CN105348353B - The preparation method of 24 ketone group steroids - Google Patents
The preparation method of 24 ketone group steroids Download PDFInfo
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- CN105348353B CN105348353B CN201510640421.5A CN201510640421A CN105348353B CN 105348353 B CN105348353 B CN 105348353B CN 201510640421 A CN201510640421 A CN 201510640421A CN 105348353 B CN105348353 B CN 105348353B
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- steroid
- autoclave
- ketone group
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- -1 ketone group steroids Chemical class 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 150000003431 steroids Chemical class 0.000 claims abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- AKKLAJYCGVIWBS-UHFFFAOYSA-N O=[N].CC1(C)CCCC(C)(C)N1 Chemical class O=[N].CC1(C)CCCC(C)(C)N1 AKKLAJYCGVIWBS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 6
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 229960003753 nitric oxide Drugs 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical group [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 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 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 235000012000 cholesterol Nutrition 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 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 2
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 239000003810 Jones reagent Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 208000026106 cerebrovascular disease Diseases 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000011647 vitamin D3 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
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Steroid Compounds (AREA)
Abstract
The invention discloses a kind of preparation method of 24 ketone group steroid, comprise the following steps：1), first by steroid and 2,2,6,6 tetramethyl piperidine nitrogen oxides, nitrite tert-butyl, transition metal salt and solvent are added in autoclave, kettle are closed, first with the air in inert gas replacement autoclave, oxygen is re-filled with until pressure is 0.1~1.0Mpa, react at room temperature, when the pressure in autoclave no longer changes, terminate reaction；2), by step 1) gained reaction solution solvent evaporated, recrystallized using methyl alcohol, obtain 24 ketone group steroids.24 ketone group steroids are prepared using the method for the present invention, gentle with rational technology, reaction condition, high income is simple to operate, the features such as environment-friendly.
Description
Technical field
The present invention relates to a kind of method that 24- ketone group steroids are prepared by 24- hydroxy steroids.
Background technology
24- ketone group steroids are isolated a kind of materials from organism, with important physiologically active, no
Only it is to prepare vitamin D3The important as precursors of derivative, be also prepare it is a series of with 24- methylene based structures marine steroids chemical combination
The important as precursors of thing, wherein, the marine steroids compound with 24- methylene based structures be widely used in it is antitumor, antibacterial with
And during the preventing and treating of cardiovascular and cerebrovascular disease, the important as precursors synthesized accordingly, as it, the synthesis of 24- ketone group steroids
Technique can largely restrict the condition of production of such compound.
In the prior art, the main method of synthesis 24- ketone group steroids is the C-24 hydroxyls oxidation based on chromium reagent
Technique, conventional chromium reagent such as (Steroids, 2009,74,81-87.J.Chem.Research such as Jones reagents, PCC
(S),1998,206-207.Russ.J.Bioor.Chem.2002,28,284-288).When using chromium reagent as oxidant,
Although with yield higher, chromium reagent toxicity is big, and toxic wastewater welding does not meet the principle of Green Chemistry, together yet
When, post processing is also complex, economical big with environmentally limitation.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of rational technology, reaction condition gently, high income, operation letter
Singly, the preparation method of environment-friendly 24- ketone group steroids.
In order to solve the above-mentioned technical problem, a kind of preparation method of 24- ketone groups steroid of present invention offer, including with
Lower step：
1), first by steroid and 2,2,6,6- tetramethyl piperidine-nitrogen-oxide (TEMPO) shown in formula (II),
Nitrite tert-butyl (TBN), transition metal salt and solvent are added in (sequentially adding) autoclave, close kettle, first use inert gas
Air in displacement autoclave, is re-filled with oxygen up to pressure is 0.1~1.0Mpa, reacts at room temperature, treats autoclave
When interior pressure no longer changes, terminate reaction；
Shown steroid is 1 with the mol ratio of 2,2,6,6- tetramethyl piperidines-nitrogen-oxide (TEMPO):0.01~
0.2, shown steroid is 1 with the mol ratio of nitrite tert-butyl (TBN):0.01~0.2, shown steroid and mistake
The mol ratio for crossing slaine is 1:0.01~0.2；
2), by step 1) gained reaction solution solvent evaporated, recrystallized using methyl alcohol, obtain the 24- ketone groups described in formula (I)
Steroid；
Steroid shown in formula (II), as：3- acetyl group -24- hydroxy cholesterols.
24- ketone group steroids described in formula (I), as：3- acetyl group -24- ketone group cholesterol.
Remarks explanation：
Step 1) gained reaction solution solvent evaporated after gains, mainly include product 24- ketone group steroids it is (insoluble
In methyl alcohol), the catalyst (being dissolved in methyl alcohol) also including TEMPO, the TBN as residual components etc..
