alcohol<1%, pH=7 is adjusted, liquid separation, precipitation, obtains -5 α of 22E- alkene -3 α, 5- ring-courage Steroid -6- ketone crude products, solvent and the recovered recycling of catalyst, the rate of recovery 90%.
(2) 22E- alkene -3 α, -5 α of 5- rings-cholesteric -6- ketone are refined
In the 500ml four-hole boiling flasks equipped with condenser, methanol 100mL is sequentially added, 22E- alkene -3 prepared by step (1) - 5 α of α, 5- ring-cholesteric -6- ketone crude product 50g, the stirring insulation 1h at 65 DEG C, slow cooling are incubated 2h to 0 DEG C, and crystallization filters Obtain -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone sterlings, content>98%, total recovery>90%.
Embodiment 2
A kind of preparation method of -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone：
(1) 22E- alkene -3 α, -5 α of 5- rings-cholesteric -6- ketone crude products are prepared
In the 500ml four-hole boiling flasks equipped with condenser, 200mL toluene, 0.5mol 22E- are sequentially added under 1atm air - 5 α of alkene -3 α, 5- ring-cholesteric -6- alcohol and 0.01mol TEMPO, are warming up to 50 DEG C, be incubated into material 22E- alkene -3 α, 5- ring - The gas spectrum normalizing content of 5 α-cholesteric -6- alcohol<1%, pH=7 is adjusted, liquid separation, precipitation, obtains -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- Ketone crude product, solvent and the recovered recycling of catalyst, the rate of recovery 90%.
(2) 22E- alkene -3 α, -5 α of 5- rings-cholesteric -6- ketone are refined
In the 500ml four-hole boiling flasks equipped with condenser, ethanol 100mL is sequentially added, 22E- alkene -3 prepared by step (1) - 5 α of α, 5- ring-cholesteric -6- ketone crude product 50g, the stirring insulation 1h at 65 DEG C, slow cooling are incubated 2h to 0 DEG C, and crystallization filters Obtain -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone sterlings, content>97%, total recovery>85%.
Embodiment 3
A kind of preparation method of -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone：
(1) 22E- alkene -3 α, -5 α of 5- rings-cholesteric -6- ketone crude products are prepared
In the 500ml four-hole boiling flasks equipped with condenser, 200mL toluene, 0.5mol 22E- are sequentially added under 1atm air - 5 α of alkene -3 α, 5- ring-cholesteric -6- alcohol and 0.01mol NHPI, are warming up to 50 DEG C, are incubated into material 22E- alkene -3 α, 5- ring -5 The gas spectrum normalizing content of α-cholesteric -6- alcohol<1%, pH=7 is adjusted, liquid separation, precipitation, obtains -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone Crude product, solvent and the recovered recycling of catalyst, the rate of recovery 90%.
(2) 22E- alkene -3 α, -5 α of 5- rings-cholesteric -6- ketone are refined：
In the 500ml four-hole boiling flasks equipped with condenser, ethanol 100mL is sequentially added, 22E- alkene -3 prepared by step (1) - 5 α of α, 5- ring-cholesteric -6- ketone crude product 50g, the stirring insulation 1h at 65 DEG C, slow cooling are incubated 2h to 0 DEG C, and crystallization filters Obtain -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone sterlings, content>97%, total recovery 80%.
Embodiment 4
A kind of preparation method of -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone：
(1) 22E- alkene -3 α, -5 α of 5- rings-cholesteric -6- ketone crude products are prepared
