CN109096318A - The method that load copper ion Y type molecular sieve catalysis prepares organoboron compound and beta-hydroxy compound - Google Patents
The method that load copper ion Y type molecular sieve catalysis prepares organoboron compound and beta-hydroxy compound Download PDFInfo
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- CN109096318A CN109096318A CN201810923555.1A CN201810923555A CN109096318A CN 109096318 A CN109096318 A CN 109096318A CN 201810923555 A CN201810923555 A CN 201810923555A CN 109096318 A CN109096318 A CN 109096318A
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- copper ion
- molecular sieve
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910001431 copper ion Inorganic materials 0.000 title claims abstract description 72
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 64
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 34
- 150000001875 compounds Chemical class 0.000 title claims abstract description 21
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 257
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 126
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 63
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- ZZPNDIHOQDQVNU-UHFFFAOYSA-N 2-hydroxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OB(O)OC1(C)C ZZPNDIHOQDQVNU-UHFFFAOYSA-N 0.000 claims abstract description 35
- -1 boron organic compound Chemical class 0.000 claims abstract description 13
- 239000000706 filtrate Substances 0.000 claims abstract description 13
- 239000011734 sodium Substances 0.000 claims abstract description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 233
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 60
- 238000005406 washing Methods 0.000 claims description 53
- 239000012074 organic phase Substances 0.000 claims description 31
- 230000035484 reaction time Effects 0.000 claims description 31
- 239000012046 mixed solvent Substances 0.000 claims description 30
- 239000003208 petroleum Substances 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 30
- 239000000284 extract Substances 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 21
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 15
- 239000012965 benzophenone Substances 0.000 claims description 15
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 8
- RDOXTESZEPMUJZ-UHFFFAOYSA-N methyl phenyl ether Natural products COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 claims description 7
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 7
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 7
- NHOWDZOIZKMVAI-UHFFFAOYSA-N (2-chlorophenyl)(4-chlorophenyl)pyrimidin-5-ylmethanol Chemical compound C=1N=CN=CC=1C(C=1C(=CC=CC=1)Cl)(O)C1=CC=C(Cl)C=C1 NHOWDZOIZKMVAI-UHFFFAOYSA-N 0.000 claims description 6
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 6
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 6
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 2
- 239000004327 boric acid Substances 0.000 claims 2
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 238000004458 analytical method Methods 0.000 claims 1
- 238000004440 column chromatography Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 claims 1
- 125000005504 styryl group Chemical group 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 8
- 229910052796 boron Inorganic materials 0.000 abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 241000903210 Bryconamericus alpha Species 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000003446 ligand Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract 2
- 238000001228 spectrum Methods 0.000 description 52
- 229910021536 Zeolite Inorganic materials 0.000 description 27
- 238000002360 preparation method Methods 0.000 description 27
- 239000010457 zeolite Substances 0.000 description 27
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 26
- 238000005160 1H NMR spectroscopy Methods 0.000 description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 26
- 239000007832 Na2SO4 Substances 0.000 description 26
- 229910052799 carbon Inorganic materials 0.000 description 26
- 229910052739 hydrogen Inorganic materials 0.000 description 26
- 239000001257 hydrogen Substances 0.000 description 26
- 239000000047 product Substances 0.000 description 26
- 238000002390 rotary evaporation Methods 0.000 description 26
- 229910052938 sodium sulfate Inorganic materials 0.000 description 26
- 229960001922 sodium perborate Drugs 0.000 description 23
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 23
- 239000007787 solid Substances 0.000 description 20
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 9
- 239000010949 copper Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000004607 11B NMR spectroscopy Methods 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229930014626 natural product Natural products 0.000 description 3
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 2
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 description 2
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 description 2
- 238000007445 Chromatographic isolation Methods 0.000 description 2
- DAJLHNABGVYSOO-UHFFFAOYSA-N boric acid;2,3-dimethylbutane-2,3-diol Chemical compound OB(O)O.CC(C)(O)C(C)(C)O DAJLHNABGVYSOO-UHFFFAOYSA-N 0.000 description 2
- 238000011097 chromatography purification Methods 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000003810 ethyl acetate extraction Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- CKGKXGQVRVAKEA-UHFFFAOYSA-N (2-methylphenyl)-phenylmethanone Chemical compound CC1=CC=CC=C1C(=O)C1=CC=CC=C1 CKGKXGQVRVAKEA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- 240000000233 Melia azedarach Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 125000004799 bromophenyl group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/24—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing hydroxy groups
- C07C49/245—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing hydroxy groups containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/255—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/82—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups
- C07C49/83—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups polycyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/82—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups
- C07C49/835—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups having unsaturation outside an aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to the methods that load copper ion Y type molecular sieve catalysis prepares organoboron compound and beta-hydroxy compound.It wherein prepares organoboron compound and mainly includes the following steps: that load copper ion Y type molecular sieve, tetrahydrofuran and water is added in A. in the reaction vessel, mixed liquor is sufficiently stirred to obtain at room temperature；B. alpha, beta-unsaturated carbonyl compound and connection boric acid pinacol ester reagent are added into mixed liquor；C. stirring sufficiently reaction at room temperature；D. after reaction, separating-purifying to get.The method for preparing beta-hydroxy compound is, after above-mentioned steps C, directly filters, then wash with tetrahydrofuran and merges cleaning solution with filtrate, four hydrated sodium perborates are added into filtrate, stir at room temperature it is abundant react, separating-purifying to get.It has the beneficial effect that, uses the Y type molecular sieve of load copper ion as the catalyst for preparing boron organic compound for the first time, be not required to additionally add ligand, high catalytic efficiency, stability are good, nontoxic environmentally protective.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to load copper ion Y type molecular sieve catalysis prepares organoboration conjunction
The method of object and beta-hydroxy compound.
Background technique
Organoboron compound is a kind of important intermediate, is widely present in the structure of natural products and drug molecule,
It is simultaneously also the important synthon of organic synthesis, C-B key can be further converted to C-O, C-N key and C-C key.Compared to tradition
Using the method for equivalent reaction reagent, under the action of catalyst, to the direct boron addition of beta-unsaturated carbonyl compounds strategy more
Directly and effectively, extensive concern is obtained in recent years.Catalyst used in document is mostly expensive transition metal, as Rh,
Ni, Pt, Pb etc., it is at high cost, it is not suitable for actual production.In addition, also having in document using cupprous method, although reaction
Activity increase, but operating process is complicated, needs highly basic (potassium tert-butoxide etc.), low temperature (- 78 DEG C), stringent anhydrous etc.
Harsh conditions, these all significantly limit the application of such method in actual production.In comparison, cupric is lower
Lian Huanbao, thus develop be based on cupric heterogeneous catalysis the current field research emphasis and difficult point, have important
Application value.
