CN101418030A - Method for preparing 7-keto-cholesterol - Google Patents
Method for preparing 7-keto-cholesterol Download PDFInfo
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- CN101418030A CN101418030A CNA2008101629975A CN200810162997A CN101418030A CN 101418030 A CN101418030 A CN 101418030A CN A2008101629975 A CNA2008101629975 A CN A2008101629975A CN 200810162997 A CN200810162997 A CN 200810162997A CN 101418030 A CN101418030 A CN 101418030A
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- cholesterol
- reaction
- ketone
- primary catalysts
- formula
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- 238000000034 method Methods 0.000 title claims abstract description 12
- YIKKMWSQVKJCOP-ABXCMAEBSA-N 7-ketocholesterol Chemical compound C1C[C@H](O)CC2=CC(=O)[C@H]3[C@@H]4CC[C@H]([C@H](C)CCCC(C)C)[C@@]4(C)CC[C@@H]3[C@]21C YIKKMWSQVKJCOP-ABXCMAEBSA-N 0.000 title 1
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound 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 abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 235000012000 cholesterol Nutrition 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 7
- -1 transition metal salt Chemical class 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 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 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- PRYIJAGAEJZDBO-ZEQHCUNVSA-N 5,6alpha-epoxy-5alpha-cholestan-3beta-ol Chemical compound C([C@]12O[C@H]1C1)[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 PRYIJAGAEJZDBO-ZEQHCUNVSA-N 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000002240 furans Chemical class 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 150000004880 oxines Chemical class 0.000 claims description 2
- 150000003527 tetrahydropyrans Chemical class 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000006837 decompression Effects 0.000 description 3
- BVWCFOXBDSMXEP-UHFFFAOYSA-N 1-(5-acetyl-2-methoxyphenyl)-3-methylbutan-1-one Chemical compound COC1=CC=C(C(C)=O)C=C1C(=O)CC(C)C BVWCFOXBDSMXEP-UHFFFAOYSA-N 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- BKFAZDGHFACXKY-UHFFFAOYSA-N cobalt(II) bis(acetylacetonate) Chemical compound [Co+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O BKFAZDGHFACXKY-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 235000019166 vitamin D Nutrition 0.000 description 2
- 239000011710 vitamin D Substances 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical class CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QNXIYXGRPXRGOB-UHFFFAOYSA-N oxolane;propan-2-one Chemical compound CC(C)=O.C1CCOC1 QNXIYXGRPXRGOB-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention provides a method for preparing 7-ketone-cholesterol by the oxidation of cholesterol. In the method, N-hydroxyl derivatives are used as main catalysts, transition metal salt is used as an auxiliary catalyst, wherein the reaction mol ratio of the cholesterol to the main catalyst to the auxiliary catalyst is between 100 to 5 to 0.5 and 100 to 150 to1.5, and the cholesterol is oxidized to generate the 7-ketone-cholesterol at a temperature of between 0 and 120 DEG C by using dioxygen or oxygen enriched gas; and after the reaction, the main catalyst is reclaimed by carbon tetrachloride for next reaction. The method has the advantages of low material cost, the reutilization of materials, little environmental pollution and the like.
Description
Technical field
The present invention relates to a kind of with the N-hydroxy derivatives as Primary Catalysts, transition metal salt is as promotor, uses molecular oxygen or oxygen rich gas, cholesterol oxide generates the method for 7-ketone-cholesterol.
Background technology
7-ketone-cholesterol is to be used to prepare vitamins D
3Important intermediate.The preparation method of relevant 7-ketone-cholesterol has described use N-hydroxyphthalimide and cholesterol with mol ratio 1:1 reaction in US5030739, obtain the method for 7-ketone-cholesterol through oxidation.The shortcoming of this method is to use a large amount of NHPI to react, and the highest yield is 73.8%, and the NHPI after reclaiming do not see and participate in applying mechanically.
