CN103788163B - The preparation method of 7-ketone group steroid - Google Patents
The preparation method of 7-ketone group steroid Download PDFInfo
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- CN103788163B CN103788163B CN201410039262.9A CN201410039262A CN103788163B CN 103788163 B CN103788163 B CN 103788163B CN 201410039262 A CN201410039262 A CN 201410039262A CN 103788163 B CN103788163 B CN 103788163B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 150000003431 steroids Chemical class 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 125000000746 allylic group Chemical group 0.000 claims abstract description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol 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)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 claims description 18
- 235000012000 cholesterol Nutrition 0.000 claims description 14
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- -1 acetoxyl group Chemical group 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- ILJTZGSGCNDILQ-UHFFFAOYSA-N 2-hydroxy-1,3-dioxoisoindole-5-carboxylic acid Chemical compound C1=C(C(O)=O)C=C2C(=O)N(O)C(=O)C2=C1 ILJTZGSGCNDILQ-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 235000019166 vitamin D Nutrition 0.000 description 2
- 239000011710 vitamin D Substances 0.000 description 2
- SJSKEJWFLFXDRK-UHFFFAOYSA-N 1-hydroxy-2,2-diphenylindol-3-one Chemical compound ON1C2=CC=CC=C2C(=O)C1(C=1C=CC=CC=1)C1=CC=CC=C1 SJSKEJWFLFXDRK-UHFFFAOYSA-N 0.000 description 1
- BAHNQCLYJBLDQR-UHFFFAOYSA-N 5,7-ditert-butyl-1-hydroxy-3,3-dimethylindol-2-one Chemical compound CC(C)(C)c1cc2c(N(O)C(=O)C2(C)C)c(c1)C(C)(C)C BAHNQCLYJBLDQR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000012027 Collins reagent Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 230000002308 calcification Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- NPRDHMWYZHSAHR-UHFFFAOYSA-N pyridine;trioxochromium Chemical compound O=[Cr](=O)=O.C1=CC=NC=C1.C1=CC=NC=C1 NPRDHMWYZHSAHR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 229940046008 vitamin d Drugs 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Steroid Compounds (AREA)
Abstract
The invention discloses a kind of preparation method of 7-ketone group steroid, comprise the following steps: 1), first using steroid be dissolved in solvent as the N-hydroxy derivatives of catalyzer, then add oxygenant and allylic oxidation reaction occurs at the temperature of 0 ~ 60 DEG C, after steroid complete oxidation, terminate reaction; Steroid is 1:0.1 ~ 10 with the mol ratio as the N-hydroxy derivatives of catalyzer, and the mol ratio of steroid and oxygenant is 1:2 ~ 10; 2), by the reaction solution solvent evaporated of step 1) gained, then reclaim the N-hydroxy derivatives as catalyzer by normal hexane, obtain 7-ketone group steroid.
Description
Technical field
The present invention relates to a kind of method being prepared 7-ketone group steroid by steroid.
Background technology
7-ketone group steroid is the precursor of vitamins D class medicine, is widely used in the fields such as medicine, food, agricultural chemicals, chemical industry, has higher practical value.Vitamins D class medicine can promote the absorption in enteron aisle of calcium, phosphorus, guarantee the content of these two kinds of elements in body fluid, promote the normal calcification of bone, formation for bone has great significance, and is that man and animal grows, grows, breeds, sustains life and keep fit requisite VITAMIN.Therefore, as the important as precursors of synthesis of vitamin d class medicine, the synthesis of 7-ketone group steroid can restrict its condition of production to a great extent.
The main method of prior art synthesis 7-ketone group steroid has following several:
1, obtain using chromium reagent as oxygenant through carrying out allylic oxidation, conventional chromium reagents ratio is as Collins reagent, PCC, PDC, Cr (CO)
6deng (J.Org.Chem, 1999,64,2475-2485.Bioorganic & MedicinalChemistryLetters, 2011,11,3011-3014.Tetrahedron, 2004,60,11477-11486.).When adopting chromium reagent as oxygenant; reaction yield is medium; but chromium reagent dosage is excessive; the use of a large amount of toxic reagent can produce more poisonous waste residue and waste water; be unfavorable for environment protection; also do not meet the principle of Green Chemistry, from the angle of economy and environment, its application receives very large restriction.