On the other hand, for heterogeneous catalysis, the selection of carrier is most important, and is widely present by nature
By the deacetylated obtained molecular sieve of chitin be undoubtedly well selection.Molecular sieve is not only cheap and easily-available, but also has very
The excellent performances such as good biocompatibility, safety, microbic resolvability.Until up to now, still not to load copper ion
Molecular sieve be catalyzed the related report for preparing organoboron compound.
In addition, organoboron compound is to a kind of important application that the conversion of beta-hydroxy compound is in industrial production, because
Beta-hydroxyl structure is widely present among natural products and drug molecular structure, if therefore can be first using the strategy of " one kettle way "
The boron addition for first realizing substrate, does not need to be separated be continuously converted to β-hydroxy compounds later, and the synthesis for simplifying natural products is walked
Suddenly, there is highly important application value.In addition, organoboron compound is in addition to the extensive use in terms of organic synthesis, it can also
Initiator, kerosene antioxidant, fungicide, anticancer drug as polymerization reaction etc..
Summary of the invention
The present invention provides a kind of load copper ion Y type molecular sieve microballoons to prepare organoboron compound and β-hydroxy compound
The method of object, it is intended to overcome following deficiency existing in the prior art at least to some extent: being synthesis organic boron with noble metal
It is at high cost when the catalyst of compound or the reagent of equivalent are synthesis material, it can not industrialize；Matched with monovalence copper and nitrogen Cabbeen
When body is catalyst, operating process is complicated, needs highly basic (potassium tert-butoxide etc.), low temperature (- 78 DEG C), strictly anhydrous equal harsh item
Part equally causes production cost higher；If anticipating when prepared by existing beta-hydroxy compound using organoboron compound as starting point
Taste need after synthesis organoboron compound to carry out it into separating-purifying processing from reaction product, without continuous production,
Therefore process route is complicated, production efficiency is lower.
The technical scheme to solve the above technical problems is that load copper ion Y type molecular sieve catalysis prepare it is organic
The method of boron compound comprising following steps:
A. load copper ion Y type molecular sieve, tetrahydrofuran and water are added in the reaction vessel, is sufficiently stirred, obtains at room temperature
Mixed liquor, load copper ion Y type molecular sieve load copper ion substance amount and water amount ratio be 0.002~
The volume ratio of 0.003mmol:1mL, tetrahydrofuran and water is 0.5~1:1；
B. alpha, beta-unsaturated carbonyl compound I and connection boric acid pinacol are added into the mixed liquor that step A is obtained
Ester, wherein the ratio between α, beta-unsaturated carbonyl compound I and the dosage of water in the mixed liquor are 0.15~0.25mmol:1mL,
The ratio between connection boric acid pinacol ester and the amount of substance of alpha, beta-unsaturated carbonyl compound I are 1.0~2.0:1；
C. it is stirred to react at room temperature, the reaction time is 10~16h；
D. after reaction, separating-purifying is to get organoboron compound II；
Chemical equation is as follows:
Wherein R1For benzophenone base, to methylbenzene ketone group, to methoxybenzene ketone group, to fluorobenzene ketone group, acetyl group or pivaloyl
Base；R2For phenyl, p-methylphenyl, p-methoxyphenyl, p-fluorophenyl, rubigan, p-bromophenyl, to trifluoromethylbenzene
Base, m-bromophenyl, chlorphenyl, 2- thienyl, 2- naphthalene or 3- acrylic phenyl.
Based on the above technical solution, the present invention can also have following further specific choice.
Specifically, the load capacity for loading copper ion in copper ion Y type molecular sieve in A is 5-10wt%.Load copper ion Y
The preparation method of type molecular sieve is the prior art, can refer in document and carries out, for example can be prepared as follows: (1) preparing
Concentration is the copper-bath of 1mol/L.(2) it weighs 10gY molecular sieve (Na type), is added in beaker, 200mL sulphur is then added
Sour copper solution is stirred five minutes, is begun to warm up after mixing, when temperature rises to 80 DEG C of beginning timing, reaction 8h.(3) just hot
Then filtering continues the operation for adding 200mL copper-bath to repeat (2) to solid.(4) turbid solution is filtered, it is multiple to solid
Washing, until being free of Cu (II) ion in detection filtrate.(5) by 80 DEG C of drying 12h of blue solid.(6) leading under condition of nitrogen gas will
Solid sample temperature programming (1 DEG C/min) after drying is cooled to room temperature taking-up sample to 500 DEG C of holding 3h, in whole process
There is a continuing need for nitrogen protection.The final Y type molecular sieve (Y-zeolite Cu (II)) for obtaining the load copper ion.
The cupric salt used is Kocide SD, copper oxide, copper cyanider, copper sulphate, copper chloride, copper fluoride, copper bromide and basic carbonate
At least one of copper.It is preferable to use copper sulphate.
Specifically, the load capacity for loading copper ion in copper ion Y type molecular sieve is 5~10wt% in step A
Specifically, the reaction temperature in step C is 0~30 DEG C.It preferably, is 20~25 DEG C.
Preferably, the ratio between the amount of substance of connection boric acid pinacol ester reagent and α in B, beta-unsaturated carbonyl compound I is
1.2:1.
Specifically, in D separating-purifying specific steps are as follows: after reaction, filter simultaneously washed with ethyl acetate, then with
Ethyl acetate extraction, after isolating organic phase, is dried, filtered with anhydrous sodium sulfate, and revolving removes solvent, and residue is through acetic acid
Ethyl ester and petroleum ether mixed solvent column chromatographic isolation and purification to get.
The present invention still further provides the method that load copper ion Y type molecular sieve catalysis prepares beta-hydroxy compound, packet
Include following steps:
A. load copper ion Y type molecular sieve, tetrahydrofuran and water are added in the reaction vessel, is sufficiently stirred at room temperature
Mixed liquor, the copper ion of load copper ion Y type molecular sieve load and the amount ratio of water are 0.01~0.015mmol:1mL, tetrahydro
The volume ratio of furans and water is 0.5~1:1；
B. alpha, beta-unsaturated carbonyl compound I and connection boric acid pinacol are added into the mixed liquor that step A is obtained
Ester, wherein α, the ratio between beta-unsaturated carbonyl compound I and the dosage of water in the mixed liquor are 0.15~0.25mmol:1mL,
The ratio between connection boric acid pinacol ester and the amount of substance of alpha, beta-unsaturated carbonyl compound I are 1.0~2.0:1；
C. it is stirred to react at room temperature, the reaction time is 10~16h, obtains the reaction solution containing organoboron compound II；
D. after reaction, reaction solution is filtered, washs filter cake with tetrahydrofuran, and cleaning solution is merged with filtrate, to
Four hydrated sodium perborates are added in filtrate after merging, are stirred to react 4~8h at room temperature, in four hydrated sodium perborates and step B
The α of addition, the ratio between amount of substance of beta-unsaturated carbonyl compound I are 2.0~4.0:1, the tetrahydro furan of washing in step D
Muttering with the volume ratio for the water being added in step A is 1.5~2:1；
E. after reaction, separating-purifying is to get beta-hydroxy compound III；
Chemical equation is as follows:
Wherein R1For benzophenone base, to methylbenzene ketone group, to methoxybenzene ketone group, to fluorobenzene ketone group, acetyl group, pivaloyl
Base；R2For phenyl, p-methylphenyl, p-methoxyphenyl, p-fluorophenyl, rubigan, p-bromophenyl, to trifluoromethylbenzene
Base, m-bromophenyl, chlorphenyl, 2- thienyl, 2- naphthalene, 3- acrylic phenyl.
