CN109046367A - Niobium pentaoxide copper-loading catalyst and the preparation method and application thereof - Google Patents
Niobium pentaoxide copper-loading catalyst and the preparation method and application thereof Download PDFInfo
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- CN109046367A CN109046367A CN201810803852.2A CN201810803852A CN109046367A CN 109046367 A CN109046367 A CN 109046367A CN 201810803852 A CN201810803852 A CN 201810803852A CN 109046367 A CN109046367 A CN 109046367A
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- copper
- niobium pentaoxide
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- loading catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000011068 loading method Methods 0.000 title claims description 28
- 239000010949 copper Substances 0.000 claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000002105 nanoparticle Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 6
- -1 mifepristone class compound Chemical class 0.000 claims description 25
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 11
- 239000010452 phosphate Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 10
- 235000019766 L-Lysine Nutrition 0.000 claims description 9
- 239000004472 Lysine Substances 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000011097 chromatography purification Methods 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 2
- UMRSVAKGZBVPKD-UHFFFAOYSA-N acetic acid;copper Chemical compound [Cu].CC(O)=O UMRSVAKGZBVPKD-UHFFFAOYSA-N 0.000 claims 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims 1
- VKHAHZOOUSRJNA-GCNJZUOMSA-N mifepristone Chemical class C1([C@@H]2C3=C4CCC(=O)C=C4CC[C@H]3[C@@H]3CC[C@@]([C@]3(C2)C)(O)C#CC)=CC=C(N(C)C)C=C1 VKHAHZOOUSRJNA-GCNJZUOMSA-N 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract 2
- 238000005470 impregnation Methods 0.000 abstract 1
- 239000010970 precious metal Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000000643 oven drying Methods 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- BFPYWIDHMRZLRN-SLHNCBLASA-N Ethinyl estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 BFPYWIDHMRZLRN-SLHNCBLASA-N 0.000 description 1
- 108090000079 Glucocorticoid Receptors Proteins 0.000 description 1
- 102100033417 Glucocorticoid receptor Human genes 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229940123788 Progesterone receptor antagonist Drugs 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- ACSIXWWBWUQEHA-UHFFFAOYSA-N clodronic acid Chemical compound OP(O)(=O)C(Cl)(Cl)P(O)(O)=O ACSIXWWBWUQEHA-UHFFFAOYSA-N 0.000 description 1
- 229960002286 clodronic acid Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229960002568 ethinylestradiol Drugs 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229960003248 mifepristone Drugs 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- REJGOFYVRVIODZ-UHFFFAOYSA-N phosphanium;chloride Chemical compound P.Cl REJGOFYVRVIODZ-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8474—Niobium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J51/00—Normal steroids with unmodified cyclopenta(a)hydrophenanthrene skeleton not provided for in groups C07J1/00 - C07J43/00
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种五氧化二铌负载铜催化剂、制备方法及其在米非司酮类化合物磷酸酯化反应中的应用。所述的催化剂载体为五氧化二铌，活性组分为铜基纳米颗粒，其中纳米颗粒中同时含有Cu纳米粒子和Cu2O纳米粒子。本发明以Nb2O5为载体，采用浸渍法，通过NaBH4还原，干燥后再在H2条件下，400～500℃下还原制得催化剂。本发明的催化剂性能稳定，催化活性高，可循环使用，在米非司酮类化合物的磷酸酯化反应中产率可达95％以上，相比于传统合成方法，避免了贵金属催化剂的使用，反应条件温和，底物耐受性好。
The invention discloses a niobium pentoxide supported copper catalyst, a preparation method and its application in the phosphating reaction of mifepristone compounds. The catalyst carrier is niobium pentoxide, and the active component is copper-based nanoparticles, wherein the nanoparticles contain both Cu nanoparticles and Cu 2 O nanoparticles. The invention uses Nb 2 O 5 as carrier, adopts impregnation method, reduces by NaBH 4 , and then reduces under H 2 condition at 400-500 DEG C to prepare the catalyst. The catalyst of the present invention has stable performance, high catalytic activity, can be recycled, and the yield in the phosphating reaction of mifepristone compounds can reach more than 95%. Compared with the traditional synthesis method, the use of precious metal catalysts is avoided, and the reaction Mild conditions and good substrate tolerance.