Room temperature generally refers to 15~25 DEG C.
During the course of the reaction, the pressure in autoclave can decline, and when pressure no longer declines, terminate reaction.
As the improvement of the preparation method of 24- ketone groups steroid of the invention：Transition metal salt is iron chloride (trichlorine
Change iron), ferric sulfate, ferric nitrate, ferrous sulfate, copper chloride.
As the further improvement of the preparation method of 24- ketone groups steroid of the invention：Step 1) in solvent be
Dichloromethane, dichloroethanes, ethyl acetate, acetonitrile, toluene, chlorobenzene (preferably dichloroethanes, less preferred dichloromethane).
As the further improvement of the preparation method of 24- ketone groups steroid of the invention：
The oxygen pressure is 0.4~1.0Mpa,
The steroid is 1 with the mol ratio of 2,2,6,6- tetramethyl piperidines-nitrogen-oxide:0.05~0.2,
The steroid is 1 with the mol ratio of nitrite tert-butyl:0.04.
As the further improvement of the preparation method of 24- ketone groups steroid of the invention：
The transition metal salt is CuCl2Or FeCl3, the steroid and FeCl3Mol ratio be 1:0.05~
0.2, the steroid and CuCl2Mol ratio be 1:0.05.
In the present invention, it is however generally that, the steroid shown in formula (II) per 5mmol, 20~30mL's of adapted is molten
Agent.
The preparation method of 24- ketone groups steroid of the invention has following technical advantage：
1), by the use of oxygen as oxidant, green, environmental protection, oxidant is inexpensive, and source is wide for the present invention, the original of whole reaction
Subeconomy is high, and the accessory substance of reaction is only water, environment-friendly, with preferable prospects for commercial application；
2), reaction can be carried out at ambient temperature, and reaction condition is gentle, simple to operate；
3) suitable catalyst, is have selected, so as to obtain preferable yield.
Specific embodiment
Embodiment 1, a kind of preparation method of 24- ketone groups cholesterol, follow the steps below successively：
By 2.22g (5mmol) 3- acetyl group -24- hydroxy cholesterols, 0.04gTEMPO (0.25mmol), 0.02gTBN
(0.2mmol), 0.04g ferric trichlorides (0.25mmol) are added sequentially in autoclave, while addition 20mL dichloroethanes (as
Solvent), kettle is closed, using oxygen is filled with after nitrogen displacement three times, make its initial pressure for 0.4MPa, stirring is opened, at room temperature
Reaction, when pressure gauge registration no longer declines, reaction terminates, pressure release, drives kettle.
After reaction terminates, solvent is removed using Rotary Evaporators, product 3- second can be obtained after absolute methanol (50ml) recrystallization
Acyl group -24- ketone group cholesterol 1.88g, yield：86.2%, purity is 99%.Fusing point:126-128℃.1H NMR(CDCl3,
400MHz):δ 5.30 (d, J=4.2Hz, 1H), 4.53 (m, 1H), 1.96 (s, 3H), 0.95 (s, 3H), 0.85 (d, J=
6.5Hz,3H),0.61(s,3H).13C NMR(CDCl3,100MHz):δ214.41,169.51,138.63,121.59,72.95,
55.65,54.87,48.99,41.35,39.82,38.70,37.10,36.19,35.98,35.57,34.35,30.85,
28.83,27.10,26.76,23.24,20.41,20.01,18.29,17.50,17.36,17.29,10.86。
Embodiment 2~7：
Change the species and consumption (as shown in table 1) of transition metal salt, remaining is equal to embodiment 1, obtains embodiment 2~7；
The yield of products therefrom is as shown in table 1 below：
Table 1
| Embodiment | Transition metal salt/mmol | Yield |
| 2 | Fe(NO3)3.9H2O/0.25 | 38.5 |
| 3 | Fe2(SO4)3.6H2O/0.25 | 30.0 |
| 4 | FeSO4.7H2O/0.25 | 29.8 |
| 5 | CuCl2/0.25 | 80.0 |
| 6 | FeCl3/0.05 | 45.5 |
| 7 | FeCl3/1.0 | 80.1 |
Embodiment 8~11：Change the consumption of TEMPO and TBN, remaining is equal to embodiment 1, obtains embodiment 8~11；Institute
The yield for obtaining product is as shown in table 2 below：
Table 2
| Embodiment | TBN/mmol | TEMPO/mmol | Yield |
| 8 | 0.2 | 0.05 | 20.9 |
| 9 | 0.2 | 1.0 | 85.9 |
| 10 | 0.05 | 0.25 | 15.8 |
| 11 | 1.0 | 0.25 | 59.8 |
Embodiment 12~15：