Based on the above technical solution, the present invention can also have following further specific choice.
Specifically, the load capacity for loading copper ion in copper ion Y type molecular sieve in A is 5-10wt%.
Specifically, the reaction temperature in step C is 0~30 DEG C.It preferably, is 20~25 DEG C.
Preferably, the ratio between the amount of substance of connection boric acid pinacol ester reagent and α in B, beta-unsaturated carbonyl compound I is
1.2:1.
Specifically, four hydrated sodium perborates being added in D and the α being added in B, the object of beta-unsaturated carbonyl compound (I)
The ratio between amount of matter is 2.0-4.0:1, and the volume ratio for the water being added in the tetrahydrofuran and A of washing in D is 1.5-2:1.
Specifically, in E separating-purifying specific steps are as follows: after reaction, filter simultaneously washed with ethyl acetate, then with
Ethyl acetate extraction, after isolating organic phase, is dried, filtered with anhydrous sodium sulfate, and revolving removes solvent, and residue is through acetic acid
Ethyl ester and petroleum ether mixed solvent column chromatographic isolation and purification to get.
Compared with prior art, the beneficial effects of the present invention are:
1. method provided by the invention uses the Y type molecular sieve of load copper ion as preparing boron organic compound for the first time
Catalyst, the ligand of carrier framework or copper ion is not only, relative to traditional absorption carriage, the copper ion of the application
And the combination of carrier framework is more stable, while not needing the additional complicated ligand of addition, high catalytic efficiency, stability
It is good, non-toxic, good biocompatibility, environmentally protective；
2. the catalyst amount of this method and reaction time greatly reduce compared with the generic reaction of the prior art, it is only necessary to
Using lower catalyst amount, the higher conversion ratio of reactant can be realized；
3. this method reaction condition is mild, it can be reacted at room temperature, without the reaction environment of anhydrous and oxygen-free, letter
Easy operation；
4. this method application is wide, it can be used for various types of α, the boron addition of beta-unsaturated carbonyl compound, at
Function prepares corresponding organoboron compound and beta-hydroxy compound.
5. the strategy of " one kettle way " can be used in this method, starting material is straight through continuous boron addition reaction, oxidation reaction
It connects and prepares the beta-hydroxy compound containing carbonyl.
6. the recyclable recycling of molecular sieve catalytic material used in this method, is reused up to 7 times or more, reaction is lived
Property can't significantly reduce, and the separation of catalysis material can be realized in simple filter operation, is more suitable for industrializing extensive life
It produces.
Specific embodiment
Technical solution of the present invention is described in further detail below in conjunction with specific embodiment, example is only used
In explaining the present invention, it is not intended to limit the scope of the present invention.
Starting material is alpha, beta-unsaturated carbonyl compound I, organoboration is prepared in the method that provides through the invention
Object II is closed, and then is converted into beta-hydroxy compound III.
The chemical formula of alpha, beta-unsaturated carbonyl compound I is in following embodimentWherein R1For benzophenone base, right
Methylbenzene ketone group, to methoxybenzene ketone group, to fluorobenzene ketone group, acetyl group, valeryl, cyano, methylbenzene ketone group；R2For
Phenyl, p-methylphenyl, p-methoxyphenyl, p-fluorophenyl, rubigan, p-bromophenyl, p-trifluoromethyl phenyl, bromine
Phenyl, chlorphenyl, 2- thienyl, 2- naphthalene, 3- acrylic phenyl.
In following embodiment, it is preferred that α, the R of beta-unsaturated carbonyl compound I-11For benzophenone base, R2For phenyl；I-2's
R1For benzophenone base, R2For p-methylphenyl；The R of I-31For benzophenone base, R2For p-methoxyphenyl；The R of I-41For to methyl benzophenone
Base, R2For phenyl；The R of I-51For to methoxybenzene ketone group, R2For phenyl；The R of I-61For to fluorobenzene ketone group, R2For phenyl；I-7
R1For benzophenone base, R2For p-fluorophenyl；The R of I-81For benzophenone base, R2For rubigan；The R of I-91For benzophenone base, R2It is right
Bromophenyl；The R of I-101For acetyl group, R2For phenyl；The R of I-111For valeryl, R2For phenyl；The R of I-121For benzophenone base,
R2For 2- thienyl；The R of I-131For to fluorobenzene ketone group, R2For 2- thienyl；The R of I-141For benzophenone base, R2For to trifluoromethyl
Phenyl；The R of I-151For to methoxybenzene ketone group, R2For p-methoxyphenyl；The R of I-161For to methylbenzene ketone group, R2It is right
Fluorophenyl；The R of I-171For to methylbenzene ketone group, R2For p-bromophenyl；The R of I-181For to fluorobenzene ketone group, R2For p-bromophenyl；
The R of I-191To face methylbenzene ketone group, R2For phenyl；The R of I-201For to methoxybenzene ketone group, R2To face chlorphenyl；The R of I-211
For benzophenone base, R2For 2- naphthalene；The R of I-221For acetyl group, R2For p-methoxyphenyl；The R of I-231For benzophenone base, R2For 3-
Acrylic phenyl.
The chemical structural formula that organoboron compound II is corresponding in turn in following embodiment is as follows:
The corresponding chemical structural formula of beta-hydroxy compound III is as follows in following embodiment:
Using the conventional method for method without special instruction being this field in following embodiment, drug used is not
It is commercial product through illustrating.
Embodiment 1:
A kind of preparation method of organoboron compound II-1, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4) 0.002mmol
(with the meter of the copper ion substance of load, load capacity 5-10wt%, similarly hereinafter), and 1.0mL tetrahydrofuran and 1.0mL water is added,
It is stirred 1 hour under room temperature (20-25 DEG C, same as below)；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-1 (41.6mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=9:1 column chromatographic purifying obtains II-1 faint yellow solid, 65.2mg, yield 97%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR (400MHz, Chloroform-d) δ 8.00-7.93 (m, 2H), 7.52 (t, J=7.5Hz, 1H), 7.41
(t, J=7.8Hz, 2H), 7.32-7.23 (m, 4H), 7.16-7.12 (m, 1H), 3.54-3.51 (m, 1H), 3.41-3.38 (m,
1H),1.26(s,6H),1.18(s,6H).
