CN114853586A - Preparation method of phenanthrone derivative - Google Patents
Preparation method of phenanthrone derivative Download PDFInfo
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- CN114853586A CN114853586A CN202210422927.9A CN202210422927A CN114853586A CN 114853586 A CN114853586 A CN 114853586A CN 202210422927 A CN202210422927 A CN 202210422927A CN 114853586 A CN114853586 A CN 114853586A
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- phenanthrone
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- NDVAMUMVOJRAJV-UHFFFAOYSA-N 10h-phenanthren-9-one Chemical class C1=CC=C2C(=O)CC3=CC=CC=C3C2=C1 NDVAMUMVOJRAJV-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- -1 aryl ketone Chemical class 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 239000003814 drug Substances 0.000 claims abstract description 4
- 230000005518 electrochemistry Effects 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 24
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 17
- QRUBYZBWAOOHSV-UHFFFAOYSA-M silver trifluoromethanesulfonate Chemical compound [Ag+].[O-]S(=O)(=O)C(F)(F)F QRUBYZBWAOOHSV-UHFFFAOYSA-M 0.000 claims description 17
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 238000004440 column chromatography Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- BTEJSUVVNDDTPL-UHFFFAOYSA-N n-fluoro-n-phenylbenzenesulfonamide Chemical compound C=1C=CC=CC=1S(=O)(=O)N(F)C1=CC=CC=C1 BTEJSUVVNDDTPL-UHFFFAOYSA-N 0.000 claims description 2
- PBDBXAQKXCXZCJ-UHFFFAOYSA-L palladium(2+);2,2,2-trifluoroacetate Chemical compound [Pd+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F PBDBXAQKXCXZCJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 238000001308 synthesis method Methods 0.000 abstract description 5
- 229940079593 drug Drugs 0.000 abstract description 2
- 238000010499 C–H functionalization reaction Methods 0.000 abstract 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 20
- 125000003118 aryl group Chemical group 0.000 description 14
- 239000007787 solid Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 10
- BSMGLVDZZMBWQB-UHFFFAOYSA-N 2-methyl-1-phenylpropan-1-one Chemical compound CC(C)C(=O)C1=CC=CC=C1 BSMGLVDZZMBWQB-UHFFFAOYSA-N 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- MHUVRVXSYXJUPK-UHFFFAOYSA-N 1-(4-fluorophenyl)-2-methylpropan-1-one Chemical compound CC(C)C(=O)C1=CC=C(F)C=C1 MHUVRVXSYXJUPK-UHFFFAOYSA-N 0.000 description 2
- LFKYTOWXZQDFKX-UHFFFAOYSA-N 2-methyl-1-(2-methylphenyl)propan-1-one Chemical compound CC(C)C(=O)C1=CC=CC=C1C LFKYTOWXZQDFKX-UHFFFAOYSA-N 0.000 description 2
- VLKIRFAISMBUCB-UHFFFAOYSA-N 2-methyl-1-(4-methylphenyl)propan-1-one Chemical compound CC(C)C(=O)C1=CC=C(C)C=C1 VLKIRFAISMBUCB-UHFFFAOYSA-N 0.000 description 2
- 206010035664 Pneumonia Diseases 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 208000025721 COVID-19 Diseases 0.000 description 1
- 241000711573 Coronaviridae Species 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 239000000321 herbal drug Substances 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a phenanthrone derivative. The preparation method mainly comprises the following steps: aryl ketone and monosubstituted arene are used as reaction substrates, and the phenanthrene ketone derivative is prepared under the combined action of a palladium-containing catalyst and an oxidant. The preparation method provided by the invention belongs to a one-step synthesis method, is simple and convenient in process and easy to operate, can selectively generate para carbon hydrogen bond activation of mono-substituted aromatic hydrocarbon, and generates an expected phenanthrone derivative. The phenanthrone derivative prepared by the method can be directly used, indirectly or in other forms in the fields of medicines, catalysis, electrochemistry, photochemistry and the like.
Description
Technical Field
The invention relates to the technical field of synthesis, in particular to a preparation method of a phenanthrene ketone derivative.