2,7-ketone group steroid can also be obtained by reacting by utilizing tertbutyl peroxide to carry out allylic oxidation as oxygenant.
Tertbutyl peroxide usually will with transition-metal catalyst as RuCl
3couplings such as (TetrahedronLetters, 1996,37,3429-3432.), its temperature of reaction is 15-25 DEG C, and solvent used is hexanaphthene; Yield is 75%.When adopting transition-metal catalyst, catalyzer cost is higher.The method all have employed the method for extraction in last handling process, this catalyzer is carried out filtered and recycled, infers and may there is the possibility of inactivation and be difficult to filtered and recycled by catalyzer after the completion of reaction.
Tertbutyl peroxide also can with other oxidising agent couplings, thus reduce the consumption of these oxygenants, as tertbutyl peroxide and PDC coupling, PDC consumption can be reduced to 4 times of equivalents (Eur.J.Org.Chem.2009,3703-3714.Synlett, 2008,13,1965-1968.).Its temperature of reaction is 0-25 DEG C, and solvent used is benzene; Yield is 75%.But same, when adopting this method, still inevitably employ poisonous reagent (for PDC), environmental pollution is serious.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of rational technology, reaction conditions is gentle, and yield is high, simple to operate, the preparation method of eco-friendly 7-ketone group steroid.
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of 7-ketone group steroid, comprising the following steps:
1), first using the steroid shown in formula (II) be dissolved in solvent as the N-hydroxy derivatives of catalyzer, then add oxygenant and allylic oxidation reaction occurs at the temperature of 0 ~ 60 DEG C, after the steroid complete oxidation shown in formula (II), (in reaction process, utilize TLC to detect, see that namely the completely dissolve of raw material point illustrates that oxidizing reaction terminates completely from chromatographic sheet, reaction times is about 20 ~ 28 hours, be such as 24 hours), terminate reaction;
Described steroid is 1:0.1 ~ 10 with the mol ratio as the N-hydroxy derivatives of catalyzer, and the mol ratio of shown steroid and oxygenant is 1:2 ~ 10;
2), by the reaction solution solvent evaporated of step 1) gained, then reclaim the N-hydroxy derivatives as catalyzer by normal hexane, obtain the 7-ketone group steroid described in formula (I);
In formula (I) and (II), R1 is hydrogen, hydroxyl or acetoxyl group.
Improvement as the preparation method of 7-ketone group steroid of the present invention:
Step 2) be: the reaction solution of step 1) gained is carried out underpressure distillation, thus realizes solvent evaporated; Then add normal hexane and be heated to 35 ~ 45 DEG C of stirrings 20 ~ 40 minutes, to be cooled to room temperature, filter, gained filter cake is the N-hydroxy derivatives (catalyzer of recovery can be directly used in allylic oxidation reaction again) as catalyzer;
Gained filtrate, through the aftertreatment of separation and purification, obtains the 7-ketone group steroid described in formula (I);
Preparation method further as 7-ketone group steroid of the present invention: N-hydroxy derivatives be following any one:
Remarks illustrate:
No. CAS of NHPI is 524-38-9, Chinese HP by name;
No. CAS of N-1 is 57309-24-7, English 1-hydroxy-2,2-diphenylindolin-3-one by name;
No. CAS of N-2 is 1155361-16-2, English 5-tert-butyl-3,3-dimethyl-2,2-diphenylindolin-1-ol by name;
No. CAS of N-3 is 32847-28-2, English 5,7-di-tert-butyl-1-hydroxy-3,3-dimethylindolin-2-one by name;
No. CAS of N-4 is 110167-77-6, Chinese 4-carboxy-N-hydroxyphthalimide by name;
No. CAS of N-5 is 6066-82-6, Chinese N-hydroxysuccinimide by name.
Further improvement as the preparation method of 7-ketone group steroid of the present invention: the oxygenant used is tertbutyl peroxide.
Further improvement as the preparation method of 7-ketone group steroid of the present invention: the solvent in step 1) is the ketone containing three to nine carbon atoms.