13C NMR (100MHz, Chloroform-d) δ=202.4,144.6,139.4,135.6,131.2,131.1,
131.0,130.7,128.3,86.1,46.0,27.2,27.1.
11B NMR(120MHz,Chloroform-d)δ32.6(s).
Embodiment 2:
A kind of preparation method of organoboron compound II-2, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4) 0.002mmol,
And 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred 1 hour under room temperature (20-25 DEG C, same as below)；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-2 (47.7mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=9:1 column chromatographic purifying obtains II-2 faint yellow solid, 72.5mg, yield 99%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR(400MHz,Chloroform-d)δ8.00–7.92(m,2H),7.57–7.36(m,3H), 7.21(d,J
=8.5Hz, 2H), 6.83 (d, J=8.6Hz, 2H), 3.76 (s, 3H), 3.51-3.45 (m, 1H), 3.39-3.35 (m, 1H),
2.74-2.70(m,1H),1.20-1.15(m,12H).
13C NMR (100MHz, Chloroform-d) δ=199.8,157.6,136.8,133.8,132.8,129.3,
128.5,128.0,113.9,83.3,55.2,43.6,24.6,24.5.
11B NMR(120MHz,Chloroform-d)δ32.9(s).
Embodiment 3:
A kind of preparation method of organoboron compound II-3, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4) 0.002mmol,
And 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred 1 hour under room temperature (20-25 DEG C, same as below)；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-3 (45.3mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=9:1 column chromatographic purifying obtains II-3 69.4mg, yield 98%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR (400MHz, Chloroform-d) δ 8.03-7.85 (m, 2H), 7.53 (t, J=7.5Hz, 1H), 7.42
(t, J=7.8Hz, 2H), 7.31-7.20 (m, 2H), 6.94 (t, J=8.8Hz, 2H), 3.50-3.45 (m, 1H), 3.40-
3.36(m,1H),2.78-2.74(m,1H),1.23(s,6H),1.16(s, 6H)
13C NMR(100MHz,Chloroform-d)δ199.5,161.9,160.3,137.6,137.5, 136.7,
133.0,129.7,129.7,128.5,128.0,115.3,115.1,83.5,43.2,24.6,24.5.
11B NMR(120MHz,Chloroform-d)δ33.3(s).
Embodiment 4:
A kind of preparation method of beta-hydroxy compound III-1, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4) 0.002mmol,
And 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred 1 hour under room temperature (20-25 DEG C, same as below)；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-1 (41.7mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, entire reaction system is filtered, after reaction, entire reaction system is filtered, with tetrahydrofuran
2mL washing.Four hydrated sodium perborate 244mg are directly added into residue, whole system is stirred at room temperature 4 hours.
E. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=4:1 column chromatographic purifying obtains III-1 colourless oil liquid, 43.9mg, yield 97%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR(400MHz)；δ=7.97 (d, J=7.2Hz, 2H), 7.61-7.57 (m, 1H), 7.49-7.44 (m,
4H), 7.41 (t, J=7.5Hz, 2H), 7.33-7.29 (m, 1H), 5.37 (t, J=6.1Hz, 1H), 3.65 (br, 1H),
3.39-3.37(m,2H).
13C NMR(100MHz)；δ=200.1,142.9,136.4,133.6,133.6,128.7,128.5,128.1,
127.6,125.7,70.0,47.3.
Embodiment 5:
A kind of preparation method of beta-hydroxy compound III-2, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4) 0.002mmol,
And 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred 1 hour under room temperature (20-25 DEG C, same as below)；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-2 (47.7mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, entire reaction system is filtered, after reaction, entire reaction system is filtered, with tetrahydrofuran
2mL washing.Four hydrated sodium perborate 244mg are directly added into residue, whole system is stirred at room temperature 4 hours.
E. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=4:1 column chromatographic purifying obtains III-2 white solid, 45.2mg, yield 94%.
The core hydrogen spectrum and carbon spectrum of target product are as follows:
1H NMR(400MHz)；δ=7.97 (d, J=7.0Hz, 2H), 7.61-7.57 (m, 1H), 7.49 (t, J=
7.7Hz, 2H), 7.21 (d, J=7.9Hz, 2H), 5.34-5.30 (m, 1H), 3.60 (s, 1H), 3.43-3.32 (m, 2H),
2.37(s,3H).
Magnetic
13C NMR(100MHz)；δ=200.1,140.0,137.3,136.5,133.5,129.2,128.6,128.1,
125.6,77.3,77.0,76.7,69.8,47.3,21.1.
Embodiment 6:
A kind of preparation method of beta-hydroxy compound III-3, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4) 0.002mmol,
And 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred 1 hour under room temperature (20-25 DEG C, same as below)；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-3 (45.3mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, entire reaction system is filtered, after reaction, entire reaction system is filtered, with tetrahydrofuran
2mL washing.Four hydrated sodium perborate 244mg are directly added into residue, whole system is stirred at room temperature 4 hours.
E. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=4:1 column chromatographic purifying obtains III-3 colourless oil liquid, 42.5mg, yield 83%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR(400MHz)；δ=7.97-7.94 (m, 2H), 7.61-7.57 (m, 1H), 7.49-7.45 (m, 2H),
7.38-7.35 (m, 2H), 6.92-6.90 (m, 2H), 5.31 (dd, J=7.6,4.6Hz, 1H), 3.81 (s, 1H), 3.38-
3.35(m,2H).
13C NMR(100MHz)；δ=200.3,159.1,136.6,135.1,133.6,128.7,128.1,127.0,
113.9,77.3,77.0,76.7,69.7,55.3,47.3.
Embodiment 7:
A kind of preparation method of beta-hydroxy compound III-4, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4) 0.002mmol,
And 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred 1 hour under room temperature (20-25 DEG C, same as below)；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-4 (44.5mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, entire reaction system is filtered, after reaction, entire reaction system is filtered, with tetrahydrofuran
2mL washing.Four hydrated sodium perborate 244mg are directly added into residue, whole system is stirred at room temperature 4 hours.
E. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=4:1 column chromatographic purifying obtains III-4 white solid, 43.3mg, yield 90%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR(400MHz)；δ=7.84 (d, J=8.3Hz, 2H), 7.42 (d, J=7.2Hz, 2H), 7.37 (t, J=
7.4Hz, 2H), 7.30 (d, J=7.2Hz, 1H), 7.26-7.23 (m, 2H), 5.33-5.30 (m, 1H), 3.71 (s, 1H),
3.36-3.27(m,2H),2.39(s,3H).
13C NMR(100MHz)；δ=199.8,144.6,142.9,134.0,129.3,128.5,128.2,127.6,
125.7,77.3,77.0,76.7,70.0,47.2,21.7.
