CN115745805A - Synthetic method of phenanthrene and naphthocycloheptene compounds - Google Patents
Synthetic method of phenanthrene and naphthocycloheptene compounds Download PDFInfo
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- CN115745805A CN115745805A CN202211523358.3A CN202211523358A CN115745805A CN 115745805 A CN115745805 A CN 115745805A CN 202211523358 A CN202211523358 A CN 202211523358A CN 115745805 A CN115745805 A CN 115745805A
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- phenanthrene
- naphthocycloheptene
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- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 title claims abstract description 80
- UIWPMNWASXGGBS-UHFFFAOYSA-N 1H-cyclohepta[a]naphthalene Chemical class C1=CC=CC2=C3CC=CC=C3C=CC2=C1 UIWPMNWASXGGBS-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000010189 synthetic method Methods 0.000 title description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003446 ligand Substances 0.000 claims abstract description 22
- 238000001308 synthesis method Methods 0.000 claims abstract description 21
- -1 aryl formic acid derivative Chemical class 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 150000003440 styrenes Chemical class 0.000 claims description 21
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 16
- 238000004440 column chromatography Methods 0.000 claims description 14
- 230000002194 synthesizing effect Effects 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 12
- TWKVUTXHANJYGH-UHFFFAOYSA-L allyl palladium chloride Chemical class Cl[Pd]CC=C.Cl[Pd]CC=C TWKVUTXHANJYGH-UHFFFAOYSA-L 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 239000012074 organic phase Substances 0.000 claims description 11
- 239000003208 petroleum Substances 0.000 claims description 11
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 11
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000010791 quenching Methods 0.000 claims description 10
- 230000000171 quenching effect Effects 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005711 Benzoic acid Substances 0.000 claims description 8
- 235000010233 benzoic acid Nutrition 0.000 claims description 8
- 150000005209 naphthoic acids Chemical class 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 125000004185 ester group Chemical group 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- HWFCHCRFQWEFMU-UHFFFAOYSA-N 2-bromo-4,5-dimethoxybenzoic acid Chemical compound COC1=CC(Br)=C(C(O)=O)C=C1OC HWFCHCRFQWEFMU-UHFFFAOYSA-N 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- DMEZDDHJCUHENA-UHFFFAOYSA-N 8-bromonaphthalene-1-carboxylic acid Chemical group C1=CC(Br)=C2C(C(=O)O)=CC=CC2=C1 DMEZDDHJCUHENA-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- QFUYDAGNUJWBSM-UHFFFAOYSA-N 1-iodo-2-phenylbenzene Chemical group IC1=CC=CC=C1C1=CC=CC=C1 QFUYDAGNUJWBSM-UHFFFAOYSA-N 0.000 claims description 3
- CEXGTXNIIFSPSF-UHFFFAOYSA-N 2-bromo-4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1Br CEXGTXNIIFSPSF-UHFFFAOYSA-N 0.000 claims description 3
- RVSXMPCELBYUSF-UHFFFAOYSA-N 2-bromothiophene-3-carboxylic acid Chemical compound OC(=O)C=1C=CSC=1Br RVSXMPCELBYUSF-UHFFFAOYSA-N 0.000 claims description 3
- IVDSIQHLCKGRCR-UHFFFAOYSA-N 3-(2-iodophenyl)thiophene Chemical compound IC1=CC=CC=C1C1=CSC=C1 IVDSIQHLCKGRCR-UHFFFAOYSA-N 0.000 claims description 3
- UZBGSJZFBUOJNE-UHFFFAOYSA-N 3-bromofuran-2-carboxylic acid Chemical compound OC(=O)C=1OC=CC=1Br UZBGSJZFBUOJNE-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- RBYGDVHOECIAFC-UHFFFAOYSA-L acetonitrile;palladium(2+);dichloride Chemical compound [Cl-].[Cl-].[Pd+2].CC#N.CC#N RBYGDVHOECIAFC-UHFFFAOYSA-L 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000004817 gas chromatography Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- 238000004809 thin layer chromatography Methods 0.000 claims description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 claims description 2
- WMKGGPCROCCUDY-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one Chemical compound C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 WMKGGPCROCCUDY-UHFFFAOYSA-N 0.000 claims 1
- 239000007983 Tris buffer Substances 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical class C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical class C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- UYNVJZIKYDILHS-UHFFFAOYSA-N 3,4-dimethoxyphenanthrene Chemical compound C1=CC=C2C3=C(OC)C(OC)=CC=C3C=CC2=C1 UYNVJZIKYDILHS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LOFDXZJSDVCYAS-UHFFFAOYSA-N Ethyl 3-furoate Chemical compound CCOC(=O)C=1C=COC=1 LOFDXZJSDVCYAS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- OYSLMAQEMAJMCL-UHFFFAOYSA-N ethyl thiophene-3-carboxylate Chemical compound CCOC(=O)C=1C=CSC=1 OYSLMAQEMAJMCL-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The application discloses a synthesis method of phenanthrene and naphthocycloheptene compounds, and belongs to the technical field of organic synthesis. According to the method, a styrene derivative and an aryl formic acid derivative are used as raw materials, alkali and an additive are added under a catalytic system of a palladium catalyst and a ligand, and phenanthrene and naphthocycloheptene compounds are prepared in an inert gas environment. The method has the advantages of simple operation, low cost, high yield, excellent regioselectivity and the like, and is suitable for gram-scale preparation. The target molecule prepared by the method can be applied to the synthesis of photoelectric material substances of a large pi conjugated system.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis method of phenanthrene and naphthocycloheptene compounds.