Description
Technical field
The invention belongs to phosphating reaction catalyst technical field, be related to a kind of niobium pentaoxide copper-loading catalyst,
Preparation method and its application in mifepristone class compound phosphating reaction.
Background technique
As progesterone receptor antagonist, the activity with Antiglucocorticoid exists mifepristone class compound in recent years
Pharmaceutical chemistry is used widely.But due to its apparent glucocorticoid receptor antagonism, clinical use is ineffective.
By carrying out Phosphation to it, obtained compound is more more efficient than mifepristone and highly selective.
The reaction of mifepristone class compound alkynyl Phosphation is mainly include the following types: (1) double trimethyl silicon substrate amino
The mifepristone class compound and phosphine chloride phosphating reaction (Steroids, 2006,71 (11-12), 949- that lithium participates in
954. patent WO2007US62274)；(2) ethinyloestradiol of copper catalysis reacts (The Journal of Organic with phosphate
Chemietry,2016,81(5),1813-1818)；(3) alkynyl sulfone compound and phosphate react (Tetrahedron
Letters,2008,49(14),2265-2267)。
However all there is disadvantage in the above method, such as used unstable Clodronate diethylester and inflammable double trimethyls
Silicon substrate lithium amide as reaction reagent, reactivity hazard is larger and reaction reagent costly, be unfavorable for amplification production；Used
Copper catalyst Cu2O, the dosages such as CuI are larger and cannot recycle；It needs using pre- function dough acetylene hydrocarbon compound；Substrate adaptability
Difference, yield is generally 50%~79% or so.
Summary of the invention
For in existing mifepristone class compound Phosphation method, the reagent risk used is big, stability is poor,
The problem of low yield, the present invention provide recyclable one kind, stability height, catalytic activity good niobium pentaoxide supported copper catalysis
Agent and preparation method thereof.
The technical solution of the present invention is as follows:
Niobium pentaoxide copper-loading catalyst, the catalyst carrier are niobium pentaoxide, and active component is copper-based receives
Rice grain wherein contains Cu nanoparticle and Cu simultaneously in nano particle2O nanoparticle.
Preferably, the load capacity of copper-based nano particle is 3% in the catalyst.
The preparation method of above-mentioned niobium pentaoxide copper-loading catalyst, the specific steps are as follows:
Niobium pentaoxide is dispersed in soluble copper salting liquid, addition L-lysine solution, under nitrogen protection, room temperature is stirred
It mixes uniformly mixed, adds NaBH under condition of ice bath4Solution is stirred to react completely, stands aging, clean with water and ethanol washing
Afterwards, it is centrifugated, it is dry, in H2Under the conditions of, 30~60min is restored at 400~500 DEG C, is obtained niobium pentaoxide supported copper and is urged
Agent.
Preferably, the soluble copper salt is selected from copper chloride, copper acetate, copper nitrate or acetylacetone copper.
Preferably, the concentration of the L-lysine solution is 0.25~0.5mmol/mL.
Preferably, the soluble copper salt and NaBH4Molar ratio 1:10.
Preferably, the time that is stirred to react is 4~8h.
Preferably, the standing ageing time be for 24 hours more than.
The present invention also provides niobium pentaoxide copper-loading catalysts in mifepristone class compound phosphating reaction
Using the specific method is as follows:
Mifepristone class compound, phosphate, niobium pentaoxide copper-loading catalyst, tri-n-butylamine are added to dimethyl
In sulfoxide (DMSO), 60~70 DEG C of reaction 12h or more, are filtered after reaction under air conditions, and filtrate is washed respectively, salt is washed,
Crude product is obtained after removing solvent, crude product obtains target product by column Chromatographic purification.