Background
Phenanthrene ketone derivatives play an important role in the fields of electrochemistry, photochemistry, pharmacy, organic synthesis and the like, and the rich chemical properties of the phenanthrene ketone derivatives enable the skeleton of the phenanthrene ketone derivatives to be widely existed in a plurality of functional molecules and materials. In Huopo and Xialing decoction recently used for treating early stage novel coronavirus pneumonia (COVID-19), phenanthrone derivatives also play an important role (Chinese Traditional and Herbal Drugs, 2020, 51 (9), 2297-. In the traditional synthesis method of phenanthrone derivatives, the phenanthrone derivatives are usually prepared by reacting specific aromatic carbonyl compounds with iodobenzene or aryl potassium fluoborate (J. AM. CHEM. SOC. 2008, 130, 17676-17677, J. AM. CHEM. SOC. 2010, 132, 8569-8571), and the defects of harsh synthesis conditions, high cost, difficulty in scale-up production and the like exist. Although phenanthrone derivatives can be prepared by other methods, the general problems of long reaction steps, poor reaction efficiency and the like are frequently encountered (ACS Cat. 2017, 7(7), 4435-. In order to optimize a synthesis method of the phenanthrene ketone derivative and realize the amplification and mass production of the phenanthrene ketone derivative as soon as possible and greatly improve the practical value of the phenanthrene ketone derivative, a one-step method phenanthrene ketone derivative preparation route is ingeniously designed, so that a plurality of side reactions possibly occurring in the phenanthrene ketone preparation process are avoided to a great extent, and the problem of low synthesis efficiency is improved.
Disclosure of Invention
Aiming at the defects of the existing method for synthesizing the phenanthrone derivative, the invention aims to provide a simple and convenient method for synthesizing the phenanthrone derivative.
The chemical structure of the phenanthrone derivative is shown as the following general formula:
wherein: r is alkyl or halogen or aromatic hydrocarbon group, R1 and R2 are hydrogen or halogen or alkyl or aromatic hydrocarbon group respectively.
The invention relates to a preparation method of phenanthrone derivative, belonging to a one-step synthesis method, comprising the following steps:
reaction substrate aryl ketone (A) and catalyst palladium dichloride (PdCl) 2 ) Silver triflate (AgOTf), an oxidant (such as potassium persulfate) and magnetons are placed in a Schlenk reaction bottle, replacement gas is subjected to inert gas protection, then monosubstituted aromatic hydrocarbon (B) is added, and the system is heated at 60 ℃ for reaction. After reacting for a certain time (for example, 48 hours), cooling the mixture to room temperature, and separating and purifying by column chromatography to obtain the phenanthrone derivative.
The reaction equation for the preparation of phenanthrone derivatives is as follows:
the preparation method of the phenanthrone derivative comprises the following steps: the catalyst is PdCl with the molar ratio of 1:2 2 And AgOTf, and may also be palladium trifluoromethanesulfonate or palladium trifluoroacetate.
Wherein: the catalyst is preferably PdCl 2 And AgOTf or palladium triflate.
In the preparation method of the phenanthrone derivative, the oxidant is potassium persulfate, sodium persulfate, ammonium persulfate, N-fluoro-diphenyl sulfonamide, manganese dioxide, potassium permanganate or hydrogen peroxide, and preferably potassium persulfate, sodium persulfate or ammonium persulfate.
In the preparation method of the phenanthrone derivative, aryl ketone and catalyst are as follows: oxidizing agent: the molar ratio of the mono-substituted aromatic hydrocarbon is 1: 0.05-1: 1-10: 10 to 10000, preferably 1:0.1:2: 100.
In the above method for producing a phenanthrone derivative, the inert gas is argon (Ar) or nitrogen (N) 2 ) Or helium (He); the reaction temperature is 40-120 deg.C o C, preferably 60 oC (ii) a The reaction time is 1 to 5 days, preferably 2 days.
In the above process for producing phenanthrone derivatives, the aryl ketone (A) is substituted with a substituent R on the benzene ring 1 Is hydrogen or halogen or alkyl or aryl, and the substituent R is alkyl or halogen or aryl.
In the above process for preparing phenanthrone derivatives, the substituent R of the mono-substituted aromatic hydrocarbon (B) 2 Hydrogen or halogen or alkyl or aryl radicals.
The phenanthrone derivatives can be used directly, indirectly or in other forms in the fields of medicine, catalysis, electrochemistry, photochemistry and the like.
The invention has the beneficial effects that:
the preparation method of the phenanthrene ketone derivative belongs to a one-step synthesis method, and has the advantage of incomparable ratio in the aspect of preparing the phenanthrene ketone derivative. The phenanthrene ketone derivative can be prepared from commercial aryl ketone and monosubstituted aromatic hydrocarbon through one-step reaction. Because the synthesis conditions are simple, the method is very hopeful to be applied to the large-scale production of the phenanthrone derivative. In addition, the phenanthrone derivative belongs to an important organic drug intermediate, and has a good application prospect in the aspect of treating novel coronary pneumonia at present.
