CN112441920B - Method for copper photocatalytic synthesis of 9-acetoxyl-9, 10-dihydrophenanthrene compound - Google Patents
Method for copper photocatalytic synthesis of 9-acetoxyl-9, 10-dihydrophenanthrene compound Download PDFInfo
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- -1 9-acetoxyl-9, 10-dihydrophenanthrene compound Chemical class 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000001699 photocatalysis Effects 0.000 title abstract description 8
- 230000015572 biosynthetic process Effects 0.000 title abstract description 6
- 238000003786 synthesis reaction Methods 0.000 title abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title abstract description 5
- 229910052802 copper Inorganic materials 0.000 title abstract description 5
- 239000010949 copper Substances 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 239000002904 solvent Substances 0.000 claims abstract description 44
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 11
- LYNFIHLVNLDCFT-UHFFFAOYSA-N C(=O)(OC1CC2=C(C3=CC=CC=C13)C=CC=C2)C Chemical class C(=O)(OC1CC2=C(C3=CC=CC=C13)C=CC=C2)C LYNFIHLVNLDCFT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005286 illumination Methods 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- 238000004440 column chromatography Methods 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000741 silica gel Substances 0.000 claims description 22
- 229910002027 silica gel Inorganic materials 0.000 claims description 22
- 239000003480 eluent Substances 0.000 claims description 18
- 239000003208 petroleum Substances 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000012295 chemical reaction liquid Substances 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000007363 ring formation reaction Methods 0.000 abstract description 3
- 239000002912 waste gas Substances 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 56
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- 238000012512 characterization method Methods 0.000 description 14
- 238000004821 distillation Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- XXPBFNVKTVJZKF-UHFFFAOYSA-N 9,10-dihydrophenanthrene Chemical class C1=CC=C2CCC3=CC=CC=C3C2=C1 XXPBFNVKTVJZKF-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- ZJTLMXISFQWDTC-UHFFFAOYSA-N 9,10-dihydrophenanthren-9-ol Chemical compound C1=CC=C2C(O)CC3=CC=CC=C3C2=C1 ZJTLMXISFQWDTC-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- HTFJIWWUGPTGNW-UHFFFAOYSA-N CC(OC(C(C=CC(Cl)=C1)=C1C1=CC=CC=C1)=C)=O Chemical compound CC(OC(C(C=CC(Cl)=C1)=C1C1=CC=CC=C1)=C)=O HTFJIWWUGPTGNW-UHFFFAOYSA-N 0.000 description 3
- YTYCOQRJGRQFPD-UHFFFAOYSA-N CC(OC(C(C=CC=C1)=C1C(C=C1)=CC=C1Cl)=C)=O Chemical compound CC(OC(C(C=CC=C1)=C1C(C=C1)=CC=C1Cl)=C)=O YTYCOQRJGRQFPD-UHFFFAOYSA-N 0.000 description 3
- WSFVBOPBEVYERZ-UHFFFAOYSA-N CC(OC(C(C=CC=C1)=C1C1=C(C)C=CC=C1)=C)=O Chemical compound CC(OC(C(C=CC=C1)=C1C1=C(C)C=CC=C1)=C)=O WSFVBOPBEVYERZ-UHFFFAOYSA-N 0.000 description 3
- WRHJDJDTXVRNRJ-UHFFFAOYSA-N CC(OC(C(C=CC=C1)=C1C1=CC=CC=C1)=C)=O Chemical compound CC(OC(C(C=CC=C1)=C1C1=CC=CC=C1)=C)=O WRHJDJDTXVRNRJ-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- PDJCUUOYBRWMCO-UHFFFAOYSA-N CC(OC(C(C=CC=C1)=C1C(C=CC=C1)=C1F)=C)=O Chemical compound CC(OC(C(C=CC=C1)=C1C(C=CC=C1)=C1F)=C)=O PDJCUUOYBRWMCO-UHFFFAOYSA-N 0.000 description 2
- 239000002246 antineoplastic agent Substances 0.000 description 2