The structural formula of the mifepristone class compound are as follows:Wherein, R '=N
(CH3)2、SMe、OMe。
The structural formula of the phosphate are as follows:Wherein, R=OPh, OMe, OEt, OBu, OtBu。
Preferably, the molar ratio of the mifepristone class compound, phosphate, copper, tri-n-butylamine is not less than 1:2:
0.06:0.2, i.e. phosphate, copper, tri-n-butylamine can be excessive.
Compared with prior art, the present invention having the advantage that
(1) oxidation of copper nano particles can effectively be inhibited, to improve as catalyst carrier using niobium pentaoxide
Catalyst activity, long service life and stability are high；
(2) niobium pentaoxide carrier is firmly combined with copper nano particles, not easy in inactivation, reunion, in mifepristone class chemical combination
Use can be recycled in the application of object Phosphation.
(3) excellent catalytic performance shown to the reaction of mifepristone class compound Phosphation, yield 85% with
On, and it is economic and environment-friendly.
Detailed description of the invention
Fig. 1 is that the TEM of niobium pentaoxide copper-loading catalyst schemes.
Fig. 2 is the XRD diagram of niobium pentaoxide copper-loading catalyst.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
Embodiment 1
Step 1, the preparation of niobium pentaoxide copper-loading catalyst: configuration CuCl first2Solution (0.46mmol), with
1gNb2O5It is uniformly mixed, L-lysine solution (0.53mmol/mL) is added under nitrogen protection, after 4h is stirred at room temperature, condition of ice bath
Under NaBH is slowly added dropwise4Solution (0.05mmol/mL) is restored, and after stirring 2h, stands aging for 24 hours.Finally by mixed solution
It is washed respectively three times with water and ethyl alcohol, centrifuge separation, vacuum drying oven drying 12h is placed under the conditions of 60 DEG C.The catalyst of drying is existed
H2Under environment, 400 DEG C of reduction 30min.
Step 2, application of the niobium pentaoxide copper-loading catalyst in mifepristone class compound phosphating reaction: point
Do not take 0.2mmol mifepristone class compound 1,0.4mmol phosphate ester 2, wherein the R in phosphate be-OEt ,-OMe ,-
OPh、-OBu、-OtThe niobium pentaoxide supported copper that one of Bu, 0.04mmol tri-n-butylamine and copper content are 0.012mmol
Catalyst sequentially adds in pressure pipe, is added the DMSO of 2mL, under air conditions, stops after reacting 12h in 60 DEG C of oil bath,
Extracted by filtration, revolving remove reaction dissolvent and obtain pure target product 3a-3e by column chromatography silica gel, and yield is as follows
Respectively 90%, 85%, 93%, 95%, 89%.
Embodiment 2
Step 1, the preparation of niobium pentaoxide copper-loading catalyst: configuration CuCl first2Solution (0.46mmol), with
1gNb2O5It is uniformly mixed, L-lysine solution (0.53mmol/mL) is added under nitrogen protection, after 4h is stirred at room temperature, condition of ice bath
Under NaBH is slowly added dropwise4Solution (0.05mmol/mL) is restored, and after stirring 2h, stands aging for 24 hours.Finally by mixed solution
It is washed respectively three times with water and ethyl alcohol, centrifuge separation, vacuum drying oven drying 12h is placed under the conditions of 60 DEG C.The catalyst of drying is existed
H2Under environment, 400 DEG C of reduction 30min.
Step 2, application of the niobium pentaoxide copper-loading catalyst in mifepristone class compound phosphating reaction: point
Do not take 0.2mmol mifepristone class compound 1, wherein R ' be one of-SMe ,-OMe, 0.4mmol diethyl phosphite 2,
The niobium pentaoxide copper-loading catalyst that 0.04mmol tri-n-butylamine and copper content are 0.012mmol sequentially adds in pressure pipe,
The DMSO of 2mL is added, under air conditions, stops after reacting 12h in 60 DEG C of oil bath, extracted by filtration, revolving is molten except dereaction
Agent obtains pure target product 3f-3g by column chromatography silica gel, and yield is respectively 91%, 96% as follows.