Embodiment 8:
A kind of preparation method of beta-hydroxy compound III-5, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4) 0.002mmol,
And 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred 1 hour under room temperature (20-25 DEG C, same as below)；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-5 (47.7mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, entire reaction system is filtered, after reaction, entire reaction system is filtered, with tetrahydrofuran
2mL washing.Four hydrated sodium perborate 244mg are directly added into residue, whole system is stirred at room temperature 4 hours.
E. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=4:1 column chromatographic purifying obtains III-5 white solid, 44.1mg, yield 86%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR(400MHz)；δ=7.95 (d, J=8.8Hz, 2H), 7.45 (d, J=6.7Hz, 2H), 7.40 (t, J=
7.3Hz, 2H), 7.32 (t, J=7.2Hz, 1H), 6.94 (d, J=8.8Hz, 2H), 5.34 (dd, J=8.3,3.8Hz, 1H),
3.87(s,3H),3.79(s,1H),3.36-3.26(m,2H).
13C NMR(100MHz)；δ=198.8,163.9,143.0,130.5,129.6,128.5,127.6,125.7,
113.8,77.3,77.0,76.7,70.1,55.5,46.9.
Embodiment 9:
A kind of preparation method of beta-hydroxy compound III-6, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4) with Cu ion
0.002mmol is calculated, and 1.0mL tetrahydrofuran and 1.0mL water is added, and it is small that 1 is stirred under room temperature (25 DEG C of 20-, same as below)
When；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-6 (45.3mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, entire reaction system is filtered, after reaction, entire reaction system is filtered, with tetrahydrofuran
2mL washing.Four hydrated sodium perborate 244mg are directly added into residue, whole system is stirred at room temperature 4 hours.
E. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=4:1 column chromatographic purifying obtains III-6 colourless oil liquid, 41.0mg, yield 84%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR(400MHz)；δ=8.00 (dd, J=8.9Hz, 5.4Hz, 2H), 7.44 (d, J=6.8 Hz, 2H),
7.40 (t, J=7.4Hz, 2H), 7.32 (t, J=7.1Hz, 1H), 7.15 (t, J=8.6Hz, 2H), 5.36 (dd, J=8.6,
3.6Hz,1H),3.55(s,1H),3.40-3.28(m,2H).
13C NMR(100MHz)；δ=198.4,167.3,164.7,142.8,132.99,132.96,130.9,130.8,
128.6,127.7,125.7,115.9,115.7,77.3,77.0,76.7,70.0,47.3.
Embodiment 10:
A kind of preparation method of beta-hydroxy compound III-7, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4) 0.002mmol,
And 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred 1 hour under room temperature (20-25 DEG C, same as below)；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-7 (44.5mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, entire reaction system is filtered, after reaction, entire reaction system is filtered, with tetrahydrofuran
2mL washing.Four hydrated sodium perborate 244mg are directly added into residue, whole system is stirred at room temperature 4 hours.
E. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=4:1 column chromatographic purifying obtains III-7 colourless oil liquid, 45.4mg, yield 93%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR(400MHz)；δ=7.96-7.94 (m, 2H), 7.61-7.57 (m, 1H), 7.49-7.39 (m, 5H),
7.08 (t, J=8.7Hz, 1H), 5.34 (t, J=6.1Hz, 1H), 3.72 (br, 1H), 3.35 (d, J=6.1Hz, 2H)
13C NMR(100MHz)；δ=200.0,163.4,160.9,138.7,138.6,136.4,133.7,128.7,
128.1,127.44,127.36,115.4,115.2,69.4,47.3.
Embodiment 11:
A kind of preparation method of beta-hydroxy compound III-8, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4) 0.002mmol,
And 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred 1 hour under room temperature (20-25 DEG C, same as below)；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-8 (48.5mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, entire reaction system is filtered, after reaction, entire reaction system is filtered, with tetrahydrofuran
2mL washing.Four hydrated sodium perborate 244mg are directly added into residue, whole system is stirred at room temperature 4 hours.
E. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=4:1 column chromatographic purifying obtains III-8 white solid, 43.8mg, yield 84%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR(400MHz)；δ=7.96 (d, J=6.9Hz, 2H), 7.62 (t, J=7.4Hz, 1H), 7.50 (t, J=
7.7Hz, 2H), 7.39-7.34 (m, 4H), 5.34 (dd, J=7.8,4.3Hz, 1H), 3.66 (s, 1H), 3.35-3.33 (m,
2H).
13C NMR(100MHz)；δ=200.0,141.4,136.4,133.8,133.3,128.74,128.68,128.1,
127.1,77.3,77.0,76.7,69.4,47.2.
Embodiment 12:
A kind of preparation method of beta-hydroxy compound III-9, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4)
0.002mmol, and 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred under room temperature (20-25 DEG C, same as below)
It mixes 1 hour；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-9 (57.4mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, entire reaction system is filtered, after reaction, entire reaction system is filtered, with tetrahydrofuran
2mL washing.Four hydrated sodium perborate 244mg are directly added into residue, whole system is stirred at room temperature 4 hours.
E. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=4:1 column chromatographic purifying obtains III-9 white solid, 40.9mg, yield 67%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR(400MHz)；δ=7.95 (d, J=7.0Hz, 2H), 7.62 (t, J=7.4Hz, 1H), 7.51-7.45
(m, 4H), 7.33 (d, J=8.4Hz, 2H), 5.32 (dd, J=7.4,4.8Hz, 1H), 3.68 (s, 1H), 3.38-3.28 (m,
2H).
13C NMR(100MHz)；δ=199.9,141.9,136.3,133.8,131.6,128.7,128.1,127.5,
121.4,77.3,77.0,76.6,69.4,47.2.
Embodiment 13:
A kind of preparation method of beta-hydroxy compound III-10, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4) 0.002mmol,
And 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred 1 hour under room temperature (20-25 DEG C, same as below)；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-10 (29.2 mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, entire reaction system is filtered, after reaction, entire reaction system is filtered, with tetrahydrofuran
2mL washing.Four hydrated sodium perborate 244mg are directly added into residue, whole system is stirred at room temperature 4 hours.
E. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=4:1 column chromatographic purifying obtains III-10 pale yellow oily liquid, 26.9mg, yield 82%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR(400MHz)；δ=7.36 (d, J=4.5Hz, 4H), 7.30-7.27 (m, 1H), 5.17-5.13 (m,
1H),3.39(s,1H),2.93-2.79(m,2H),2.79(s,3H).
13C NMR(100MHz)；δ=209.1,142.7,128.5,127.6,125.6,77.3,77.0,76.7,69.8,
51.9,30.7.
Embodiment 14:
A kind of preparation method of beta-hydroxy compound III-11, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4) 0.002mmol,
And 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred 1 hour under room temperature (20-25 DEG C, same as below)；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-11 (37.7 mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, entire reaction system is filtered, after reaction, entire reaction system is filtered, with tetrahydrofuran
2mL washing.Four hydrated sodium perborate 244mg are directly added into residue, whole system is stirred at room temperature 4 hours.
E. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=4:1 column chromatographic purifying obtains III-11 pale yellow oily liquid, 29.3mg, yield 71%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR(400MHz)；δ=7.38-7.28 (m, 5H), 5.15-5.11 (m, 1H), 3.64 (s, 1H), 2.89-
2.87(m,2H),1.13(s,9H).
13C NMR(100MHz)；δ=216.8,143.0,128.4,127.5,125.6,77.3,77.0,76.7,70.0,
45.4,44.3,26.1,30.7.
Embodiment 15:
A kind of preparation method of beta-hydroxy compound III-12, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4) 0.002mmol,
And 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred 1 hour under room temperature (20-25 DEG C, same as below)；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-12 (42.9 mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, entire reaction system is filtered, after reaction, entire reaction system is filtered, with tetrahydrofuran
2mL washing.Four hydrated sodium perborate 244mg are directly added into residue, whole system is stirred at room temperature 4 hours.
E. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=4:1 column chromatographic purifying obtains III-12 colourless oil liquid, 37.2mg, yield 80%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR(400MHz)；δ=7.97 (d, J=8.1Hz, 2H), 7.61-7.57 (m, 1H), 7.49-7.45 (m,
2H),7.26-7.25(m,1H),7.03-6.97(m,2H),5.61-5.57(m,1H),3.83 (s,1H),3.51-3.48(m,
2H).
13C NMR(100MHz)；δ=199.5,146.6,136.3,133.7,128.7,128.1,126.6,124.6,
123.5,77.3,70.0,76.7,66.4,47.1.
Embodiment 16:
A kind of preparation method of beta-hydroxy compound III-13, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4) 0.002mmol,
And 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred 1 hour under room temperature (20-25 DEG C, same as below)；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-13 (46.5 mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, entire reaction system is filtered, after reaction, entire reaction system is filtered, with tetrahydrofuran
2mL washing.Four hydrated sodium perborate 244mg are directly added into residue, whole system is stirred at room temperature 4 hours.
E. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=4:1 column chromatographic purifying obtains III-13 pale yellow oily liquid, 34.5mg, yield 69%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR(400MHz)；δ=8.01-7.98 (m, 2H), 7.28-7.26 (m, 1H), 7.17 (t, J=8.6Hz,
2H),7.04-6.98(m,2H),5.61-5.58(m,1H),3.75(s,1H),3.54-3.41(m, 2H).
13C NMR(100MHz)；δ=197.8,167.3,164.8,146.6,132.90,132.87,130.9,130.8,
126.7,124.7,123.5,115.9,115.7,77.3,77.0,76.7,66.3,47.1.
Embodiment 17:
A kind of preparation method of beta-hydroxy compound III-14, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4) 0.002mmol,
And 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred 1 hour under room temperature (20-25 DEG C, same as below)；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-14 (55.3 mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, entire reaction system is filtered, after reaction, entire reaction system is filtered, with tetrahydrofuran
2mL washing.Four hydrated sodium perborate 244mg are directly added into residue, whole system is stirred at room temperature 4 hours.
E. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=4:1 column chromatographic purifying obtains III-14 colourless oil liquid, 32.9mg, yield 56%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR(400MHz)；δ=7.96 (d, J=7.0Hz, 2H), 7.65-7.55 (m, 5H), 7.50 (t, J=
7.8Hz, 2H), 7.49 (t, J=7.7Hz, 2H), 5.43 (dd, J=8.1,5.4Hz, 1H), 3.79 (s, 1H), 3.41-3.31
(m,2H).
13C NMR(100MHz)；δ=199.8,146.9,136.3,133.9,130.3,130.0,129.6,129.3,
128.8,128.1,126.0,125.53,125.50,125.46,125.42,122.7,77.3,77.0, 76.7,47.2.
Embodiment 18:
A kind of preparation method of beta-hydroxy compound III-15, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4) 0.002mmol,
And 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred 1 hour under room temperature (20-25 DEG C, same as below)；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-15 (53.7 mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, entire reaction system is filtered, after reaction, entire reaction system is filtered, with tetrahydrofuran
2mL washing.Four hydrated sodium perborate 244mg are directly added into residue, whole system is stirred at room temperature 4 hours.
E. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=4:1 column chromatographic purifying obtains III-15 white solid, 57.3mg, yield > 99%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR(400MHz)；δ=7.95 (d, J=8.8Hz, 2H), 7.37 (d, J=8.6Hz, 2H), 6.94 (t, J=
8.2Hz,4H),5.29-5.26(m,1H),3.87(s,3H),3.81(s,3H),3.72(s, 1H),3.34-3.25(m,2H).
13C NMR(100MHz)；δ=198.9,163.9,159.0,135.2,130.5,129.6,127.0,113.9,
113.8,77.3,77.0,76.7,69.8,55.5,55.3,46.8.
Embodiment 19:
A kind of preparation method of beta-hydroxy compound III-16, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4) 0.002mmol,
And 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred 1 hour under room temperature (20-25 DEG C, same as below)；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-16 (48.1 mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, entire reaction system is filtered, after reaction, entire reaction system is filtered, with tetrahydrofuran
2mL washing.Four hydrated sodium perborate 244mg are directly added into residue, whole system is stirred at room temperature 4 hours.
E. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=4:1 column chromatographic purifying obtains III-16 white solid, 43.9mg, yield 85%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR(400MHz)；δ=7.86 (d, J=8.3Hz, 2H), 7.42-7.39 (m, 2H), 7.27 (d, J=
8.0Hz, 2H), 7.08 (t, J=8.7Hz, 2H), 5.33-5.29 (m, 1H), 3.77 (s, 1H), 3.32-3.25 (m, 1H),
2.42(s,3H).
13C NMR(100MHz)；δ=199.7,163.4,160.9,144.7,138.74,138.71,134.0,129.4,
128.2,127.44,127.36,115.4,115.2,77.3,77.0,76.7,69.5,47.1,21.7.
Embodiment 20:
A kind of preparation method of beta-hydroxy compound III-17, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4) 0.002mmol,
And 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred 1 hour under room temperature (20-25 DEG C, same as below)；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-17 (63.4 mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, entire reaction system is filtered, after reaction, entire reaction system is filtered, with tetrahydrofuran
2mL washing.Four hydrated sodium perborate 244mg are directly added into residue, whole system is stirred at room temperature 4 hours.
E. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=4:1 column chromatographic purifying obtains III-17 white solid, 30.8mg, yield 46%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR(400MHz)；δ=7.92 (d, J=8.9Hz, 2H), 7.50 (d, J=8.4Hz, 2H), 7.32-7.30
(m, 2H), 6.94 (d, J=8.9Hz, 2H), 5.29-5.26 (m, 1H), 3.874 (br, 1H), 3.867 (s, 3H), 3.32-
3.25(m,2H).