- 229940041181 antineoplastic drug Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- BGYFUBDBUFZYNK-UHFFFAOYSA-N 1-iodo-2-(2-phenylethyl)benzene Chemical compound IC1=C(C=CC=C1)CCC1=CC=CC=C1 BGYFUBDBUFZYNK-UHFFFAOYSA-N 0.000 description 1
- HJNAELFLZXCHQK-UHFFFAOYSA-N 2-chlorophenanthrene Chemical compound C1=CC=C2C3=CC=C(Cl)C=C3C=CC2=C1 HJNAELFLZXCHQK-UHFFFAOYSA-N 0.000 description 1
- BVFJTESUEYBUOL-UHFFFAOYSA-N 3-chlorophenanthrene Chemical compound C1=CC=C2C3=CC(Cl)=CC=C3C=CC2=C1 BVFJTESUEYBUOL-UHFFFAOYSA-N 0.000 description 1
- UOXGQCABTNEVPI-UHFFFAOYSA-N 4-fluorophenanthrene Chemical compound C1=CC=CC2=C3C(F)=CC=CC3=CC=C21 UOXGQCABTNEVPI-UHFFFAOYSA-N 0.000 description 1
- LOCGAKKLRVLQAM-UHFFFAOYSA-N 4-methylphenanthrene Chemical compound C1=CC=CC2=C3C(C)=CC=CC3=CC=C21 LOCGAKKLRVLQAM-UHFFFAOYSA-N 0.000 description 1
- MFXNBQWUTDDOKE-UHFFFAOYSA-N 9,10-dihydrophenanthrene-9,10-diol Chemical compound C1=CC=C2C(O)C(O)C3=CC=CC=C3C2=C1 MFXNBQWUTDDOKE-UHFFFAOYSA-N 0.000 description 1
- JXUPZPPEUXHBOS-UHFFFAOYSA-N CC(OC(C1)C2=CC=CC=C2C(C=C2)=C1C=C2Cl)=O Chemical compound CC(OC(C1)C2=CC=CC=C2C(C=C2)=C1C=C2Cl)=O JXUPZPPEUXHBOS-UHFFFAOYSA-N 0.000 description 1
- ISGFFFIWVPUKKV-UHFFFAOYSA-N CC(OC(C1)C2=CC=CC=C2C2=C1C=CC=C2C)=O Chemical compound CC(OC(C1)C2=CC=CC=C2C2=C1C=CC=C2C)=O ISGFFFIWVPUKKV-UHFFFAOYSA-N 0.000 description 1
- FILXOTYGRVITAT-UHFFFAOYSA-N CC(OC(C1)C2=CC=CC=C2C2=C1C=CC=C2F)=O Chemical compound CC(OC(C1)C2=CC=CC=C2C2=C1C=CC=C2F)=O FILXOTYGRVITAT-UHFFFAOYSA-N 0.000 description 1
- NPJBRXYJYOTRKO-UHFFFAOYSA-N CC(OC(CC(C=CC=C1)=C1C1=C2)C1=CC=C2Cl)=O Chemical compound CC(OC(CC(C=CC=C1)=C1C1=C2)C1=CC=C2Cl)=O NPJBRXYJYOTRKO-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012822 chemical development Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 241000411851 herbal medicine Species 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002757 inflammatory effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 150000002987 phenanthrenes Chemical class 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
- B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
- B01J31/2457—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings, e.g. Xantphos
-
- 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
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
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- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/26—Phenanthrenes; Hydrogenated phenanthrenes
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Abstract
A method for copper photocatalytic synthesis of 9-acetoxyl-9, 10-dihydrophenanthrene compounds comprises the following steps: mixing a substrate (I), a photosensitizer, an alkaline substance and a solvent, reacting for 20-36 h under the conditions of illumination of a blue LED, temperature of 15-40 ℃ and protection of inert gas, and then carrying out aftertreatment on a reaction solution to obtain a 9-acetoxyl-9, 10-dihydrophenanthrene compound (II); the invention is safe and environment-friendly, does not generate waste gas and has low operation risk; the substrate has good adaptability, and various substituents can realize cyclization; the reaction condition is mild; meanwhile, the reaction has certain innovativeness and high atom economy, adopts a photocatalysis mode to replace the traditional heating mode, reduces energy consumption and better conforms to the modern green chemistry idea;
Description
(I) technical field
The invention relates to a method for synthesizing 9-acetoxyl-9, 10-dihydrophenanthrene compounds by copper photocatalysis.