Background
Aromatic hydrocarbons containing a large pi conjugated system, such as phenanthrene and naphthocycloheptene compounds, have unique photoelectric property characteristics and abnormal chemical stability, and play an important role in functional organic materials; such as in the fabrication of organic light emitting diode light emitting devices (OLEDs).
Because the nature, steric environment, and electrical properties of the individual carbon sites on an aromatic ring are not very different, the desire to react at a particular site is fraught with significant challenges. The prior synthesis research on compounds containing large pi conjugated systems (such as phenanthrene, naphthalene and anthracene derivatives) generally has the problem of poor regioselectivity, and the separation by column chromatography is particularly difficult due to the close properties of isomers.
In view of the foregoing, there is a lack in the art of a highly selective synthesis for the preparation of large pi conjugated systems such as phenanthrene and naphthocycloheptene compounds.
Disclosure of Invention
The technical problem to be solved is as follows:
aiming at the defects of the prior art, the method solves the technical problems that the reaction is difficult to occur at a specific site, the regioselectivity is poor and the like at present, and provides a synthesis method of phenanthrene and naphthocycloheptene compounds, which has high selectivity, high yield and low cost.
The technical scheme is as follows:
in order to achieve the purpose, the application is realized by the following technical scheme:
a method for synthesizing phenanthrene and naphthocycloheptene compounds comprises the steps of taking styrene derivatives and aryl formic acid derivatives as raw materials, adding a ligand, alkali and an additive under the action of a palladium catalyst, and reacting to prepare phenanthrene and naphthocycloheptene compounds; the aryl formic acid derivative is benzoic acid or naphthoic acid derivative.
Further, the synthesis method comprises the following specific steps:
the first step is as follows: placing styrene derivatives, benzoic acid or naphthoic acid derivatives in a reaction tube, adding palladium catalyst, ligand, alkali, solvent, and additive, ventilating, removing air in the reaction bottle, introducing argon or nitrogen, sealing,
stirring for 15 minutes at room temperature, and then putting into an oil bath at the temperature of 110-150 ℃ for reaction for 10-16 hours;
the second step: detecting whether the reaction of the raw materials in the reaction system is complete by gas chromatography or thin layer chromatography, cooling the reaction bottle to room temperature if the reaction is complete, adding 5mL of water for quenching, extracting with ethyl acetate, washing with water for 3 times, combining organic phases, and adding anhydrous Na 2 SO 4 Drying, spin-drying and separating by column chromatography to obtain phenanthrene and naphthocycloheptene compounds; the eluent in the column chromatography separation is petroleum ether according to the volume ratio: ethyl acetate = 10.
Further, the reaction formula of the method is as follows:
in the formula, a group X is I, br, cl or trifluoromethanesulfonic group; the group Y is one of I, br and Cl; z is one of N, O and S; the group R includes, but is not limited to, methyl, methoxy, trifluoromethyl, nitro, ester group; r 1 、R 2 Including but not limited to alkyl, ester, aryl; radical R 3 Including but not limited to methyl, methoxy, trifluoromethyl, halogen, nitro, ester groups.
