CN116515089A - Preparation method for synthesizing phenanthrenedione unit-containing conjugated polymer through direct functionalization of C-H bond - Google Patents
Preparation method for synthesizing phenanthrenedione unit-containing conjugated polymer through direct functionalization of C-H bond Download PDFInfo
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- CN116515089A CN116515089A CN202310426797.0A CN202310426797A CN116515089A CN 116515089 A CN116515089 A CN 116515089A CN 202310426797 A CN202310426797 A CN 202310426797A CN 116515089 A CN116515089 A CN 116515089A
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- Prior art keywords
- acid
- phenanthrenedione
- conjugated polymer
- units
- polymer containing
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 26
- SCOAVUHOIJMIBW-UHFFFAOYSA-N phenanthrene-1,2-dione Chemical group C1=CC=C2C(C=CC(C3=O)=O)=C3C=CC2=C1 SCOAVUHOIJMIBW-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000007306 functionalization reaction Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 13
- 239000003446 ligand Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000002585 base Substances 0.000 claims abstract description 4
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 46
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 37
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 28
- -1 palladium ions Chemical class 0.000 claims description 14
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 14
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 14
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 125000005549 heteroarylene group Chemical group 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000000944 Soxhlet extraction Methods 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 4
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 4
- 238000009388 chemical precipitation Methods 0.000 claims description 3
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical class [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 48
- 238000005481 NMR spectroscopy Methods 0.000 description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- 239000012043 crude product Substances 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 24
- 239000002904 solvent Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 13
- LTZIIBSPYWTOQV-UHFFFAOYSA-N 2,7-dibromophenanthrene-9,10-dione Chemical compound BrC1=CC=C2C3=CC=C(Br)C=C3C(=O)C(=O)C2=C1 LTZIIBSPYWTOQV-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 12
- 238000000605 extraction Methods 0.000 description 12
- 239000012074 organic phase Substances 0.000 description 12
- 238000004062 sedimentation Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000006467 substitution reaction Methods 0.000 description 10
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000002955 isolation Methods 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- JAYBIBLZTQMCAY-UHFFFAOYSA-N 3-decylthiophene Chemical compound CCCCCCCCCCC=1C=CSC=1 JAYBIBLZTQMCAY-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- RDLNFVAOYHPCCD-UHFFFAOYSA-N 3,4-bis[2-(2-methoxyethoxy)ethoxy]thiophene Chemical compound COCCOCCOC1=CSC=C1OCCOCCOC RDLNFVAOYHPCCD-UHFFFAOYSA-N 0.000 description 2
- LHYNYTDUZMSYNO-UHFFFAOYSA-N 3-[2-(2-methoxyethoxy)ethoxy]thiophene Chemical compound COCCOCCOC=1C=CSC=1 LHYNYTDUZMSYNO-UHFFFAOYSA-N 0.000 description 2
- JEDHEMYZURJGRQ-UHFFFAOYSA-N 3-hexylthiophene Chemical compound CCCCCCC=1C=CSC=1 JEDHEMYZURJGRQ-UHFFFAOYSA-N 0.000 description 2
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- OYSLMAQEMAJMCL-UHFFFAOYSA-N ethyl thiophene-3-carboxylate Chemical compound CCOC(=O)C=1C=CSC=1 OYSLMAQEMAJMCL-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 1
- KXSFECAJUBPPFE-UHFFFAOYSA-N 2,2':5',2''-terthiophene Chemical compound C1=CSC(C=2SC(=CC=2)C=2SC=CC=2)=C1 KXSFECAJUBPPFE-UHFFFAOYSA-N 0.000 description 1
- DNXOCFKTVLHUMU-UHFFFAOYSA-N 2-[4-(carboxymethoxy)phenoxy]acetic acid Chemical compound OC(=O)COC1=CC=C(OCC(O)=O)C=C1 DNXOCFKTVLHUMU-UHFFFAOYSA-N 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1412—Saturated aliphatic units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1428—Side-chains containing oxygen containing acyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/18—Definition of the polymer structure conjugated
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/22—Molecular weight
- C08G2261/226—Oligomers, i.e. up to 10 repeat units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/22—Molecular weight
- C08G2261/228—Polymers, i.e. more than 10 repeat units
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Abstract
The invention discloses a preparation method for synthesizing a conjugated polymer containing phenanthrenedione units through direct functionalization of a C-H bond, which relates to the technical field of organic synthesis and has the technical scheme that: reacting a compound of formula II with a compound of formula III in the presence of a palladium catalyst, an acid additive, a base additive, a catalyst ligand and an organic solvent to obtain a compound of formula I. Wherein the structural formula of the compounds of formulae I-III is as follows:the invention selects the compound of the formula II and the compound of the formula III to react in the presence of a palladium catalyst, an acid additive, an alkali additive, a catalyst ligand and an organic solvent to obtain the compound of the formula I.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method for synthesizing a conjugated polymer containing phenanthrenedione units through direct functionalization of a C-H bond.