(II) background of the invention
Dihydrophenanthrenes, also known as 9, 10-dihydrophenanthrenes, are found in nature and are found in a wide variety of herbal medicine. Because of the structural particularity, the dihydrophenanthrene compound has unique application value in industry, and can effectively inhibit the generation of inflammatory factors and synthesize a series of anticancer drugs as an important medical intermediate, thereby being a main framework of a plurality of anticancer drugs. In addition, substituted dihydrophenanthrenes have one or two chiral centers and can be designed to synthesize a series of chiral ligands. For example, in 2002, a series of chiral ligands derived from 9, 10-dihydrophenanthrene-9, 10-diol have been reported to be designed, synthesized and applied to asymmetric catalysis (Chin. J. Synth. chem.,2002,10,95-97), so that the dihydrophenanthrene compounds have a great application prospect in the aspect of chiral ligands. The 9-acetoxyl-9, 10-dihydrophenanthrene reported by the invention can be further oxidized to obtain a 9-acetoxyl phenanthrene compound, and the phenanthrene compound is also an important medical intermediate and a chemical raw material. Furthermore, 9-acetoxyl-9, 10-dihydrophenanthrene can be hydrolyzed to obtain 9-hydroxy-9, 10-dihydrophenanthrene, and the compound has a chiral center and can be applied to chiral ligands (scheme 1).
Currently, many methods for synthesizing dihydrophenanthrene compounds are available, for example, in 2011, Daniela et al (org.lett.,2011,13,12) report that 2-phenethyliodobenzene is used as a substrate, potassium tert-butoxide is used as a base, pyridine is used as a solvent, and a free radical addition cyclization mode is adopted at a high temperature of 160 ℃ to synthesize the dihydrophenanthrene compounds, but the synthesis mode has great limitation and needs to be carried out at a high temperature, and meanwhile, pyridine, a solvent with high toxicity, has great influence on the environment and is not beneficial to industrial production. The synthesis reports of the dihydrophenanthrene compounds are relatively more, but the reports of the relevant documents for synthesizing the 9-substituted dihydrophenanthrene compounds are obviously less, while the 9-acetoxyl-9, 10-dihydrophenanthrene is synthesized by heating and reacting 9-hydroxy-9, 10-dihydrophenanthrene and acetic anhydride which are used as substrates and pyridine which is used as a solvent in the traditional method, and the method also adopts an unfriendly solvent pyridine, and simultaneously needs to prepare the 9-hydroxy-9, 10-dihydrophenanthrene in advance, so that the raw materials are relatively not easily obtained. The invention adopts a photocatalysis way to synthesize 2-Phenyl-alpha-acetoxyl-styrene compound is used as a substrate, a photocatalysis mode which is in line with the current situation of social development at present is adopted, a cheaper copper photosensitizer is used as a catalyst, tetrahydrofuran with relatively low toxicity is used as a solvent, and common K is used3PO4The target product 9-acetoxyl-9, 10-dihydrophenanthrene compound is obtained with high yield at room temperature as alkali. The method does not need additional heating, has low energy consumption and simple operation, has 100 percent of atomic utilization rate, and accords with the era theme of current green chemical development.
Disclosure of the invention
Aiming at the defects of the prior art, the invention provides a universal, simple and efficient method for synthesizing 9-acetoxyl-9, 10-dihydrophenanthrene compounds.
The technical scheme of the invention is as follows:
a method for synthesizing 9-acetoxyl-9, 10-dihydrophenanthrene compounds, which comprises the following steps:
mixing a substrate (I), a photosensitizer, an alkaline substance and a solvent, reacting for 20-36 h (preferably 24h) under the conditions of illumination of a blue LED (15w), temperature of 15-40 ℃ (preferably 25 ℃), and protection of inert gas, and then carrying out aftertreatment on a reaction solution to obtain a 9-acetoxyl-9, 10-dihydrophenanthrene compound (II);
the ratio of the amounts of the substrate (I), the photosensitizer and the alkaline substance is 1: 0.01-0.1: 1-2, preferably 1: 0.05: 1.5;
the volume usage amount of the solvent is 10-20 mL/mmol based on the substance amount of the substrate (I);
the photosensitizer is one or a mixture of two of a formula (III) and a formula (IV) in any proportion;
the alkaline substance is one or a mixture of more than two of potassium phosphate, potassium carbonate and sodium carbonate in any proportion;
the solvent is one or a mixed solvent of more than two of acetonitrile, tetrahydrofuran and 1, 4-dioxane in any proportion, and tetrahydrofuran is preferred;
the post-treatment method comprises the following steps: after the reaction is finished, adding column chromatography silica gel (100-200 meshes) into the reaction solution, evaporating under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether to ethyl acetate is 20:1 as eluent, collecting eluent containing target product, evaporating solvent and drying to obtain 9-acetoxyl-9, 10-dihydrophenanthrene compound (II);
the reaction formula is as follows:
in the formula (I) or the formula (II),
R1is chlorine or hydrogen;
R2is fluorine, chlorine, methyl or hydrogen;
the structural formula of the photosensitizer is as follows:
specifically, the 9-acetoxy-9, 10-dihydrophenanthrene compound (II) according to the present invention is preferably one of the following compounds:
compared with the prior art, the invention has the beneficial effects that:
(1) the method is safe and environment-friendly, does not generate waste gas, and has low operation risk;
(2) the substrate has good adaptability, and various substituents can realize cyclization;
(3) the reaction condition is mild;
(4) meanwhile, the reaction has certain innovativeness and high atom economy, adopts a photocatalysis mode to replace the traditional heating mode, reduces energy consumption, and better conforms to the modern green chemistry concept.