Further, the styrene derivatives are (E) -3- (2-iodophenyl) butyl-2-ethyl enoate, 4-fluoro-1-iodo-2- (prop-1-en-2-yl) benzene, 3- (2-iodophenyl) thiophene, 2-iodo-1, 1' -biphenyl, (E) -3- (2-iodophenyl) butenenitrile; the benzoic acid is 2-bromo-4-nitrobenzoic acid, 3-bromofuran-2-carboxylic acid, 2-bromothiophene-3-carboxylic acid, 2-bromo-4, 5-dimethoxybenzoic acid; the naphthoic acid derivative is 8-bromo-1-naphthoic acid.
Further, the palladium catalyst is tris-dibenzylideneacetone dipalladium, palladium chloride, bis (acetonitrile) palladium (II) chloride, allyl palladium chloride dimer, palladium acetate, bis-triphenylphosphine palladium dichloride, or tetratriphenylphosphine palladium.
Further, the ligand is a triphenylphosphine derivative, a bidentate phosphine ligand, a Buchwald ligand derivative or a carbene ligand, and preferably 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl.
Further, the base is one of potassium tert-butoxide, cesium carbonate, potassium carbonate and lithium tert-butoxide.
Further, the additive is one of trimethyl acetic acid, tetrabutyl ammonium bromide, acetic acid, sodium phosphate and phosphoric acid.
Further, the solvent is N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide or dioxane.
Further, the molar ratio of the palladium catalyst to the ligand is 1; the molar ratio of the palladium catalyst to the styrene derivative is 1; the molar ratio of the styrene derivative to the arylcarboxylic acid derivative is 1; the molar ratio of base to styrene derivative is 3; the molar ratio of the additive to the styrene derivative is 1.
The principle of the synthesis method of the phenanthrene and naphthocycloheptene compounds is as follows: under the action of alkali and additives, a relatively stable five-membered palladium ring intermediate is generated by activating the alkene hydrogen in the styrene derivative, and then the intermediate and the aryl carboxylic acid derivative undergo addition and reduction elimination processes, and finally, the synthesis of phenanthrene and naphthocycloheptene compounds is realized.
Has the advantages that:
compared with the prior art, the synthesis method of phenanthrene and naphthocycloheptene compounds has the following beneficial effects:
1. the synthesis method of phenanthrene and naphthocycloheptene compound derivatives provided by the invention has the advantages that phenanthrene and naphthocycloheptene compounds are synthesized in a one-step high regioselectivity manner;
2. the product can be used for synthesizing substances of photoelectric materials;
3. the yield reaches 94%; the operation steps are simple and convenient; the cost is low;
4. the selectivity ratio of the phenanthrene and naphthocycloheptene compounds generated by the invention to the isomers thereof is more than 30:1, is much larger than the ratio value of the prior art (3.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
A method for synthesizing phenanthrene and naphthocycloheptene compounds comprises the steps of taking styrene derivatives and aryl formic acid derivatives as raw materials, adding a ligand, alkali and an additive under the action of a palladium catalyst, and reacting to prepare phenanthrene and naphthocycloheptene compounds, wherein the aryl formic acid derivatives are benzoic acid or naphthoic acid derivatives; the synthesis method is shown as the following formula:
in the formula, the group X is I, br, cl or trifluoromethanesulfonic group; the group Y is one of I, br and Cl; z is one of N, O and S; the group R includes but is not limited to methyl, methoxy, trifluoromethyl, nitro, ester group; r is 1 、R 2 Including but not limited to alkyl, ester, aryl; radical R 3 Including but not limited to methyl, methoxy, trifluoromethyl, halogen, nitro, ester groups.
The method comprises the following specific steps:
(1) Putting the styrene derivative, the benzoic acid or the naphthoic acid derivative into a reaction tube, adding a palladium catalyst, a ligand and alkali, adding a solvent, finally adding an additive, ventilating, expelling air in a reaction bottle, filling argon or nitrogen, sealing, stirring for 15 minutes at room temperature, and then putting into an oil bath at 110-150 ℃ for reaction for 10-16 hours.
(2) Detecting whether the reaction of the raw materials in the reaction system is complete by gas chromatography or thin layer chromatography, and if the reaction is complete, detecting whether the reaction is completeThe reaction flask was cooled to room temperature, quenched with 5mL of water, extracted with ethyl acetate, washed with 5mL of water, the organic phases combined and Na anhydrous 2 SO 4 Drying, spin-drying and column chromatography (eluent is petroleum ether: ethyl acetate =10 by volume ratio: 1-50).
The palladium catalyst is tris-dibenzylideneacetone dipalladium, palladium chloride, bis (acetonitrile) palladium (II) chloride, allyl palladium chloride dimer, palladium acetate, palladium bis (triphenylphosphine) palladium dichloride or palladium tetrakis (triphenylphosphine) palladium.