Summary of the invention
The novel method that the purpose of this invention is to provide a kind of 7-of preparation ketone-cholesterol, solving the defective that exists in the prior art in some cases, for example raw materials used cost height, environmental pollution are serious, raw material is recycled difficulty etc.
The following approach that passes through that above purpose is concrete realizes: with the N-hydroxy derivatives as Primary Catalysts, transition metal salt is as promotor, the cholesterol and the Primary Catalysts of certain proportioning are dissolved back adding promotor in appropriate solvent, feed oxygen-containing gas at a certain temperature, cholesterol oxide, after treating the cholesterol complete oxidation,, obtain 7-ketone-cholesterol with the solvent evaporate to dryness; Can easily product and catalyst separating be come by tetracol phenixin, it is reusable edible that gained catalyzer drying is handled.
Reaction formula is as follows:
R wherein
1Be OAc, R
2Be C
8H
17, described Primary Catalysts is: the Primary Catalysts that uses is N-2 and N-hydroxy derivatives thereof; Promotor is a transition metal salt.
Product process of the present invention aftertreatment: solvent evaporated in pyridine and after the diacetyl oxide effect, add methyl alcohol and make product separate out, also available ketone reagent carries out recrystallization to it purifies, and the raffinate in the aftertreatment also can be used for recycle.
Solvent of the present invention is generally ketone, the ethers of three to nine carbon atoms, furans, tetrahydrofuran (THF), pyrans, tetrahydropyrans, dimethyl sulfoxide (DMSO), N, N-dimethyl imide.
Primary Catalysts of the present invention is N-2 and N-hydroxy derivatives thereof, a kind of among following structural formula label NHPI, N-1, N-2, N-3, N-4, N-5, N-6, N-7, N-8, the N-9:
The positively charged ion of promotor transition metal salt of the present invention is: Fe
3+, Cr
3+, V
3+, Ti
2+, Mn
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+In one or both; Negatively charged ion is Cl
-, Br
-, F
-, PO
4 3-, SO
4 2-, NO
3 -, CH
3COO
-, acac
-, OAc
-In one or both, the acetic ester salt coupling of preferred cobalt, manganese metal.
Proportioning between cholesterol of the present invention and Primary Catalysts and the promotor is cholesterol: Primary Catalysts: the promotor mol ratio is: between 100: 150: 1.5 to 100: 5: 0.5.
Employed oxygenant can be pure oxygen, be rich in gas, the air of oxygen among the present invention.In 1 kilogram of cholesterol, oxygen-supply quantity hourly is 5～100L normally, and preferably at 10～50L.Oxygenous for other, its air flow can be converted accordingly according to oxygen level.Especially, under the situation of using molecular oxygen or oxygen rich gas, react under the condition of pressurization, oxygen pressure is controlled at 0.2～2atm, and preferably at 1～1.5atm.
It is general suitable with solvent boiling point to be suitable for temperature of reaction of the present invention, between 0 ℃～120 ℃, and preferably between 20 ℃～50 ℃.
Advantage of the present invention:
(1) use relatively inexpensive N-hydroxyphthalimide and derivative thereof to be catalyzer, these materials can freely be buied on market, reduce reaction cost.
(2) employed catalyst levels is few, and the reaction times is short, and catalyzer can be recycled after reaction finishes easily.
(3) this reaction is a vitamins D
3syntheticly provide new production route, avoided the bromo-reaction in original technology, thereby reduced pollution, and had higher yield, thereby favorable industrial application prospect has been arranged environment.