(IV) detailed description of the preferred embodiments
The invention will be further illustrated by the following examples, without limiting the scope of the invention:
example 1
Alpha-acetoxy-2-phenylstyrene (0.3mmol, 0.0714g), photosensitizer (III) (0.015mmol, 0.0167g), K3PO4(0.45mmol, 0.0954g) was added to a 15mL stoppered reaction tube, and 3mL tetrahydrofuran was added as a solvent. Then, under the irradiation of 15w Blue LED, reacting for 24h at 25 ℃ in a nitrogen environment, after the reaction is finished, adding two spoons (0.5g) of column chromatography silica gel (100 meshes and 200 meshes) into the reaction liquid, removing the solvent by reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate 20:1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 87% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.86(t,J＝5.5Hz,2H),7.50(d,J＝7.5Hz,1H),7.48-7.45(m,1H),7.39-7.37(m,1H),7.36-7.33(m,1H),7.32-7.29(m,1H),6.09(t,J＝5Hz,1H),3.23-3.16(m,2H),2.00(s,3H).13C NMR(125MHz,CDCl3)δ170.82,135.94,134.50,134.32,134.22,133.211,131.11,128.37,127.87,127.14,127.01,126.83,126.65,70.27,35.89,21.28.
example 2
Alpha-acetoxy-2-phenylstyrene (0.3mmol, 0.0714g), photosensitizer (IV) (0.015mmol, 0.0172g), K3PO4(0.45mmol, 0.0954g) was added to a 15mL stoppered reaction tube, and 3mL tetrahydrofuran was added as a solvent. And then, reacting for 24 hours under the condition of 25 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 77% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.86(t,J＝5.5Hz,2H),7.50(d,J＝7.5Hz,1H),7.48-7.45(m,1H),7.39-7.37(m,1H),7.36-7.33(m,1H),7.32-7.29(m,1H),6.09(t,J＝5Hz,1H),3.23-3.16(m,2H),2.00(s,3H).13C NMR(125MHz,CDCl3)δ170.82,135.94,134.50,134.32,134.22,133.211,131.11,128.37,127.87,127.14,127.01,126.83,126.65,70.27,35.89,21.28.
example 3
Alpha-acetoxy-2-phenylstyrene (0.3mmol, 0.0714g), photosensitizer (III) (0.015mmol, 0.0167g), K3PO4(0.3mmol, 0.0636g) was added to a 15mL stoppered reaction tube, and 3mL tetrahydrofuran was added as a solvent. And then, reacting for 24 hours under the condition of 25 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 67% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.86(t,J＝5.5Hz,2H),7.50(d,J＝7.5Hz,1H),7.48-7.45(m,1H),7.39-7.37(m,1H),7.36-7.33(m,1H),7.32-7.29(m,1H),6.09(t,J＝5Hz,1H),3.23-3.16(m,2H),2.00(s,3H).13C NMR(125MHz,CDCl3)δ170.82,135.94,134.50,134.32,134.22,133.211,131.11,128.37,127.87,127.14,127.01,126.83,126.65,70.27,35.89,21.28.