Background
The conjugated polymer with the D-A (Donor-Accepter) structure has good electrical and optical characteristics, has outstanding contribution to battery and semiconductor manufacturing, has stronger light capturing capability, can be used for amplifying fluorescence sensing signals, and plays an increasingly important role in disease diagnosis, biological detection, photodynamic (active oxygen and photo-thermal effect) treatment of cancers and the like. The use of conjugated polymers in fluorescence imaging at the cellular and animal level has also gained great attention in recent years in the biomedical field. The direct functionalization reaction of C-H is an organic chemical reaction for efficiently constructing C-C bonds, which is widely paid attention in recent years, and has the characteristics of atom economy, high reaction efficiency and the like. In contrast to conventional metal catalyzed coupling polymerizations, the C-H direct functionalization reaction does not require the preparation of precursors for the coupling reaction, such as boron esters, alkenes and alkynes, and organometallic compounds, in advance. However, the conventional method for constructing a C-C bond by using this reaction still has a problem of poor regioselectivity. Increasing the selectivity of the direct functionalization of C-H is a great challenge to research in this field, and currently common solutions are either methods of introducing substituents at the β -position or other active reactive sites to eliminate reactive sites that are susceptible to side reactions or methods of introducing directing groups onto the substrate, which however limit the diversity of the substrate. Therefore, it is particularly important to find a simple and effective direct C-H functionalization reaction with good regioselectivity and wide substrate application.
Disclosure of Invention
The invention aims to provide a preparation method for synthesizing a phenanthrenedione unit-containing conjugated polymer through direct functionalization of a C-H bond, which has the advantages of simple preparation method, good reaction selectivity, high atom utilization rate and high yield.
The technical aim of the invention is realized by the following technical scheme: a preparation method for synthesizing a conjugated polymer containing phenanthrenedione units through direct functionalization of a C-H bond comprises the following steps:
reacting a compound of formula II with a compound of formula III in the presence of a palladium catalyst, an acid additive, a base additive, a catalyst ligand and an organic solvent to obtain a compound of formula I;
wherein the structural formula of the compounds of formulae I-III is as follows:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 Independently selected from hydrogen, halogen, substituted boric acid, borate or unsubstituted C 1～10 Alkyl, substituted or unsubstituted C 6～20 Aryl, substituted or unsubstituted C 1～10 Alkoxy, carboxyl, C 2～10 Any one of an ester group, a substituted or unsubstituted amino group, an acyl group, a cyano group, a nitro group, a hydroxyl group, or an azide group;is arylene, heteroarylene, or a bond; n is more than or equal to 5.
As preferable: n=5 to 150.
The catalyst coordination agent and the catalyst have linkage effect to participate in the reaction, so as to play roles of improving the reaction rate and reducing the reaction activation energy, and the acid additive and the alkali additive have the roles of balancing the acid-alkali environment of the system on one hand and participating in the reaction process on the other hand; the specific reaction formula is as follows:
the invention is further provided with: the saidIs C 3 ～C 16 Arylene or C of (2) 3 ～C 16 Heteroarylene group.
As preferable: each of the smallest heteroarylene structures in the heteroarylene is a mono-and/or poly-heteroarylene.
Further preferred is:is a thiophene, furan, thiazole, pyrrole, N-methylpyrrole, imidazole, N-methylimidazole, bithiophene, terthiophene, 2, 5-dithiophene-thiadiazole, 2, 5-difuran-thiadiazole, p-anisole or hydroquinone-O, O' -diacetic acid forming subunit.