The ligand is triphenylphosphine derivatives, bidentate phosphine ligands, buchwald ligand derivatives or carbene ligands. 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl is preferred.
The base is one of potassium tert-butoxide, cesium carbonate, potassium carbonate and lithium tert-butoxide.
The additive is one of trimethyl acetic acid, tetrabutyl ammonium bromide, acetic acid, sodium phosphate and phosphoric acid.
The solvent is N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide or dioxane; the molar ratio of the palladium catalyst to the ligand is 1; the molar ratio of the palladium catalyst to the styrene derivative is 1; the molar ratio of the styrene derivative to the arylcarboxylic acid derivative is 1; the molar ratio of base to styrene derivative is 3; the molar ratio of the additive to the styrene derivative is 1.
Example 1:
synthesis method of phenanthrene and naphthocycloheptene compounds, namely synthesis of 10-methyl-6-nitrophenanthrene-9-carboxylic acid ethyl ester
To a 25mL reaction tube were added in this order (E) -ethyl 3- (2-iodophenyl) but-2-enoate (63.2mg, 0.2mmol), 2-bromo-4-nitrobenzoic acid (98.4 mg,0.4 mmol), allylpalladium chloride dimer (7.3mg, 0.02mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (19mg, 0.04mmol), and potassium carbonate (82.8mg, 0.6mmol). Then 2 ml of N, N-dimethyl ether are addedDimethylformamide, trimethylacetic acid (4 mg, 0.04mmol), argon gas under vacuum, sealed at room temperature and stirred for 15 minutes, followed by stirring in a constant temperature oil bath at 130 ℃ for 12 hours. After the reaction is completed, adding 5mL of water for quenching, extracting by ethyl acetate, washing by water for 3 times, combining organic phases and anhydrous Na 2 SO 4 Dried, spun-dried and finally purified by column chromatography (petroleum ether/ethyl acetate = 10) to give a colorless liquid (48 mg, yield 78%).
1 H NMR(400MHz,CDCl 3 )δ9.50(d,J＝2.3Hz,1H),8.71(dd,J＝7.8,1.6Hz,1H),8.33(dd,J＝9.0,2.3Hz,1H),8.22–8.10(m,1H),7.88–7.73(m,3H),4.61(q,J＝7.1Hz,2H),2.74(s,3H),1.51(t,J＝7.2Hz,3H). 13 C NMR(101MHz,CDCl 3 )δ169.42,145.72,134.77,131.92,131.45,130.28,129.85,129.21,128.63,128.59,126.67,125.65,123.37,120.96,119.13,62.10,17.59,14.49.HRMS(ESI)m/z:[M+H] + calcd for C 18 H 16 NO 4 310.1074；found:310.1077.
Example 2:
synthesis method of phenanthrene and naphthocycloheptene compounds, namely synthesis of 5-methylnaphthalene [2,1-b ] furan-4-carboxylic acid ethyl ester
To a 25mL reaction tube were added (E) -ethyl 3- (2-iodophenyl) but-2-enoate (63.2mg, 0.2mmol), 3-bromofuran-2-carboxylic acid (76.4 mg,0.4 mmol), allyl palladium chloride dimer (7.3mg, 0.02mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (19mg, 0.04mmol), and potassium carbonate (82.8mg, 0.6 mmol) in this order. Then, 2 ml of N, N-dimethylformamide and trimethylacetic acid (4 mg, 0.04mmol) were added thereto, and argon gas was introduced under vacuum, and the mixture was sealed and stirred at room temperature for 15 minutes, and then placed in a constant temperature oil bath at 130 ℃ and stirred for 16 hours. After the reaction is completed, adding 5mL of water for quenching, extracting by ethyl acetate, washing by water for 3 times, combining organic phases, and adding anhydrous Na 2 SO 4 Drying, spin-drying, and finally performing column chromatography separation and purification (petroleum ether/ethyl acetate = 20)Pale yellow liquid (41 mg, 81% yield).
1 H NMR(400MHz,CDCl 3 )δ8.23–8.08(m,2H),7.74(d,J＝2.1Hz,1H),7.59(dddd,J＝31.5,8.4,6.9,1.3Hz,2H),7.23(d,J＝2.2Hz,1H),4.56(q,J＝7.1Hz,2H),2.83(s,3H),1.48(t,J＝7.1Hz,3H). 13 C NMR(101MHz,CDCl 3 )δ167.10,149.19,144.30,131.10,129.70,128.50,127.41,126.03,125.21,124.06,121.88,118.70,105.52,61.78,16.46,14.52.HRMS(ESI)m/z:[M+H] + calcd for C 16 H 15 O 3 255.1016；found:255.1016.