Drawings
FIG. 1 is a one-dimensional nuclear magnetic spectrum hydrogen spectrum of the phenanthrone derivative prepared in example 1 of the present invention.
FIG. 2 is a one-dimensional nuclear magnetic spectrum carbon spectrum of the phenanthrone derivative prepared in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Examples 1,
148 mg (1 mmol) of reaction substrate phenyl isopropyl ketone and catalyst PdCl are weighed 2 18 mg (0.1 mmol), AgOTf 51 mg (0.2 mmol) and 540 mg (2 mmol) of potassium persulfate are put in a Schlenk reaction bottle, the replacement gas is protected by argon, then 10mL of mono-substituted aromatic anisole is added, and the system is heated and reacted at 60 ℃. After 48 hours of reaction, the mixture was cooled to room temperature and purified by column chromatography to give 10, 10-dimethyl-2-methoxyphenanthrene-9 (10) as a white solid powderH) -ketone (C1) (250 mg, 99%). The chemical reaction equation is as follows:
the hydrogen spectrum of a nuclear magnetic spectrum (figure 1) shows that the phenanthrone derivative C1 prepared by the method contains two methyl groups, one methoxy group and 7 aromatic hydrogens.
The carbon spectrum of nuclear magnetic spectrum (figure 2) shows that the phenanthrene ketone derivative C1 prepared by the method contains methyl carbon, methoxy carbon, carbonyl carbon, aliphatic carbon and ten aromatic carbons.
Examples 2,
148 mg (1 mmol) of reaction substrate phenyl isopropyl ketone and catalyst PdCl are weighed 2 36 mg (0.2 mmol), AgOTf 102 mg (0.4 mmol) and potassium persulfate 540 mg (2 mmol) are put in a Schlenk reaction bottle, argon gas protection is carried out on replacement gas, then 10mL of mono-substituted aromatic anisole is added, and the system is heated at 60 ℃ for reaction. After 48 hours of reaction, the mixture was cooled to room temperature and purified by column chromatographyTo obtain white solid powder 10, 10-dimethyl-2-methoxy phenanthrene-9 (10)H) -ketone (C1) (250 mg, 99%).
Examples 3,
148 mg (1 mmol) of reaction substrate phenyl isopropyl ketone and catalyst PdCl are weighed 2 18 mg (0.1 mmol), AgOTf 51 mg (0.2 mmol) and potassium persulfate 270 mg (1 mmol) are put in a Schlenk reaction bottle, argon gas protection is carried out on replacement gas, then 10mL of mono-substituted aromatic anisole is added, and the system is heated at 60 ℃ for reaction. After 48 hours of reaction, the mixture was cooled to room temperature and purified by column chromatography to give 10, 10-dimethyl-2-methoxyphenanthrene-9 (10) as a white solid powderH) -ketone (C1) (179 mg, 71%).
Examples 4,
148 mg (1 mmol) of reaction substrate phenyl isopropyl ketone and catalyst PdCl are weighed 2 18 mg (0.1 mmol), AgOTf 51 mg (0.2 mmol) and potassium persulfate 540 mg (2 mmol) are put in a Schlenk reaction bottle, argon gas protection is carried out on replacement gas, then 10mL of mono-substituted aromatic anisole is added, and the system is heated at 60 ℃ for reaction. After 24 hours of reaction, the mixture was cooled to room temperature and purified by column chromatography to give 10, 10-dimethyl-2-methoxyphenanthrene-9 (10) as a white solid powderH) -ketone (C1) (182 mg, 72%).
Examples 5,
148 mg (1 mmol) of reaction substrate phenyl isopropyl ketone and catalyst PdCl are weighed 2 18 mg (0.1 mmol), AgOTf 51 mg (0.2 mmol) and potassium persulfate 540 mg (2 mmol) are put in a Schlenk reaction bottle, argon gas protection is carried out on replacement gas, then 20mL of mono-substituted aromatic anisole is added, and the system is heated at 60 ℃ for reaction. After 48 hours of reaction, the mixture was cooled to room temperature and purified by column chromatography to give 10, 10-dimethyl-2-methoxyphenanthrene-9 (10) as a white solid powderH) -ketone (C1) (246 mg, 98%).