Embodiment
Embodiment 1
The cholesterol of 4.28g (0.1mol) and the N-2 (1mmol) of 0.349g are joined in the four neck flasks of 100ml, add the acetone of 65ml simultaneously, feed molecular oxygen, simultaneously vigorous stirring (1000rpm) by grass tube.Four neck flask flasks place water-bath, are heated to 40 ℃.Treat that cholesterol and N-2 dissolve postcooling fully to room temperature, add manganous acetate 0.0246g (0.1mmol), reacted 12 hours.Reaction is distilled to yellow oil with solution decompression after finishing, and adds tetracol phenixin 30ml, the vibration after-filtration, and filter cake is N-2.Filtrate decompression is distilled to the diacetyl oxide that adds pyridine 20ml and 5ml after the brown oil, and placement is spent the night.With the solution decompression distillation, add methyl alcohol 10ml, ice bath after 3 hours filters the crystal of separating out, and filter cake is product 7-ketone-cholesterol, productive rate 81.9%.
Embodiment 2-7
Being similar to embodiment 1, is Primary Catalysts with N-2, and the productive rate that changes promotor is as follows:
| Embodiment | Cholesterol/mmol | Primary Catalysts/mmol | Promotor/mmol | Reaction times/h | Productive rate % |
| 3 | 10 | N-2/1 | Fe(acac) 3/0.1 | 6 | 28.4 |
| 4 | 10 | N-2/1 | Co(acac) 2/0.1 | 7 | 50.3 |
| 5 | 10 | N-2/1 | Co(OAc) 2/0.1 | 8 | 59.1 |
| 6 | 10 | N-2/1 | Co(acac) 2/0.05 Mn(OAc) 2/0.05 | 7.5 | 75.7 |
| 7 | 10 | N-2/1 | Co(OAc) 2/0.05 Mn(OAc) 2/0.05 | 8.5 | 85.6 |
Embodiment 8-10
Be similar to embodiment 1, with Mn (OAc)
2Be promotor, the yield that changes Primary Catalysts is as follows:
Embodiment 11-15
Be similar to embodiment 1, temperature of reaction, reaction solvent are to the influence of productive rate under the situation that does not change catalyzer:
| Embodiment | 11 | 12 | 13 | 14 | 15 |
| Temperature of reaction | 20℃ | 30℃ | 40℃ | 75℃ | 100℃ |
| Reaction solvent | Acetone | Tetrahydrofuran (THF) | Acetone | Espeleton | Isophorone |
| 7-ketone-cholesterol productive rate | 42.9％ | 59.3％ | 81.9％ | 53.2％ | 61.8％ |
Embodiment 16
Primary Catalysts N-2 among the embodiment 1 adopts the isolating method of tetracol phenixin to reclaim, after reaction finishes, reaction solution is carried out underpressure distillation, adding tetracol phenixin filters, catalyzer after the recovery, drying is handled, and directly is used for the oxidizing reaction of cholesterol once more, and the yield of 7-ketone-cholesterol is 81.4%.
Claims (6)
1, a kind ofly prepare the method for 7-ketone-cholesterol by the cholesterol oxidation, reaction formula is as follows:
In the formula: R
1Be OAc, R
2Be C
8H
17As Primary Catalysts, transition metal salt is as promotor with the N-hydroxy derivatives for catalyzer;
Preparation process is: after the cholesterol of certain proportioning and Primary Catalysts are dissolved in appropriate solvent, add promotor, wherein the reaction mol ratio of cholesterol and Primary Catalysts and promotor is: between 100: 150: 1.5 to 100: 5: 0.5, feed oxygen-containing gas, cholesterol oxide under 0 ℃～120 ℃ temperature, after treating the cholesterol complete oxidation,, obtain 7-ketone-cholesterol with the solvent evaporate to dryness; By tetracol phenixin product and catalyst separating are come, gained catalyzer drying is handled reusable edible.
2,, it is characterized in that employed N-hydroxy derivatives Primary Catalysts, a kind of among following structural formula label NHPI, N-1, N-2, N-3, N-4, N-5, N-6, N-7, N-8, the N-9 according to the described preparation method of claim 1:
3,, it is characterized in that the positively charged ion of transition metal salt is: Fe according to the described preparation method of claim 1
3+, Cr
3+, V
3+, Ti
2+, Mn
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+In one or both; Negatively charged ion is Cl
-, Br
-, F
-, PO
4 3-, SO
4 2-, NO
3 -, CH
3COO
-, acac
-, OAc
-In one or both.