Comparative example 1
Step 1, the preparation of niobium pentaoxide copper-loading catalyst: configuration CuCl first2Solution (0.46mmol), with
1gNb2O5It is uniformly mixed, L-lysine solution (0.53mmol/mL) is added under nitrogen protection, after 4h is stirred at room temperature, condition of ice bath
Under NaBH is slowly added dropwise4Solution (0.05mmol/mL) is restored, and after stirring 2h, stands aging for 24 hours.Finally by mixed solution
It is washed respectively three times with water and ethyl alcohol, centrifuge separation, vacuum drying oven drying 12h is placed under the conditions of 60 DEG C.The catalyst of drying is existed
H2Under environment, 400 DEG C of reduction 30min.
Step 2, application of the niobium pentaoxide copper-loading catalyst in mifepristone class compound phosphating reaction: according to
It is secondary that pressure resistance is added in mifepristone class compound 1, diethyl phosphite 2, tri-n-butylamine and niobium pentaoxide copper-loading catalyst
Guan Zhong, wherein mifepristone class compound, diethyl phosphite, copper dosage, the molar ratio of tri-n-butylamine are 1:1:0.06:0.2,
The DMSO of 2mL is added, under air conditions, stops after reacting 12h in 60 DEG C of oil bath, extracted by filtration, revolving is molten except dereaction
Agent obtains pure target product 3a, yield 67% by column chromatography silica gel.
Comparative example 2
Step 1, the preparation of niobium pentaoxide copper-loading catalyst: configuration CuCl first2Solution (0.46mmol), with
1gNb2O5It is uniformly mixed, L-lysine solution (0.53mmol/mL) is added under nitrogen protection, after 4h is stirred at room temperature, condition of ice bath
Under NaBH is slowly added dropwise4Solution (0.05mmol/mL) is restored, and after stirring 1-2h, stands aging for 24 hours.It will finally mix molten
Liquid water and ethyl alcohol are washed three times respectively, centrifuge separation, and vacuum drying oven drying 12h is placed under the conditions of 60 DEG C.By the catalyst of drying
In H2Under environment, 400 DEG C of reduction 30min.
Step 2, application of the niobium pentaoxide copper-loading catalyst in mifepristone class compound phosphating reaction: according to
It is secondary that pressure resistance is added in mifepristone class compound 1, diethyl phosphite 2, tri-n-butylamine and niobium pentaoxide copper-loading catalyst
Guan Zhong, wherein mifepristone class compound, diethyl phosphite, copper dosage, the molar ratio of tri-n-butylamine are 1:2:0.05:0.2,
The DMSO of 2mL is added, under air conditions, stops after reacting 12h in 60 DEG C of oil bath, extracted by filtration, revolving is molten except dereaction
Agent obtains pure target product 3a, yield 75% by column chromatography silica gel.
Comparative example 3
Step 1, the preparation of niobium pentaoxide copper-loading catalyst: configuration CuCl first2Solution (0.46mmol), with
1gNb2O5It is uniformly mixed, L-lysine solution (0.53mmol/mL) is added under nitrogen protection, after 4h is stirred at room temperature, condition of ice bath
Under NaBH is slowly added dropwise4Solution (0.05mmol/mL) is restored, and after stirring 1-2h, stands aging for 24 hours.It will finally mix molten
Liquid water and ethyl alcohol are washed three times respectively, centrifuge separation, and vacuum drying oven drying 12h is placed under the conditions of 60 DEG C.By the catalyst of drying
In H2Under environment, 400 DEG C of reduction 30min.
Step 2, application of the niobium pentaoxide copper-loading catalyst in mifepristone class compound phosphating reaction: according to
It is secondary that pressure resistance is added in mifepristone class compound 1, diethyl phosphite 2, tri-n-butylamine and niobium pentaoxide copper-loading catalyst
Guan Zhong, wherein mifepristone class compound, diethyl phosphite, copper dosage, the molar ratio of tri-n-butylamine are 1:2:0.06:0.1,
The DMSO of 2mL is added, under air conditions, stops after reacting 12h in 60 DEG C of oil bath, extracted by filtration, revolving is molten except dereaction
Agent obtains pure target product 3a, yield 56% by column chromatography silica gel.