Examples 6,
148 mg (1 mmol) of reaction substrate phenyl isopropyl ketone and catalyst PdCl are weighed 2 18 mg (0.1 mmol), AgOTf 51 mg (0.2 mmol) and 456 mg (2 mmol) of ammonium persulfate are put in a Schlenk reaction bottle, and the replacement gas is protected by argonThen adding 10mL of mono-substituted aromatic anisole, and heating the system at 60 ℃ for reaction. After 48 hours of reaction, the mixture was cooled to room temperature and purified by column chromatography to give 10, 10-dimethyl-2-methoxyphenanthrene-9 (10) as a white solid powderH) -ketone (C1) (249 mg, 99%). The chemical reaction equation is as follows:
example 7,
148 mg (1 mmol) of reaction substrate phenyl isopropyl ketone and catalyst PdCl are weighed 2 18 mg (0.1 mmol), AgOTf 51 mg (0.2 mmol) and potassium persulfate 540 mg (2 mmol) are put in a Schlenk reaction bottle, argon protection is carried out on replacement gas, then 10mL of mono-substituted aromatic hydrocarbon toluene is added, and the system is heated at 60 ℃ for reaction. After 48 hours of reaction, the mixture was cooled to room temperature and purified by column chromatography to give 2,10, 10-trimethylphenanthrene-9 (10) as a white solid powderH) -ketone (C2) (227 mg, 96%). The chemical reaction equation is as follows:
example 8,
148 mg (1 mmol) of reaction substrate phenyl isopropyl ketone and catalyst PdCl are weighed 2 18 mg (0.1 mmol), AgOTf 51 mg (0.2 mmol) and potassium persulfate 540 mg (2 mmol) are put in a Schlenk reaction bottle, argon protection is carried out on replacement gas, then 10mL of mono-substituted aromatic fluorobenzene is added, and the system is heated at 60 ℃ for reaction. After 48 hours of reaction, the mixture was cooled to room temperature and purified by column chromatography to give 10, 10-dimethyl-2-fluorophenanthrene-9 (10) as a white solid powderH) -ketone (C3) (211 mg, 88%). The chemical reaction equation is as follows:
examples 9,
162 mg (1 mmol) of reaction substrate 2-methyl phenyl isopropyl ketone (A2) and catalyst PdCl are weighed 2 18 mg (0.1 mmol), AgOTf 51 mg (0.2 mmol) and potassium persulfate 540 mg (2 mmol) are put in a Schlenk reaction bottle, argon gas protection is carried out on replacement gas, then 10mL of mono-substituted aromatic anisole is added, and the system is heated at 60 ℃ for reaction. After 48 hours of reaction, the mixture was cooled to room temperature and purified by column chromatography to give 8,10, 10-trimethyl-2-methoxyphenanthrene-9 (10) as a white solid powderH) -ketone (C4) (226 mg, 85%). The chemical reaction equation is as follows:
examples 10,
162 mg (1 mmol) of reaction substrate 4-methyl phenyl isopropyl ketone (A3) and catalyst PdCl are weighed 2 18 mg (0.1 mmol), AgOTf 51 mg (0.2 mmol) and potassium persulfate 540 mg (2 mmol) are put in a Schlenk reaction bottle, argon gas protection is carried out on replacement gas, then 10mL of mono-substituted aromatic anisole is added, and the system is heated at 60 ℃ for reaction. After 48 hours of reaction, the mixture was cooled to room temperature and purified by column chromatography to give 7,10, 10-trimethyl-2-methoxyphenanthrene-9 (10) as a white solid powderH) -ketone (C5) (240 mg, 90%). The chemical reaction equation is as follows:
examples 11,
166 mg (1 mmol) of reaction substrate 4-fluorophenyl isopropyl ketone (A4) and catalyst PdCl are weighed 2 18 mg (0.1 mmol), AgOTf 51 mg (0.2 mmol) and potassium persulfate 540 mg (2 mmol) are put in a Schlenk reaction bottle, argon gas protection is carried out on replacement gas, then 10mL of mono-substituted aromatic anisole is added, and the system is heated at 60 ℃ for reaction. After 48 hours of reaction, the mixture was cooled to room temperature and purified by column chromatography to give 10, 10-dimethyl-2-methoxy-7-fluorophenanthrene-9 (1) as a white solid powder0H) -ketone (C6) (221 mg, 82%). The chemical reaction equation is as follows:
examples 12,