In the present invention:
Room temperature refers to 10 ~ 25 DEG C.
In step 1), the solvent of the steroid adapted 50 ~ 100mL of every 0.01mol; Ketone containing three to nine carbon atoms is specially: acetone, butanone, mibk, isophorone etc.
Work as R
1during for hydrogen, shown in formula (II), steroid is called 3-ethanoyl cholesterol; The 7-ketone group steroid of gained is called 3-ethanoyl-7-ketone group cholesterol;
Work as R
1during for hydroxyl, shown in formula (II), steroid is called 3-ethanoyl-25-HYDROXY CHOLESTEROL; The 7-ketone group steroid of gained is called 3-ethanoyl-7-ketone group-25-HYDROXY CHOLESTEROL;
Work as R
1during for acetoxyl group, 3, the 25-diacetyl cholesterol by name of steroid shown in formula (II); The 7-ketone group steroid of gained is called 7-ketone group-3,25-diacetoxy cholesterol.
The preparation method of 7-ketone group steroid of the present invention has following technical superiority:
1), the present invention utilizes tertbutyl peroxide as allylic oxidation reagent, and this reagent can be decomposed into water and the trimethyl carbinol after oxidation, very little on the impact of environment, and environmental friendliness, has good prospects for commercial application;
2), react and can carry out at ambient temperature, reaction conditions is gentle; The catalyst levels used in reaction process is few, and cost is low, and easily obtains, and greatly reduces reaction cost, and meanwhile, catalyzer can be recycled after the completion of reaction easily.
Embodiment
The preparation method of embodiment 1, a kind of 7-ketone group cholesterol, carries out following steps successively:
By 4.28g(0.01mol) 3-ethanoyl cholesterol and 1.63g(0.01mol) NHPI join in there-necked flask; add the acetone of 60mL simultaneously; after 3-ethanoyl cholesterol and NHPI are dissolved completely; drip 5.14g(0.04mol) tertbutyl peroxide; open stirring simultaneously, at 20 ~ 25 DEG C, react 24h.
After reaction terminates, reaction solution decompression (0.09MPa) is distilled to yellow oil, adds 30mL normal hexane and again stir, be heated to 40 DEG C and stir 30 minutes, be then cooled to room temperature, filter, filter cake is catalyst n HPI.
Filtrate decompression (0.09MPa) adds 20mL pyridine and 5mL aceticanhydride after being distilled to and substantially not having normal hexane; kept at room temperature overnight; reduce pressure again (0.09MPa) distillation; then 10mL methyl alcohol is added; after ice bath 1h, the crystal of separating out is filtered; filter cake is product 3-ethanoyl-7-ketone group cholesterol, yield 67.9%.
Remarks illustrate: tertbutyl peroxide is oxidized the trimethyl carbinol produced, and reaction solution underpressure distillation after the completion of reaction can remove a part except during desolventizing; Meanwhile, because the trimethyl carbinol is liquid, when the crystal of separating out the most at last filters, to be remainingly filtered in filtrate.
Embodiment 2-10:
Change kind and the consumption (as shown in table 1) of catalyzer, all the other are equal to embodiment 1, obtain embodiment 2 ~ 10; The yield of products therefrom is as shown in table 1 below:
Table 1
Embodiment 11-14:
In change oxygenant--the consumption of tertbutyl peroxide and the reaction times, all the other are equal to embodiment 1, obtain embodiment 11 ~ 14; The yield of products therefrom is as shown in table 2 below:
Table 2
| Embodiment | 3-ethanoyl cholesterol | Oxygenant consumption/mol | Yield % |
| /mol | |||
| 11 | 0.01 | 0.02 | 50.5 |
| 12 | 0.01 | 0.06 | 63.8 |
| 13 | 0.01 | 0.08 | 63.0 |
| 14 | 0.01 | 0.1 | 63.3 |
Embodiment 15-19:
Change temperature of reaction and reaction solvent used; All the other are equal to embodiment 1, obtain embodiment 15 ~ 19; The yield of products therefrom is as shown in table 3 below:
Table 3
Embodiment 20,
In this embodiment, reaction substrate is replaced by 3-ethanoyl-25-HYDROXY CHOLESTEROL, all the other conditions are all equal to embodiment 1, and finally can prepare product 3-ethanoyl-7-ketone group-25-HYDROXY CHOLESTEROL, yield is 62.3%.