example 4
Alpha-acetoxy-2-phenyl-4-chlorostyrene (0.3mmol, 0.0816g), photosensitizer (III) (0.015mmol, 0.0167g), K3PO4(0.6mmol，01272g) was added to a 15mL sealed reaction tube, and 3mL of tetrahydrofuran was added as a solvent. And then, reacting for 24 hours under the condition of 25 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 85% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.82(d,J＝2Hz,1H),7.79(d,J＝7.5Hz,1H),7.44(d,J＝8.5Hz,1H),7.38(td,J1＝7.5Hz,J2＝1Hz,1H),7.33(td,J1＝7.5Hz,J2＝1.5Hz,1H),7.31-7.28(m,2H),6.04(t,J＝4.5Hz,1H),3.17(d,J＝4.5Hz,2H),1.99(s,3H).13C NMR(125MHz,CDCl3)δ170.62,135.92,135.30,132.98,132.02,131.82,130.01,129.22,128.61,127.56,127.54,124.09,123.70,69.13,34.28,21.24.
example 5
Alpha-acetoxy-2-phenyl-4-chlorostyrene (0.3mmol, 0.0816g), photosensitizer (III) (0.015mmol, 0.0167g), K3PO4(0.45mmol, 0.0954g) was added to a 15mL stoppered reaction tube, and 3mL acetonitrile was added as a solvent. And then, reacting for 24 hours under the condition of 25 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 53% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.82(d,J＝2Hz,1H),7.79(d,J＝7.5Hz,1H),7.44(d,J＝8.5Hz,1H),7.38(td,J1＝7.5Hz,J2＝1Hz,1H),7.33(td,J1＝7.5Hz,J2＝1.5Hz,1H),7.31-7.28(m,2H),6.04(t,J＝4.5Hz,1H),3.17(d,J＝4.5Hz,2H),1.99(s,3H).13C NMR(125MHz,CDCl3)δ170.62,135.92,135.30,132.98,132.02,131.82,130.01,129.22,128.61,127.56,127.54,124.09,123.70,69.13,34.28,21.24.
example 6
Alpha-acetoxy-2-phenyl-4-chlorostyrene (0.3mmol, 0.0816g), photosensitizer (III) (0.015mmol, 0.0167g), K3PO4(0.45mmol, 0.0954g) was added to a 15mL sealed reaction tube, and 3mL of 1, 4-dioxane was added as a solvent. And then, reacting for 24 hours under the condition of 25 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 63% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.82(d,J＝2Hz,1H),7.79(d,J＝7.5Hz,1H),7.44(d,J＝8.5Hz,1H),7.38(td,J1＝7.5Hz,J2＝1Hz,1H),7.33(td,J1＝7.5Hz,J2＝1.5Hz,1H),7.31-7.28(m,2H),6.04(t,J＝4.5Hz,1H),3.17(d,J＝4.5Hz,2H),1.99(s,3H).13C NMR(125MHz,CDCl3)δ170.62,135.92,135.30,132.98,132.02,131.82,130.01,129.22,128.61,127.56,127.54,124.09,123.70,69.13,34.28,21.24.
example 7
Alpha-acetoxy-2- (2-methyl-phenyl) styrene (0.3mmol, 0.0756g), photosensitizer (III) (0.015mmol, 0.0167g), sodium carbonate (0.45mmol, 0.0477g) were added to a 15mL tube-sealed reaction tube, and 3mL tetrahydrofuran was added as a solvent. And then, reacting for 24 hours under the condition of 25 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 81% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.77-7.75(m,1H),7.50-7.48(m,1H),7.43(td,J1＝7.5Hz,J2＝1.5Hz,1H),7.33(td,J1＝7.5Hz,J2＝1.5Hz,1H),7.24(d,J＝7.5Hz,1H),7.19(t,J＝7.5Hz,1H),7.14(d,J＝6.5Hz,1H),5.95(t,J＝5.5Hz,1H),3.08(d,J＝5.5Hz,2H),2.68(s,3H),2.04(s,3H).13C NMR(125MHz,CDCl3)δ170.84,135.98,134.53,134.38,134.36,133.23,131.17,128.43,127.91,127.19,127.02,126.88,126.68,70.33,35.92,23.07,21.32
example 8