Example 3:
synthesis method of phenanthrene and naphthocycloheptene compounds, namely synthesis method of 5-methylnaphthalene [1,2-b ] thiophene-4-carboxylic acid ethyl ester
To a 25mL reaction tube were added (E) -ethyl 3- (2-iodophenyl) but-2-enoate (63.2mg, 0.2mmol), 2-bromothiophene-3-carboxylic acid (82.8mg, 0.4mmol), allyl palladium chloride dimer (7.3mg, 0.02mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (19mg, 0.04mmol), and potassium carbonate (82.8mg, 0.6mmol) in this order. Then, 2 ml of N, N-dimethylformamide and trimethylacetic acid (4 mg, 0.04mmol) were added thereto, and argon gas was introduced under vacuum, and the mixture was sealed and stirred at room temperature for 15 minutes, and then placed in a constant temperature oil bath at 130 ℃ and stirred for 16 hours. After the reaction is completed, adding 5mL of water for quenching, extracting by ethyl acetate, washing by water for 3 times, combining organic phases, and adding anhydrous Na 2 SO 4 Dried, spun-dried and finally purified by column chromatography (petroleum ether/ethyl acetate =15: 1-10) to give a light yellow liquid (37 mg, 69% yield).
1 H NMR(400MHz,CDCl 3 )δ8.19–8.11(m,2H),7.67–7.56(m,2H),7.55–7.45(m,2H),4.54(q,J＝7.1Hz,2H),2.78(s,3H),1.48(t,J＝7.1Hz,3H). 13 C NMR(101MHz,CDCl 3 )δ169.53,136.77,134.20,130.38,130.19,129.52,127.64,126.80,126.31,126.09,125.46,124.34,124.32,61.57,16.60,14.56.HRMS(ESI)m/z:[M+H] + calcd for C 16 H 15 O 2 S 271.0787；found:271.0794.
Example 4
Synthesis method of phenanthrene and naphthocycloheptene compounds, namely synthesis method of 7-fluoro-2, 3-dimethoxy-9-methylphenol
To a 25mL reaction tube were added 4-fluoro-1-iodo-2- (prop-1-en-2-yl) benzene (52.4 mg, 0.2mmol), 2-bromo-4, 5-dimethoxybenzoic acid (104.4 mg,0.4 mmol), allyl palladium chloride dimer (7.3mg, 0.02mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (19mg, 0.04mmol), and potassium carbonate (82.8mg, 0.6mmol) in this order. Then 2 ml of N, N-dimethylformamide, trimethylacetic acid (4 mg, 0.04mmol) were added, and argon gas was introduced under vacuum, and the mixture was sealed and stirred at room temperature for 15 minutes, and then stirred in a constant temperature oil bath at 130 ℃ for 12 hours. After the reaction is completed, adding 5mL of water for quenching, extracting by ethyl acetate, washing by water for 3 times, combining organic phases and anhydrous Na 2 SO 4 Dried, spun-dried, and finally purified by column chromatography (petroleum ether/ethyl acetate =15: 1-10) to give a colorless liquid (45 mg, 83% yield).
1 H NMR(400MHz,CDCl 3 )δ8.49(dd,J＝9.2,5.6Hz,1H),7.86(s,1H),7.62(dd,J＝10.8,2.7Hz,1H),7.49(s,1H),7.35(ddd,J＝9.1,7.9,2.7Hz,1H),7.13(s,1H),4.08(s,3H),4.01(s,3H),2.64(d,J＝1.1Hz,3H). 13 C NMR(101MHz,CDCl 3 )δ159.70,149.31,149.17,132.87,132.79,130.13,130.09,127.20,126.62,126.61,124.86,124.77,123.95,114.89,114.65,109.46,109.25,107.90,103.15,56.10,56.01,19.94. 19 F NMR(376MHz,CDCl 3 )δ-115.75.HRMS(ESI)m/z:[M+H] + calcd for C 17 H 16 O 2 F271.1129；found:271.1129.