Claims (10)
1. niobium pentaoxide copper-loading catalyst, which is characterized in that the catalyst carrier is niobium pentaoxide, active component
For copper-based nano particle, wherein contain Cu nanoparticle and Cu in nano particle simultaneously2O nanoparticle.
2. niobium pentaoxide copper-loading catalyst according to claim 1, which is characterized in that the copper-based nano particle
Load capacity be 3%.
3. the preparation method of niobium pentaoxide copper-loading catalyst according to claim 1 or 2, which is characterized in that specific
Steps are as follows:
Niobium pentaoxide is dispersed in soluble copper salting liquid, addition L-lysine solution, under nitrogen protection, is stirred at room temperature mixed
It closes uniformly, adds NaBH under condition of ice bath4Solution, be stirred to react completely, stand aging, with water and ethanol washing it is clean after,
Centrifuge separation, it is dry, in H2Under the conditions of, 30~60min is restored at 400~500 DEG C, obtains the catalysis of niobium pentaoxide supported copper
Agent.
4. preparation method according to claim 3, which is characterized in that the soluble copper salt is selected from copper chloride, acetic acid
Copper, copper nitrate or acetylacetone copper.
5. preparation method according to claim 3, which is characterized in that the concentration of the L-lysine solution be 0.25~
0.5mmol/mL。
6. preparation method according to claim 3, which is characterized in that the soluble copper salt and NaBH4Molar ratio 1:
10；The time that is stirred to react is 4~8h；The standing ageing time be for 24 hours more than.
7. niobium pentaoxide copper-loading catalyst according to claim 1 or 2 is in mifepristone class compound Phosphation
Application in reaction.
8. application according to claim 7, which is characterized in that the specific method is as follows:
Mifepristone class compound, phosphate, niobium pentaoxide copper-loading catalyst, tri-n-butylamine are added to dimethyl sulfoxide
In, 60~70 DEG C of reaction 12h or more, are filtered after reaction under air conditions, and filtrate is washed respectively, salt is washed, after removing solvent
Crude product is obtained, crude product obtains target product by column Chromatographic purification.
9. application according to claim 8, which is characterized in that the structural formula of the mifepristone class compound are as follows:Wherein, R '=N (CH3)2,SMe,OMe；The structural formula of the phosphate are as follows:Wherein, R=OPh, OMe, OEt, OBu, OtBu。
10. application according to claim 7, which is characterized in that the mifepristone class compound, phosphate, copper, three
The molar ratio of n-butylamine is not less than 1:2:0.06:0.2.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113617353A (en) * | 2021-08-02 | 2021-11-09 | 常州大学 | Preparation method of silicon carbide-based silver nano catalyst and application of silicon carbide-based silver nano catalyst in synthesis of ethylene oxide |
| CN117205952A (en) * | 2023-09-14 | 2023-12-12 | 化学与精细化工广东省实验室潮州分中心 | A SiC nanowire-loaded platinum nanoparticle catalyst and its preparation method |
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| TAO YUAN, ET AL.: "Direct synthesis of alkynylphosphonates from alkynes and phosphite esters catalyzed by Cu/Cu2O nanoparticles supported on Nb2O5", 《NEW JOURNAL OF CHEMISTRY》 * |
| WEIQIN JIANG, ET AL.: "Novel phosphorus-containing 17-side chain mifepristone analogues as progesterone receptor antagonists", 《STEROIDS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113617353A (en) * | 2021-08-02 | 2021-11-09 | 常州大学 | Preparation method of silicon carbide-based silver nano catalyst and application of silicon carbide-based silver nano catalyst in synthesis of ethylene oxide |
| CN113617353B (en) * | 2021-08-02 | 2023-09-22 | 常州大学 | Preparation method of silicon carbide-based silver nanocatalyst and its application in ethylene oxide synthesis |
| CN117205952A (en) * | 2023-09-14 | 2023-12-12 | 化学与精细化工广东省实验室潮州分中心 | A SiC nanowire-loaded platinum nanoparticle catalyst and its preparation method |
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