13C NMR(100MHz)；δ=198.5,164.0,142.0,131.5,130.5,129.4,127.5,121.3,
113.9,69.5,55.5,46.7.
Embodiment 21:
A kind of preparation method of beta-hydroxy compound III-18, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4) 0.002mmol,
And 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred 1 hour under room temperature (20-25 DEG C, same as below)；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-18 (61.0 mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, entire reaction system is filtered, after reaction, entire reaction system is filtered, with tetrahydrofuran
2mL washing.Four hydrated sodium perborate 244mg are directly added into residue, whole system is stirred at room temperature 4 hours.
E. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=4:1 column chromatographic purifying obtains III-18 faint yellow solid, 37.5mg, yield 58%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR(400MHz)；δ=7.99 (dd, J=8.9Hz, 5.4Hz, 2H), 7.51 (d, J=8.4 Hz, 1H),
7.32 (d, J=8.4Hz, 2H), 7.16 (t, J=8.6Hz, 2H), 5.32-5.28 (m, 1H), 3.59 (s, 1H), 3.29 (s,
1H).
13C NMR(100MHz)；δ=198.2,167.4,164.8,141.8,132.83,132.80,131.7,130.9,
130.8,127.4,1215,116.0,115.8,77.3,77.2,77.0,76.7,69.4,47.1.
Embodiment 22:
A kind of preparation method of beta-hydroxy compound III-19, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4) 0.002mmol,
And 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred 1 hour under room temperature (20-25 DEG C, same as below)；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-19 (61.0 mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, entire reaction system is filtered, after reaction, entire reaction system is filtered, with tetrahydrofuran
2mL washing.Four hydrated sodium perborate 244mg are directly added into residue, whole system is stirred at room temperature 4 hours.
E. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=4:1 column chromatographic purifying obtains III-19 white solid, 41.3mg, yield 86%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR(400MHz)；δ=7.77-7.74 (m, 2H), 7.46-7.44 (m, 2H), 7.41-7.35 (m, 4H),
7.33-7.29 (m, 1H), 5.36 (dd, J=7.0,5.1Hz, 1H), 3.64 (s, 1H), 3.37-3.36 (m, 2H), 2.41 (s,
3H).
13C NMR(100MHz)；δ=200.4,142.9,138.5,136.6,134.4,128.7,128.6,128.5,
127.6,125.7,125.4,77.3,77.0,76.7,70.0,47.4,21.3.
Embodiment 23:
A kind of preparation method of beta-hydroxy compound III-20, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4)
0.002mmol, and 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred under room temperature (20-25 DEG C, same as below)
It mixes 1 hour；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-20 (61.0 mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, entire reaction system is filtered, after reaction, entire reaction system is filtered, with tetrahydrofuran
2mL washing.Four hydrated sodium perborate 244mg are directly added into residue, whole system is stirred at room temperature 4 hours.
E. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=4:1 column chromatographic purifying obtains III-20 white solid, 54.7mg, yield 94%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR(400MHz)；δ=7.95 (d, J=8.9Hz, 2H), 7.7.-7.70 (m, 1H), 7.35-7.31 (m,
2H), 7.25-7.20 (m, 1H), 6.93 (d, J=9.0Hz, 2H), 5.67-5.61 (m, 1H), 4.07 (br, 1H), 3.86 (s,
3H),3.54-3.49(m,1H),3.11-3.04(m,1H).
13C NMR(100MHz)；δ=198.8,163.9,140.4,131.1,130.5,129.4,129.2,128.5,
127.23,127.18,113.8,66.9,55.5,44.8.
Embodiment 24:
A kind of preparation method of beta-hydroxy compound III-21, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4)
0.002mmol, and 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred under room temperature (20-25 DEG C, same as below)
It mixes 1 hour；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-21 (61.0 mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, entire reaction system is filtered, after reaction, entire reaction system is filtered, with tetrahydrofuran
2mL washing.Four hydrated sodium perborate 244mg are directly added into residue, whole system is stirred at room temperature 4 hours.
E. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=4:1 column chromatographic purifying obtains III-21 white solid, 45.3mg, yield 82%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR(400MHz)；δ=8.07-8.05 (m, 1H), 8.00-7.90 (m, 3H), 7.83-7.81 (m, 2H),
7.59-7.43 (m, 6H), 6.18 (dd, J=9.0,2.6Hz, 1H), 3.83 (br, 1H), 3.58-3.49 (m, 2H)
13C NMR(100MHz)；δ=200.2,138.4,136.4,133.7,133.6,129.8,129.0,128.6,
128.1,128.0,126.2,125.6,125.5,123.1,122.7,66.7,46.7.
Embodiment 25:
A kind of preparation method of beta-hydroxy compound III-22, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4) 0.002mmol,
And 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred 1 hour under room temperature (20-25 DEG C, same as below)；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-22 (61.0 mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, entire reaction system is filtered, after reaction, entire reaction system is filtered, with tetrahydrofuran
2mL washing.Four hydrated sodium perborate 244mg are directly added into residue, whole system is stirred at room temperature 4 hours.
E. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=4:1 column chromatographic purifying obtains III-22 white solid, 31.9mg, yield 82%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR(400MHz)；δ=7.29-7.26 (m, 2H), 6.89 (d, J=8.7Hz, 2H), 5.12-5.08 (m,
1H),3.80(s,3H),3.23(s,1H),2.89-2.76(m,2H),2.19(s,3H).
13C NMR(100MHz)；δ=209.2,159.1,134.8 126.9,113.9,77.3,77.0,76.7,69.5,
55.3,51.9,30.8.
Embodiment 26:
A kind of preparation method of beta-hydroxy compound III-23, the steps include:
A. load copper ion Y type molecular sieve (Y-zeolite CuSO is added in 2.5mL reaction tube4) 0.002mmol,
And 1.0mL tetrahydrofuran and 1.0mL water is added, it is stirred 1 hour under room temperature (20-25 DEG C, same as below)；
B. into above-mentioned system, α is continuously sequentially added respectively, beta-unsaturated carbonyl compound I-23 (61.0 mg,
0.2mmol) and connection boric acid pinacol ester (B2(pin)2)(60.9mg,2.4mmol)；
C. reaction is stirred at room temperature in entire reaction system, and the reaction time is 12 hours；
D. after reaction, entire reaction system is filtered, after reaction, entire reaction system is filtered, with tetrahydrofuran
2mL washing.Four hydrated sodium perborate 244mg are directly added into residue, whole system is stirred at room temperature 4 hours.
E. after reaction, filter entire reaction system, with ethyl acetate 10mL washing, then with ethyl acetate (3 ×
It 10mL) extracts, after isolating organic phase, uses anhydrous Na2SO4It dries, filters, rotary evaporation removes solvent.Residue is through acetic acid
Ethyl ester/petroleum ether mixed solvent=4:1 column chromatographic purifying obtains III-23 white solid, 15.1mg, yield 30%.