In the 500ml four-hole boiling flasks equipped with condenser, 200mL toluene, 0.5mol 22E- are sequentially added under 1atm oxygen - 5 α of alkene -3 α, 5- ring-cholesteric -6- alcohol, 0.01molAIBN, 0.01mol Co (OAc)2, 50 DEG C are warming up to, is incubated into material The gas spectrum normalizing content of -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- alcohol<1%, pH=7 is adjusted, liquid separation, precipitation, obtains the α of 22E- alkene -3, - 5 α of 5- rings-cholesteric -6- ketone crude products, solvent and recovered recycling of catalyst, the rate of recovery 90%.
(2) 22E- alkene -3 α, -5 α of 5- rings-cholesteric -6- ketone are refined
In the 500ml four-hole boiling flasks equipped with condenser, ethanol 100mL is sequentially added, 22E- alkene -3 prepared by step (1) - 5 α of α, 5- ring-cholesteric -6- ketone crude product 50g, the stirring insulation 1h at 65 DEG C, slow cooling are incubated 2h to 0 DEG C, and crystallization filters Obtain -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone sterlings, content>97%, total recovery 81.5%.
Embodiment 5
A kind of preparation method of -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone
(1) 22E- alkene -3 α, -5 α of 5- rings-cholesteric -6- ketone crude products are prepared
In the 500ml four-hole boiling flasks equipped with condenser, 200mL toluene, 0.5mol 22E- are sequentially added under 1atm air - 5 α of alkene -3 α, 5- ring-cholesteric -6- alcohol, 0.01mol NHPI, 0.01mol Co (acac)2, 50 DEG C are warming up to, is incubated to material The gas spectrum normalizing content of -5 α of middle 22E- alkene -3 α, 5- ring-cholesteric -6- alcohol<1%, pH=7 is adjusted, liquid separation, precipitation, obtains 22E- alkene -3 - 5 α of α, 5- ring-cholesteric -6- ketone crude products, solvent and recovered recycling of catalyst, the rate of recovery 90%.
(2) 22E- alkene -3 α, -5 α of 5- rings-cholesteric -6- ketone are refined
In the 500ml four-hole boiling flasks equipped with condenser, ethanol 100mL is sequentially added, 22E- alkene -3 prepared by step (1) - 5 α of α, 5- ring-cholesteric -6- ketone crude product 50g, the stirring insulation 1h at 65 DEG C, slow cooling are incubated 2h to 0 DEG C, and crystallization filters Obtain -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone sterlings, content>97%, total recovery 90%.
Embodiment 6
A kind of preparation method of -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone
(1) 22E- alkene -3 α, -5 α of 5- rings-cholesteric -6- ketone crude products are prepared
In the 500ml four-hole boiling flasks equipped with condenser, 200mL toluene, 0.5mol 22E- are sequentially added under 1atm oxygen - 5 α of alkene -3 α, 5- ring-cholesteric -6- alcohol, 0.01mol NDHPI, 0.01mol Co (acac)2, 50 DEG C are warming up to, is incubated to material The gas spectrum normalizing content of -5 α of middle 22E- alkene -3 α, 5- ring-cholesteric -6- alcohol<1%, pH=7 is adjusted, liquid separation, precipitation, obtains 22E- alkene -3 - 5 α of α, 5- ring-cholesteric -6- ketone crude products, solvent and recovered recycling of catalyst, the rate of recovery 90%.
(2) 22E- alkene -3 α, -5 α of 5- rings-cholesteric -6- ketone are refined
In the 500ml four-hole boiling flasks equipped with condenser, ethanol 100mL is sequentially added, 22E- alkene -3 prepared by step (1) - 5 α of α, 5- ring-cholesteric -6- ketone crude product 50g, the stirring insulation 1h at 65 DEG C, slow cooling are incubated 2h to 0 DEG C, and crystallization filters Obtain -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone sterlings, content>97%, total recovery 71%.
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair The equivalent structure or equivalent flow conversion that bright specification is made, or other related technical areas are directly or indirectly used in, Similarly it is included within the scope of the present invention.