Example 5
Synthesis method of phenanthrene and naphthocycloheptene compounds, namely synthesis of 5, 6-dimethoxyphenanthrene [9,10-c ] thiophene
To a 25mL reaction tube were added 3- (2-iodophenyl) thiophene (57.2mg, 0.2mmol), 2-bromo-4, 5-dimethoxybenzoic acid (104.4mg, 0.4mmol), allyl palladium chloride dimer (7.3mg, 0.02mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (19mg, 0.04mmol), and potassium carbonate (82.8mg, 0.6mmol) in this order. Then 2 ml of N, N-dimethylformamide, trimethylacetic acid (4 mg, 0.04mmol) were added, and argon gas was introduced under vacuum, and the mixture was sealed and stirred at room temperature for 15 minutes, and then placed in a constant temperature oil bath at 130 ℃ and stirred for 14 hours. After the reaction is completed, adding 5mL of water for quenching, extracting by ethyl acetate, washing by water for 3 times, combining organic phases and anhydrous Na 2 SO 4 Dried, spun-dried, and finally purified by column chromatography (petroleum ether/ethyl acetate =15: 1-10) to give a colorless liquid (52 mg, 89% yield).
1 H NMR(400MHz,CDCl 3 )δ8.47–8.37(m,1H),8.27–8.18(m,1H),7.91–7.80(m,2H),7.61–7.51(m,2H),7.43(d,J＝5.3Hz,1H),7.27(s,1H),4.03(d,J＝9.6Hz,6H). 13 C NMR(101MHz,CDCl 3 )δ149.59,148.85,136.00,133.84,128.61,128.05,126.02,125.66,124.39,123.59,123.31,123.01,122.93,122.77,104.57,104.42,56.06,56.02.HRMS(ESI)m/z:[M+H] + calcd for C 18 H 15 O 2 S 295.0787；found:295.0794.
Example 6:
synthesis method of phenanthrene and naphthocycloheptene compounds, namely synthesis of 2, 3-dimethoxytriphenyl
2-iodo-1, 1 '-biphenyl (56.0mg, 0.2mmol), 2-bromo-4, 5-dimethoxybenzoic acid (104.4mg, 0.4mmol), allyl palladium chloride dimer (7.3mg, 0.02mmol), 2-dicyclohexylphosphine-2', 4',6' -triisopropylbiphenyl (Triphenyl) were sequentially added to a 25mL reaction tube(19mg, 0.04mmol) and potassium carbonate (82.8mg, 0.6mmol). Then, 2 ml of N, N-dimethylformamide and trimethylacetic acid (4 mg, 0.04mmol) were added thereto, and argon gas was introduced under vacuum, and the mixture was sealed and stirred at room temperature for 15 minutes, and then placed in a constant temperature oil bath at 130 ℃ and stirred for 12 hours. After the reaction is completed, adding 5mL of water for quenching, extracting by ethyl acetate, washing by water for 3 times, combining organic phases and anhydrous Na 2 SO 4 Dried, spun-dried and finally purified by column chromatography (petroleum ether/ethyl acetate =15: 1-10) to give a colorless liquid (53 mg, 92% yield).
1 H NMR(400MHz,CDCl 3 )δ8.56(dd,J＝7.4,2.1Hz,2H),8.37(dd,J＝7.4,2.1Hz,2H),7.83(s,2H),7.56(ddt,J＝11.1,7.1,3.5Hz,4H),4.04(s,6H). 13 C NMR(101MHz,CDCl 3 )δ149.30,129.45,129.12,126.97,126.22,124.08,123.36,122.74,104.34,55.92.HRMS(ESI)m/z:[M+H] + calcd for C 20 H 17 O 2 289.1223；found:289.1223.
Example 7:
synthesis method of phenanthrene and naphthocycloheptene compounds, namely synthesis of 8-methylbenzo [4,5] cyclohepta [1,2,3-de ] naphthalene-7-nitrile
To a 25mL reaction tube were added (E) -3- (2-iodophenyl) butenenitrile (53.8mg, 0.2mmol), 8-bromo-1-naphthoic acid (100.4mg, 0.4mmol), allylpalladium chloride dimer (7.3mg, 0.02mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (19mg, 0.04mmol), and potassium carbonate (82.8mg, 0.6 mmol) in this order. Then, 2 ml of N, N-dimethylformamide and trimethylacetic acid (4 mg, 0.04mmol) were added thereto, and argon gas was introduced under vacuum, and the mixture was sealed and stirred at room temperature for 15 minutes, and then placed in a constant temperature oil bath at 130 ℃ and stirred for 16 hours. After the reaction is completed, adding 5mL of water for quenching, extracting by ethyl acetate, washing by water for 3 times, combining organic phases and anhydrous Na 2 SO 4 Drying, spin-drying, and finally column chromatography separation and purification (petroleum ether/ethyl acetate =15 =1 to 30The rate was 70%).