Nucleus magnetic hydrogen spectrum and the carbon spectrum of target product are as follows:
1H NMR(400MHz)；δ=7.91-7.88 (m, 2H), 7.54-7.50 (m, 1H), 7.42-7.38 (m, 2H),
7.33-7.31 (m, 2H), 7.26-7.22 (m, 2H), 7.18-7.15 (m, 1H), 6.65-6.61 (m, 1H), 6.27 (dd, J=
15.9Hz,6.0Hz,1H),4.89-4.86(m,1H),3.38(s,1H), 3.26-3.16(m,2H).
13C NMR(100MHz)；δ=200.3,136.54,136.51,133.6,130.4,130.2,128.7,128.5,
128.1,127.7,126.5,77.3,77.0,76.7,68.6,45.2.
It can be obtained from the above various embodiments, organoboron compound and the beta-hydroxy compound provided by the invention of preparing
Method has the characteristics that reaction rate is fast, yield is high, reaction condition is mild and simple process.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of method that load copper ion Y type molecular sieve catalysis prepares organoboron compound, which is characterized in that including walking as follows
It is rapid:
A. load copper ion Y type molecular sieve, tetrahydrofuran and water are added in the reaction vessel, is sufficiently stirred, must mix at room temperature
Liquid, the amount of substance and the amount ratio of water of the copper ion of load copper ion Y type molecular sieve load are 0.002~0.003mmol:
The volume ratio of 1mL, tetrahydrofuran and water is 0.5~1:1；
B. α, beta-unsaturated carbonyl compound I and connection boric acid pinacol ester are added into the mixed liquor that step A is obtained,
In, the ratio between α, beta-unsaturated carbonyl compound I and the dosage of water in the mixed liquor are 0.15~0.25mmol:1mL, join boric acid
The ratio between amount of substance of pinacol ester and alpha, beta-unsaturated carbonyl compound I is 1.0~2.0:1；
C. it is stirred to react at room temperature, the reaction time is 10~16h；
D. after reaction, separating-purifying is to get organoboron compound II；
Chemical equation is as follows:
Wherein R1For benzophenone base, to methylbenzene ketone group, to methoxybenzene ketone group, to fluorobenzene ketone group, acetyl group or valeryl；R2
For phenyl, p-methylphenyl, p-methoxyphenyl, p-fluorophenyl, rubigan, p-bromophenyl, p-trifluoromethyl phenyl, bromine
Phenyl, chlorphenyl, 2- thienyl, 2- naphthalene or 3- acrylic phenyl.
2. the method that load copper ion Y type molecular sieve catalysis according to claim 1 prepares organoboron compound, feature
Be: in step A, the load capacity for loading copper ion in copper ion Y type molecular sieve is 5~10wt%.
3. the method that load copper ion Y type molecular sieve catalysis according to claim 1 prepares organoboron compound, feature
Be: in step B, connection boric acid pinacol ester and α, the ratio between amount of substance of beta-unsaturated carbonyl compound I are 1.2:1.
4. the side that load copper ion Y type molecular sieve catalysis according to any one of claims 1 to 3 prepares organoboron compound
Method, it is characterised in that: the specific steps of separating-purifying in step D are as follows: after reaction, reaction solution is filtered, and with acetic acid second
Ester washs filter cake, and filtrate is merged with cleaning solution, then extracts filtrate with ethyl acetate, after isolating organic phase, uses anhydrous slufuric acid
Sodium dries organic phase, refilters, and revolving removes the solvent in filtrate, and residue is through ethyl acetate and petroleum ether mixed solvent column layer
Analysis isolate and purify to get.
5. a kind of method that load copper ion Y type molecular sieve catalysis prepares beta-hydroxy compound, which is characterized in that including walking as follows
It is rapid:
A. load copper ion Y type molecular sieve, tetrahydrofuran and water are added in the reaction vessel, mixing is sufficiently stirred to obtain at room temperature
Liquid, the copper ion of load copper ion Y type molecular sieve load and the amount ratio of water are 0.01~0.015mmol:1mL, tetrahydrofuran
Volume ratio with water is 0.5~1:1；
B. α, beta-unsaturated carbonyl compound I and connection boric acid pinacol ester are added into the mixed liquor that step A is obtained, wherein
The ratio between α, beta-unsaturated carbonyl compound I and the dosage of water in the mixed liquor are 0.15~0.25mmol:1mL, connection boric acid frequency
The ratio between amount of substance of that alcohol ester and alpha, beta-unsaturated carbonyl compound I is 1.0~2.0:1；
C. it is stirred to react at room temperature, the reaction time is 10~16h, obtains the reaction solution containing organoboron compound II；
D. after reaction, reaction solution is filtered, filter cake is washed with tetrahydrofuran, and cleaning solution is merged with filtrate, to merging
Four hydrated sodium perborates are added in filtrate afterwards, is stirred to react 4~8h at room temperature, is added in four hydrated sodium perborates and step B
α, the ratio between amount of substance of beta-unsaturated carbonyl compound I is 2.0~4.0:1, the tetrahydrofuran and step of washing in step D
The volume ratio for the water being added in rapid A is 1.5~2:1；
E. after reaction, separating-purifying is to get beta-hydroxy compound III；
Chemical equation is as follows:
Wherein R1For benzophenone base, to methylbenzene ketone group, to methoxybenzene ketone group, to fluorobenzene ketone group, acetyl group or valeryl；R2
For phenyl, p-methylphenyl, p-methoxyphenyl, p-fluorophenyl, rubigan, p-bromophenyl, p-trifluoromethyl phenyl, bromine
Phenyl, chlorphenyl, 2- thienyl, 2- naphthalene, styryl.
6. the method that load copper ion Y type molecular sieve catalysis according to claim 5 prepares beta-hydroxy compound, feature
Be: in step A, the load capacity for loading copper ion in copper ion Y type molecular sieve is 5~10wt%.
7. the method that load copper ion Y type molecular sieve catalysis prepares beta-hydroxy compound, feature exist according to claim 5
In: in step B, connection boric acid pinacol ester and α, the ratio between amount of substance of beta-unsaturated carbonyl compound I are 1.2:1.
8. preparing the side of beta-hydroxy compound according to the described in any item load copper ion Y type molecular sieve catalysis of claim 5 to 7
Method, it is characterised in that: the specific steps of separating-purifying in step E are as follows: after reaction, filter and washed with ethyl acetate and filtered
Cake merges filtrate with cleaning solution, then extracts filtrate with ethyl acetate, after isolating organic phase, has with anhydrous sodium sulfate drying
Machine phase, refilters, and revolving removes the solvent in filtrate, and residue is pure through ethyl acetate and petroleum ether mixed solvent column chromatography for separation
Change to get.
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