Change oxygen pressure, remaining is equal to embodiment 1, obtains embodiment 12~15；The yield of products therefrom such as table 3 below institute
Show：
Table 3
| Embodiment | Oxygen pressure/MPa | Yield |
| 12 | 0.2 | 62.8 |
| 13 | 0.6 | 85.5 |
| 14 | 0.8 | 86.0 |
| 15 | 1.0 | 85.2 |
Embodiment 16~20
Change solvent used, remaining is equal to embodiment 1, obtains embodiment 16~20；The yield of products therefrom such as table 4 below
It is shown：
Table 4
| Embodiment | Solvent | Yield |
| 16 | Dichloromethane | 80.0 |
| 17 | Ethyl acetate | 20.0 |
| 18 | Acetonitrile | 25.8 |
| 19 | Toluene | 40.9 |
| 20 | Chlorobenzene | 58.0 |
Comparative example 1 is serial, make the TEMPO in embodiment 1 into NHPI, 4-OH-TEMPO, and remaining is equal to embodiment 1,
The yield of products therefrom is as shown in table 5 below：
Table 5
| Comparative example | The substitute of TEMPO | Yield |
| 1-1 | NHPI | 0 |
| 1-2 | 4-OH-TEMPO | 52.4 |
Comparative example 2 is serial, make the TBN in embodiment 1 into NaNO2、Fe(NO3)3.9H2O, remaining is equal to embodiment 1,
The yield of products therefrom is as shown in table 6 below：
Table 6
| Comparative example | The substitute of TBN | Yield |
| 2-1 | NaNO2 | 40.7 |
| 2-2 | Fe(NO3)3.9H2O | 48.3 |
Comparative example 3, the use for cancelling " 0.04g ferric trichlorides (0.25mmol) " in embodiment 1, accordingly by TEMPO's
Consumption makes 0.5mmol into by 0.25mmol, and remaining is equal to embodiment 1, and the yield of products therefrom is 30.1%.
Comparative example 4, the use for cancelling " 0.04g ferric trichlorides (0.25mmol) " in embodiment 1, accordingly by the use of TBN
Amount makes 0.45mmol into by 0.2mmol, and remaining is equal to embodiment 1, and the yield of products therefrom is 37.2%.
Finally, in addition it is also necessary to it is noted that listed above is only some specific embodiments of the invention.Obviously, the present invention
Above example is not limited to, there can also be many deformations.One of ordinary skill in the art can be straight from present disclosure
The all deformations derived or associate are connect, protection scope of the present invention is considered as.
Claims (2)
- The preparation method of 1.24- ketone group steroids, it is characterised in that comprise the following steps：1), first by steroid and 2,2,6,6- tetramethyl piperidine-nitrogen-oxide, the tertiary fourth of nitrous acid shown in formula (II) Ester, transition metal salt and solvent are added in autoclave, close kettle, first with the air in inert gas replacement autoclave, are re-filled with Oxygen is 0.4~1.0Mpa up to pressure, is reacted at room temperature, when the pressure in autoclave no longer changes, knot Shu Fanying；Shown steroid is 1 with the mol ratio of 2,2,6,6- tetramethyl piperidines-nitrogen-oxide:0.05~0.2, shown steroid Class compound is 1 with the mol ratio of nitrite tert-butyl:0.04, shown steroid is 1 with the mol ratio of transition metal salt: 0.01~0.2；The transition metal salt is iron chloride, copper chloride, and the solvent is dichloromethane, dichloroethanes；2), by step 1) gained reaction solution solvent evaporated, recrystallized using methyl alcohol, obtain the 24- ketone group steroids described in formula (I) Compound；
- 2. the preparation method of 24- ketone groups steroid according to claim 1, it is characterised in that：The transition metal salt is CuCl2Or FeCl3, the steroid and FeCl3Mol ratio be 1:0.05~0.2, institute State steroid and CuCl2Mol ratio be 1:0.05.
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| CN104387251A (en) * | 2014-11-10 | 2015-03-04 | 江西仁明医药化工有限公司 | Method for synthesizing 2-norbornane ketone |
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| CN104387251A (en) * | 2014-11-10 | 2015-03-04 | 江西仁明医药化工有限公司 | Method for synthesizing 2-norbornane ketone |
Non-Patent Citations (1)
| Title |
|---|
| A facile synthesis of C-24 and C-25 oxysterols by in situ generated ethyl(trifluoromethyl)dioxirane;Shoujiro Ogawa et al.;《steroids》;20081019;第74卷;81-87 * |
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