4,, it is characterized in that employed solvent is: the ketone, the ethers that contain three to nine carbon atoms: furans, tetrahydrofuran (THF), pyrans, tetrahydropyrans, N, N-dimethyl imide according to the described preparation method of claim 1.
5, according to the described preparation method of claim 1, it is characterized in that under the condition of pressurization, reacting, oxygen pressure is controlled at 0.2～2atm, and temperature of reaction is between 0 ℃～120 ℃.
6, according to the described preparation method of claim 1, it is characterized in that Primary Catalysts adopts the isolating method of tetracol phenixin to reclaim, reaction is carried out underpressure distillation with reaction solution after finishing, and adds tetracol phenixin, filters, and drying treatment reclaims catalyzer; Reclaim the oxidizing reaction that catalyzer directly is used for cholesterol once more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101629975A CN101418030A (en) | 2008-12-11 | 2008-12-11 | Method for preparing 7-keto-cholesterol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101629975A CN101418030A (en) | 2008-12-11 | 2008-12-11 | Method for preparing 7-keto-cholesterol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101418030A true CN101418030A (en) | 2009-04-29 |
Family
ID=40629045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008101629975A Pending CN101418030A (en) | 2008-12-11 | 2008-12-11 | Method for preparing 7-keto-cholesterol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101418030A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788163A (en) * | 2014-01-27 | 2014-05-14 | 浙江大学 | Preparation method of 7-ketone sterides |
| CN104148110A (en) * | 2014-08-07 | 2014-11-19 | 湘潭大学 | Preparation method and application of immobilized catalyst for hydrocarbon oxidation |
| CN110885354A (en) * | 2019-11-14 | 2020-03-17 | 浙江新和成股份有限公司 | Preparation method of 7-ketone-cholesterol acetate |
| CN111138510A (en) * | 2019-12-30 | 2020-05-12 | 浙江新和成药业有限公司 | Preparation method of vitamin D3 intermediate 7-ketocholesterol acetate |
| CN115448823A (en) * | 2022-08-26 | 2022-12-09 | 华中科技大学 | Method for catalyzing allylic oxidation of olefin by heterogeneous iron catalyst |
-
2008
- 2008-12-11 CN CNA2008101629975A patent/CN101418030A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788163A (en) * | 2014-01-27 | 2014-05-14 | 浙江大学 | Preparation method of 7-ketone sterides |
| CN103788163B (en) * | 2014-01-27 | 2015-11-18 | 浙江大学 | The preparation method of 7-ketone group steroid |
| CN104148110A (en) * | 2014-08-07 | 2014-11-19 | 湘潭大学 | Preparation method and application of immobilized catalyst for hydrocarbon oxidation |
| CN110885354A (en) * | 2019-11-14 | 2020-03-17 | 浙江新和成股份有限公司 | Preparation method of 7-ketone-cholesterol acetate |
| CN110885354B (en) * | 2019-11-14 | 2021-04-02 | 浙江新和成股份有限公司 | Preparation method of 7-ketone-cholesterol acetate |
| CN111138510A (en) * | 2019-12-30 | 2020-05-12 | 浙江新和成药业有限公司 | Preparation method of vitamin D3 intermediate 7-ketocholesterol acetate |
| CN111138510B (en) * | 2019-12-30 | 2021-03-16 | 浙江新和成药业有限公司 | Preparation method of vitamin D3 intermediate 7-ketocholesterol acetate |
| CN115448823A (en) * | 2022-08-26 | 2022-12-09 | 华中科技大学 | Method for catalyzing allylic oxidation of olefin by heterogeneous iron catalyst |
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Open date: 20090429 |