176 mg (1 mmol) of reaction substrate 2-ethyl-1-phenylbutanone (A5) and catalyst PdCl are weighed 2 18 mg (0.1 mmol), AgOTf 51 mg (0.2 mmol) and potassium persulfate 540 mg (2 mmol) are put in a Schlenk reaction bottle, argon gas protection is carried out on replacement gas, then 10mL of mono-substituted aromatic anisole is added, and the system is heated at 60 ℃ for reaction. After 48 hours of reaction, the mixture was cooled to room temperature and purified by column chromatography to give 10, 10-diethyl-2-methoxyphenanthrene-9 (10) as a white solid powderH) -ketone (C7) (218 mg, 78%). The chemical reaction equation is as follows:
the above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. A preparation method of phenanthrene ketone derivative is characterized in that aryl ketone and mono-substituted aromatic hydrocarbon are used as raw materials and prepared under the protection of inert gas; the preparation method of the phenanthrone derivative comprises the following steps:
placing reaction substrates aryl ketone, a catalyst and an oxidant in a reaction bottle, carrying out inert gas protection on replacement gas, then adding mono-substituted aromatic hydrocarbon, heating the system at 60 ℃ for reaction, cooling the mixture to room temperature after reacting for a certain time, and separating and purifying by column chromatography to obtain the phenanthrene ketone derivative.
2. The method for producing a phenanthrone derivative according to claim 1, wherein the catalyst is palladium dichloride and silver triflate in a molar ratio of 1:2, or palladium triflate or palladium trifluoroacetate.
3. The method for producing a phenanthrone derivative according to claim 1, wherein the oxidizing agent is potassium persulfate, sodium persulfate, ammonium persulfate, N-fluorobisphenylsulfonamide, manganese dioxide, potassium permanganate, or hydrogen peroxide.
4. The method for producing a phenanthrone derivative according to claim 1, wherein the ratio of aryl ketone to catalyst: oxidizing agent: the molar ratio of the mono-substituted aromatic hydrocarbon is 1: 0.05-1: 1-10: 10 to 10000.
5. The method for producing a phenanthrone derivative according to claim 1, wherein the inert gas is argon gas, nitrogen gas, or helium gas; the reaction temperature is 40-120 deg.C o C; the reaction time is 1-5 days.
6. The method for producing a phenanthrone derivative according to claim 1, wherein the substituent on the aryl ketone phenyl ring is hydrogen or halogen, or an alkyl group or an aromatic hydrocarbon group.
7. The method for producing a phenanthrone derivative according to claim 1, wherein a substituent of the mono-substituted aromatic hydrocarbon is hydrogen or halogen, or an alkyl group or an aromatic hydrocarbon group.
8. Phenanthrone derivatives prepared according to any of claims 1 to 7, for use directly, or indirectly or in other forms in the fields of medicine, catalysis, electrochemistry, photochemistry, etc.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101238756A (en) * | 2005-08-10 | 2008-08-06 | 默克专利有限公司 | Electroluminescent polymers and use thereof |
| CN108424344A (en) * | 2018-04-11 | 2018-08-21 | 华南协同创新研究院 | Monomer and polymer containing luxuriant and rich with fragrance five yuan and ring element and the preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101238756A (en) * | 2005-08-10 | 2008-08-06 | 默克专利有限公司 | Electroluminescent polymers and use thereof |
| CN108424344A (en) * | 2018-04-11 | 2018-08-21 | 华南协同创新研究院 | Monomer and polymer containing luxuriant and rich with fragrance five yuan and ring element and the preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| CHENG CHIEN-HONG等: "Synthesis of Phenanthrone Derivatives from sec-Alkyl Aryl Ketones and Aryl Halides via a Palladium-Catalyzed Dual C-H Bond Activation and Enolate Cyclization", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 132, no. 25, pages 8569 - 8571 * |
| LIU YI等: "Accessing Axially Chiral Biaryls via Organocatalytic Enantioselective Dynamic-Kinetic Resolution-Semipinacol Rearrangement", ACS CATALYSIS, vol. 7, no. 7, pages 4436 * |
| WANG DONG-HUI等: "Versatile Pd(II)-Catalyzed C-H Activation/Aryl-Aryl Coupling of Benzoic and Phenyl Acetic Acids", J. AM. CHEM. SOC., vol. 130, no. 52, pages 17677 * |
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