Alpha-acetoxy-2- (2-methyl-phenyl) styrene (0.3mmol, 0.0756g), photosensitizer (III) (0.015mmol, 0.0167g), potassium carbonate (0.45mmol, 0.0621g) were added to a 15mL tube-sealed reaction tube, and 3mL tetrahydrofuran was added as a solvent. And then, reacting for 24 hours under the condition of 25 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 85% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.77-7.75(m,1H),7.50-7.48(m,1H),7.43(td,J1＝7.5Hz,J2＝1.5Hz,1H),7.33(td,J1＝7.5Hz,J2＝1.5Hz,1H),7.24(d,J＝7.5Hz,1H),7.19(t,J＝7.5Hz,1H),7.14(d,J＝6.5Hz,1H),5.95(t,J＝5.5Hz,1H),3.08(d,J＝5.5Hz,2H),2.68(s,3H),2.04(s,3H).13C NMR(125MHz,CDCl3)δ170.84,135.98,134.53,134.38,134.36,133.23,131.17,128.43,127.91,127.19,127.02,126.88,126.68,70.33,35.92,23.07,21.32
example 9
Alpha-acetoxy-2- (2-methyl-phenyl) styrene (0.3mmol, 0.0756g), photosensitizer (III) (0.003mmol, 0.0167g), K3PO4(0.45mmol, 0.0954g) was added to a 15mL stoppered reaction tube, and 3mL tetrahydrofuran was added as a solvent. And then, reacting for 24 hours under the condition of 25 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 51% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.77-7.75(m,1H),7.50-7.48(m,1H),7.43(td,J1＝7.5Hz,J2＝1.5Hz,1H),7.33(td,J1＝7.5Hz,J2＝1.5Hz,1H),7.24(d,J＝7.5Hz,1H),7.19(t,J＝7.5Hz,1H),7.14(d,J＝6.5Hz,1H),5.95(t,J＝5.5Hz,1H),3.08(d,J＝5.5Hz,2H),2.68(s,3H),2.04(s,3H).13C NMR(125MHz,CDCl3)δ170.84,135.98,134.53,134.38,134.36,133.23,131.17,128.43,127.91,127.19,127.02,126.88,126.68,70.33,35.92,23.07,21.32
example 10
Alpha-acetoxy-2- (4-chlorophenyl) styrene (0.3mmol, 0.0816g), photosensitizer (III) (0.03mmol, 0.0335g), and K3PO4(0.45mmol, 0.0954g) was added to a 15mL stoppered reaction tube, and 3mL tetrahydrofuran was added as a solvent. Then, under the irradiation of 15w Blue LED, the temperature is 25 ℃ and the nitrogen atmosphereAfter the reaction is finished for 24h, adding two-spoon column chromatography silica gel (100-200 mesh), removing the solvent by reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate 20:1 is used as eluent) shown in the structural formula. The material was a yellow liquid in 86% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.82(d,J＝2Hz,1H),7.79(d,J＝7.5Hz,1H),7.44(d,J＝8.5Hz,1H),7.38(td,J1＝7.5Hz,J2＝1Hz,1H),7.33(td,J1＝7.5Hz,J2＝1.5Hz,1H),7.31-7.28(m,2H),6.04(t,J＝4.5Hz,1H),3.17(d,J＝4.5Hz,2H),1.99(s,3H).13C NMR(125MHz,CDCl3)δ170.62,135.92,135.30,132.98,132.02,131.82,130.01,129.22,128.61,127.56,127.54,124.09,123.70,69.13,34.28,21.24.
example 11
Alpha-acetoxy-2- (4-chlorophenyl) styrene (0.3mmol, 0.0816g), photosensitizer (III) (0.015mmol, 0.0167g), and K3PO4(0.45mmol, 0.0954g) was added to a 15mL stoppered reaction tube, and 3mL tetrahydrofuran was added as a solvent. And then, reacting for 24 hours under the condition of 15w of Blue LED irradiation and 15 ℃ in a nitrogen environment, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating through column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 82% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.82(d,J＝2Hz,1H),7.79(d,J＝7.5Hz,1H),7.44(d,J＝8.5Hz,1H),7.38(td,J1＝7.5Hz,J2＝1Hz,1H),7.33(td,J1＝7.5Hz,J2＝1.5Hz,1H),7.31-7.28(m,2H),6.04(t,J＝4.5Hz,1H),3.17(d,J＝4.5Hz,2H),1.99(s,3H).13C NMR(125MHz,CDCl3)δ170.62,135.92,135.30,132.98,132.02,131.82,130.01,129.22,128.61,127.56,127.54,124.09,123.70,69.13,34.28,21.24.