The invention is further provided with: the catalyst ligand is a bidentate ligand which can coordinate with palladium ions. The added catalyst ligand and the catalyst have linkage effect to participate in the reaction, thereby playing roles of improving the reaction rate and reducing the reaction activation energy.
The invention is further provided with: the palladium catalyst is one or more of palladium acetate, palladium chloride, tetraphenylphosphine palladium and di (tri-tert-butylphosphine) palladium.
The invention is further provided with: the acid additive is one or more of hydrochloric acid, acetic acid, pivalic acid, phosphoric acid, formic acid, carbonic acid, hydrofluoric acid, cyanic acid, thiocyanic acid, nitrous acid and hypochlorous acid.
The invention is further provided with: the alkali additive is one or more of sodium hydroxide, sodium bicarbonate, sodium carbonate, potassium hydroxide, potassium carbonate, ammonia water, ammonium chloride, barium hydroxide and calcium hydroxide.
The invention is further provided with: the organic solvent is one or more of dichloroethane, dichloromethane, chloroform, tetrahydrofuran, dioxane, benzene, toluene, benzotrifluoride, acetonitrile, ethyl acetate, diethyl ether, methyl tert-butyl ether, n-hexane, cyclohexane and petroleum ether.
The invention is further provided with: the mol ratio of the compound of the formula II to the compound of the formula III is 1:1-1.5.
The invention is further provided with: the reaction time of the preparation method is 12-36 h, and the reaction temperature is 80-180 ℃.
The invention is further provided with: the conjugated polymer containing phenanthrenedione units is synthesized and then subjected to a purification step, wherein the purification step comprises concentration, chemical precipitation or Soxhlet extraction; concentrating, and evaporating the solvent by normal pressure distillation, reduced pressure distillation or rotary evaporation; the chemical precipitation adopts the solubility difference of the polymer in different solvents to purify and separate out the polymer in the reaction liquid; soxhlet extraction uses different solvents to extract and purify the solubility differences of polymer solids, and Soxhlet extraction is performed using a Soxhlet extractor.
The invention is further provided with: the compound of formula I is selected from at least one of the following structural formulas:
in summary, the invention has the following beneficial effects: the invention selects the compound of formula II and the compound of formula III to react in the presence of palladium catalyst, acid additive, alkali additive, catalyst ligand and organic solvent to obtain the compound of formula I, which has the advantages of simple preparation method, good reaction selectivity, high atom utilization rate and high yield, the catalyst ligand and the catalyst take linkage effect to participate in the reaction to play the roles of improving the reaction rate and reducing the reaction activation energy, the acid additive and the alkali additive have the roles of balancing the acid-base environment of the system on one hand and participating in the reaction process on the other hand, and the catalyst ligand and the catalyst are added to take linkage effect to participate in the reaction to play the roles of improving the reaction rate and reducing the reaction activation energy.
Drawings
FIG. 1 shows a compound (I-a) prepared in example 1 of the present invention 1 H NMR chart;
FIG. 2 shows the compound (I-a) prepared in example 1 of the present invention 13 C NMR chart;
FIG. 3 is a block diagram of an embodiment 2 of the present inventionThe compound (I-b) 1 H NMR chart;
FIG. 4 shows a compound (I-b) prepared in example 2 of the present invention 13 C NMR chart;
FIG. 5 shows the compound (I-c) prepared in example 3 of the present invention 1 H NMR chart;
FIG. 6 shows a compound (I-c) prepared in example 3 of the present invention 13 C NMR chart;
FIG. 7 shows a compound (I-d) prepared in example 4 of the present invention 1 H NMR chart;
FIG. 8 shows a compound (I-d) prepared in example 4 of the present invention 13 C NMR chart;
FIG. 9 shows a compound (I-e) prepared in example 5 of the present invention 1 H NMR chart;
FIG. 10 shows a compound (I-e) prepared in example 5 of the present invention 13 C NMR chart;
FIG. 11 shows a compound (I-f) prepared in example 6 of the present invention 1 H NMR chart;
FIG. 12 shows a compound (I-f) prepared in example 6 of the present invention 13 C NMR chart;
FIG. 13 is a reaction scheme of the present invention.