1 H NMR(400MHz,CDCl 3 )δ7.77–7.63(m,3H),7.58(d,J＝7.2Hz,1H),7.50(d,J＝7.8Hz,2H),7.45–7.29(m,3H),6.99(d,J＝7.8Hz,1H),2.73(s,3H). 13 C NMR(101MHz,CDCl 3 )δ150.82,141.67,139.28,137.19,137.09,134.58,133.62,131.34,130.05,129.00,128.34,128.06,128.03,127.97,127.61,126.65,125.68,119.62,117.08,24.96.HRMS(ESI)m/z:[M+Na] + calcd for C 20 H 13 NNa 290.0940；found:290.0939.
Example 8
Synthesis method of phenanthrene and naphthocycloheptene compounds, namely synthesis method of 10-chloro-8-methylbenzo [4,5] cyclohepta [1,2,3-de ] naphthalene
To a 25mL reaction tube were added 4-chloro-1-iodo-2- (prop-1-en-2-yl) benzene (55.6 mg, 0.2mmol), 8-bromo-1-naphthoic acid (100.4 mg,0.4 mmol), allyl palladium chloride dimer (7.3mg, 0.02mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (19mg, 0.04mmol), and potassium carbonate (82.8mg, 0.6mmol) in this order. Then, 2 ml of N, N-dimethylformamide and trimethylacetic acid (4 mg, 0.04mmol) were added thereto, and argon gas was introduced under vacuum, and the mixture was sealed and stirred at room temperature for 15 minutes, and then placed in a constant temperature oil bath at 130 ℃ and stirred for 16 hours. After the reaction is completed, adding 5mL of water for quenching, extracting by ethyl acetate, washing by water for 3 times, combining organic phases, and adding anhydrous Na 2 SO 4 Dried, spun-dried and finally purified by column chromatography (petroleum ether/ethyl acetate = 30) to give a colorless liquid (40 mg, yield 72%).
1 H NMR(400MHz,CDCl 3 )δ7.63(dd,J＝6.4,2.9Hz,1H),7.59–7.50(m,1H),7.45–7.36(m,3H),7.34–7.22(m,2H),7.13(d,J＝7.1Hz,1H),6.99(d,J＝8.5Hz,1H),6.58(s,1H),2.30(d,J＝1.4Hz,3H). 13 C NMR(101MHz,CDCl 3 )δ140.36,139.32,138.07,137.91,136.09,136.03,134.64,134.37,133.91,133.39,129.42,128.95,128.72,128.06,126.62,126.35,126.16,125.77,24.54.HRMS(ESI)m/z:[M+H] + calcd for C 19 H 14 Cl 277.0779；found:277.0769.
It should be understood that the above-mentioned embodiments are only preferred embodiments of the present invention, and should not be limited by the present invention in any way, and it should be understood that any simple modifications, equivalent substitutions and improvements made by those skilled in the art can be made within the scope and spirit of the present invention without departing from the technical scheme and principle scope of the present invention.
Claims (10)
1. A method for synthesizing phenanthrene and naphthocycloheptene compounds is characterized in that: styrene derivatives and aryl formic acid derivatives are taken as raw materials, and under the action of a palladium catalyst, a ligand, alkali and an additive are added to react to prepare phenanthrene and naphthocycloheptene compounds; the aryl formic acid derivative is benzoic acid or naphthoic acid derivative.
2. The method of synthesizing phenanthrene and naphthocycloheptene compounds according to claim 1, wherein: the synthesis method comprises the following specific steps:
the first step is as follows: placing styrene derivatives, benzoic acid or naphthoic acid derivatives in a reaction tube, adding palladium catalyst, ligand, alkali, adding solvent, adding additive, ventilating, removing air from the reaction bottle, introducing argon or nitrogen, sealing,
stirring at room temperature for 15 min, and reacting in 110-150 deg.c oil bath for 10-16 hr;
the second step: detecting whether the reaction of the raw materials in the reaction system is complete by gas chromatography or thin layer chromatography, cooling the reaction flask to room temperature if the reaction is complete, adding 5mL of water for quenching, extracting with ethyl acetate, washing with water for 3 times, combining organic phases, and adding anhydrous Na 2 SO 4 Drying, spin-drying and separating by column chromatography to obtain phenanthrene and naphthocycloheptene compounds; the eluent in the column chromatography separation is petroleum ether according to the volume ratio: ethyl acetate = 10.