example 12
Alpha-acetoxy-2- (4-chlorophenyl) styrene (0.3mmol, 0.0816g), photosensitizer (III) (0.015mmol, 0.0167g), and K3PO4(0.45mmol, 0.0954g) was added to a 15mL stoppered reaction tube, and 3mL tetrahydrofuran was added as a solvent. And then, reacting for 24 hours under the condition of 40 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 81% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ7.82(d,J＝2Hz,1H),7.79(d,J＝7.5Hz,1H),7.44(d,J＝8.5Hz,1H),7.38(td,J1＝7.5Hz,J2＝1Hz,1H),7.33(td,J1＝7.5Hz,J2＝1.5Hz,1H),7.31-7.28(m,2H),6.04(t,J＝4.5Hz,1H),3.17(d,J＝4.5Hz,2H),1.99(s,3H).13C NMR(125MHz,CDCl3)δ170.62,135.92,135.30,132.98,132.02,131.82,130.01,129.22,128.61,127.56,127.54,124.09,123.70,69.13,34.28,21.24.
example 13
Alpha-acetoxy-2- (2-fluorophenyl) styrene (0.3mmol, 0.0768g), photosensitizer (III) (0.015mmol, 0.0167g), K3PO4(0.45mmol, 0.0954g) was added to a 15mL stoppered reaction tube, and 3mL tetrahydrofuran was added as a solvent. Then, reacting for 20h under the condition of 25 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent by reduced pressure distillation, and then performing column chromatographyThe product was isolated as pure as shown by the formula (petroleum ether/ethyl acetate 20:1 as eluent). The material was a yellow liquid in 83% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ8.17(d,J＝8Hz,1H),7.51(d,J＝7.5Hz,1H),7.48-7.45(m,1H),7.36(td,J1＝7.5Hz，J2＝1Hz,1H),7.26-7.22(m,1H),7.11-7.07(m,2H),6.02(t,J＝4.5Hz,1H),3.21-3.12(m,2H),2.00(s,3H).13C NMR(125MHz,CDCl3)δ170.68,161.38,159.38,136.03(J＝3.75Hz),134.01,130.48(J＝3.75Hz),129.20,128.64(J＝10Hz),128.34,128.21,127.99,124.76(J＝2.5Hz),121.34(J＝10Hz),115.36(J＝23.75Hz),69.79,34.74(J＝2.5Hz),21.26.
example 14
Alpha-acetoxy-2- (2-fluorophenyl) styrene (0.3mmol, 0.0768g), photosensitizer (III) (0.015mmol, 0.0167g), K3PO4(0.45mmol, 0.0954g) was added to a 15mL stoppered reaction tube, and 3mL tetrahydrofuran was added as a solvent. And then, reacting for 36h under the condition of 25 ℃ and nitrogen atmosphere under the irradiation of 15w Blue LED, adding two-spoon column chromatography silica gel (100-200 meshes) into the reaction liquid after the reaction is finished, removing the solvent through reduced pressure distillation, and separating by column chromatography to obtain a pure product (petroleum ether/ethyl acetate-20: 1 is used as an eluent) shown in the structural formula. The material was a yellow liquid in 87% yield.
Characterization data:1H NMR(500MHz,CDCl3)δ8.17(d,J＝8Hz,1H),7.51(d,J＝7.5Hz,1H),7.48-7.45(m,1H),7.36(td,J1＝7.5Hz，J2＝1Hz,1H),7.26-7.22(m,1H),7.11-7.07(m,2H),6.02(t,J＝4.5Hz,1H),3.21-3.12(m,2H),2.00(s,3H).13C NMR(125MHz,CDCl3)δ170.68,161.38,159.38,136.03(J＝3.75Hz),134.01,130.48(J＝3.75Hz),129.20,128.64(J＝10Hz),128.34,128.21,127.99,124.76(J＝2.5Hz),121.34(J＝10Hz),115.36(J＝23.75Hz),69.79,34.74(J＝2.5Hz),21.26.
meanwhile, the product synthesized by the invention can be used in the following industrial fields, and can synthesize 9, 10-dihydrophenanthrene compounds and phenanthrene compounds, which are shown in the following (general formula).