Claims (9)

  1. A kind of 1. preparation method of -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone, it is characterised in that：By 22E- alkene -3 α, 5- ring -5 α-cholesteric -6- alcohol is placed in organic solvent, and catalyst is added under certain temperature, carries out aoxidizing instead under air or oxygen atmosphere Should, final products are made after the crystallized suction filtration of crude product, reaction equation is：
    In formula, R is expressed as H atom or methyl.
  2. 2. the preparation method of -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone according to claim 1, it is characterised in that described Oxidation reaction includes：Organic solvent, catalyst and 22E- alkene -3 are sequentially added into reaction vessel under air or oxygen atmosphere - 5 α of α, 5- ring-cholesteric -6- alcohol, the stirring reaction at 0-100 DEG C, are incubated into total material 22E- alkene -3 α, 5- at this temperature The α of ring-5-cholesteric-6- alcohol gas spectrum normalizing content ＜ 1%；Adjust after total material pH is 7 and carry out liquid separation, precipitation obtains 22E- alkene -3 α, 5- The α of ring-5-cholesteric-6- ketone crude products.
  3. 3. the preparation method of -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone according to claim 1, it is characterised in that described Crystallization suction filtration includes：In another reaction vessel, organic solvent and prepared -5 α of 22E- alkene -3 α, 5- ring-courage are sequentially added Steroid -6- ketone crude products, the stirring insulation 1h at 0-100 DEG C, slow cooling are incubated 2h to 0 DEG C, and crystallization filters to obtain 22E- alkene -3 α, 5- The α of ring-5-cholesteric-6- ketone sterlings.
  4. 4. the preparation method of -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone according to claim 1, it is characterised in that：It is described The mol ratio of -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- alcohol and catalyst is 1:0.01-0.2；Organic solvent and the 22E- alkene- The mol ratio of -5 α of 3 α, 5- ring-cholesteric -6- alcohol is 1-10:1.
  5. 5. the preparation method of -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone according to claim 3, it is characterised in that：Crystallization The mol ratio of the dosage of the organic solvent and 22E- alkene -3 α, 5- ring -5 α-cholesteric -6- ketone is 1-10 during suction filtration:1.
  6. 6. the preparation method of -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone according to claim 1, it is characterised in that：It is described Catalyst is any one in free radical catalyst, metal salt or free radical catalyst+metal salt.
  7. 7. the preparation method of -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone according to claim 6, it is characterised in that：It is described Free radical catalyst is any one in TEMPO, NHPI, NDHPI, AIBN, benzoyl peroxide；The metal salt is Co (OAc)2、Co(acac)2、MnO2、Mn(acac)2、FeCl2、FeCl3、PdCl2、Pd(OAc)2, any one in CuCl, CuO.
  8. 8. the preparation method of -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone according to claim 1, it is characterised in that：It is described Organic solvent is any one in halogenated hydrocarbon solvent, fragrant same clan's solvent, ether solvent, esters solvent or alcohols solvent.
  9. 9. the preparation method of -5 α of 22E- alkene -3 α, 5- ring-cholesteric -6- ketone according to claim 8, it is characterised in that：It is described Halogenated hydrocarbon solvent is dichloromethane, dichloroethanes, chloroform, and fragrant same clan's solvent is chlorine benzene,toluene,xylene, described Ether solvent is tetrahydrofuran, and the esters solvent is methyl acetate, ethyl acetate etc., the alcohols solvent be methanol, ethanol, Isopropanol.
CN201710872138.4A 2017-09-25 2017-09-25 A kind of -3 α of 22E- alkene, -5 α of 5- ring-cholesteric -6- ketone preparation method Active CN107474096B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111004303A (en) * 2019-12-17 2020-04-14 京博农化科技有限公司 Method for synthesizing 24-epibrassinolide
CN115651053A (en) * 2022-11-11 2023-01-31 广东五洲药业有限公司 Preparation method of 3 alpha-5-cyclo-5 alpha-ergosta-22-ene-6-ketone

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN87106588A (en) * 1986-09-25 1988-07-06 日本化药株式会社 The method for preparing steroid derivatives

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN87106588A (en) * 1986-09-25 1988-07-06 日本化药株式会社 The method for preparing steroid derivatives

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111004303A (en) * 2019-12-17 2020-04-14 京博农化科技有限公司 Method for synthesizing 24-epibrassinolide
CN111004303B (en) * 2019-12-17 2022-08-02 京博农化科技有限公司 Method for synthesizing 24-epibrassinolide
CN115651053A (en) * 2022-11-11 2023-01-31 广东五洲药业有限公司 Preparation method of 3 alpha-5-cyclo-5 alpha-ergosta-22-ene-6-ketone
CN115651053B (en) * 2022-11-11 2024-03-29 广东五洲药业有限公司 Preparation method of 3 alpha-5-cyclo-5 alpha-ergosta-22-en-6-one

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