Embodiment 21,
In this embodiment, reaction substrate is replaced by 3,25-diacetyl cholesterol, all the other conditions are all equal to embodiment 1, and finally can prepare product 7-ketone group-3,25-diacetyl cholesterol, yield is 61.7%.
Comparative example 1, make solvent for use in embodiment 1 into hexanaphthene by acetone; All the other are equal to embodiment 1.
Gained yield is only 25.3%.
Comparative example 2, make solvent for use in embodiment 1 into benzene by acetone; All the other are equal to embodiment 1.
Gained yield is only 20%.
Finally, it is also to be noted that what enumerate above is only some specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (3)
- The preparation method of 1.7-ketone group steroid, is characterized in that comprising the following steps:1), first using the steroid shown in formula (II) be dissolved in solvent as the N-hydroxy derivatives of catalyzer, then add oxygenant and allylic oxidation reaction occurs at the temperature of 0 ~ 60 DEG C, after the steroid complete oxidation shown in formula (II), terminate reaction;Described steroid is 1:0.1 ~ 10 with the mol ratio as the N-hydroxy derivatives of catalyzer, and the mol ratio of shown steroid and oxygenant is 1:2 ~ 10;Described N-hydroxy derivatives be following any one:Described oxygenant is tertbutyl peroxide;Described solvent is the ketone containing three to nine carbon atoms;2), by step 1) the reaction solution solvent evaporated of gained, then reclaims the N-hydroxy derivatives as catalyzer by normal hexane, obtains the 7-ketone group steroid described in formula (I);In formula (I) and (II), R 1for hydrogen, hydroxyl or acetoxyl group.
- 2. the preparation method of 7-ketone group steroid according to claim 1, is characterized in that:Described step 2) be: by step 1) reaction solution of gained carries out underpressure distillation, thus realizes solvent evaporated; Then add normal hexane and be heated to 35 ~ 45 DEG C of stirrings 20 ~ 40 minutes, to be cooled to room temperature, filter, gained filter cake is the N-hydroxy derivatives as catalyzer;Gained filtrate, through the aftertreatment of separation and purification, obtains the 7-ketone group steroid described in formula (I).
- 3. the preparation method of 7-ketone group steroid according to claim 1 and 2, is characterized in that:Be dissolved in as in the acetone of solvent using 3-ethanoyl cholesterol with as the N-hydroxy derivatives of catalyzer, the tertbutyl peroxide then added as oxygenant is that 20 ~ 25 DEG C allylic oxidation reaction occurs, and the reaction times is 24h;The mol ratio of described 3-ethanoyl cholesterol and N-hydroxy derivatives is 1:1, and the mol ratio of shown 3-ethanoyl cholesterol and tertbutyl peroxide is 1:4;Described N-hydroxy derivatives is
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| CN105859815B (en) * | 2016-04-29 | 2019-07-16 | 大连大学 | The synthetic method of 7- ketone group cholesterine -9- carboxyl nonane and its fluorescent marker |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5030739A (en) * | 1985-04-17 | 1991-07-09 | Hoffman-La Roche Inc. | Process for the catalytic oxidation of isoprenoids having allylic groups |
| CN1152316A (en) * | 1994-05-19 | 1997-06-18 | 麦克公司 | Oxidation of steroids having allylic groups |
| CN101418030A (en) * | 2008-12-11 | 2009-04-29 | 浙江大学 | Method for preparing 7-keto-cholesterol |
-
2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5030739A (en) * | 1985-04-17 | 1991-07-09 | Hoffman-La Roche Inc. | Process for the catalytic oxidation of isoprenoids having allylic groups |
| CN1152316A (en) * | 1994-05-19 | 1997-06-18 | 麦克公司 | Oxidation of steroids having allylic groups |
| CN101418030A (en) * | 2008-12-11 | 2009-04-29 | 浙江大学 | Method for preparing 7-keto-cholesterol |
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Granted publication date: 20151118 Termination date: 20170127 |