Dissolving the synthesized compound 9-acetoxyl-9, 10-dihydrophenanthrene compound (0.3mmol) in 5ml of dichloromethane, adding 3.5g of silica gel, reacting for 30 minutes at 110 ℃, eluting with dichloromethane after the reaction is finished, and spin-drying to obtain the target product phenanthrene compound.
Synthesis of specific substances such as:
dissolving the compound 9-acetoxyl-9, 10-dihydrophenanthrene (0.3mmol, 0.0714g) in 5ml dichloromethane, adding 3.5g silica gel, reacting at 110 ℃ for 30 minutes, eluting with dichloromethane after the reaction is finished, and spin-drying to obtain the target product phenanthrene, wherein the yield is 92%.
6-chloro-9-acetoxyl-9, 10-dihydrophenanthrene (0.3mmol, 0.0816g) is dissolved in 5ml dichloromethane, 3.5g silica gel is added, the reaction is carried out for 30 minutes at 110 ℃, and after the reaction is finished, the target product 3-chlorophenanthrene is obtained by eluting with dichloromethane and spin-drying, wherein the yield is 90%.
4-methyl-9-acetoxyl-9, 10-dihydrophenanthrene (0.3mmol, 0.0756g) is dissolved in 5ml dichloromethane, 3.5g silica gel is added, the reaction is carried out for 30 minutes at 110 ℃, and after the reaction is finished, the target product 4-methylphenanthrene is obtained by eluting with dichloromethane and spin-drying, wherein the yield is 93%.
Dissolving 2-chloro-9-acetoxyl-9, 10-dihydrophenanthrene (0.3mmol, 0.0816g) in 5ml dichloromethane, adding 3.5g silica gel, reacting for 30 minutes at 110 ℃, eluting with dichloromethane after the reaction is finished, and spin-drying to obtain the target product 2-chlorophenanthrene with the yield of 91%.
Dissolving 4-fluoro-9-acetoxyl-9, 10-dihydrophenanthrene (0.3mmol, 0.0816g) in 5ml dichloromethane, adding 3.5g silica gel, reacting for 30 minutes at 110 ℃, eluting with dichloromethane after the reaction is finished, and spin-drying to obtain the target product 4-fluorophenanthrene, wherein the yield is 90%.
Claims (4)
1. A method for synthesizing 9-acetoxyl-9, 10-dihydrophenanthrene compounds is characterized by comprising the following steps:
mixing a substrate (I), a photosensitizer, an alkaline substance and a solvent, reacting for 20-36 h under the conditions of illumination of a blue LED, temperature of 15-40 ℃ and protection of inert gas, and then carrying out aftertreatment on a reaction solution to obtain a 9-acetoxyl-9, 10-dihydrophenanthrene compound (II);
the ratio of the amounts of the substrate (I), the photosensitizer and the alkaline substance is 1: 0.01-0.1: 1-2;
the photosensitizer is one or a mixture of two of a formula (III) and a formula (IV) in any proportion;
the alkaline substance is one or a mixture of more than two of potassium phosphate, potassium carbonate and sodium carbonate in any proportion;
the solvent is one or a mixed solvent of more than two of acetonitrile, tetrahydrofuran and 1, 4-dioxane in any proportion;
the reaction formula is as follows:
in the formula (I) or the formula (II),
R1is chlorine or hydrogen;
R2is fluorine, chlorine, methyl or hydrogen.
2. The method for synthesizing a 9-acetoxy-9, 10-dihydrophenanthrene compound according to claim 1, wherein the ratio of the amounts of the substrate (I), the photosensitizer, and the basic substance is 1: 0.05: 1.5.
3. the method for synthesizing 9-acetoxy-9, 10-dihydrophenanthrene compound according to claim 1, wherein the volume of the solvent is 10 to 20mL/mmol based on the amount of the substance of the substrate (I).
4. The method for synthesizing a 9-acetoxy-9, 10-dihydrophenanthrene compound according to claim 1, wherein the post-treatment method is: after the reaction is finished, adding column chromatography silica gel into the reaction liquid, evaporating the solvent under reduced pressure, and performing column chromatography separation, wherein the volume ratio of petroleum ether to ethyl acetate is 20:1 as eluent, collecting eluent containing target product, evaporating solvent and drying to obtain 9-acetoxyl-9, 10-dihydrophenanthrene compound (II).
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