3. The method of synthesizing phenanthrene and naphthocycloheptene compounds according to claim 1, wherein: the reaction formula of the synthesis method is as follows:
in the formula, a group X is I, br, cl or trifluoromethanesulfonic group; the group Y is one of I, br and Cl; z is one of N, O and S; the group R includes, but is not limited to, methyl, methoxy, trifluoromethyl, nitro, ester group; r is 1 、R 2 Including but not limited to alkyl, ester, aryl; radical R 3 Including but not limited to methyl, methoxy, trifluoromethyl, halogen, nitro, ester groups.
4. The method of synthesizing phenanthrene and naphthocycloheptene compounds according to claim 1, wherein: the styrene derivatives are (E) -3- (2-iodophenyl) butyl-2-ethyl enoate, 4-fluoro-1-iodo-2- (prop-1-en-2-yl) benzene, 3- (2-iodophenyl) thiophene, 2-iodo-1, 1' -biphenyl, and (E) -3- (2-iodophenyl) butenenitrile; the benzoic acid is 2-bromo-4-nitrobenzoic acid, 3-bromofuran-2-carboxylic acid, 2-bromothiophene-3-carboxylic acid, 2-bromo-4, 5-dimethoxybenzoic acid; the naphthoic acid derivative is 8-bromo-1-naphthoic acid.
5. The method of synthesizing phenanthrene and naphthocycloheptene compounds according to claim 1, wherein: the palladium catalyst is tris (dibenzylidene) acetone dipalladium, palladium chloride, bis (acetonitrile) palladium chloride (II), allyl palladium chloride dimer, palladium acetate, bis (triphenylphosphine) palladium dichloride or tetra (triphenylphosphine) palladium.
6. The method of synthesizing phenanthrene and naphthocycloheptene compounds according to claim 1, wherein: the ligand is triphenylphosphine derivatives, bidentate phosphine ligands, buchwald ligand derivatives or carbene ligands, and 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl is preferred.
7. The method for synthesizing phenanthrene and naphthocycloheptene compounds as claimed in claim 1, wherein the base is one of potassium tert-butoxide, cesium carbonate, potassium carbonate and lithium tert-butoxide.
8. The method of synthesizing phenanthrene and naphthocycloheptenes compounds of claim 1, wherein: the additive is one of trimethyl acetic acid, tetrabutyl ammonium bromide, acetic acid, sodium phosphate and phosphoric acid.
9. The method for synthesizing phenanthrene and naphthocycloheptene compounds according to claim 1, characterized in that: the solvent is N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide or dioxane.
10. The method of synthesizing phenanthrene and naphthocycloheptene compounds according to claim 1, wherein the molar ratio of the palladium catalyst to the ligand is 1; the molar ratio of the palladium catalyst to the styrene derivative is 1; the molar ratio of the styrene derivative to the arylcarboxylic acid derivative is 1; the molar ratio of the base to the styrene derivative is 3; the molar ratio of the additive to the styrene derivative is 1.
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| WO2022168989A1 (en) * | 2021-02-08 | 2022-08-11 | ホヤ レンズ タイランド リミテッド | Photochromic compound, photochromic composition, photochromic article, and eyeglasses |
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| JP2020132549A (en) * | 2019-02-15 | 2020-08-31 | 東ソー株式会社 | Triphenylene compound and use therefor |
| WO2022168989A1 (en) * | 2021-02-08 | 2022-08-11 | ホヤ レンズ タイランド リミテッド | Photochromic compound, photochromic composition, photochromic article, and eyeglasses |
Non-Patent Citations (3)
| Title |
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| GUOMIN JIANG等: "Palladium-Catalyzed Sequential Vinyl C−H Activation/Dual Decarboxylation: Regioselective Synthesis of Phenanthrenes and Cyclohepta[1, 2, 3-de]naphthalenes", 《ORG. LETT.》, vol. 23, pages 9398 - 9402 * |
| MINGHAO ZHANG等: "α‐Bromoacrylic Acids as C1 Insertion Units for Palladium-Catalyzed Decarboxylative Synthesis of Diverse Dibenzofulvenes", 《ORG. LETT.》, vol. 23, pages 5744 - 5749 * |
| NING-HUI CHANG等: "Synthesis of Substituted Picenes through Pd-Catalyzed Cross-Coupling Reaction/ Annulation Sequences and Their Physicochemical Properties", 《ORG. LETT.》, vol. 15, no. 14, pages 3558 - 3561 * |
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