Detailed Description
The invention is described in further detail below with reference to fig. 1-13.
Example 1: a preparation method for synthesizing a conjugated polymer containing phenanthrenedione units through direct functionalization of C-H bonds comprises the following steps:
the method comprises the following steps: 2, 7-Dibromophenanthrene-9, 10-dione (1 mmol, 365 mg), palladium acetate (0.1 mmol,16 mg), potassium carbonate (0.1 mmol,13 mg), pivalic acid (0.1 mmol,10 mg) were weighed into a 25mL tube sealer, magnetons were added, and after three substitutions with high purity nitrogen, 3-decyl thiophene (1.2 mmol, 268 mg) was added to the tube sealer under nitrogen protection, 3mL toluene was screwed into the tube sealer, and the mixture was transferred into an oil bath at 100℃and stirred, and reacted overnight. After the reaction was completed, the tube was sealed and cooled to room temperature. Adding 5mL of distilled water into the system, and stirring; extraction with diethyl ether (5 mL. Times.3). Combining the organic phases, and removing the solvent by using a rotary evaporator to obtain a crude product; the crude product is poured into 300mL of ethanol for sedimentation, filtered and extracted by a Soxhlet extractor to obtain pure poly (2- (3-decyl-5-methylthiophene-2-yl) -7-methylphenanthrene-9, 10-dione) as yellow solid with the separation yield of 86%.
The second method is as follows: 2, 7-Dibromophenanthrene-9, 10-dione (1 mmol, 365 mg), palladium acetate (0.1 mmol,16 mg), potassium carbonate (0.1 mmol,13 mg), pivalic acid (0.1 mmol,10 mg) were weighed into a 25mL tube sealer, magnetons were added, and after three substitutions with high purity nitrogen, 3-decyl thiophene (1.2 mmol, 268 mg) was added to the tube sealer under nitrogen protection, 3mL toluene was screwed into the tube sealer, and the mixture was transferred into an oil bath at 160℃and stirred, and reacted overnight. After the reaction was completed, the tube was sealed and cooled to room temperature. Adding 5mL of distilled water into the system, and stirring; extraction with diethyl ether (5 mL. Times.3). Combining the organic phases, and removing the solvent by using a rotary evaporator to obtain a crude product; the crude product is poured into 300mL of ethanol for sedimentation, filtered and extracted by a Soxhlet extractor to obtain pure poly (2- (3-decyl-5-methylthiophene-2-yl) -7-methylphenanthrene-9, 10-dione) as yellow solid, and the isolation yield is 91%.
Structural identification of structural formula (I-a):
nuclear magnetic resonance data:
1 H NMR(400MHz,Chloroform-d)δ7.78(s,1H),7.70(s,1H),7.41(s,1H),6.92(d,J＝9.1Hz,1H),2.64–2.58(m,2H),1.63–1.59(m,2H),1.26(s,14H),0.86(s,3H)； 13 C NMR(101MHz,Chloroform-d)δ180.13(d,J＝6.3Hz),138.97,136.33,136.21,135.86,133.27(d,J＝25.6Hz),130.89,130.64,129.73,128.40,125.77,125.12,124.60,124.12,119.84,32.00,30.66,30.38,29.71,29.57,22.78,14.23.
the compounds of formula (I-a) 1 H NMR 13 The C NMR spectra are shown in FIG. 1 and FIG. 2, and the analysis result shows that the obtained target product is correct.
Example 2
Example 2 provides a method for preparing a conjugated polymer containing phenanthrenedione units, which has the following structural formula and preparation method:
the method comprises the following steps: 2, 7-Dibromophenanthrene-9, 10-dione (1 mmol, 365 mg), palladium acetate (0.1 mmol,16 mg), potassium carbonate (0.1 mmol,13 mg), pivalic acid (0.1 mmol,10 mg) were weighed into a 25mL tube sealer, magnetons were added, replaced three times with high purity nitrogen, 3-hexylthiophene (1.2 mmol,202 mg) was added to the tube sealer under nitrogen protection, 3mL toluene was screwed up to seal the tube, and the tube was moved into an oil bath at 100℃and stirred, and reacted overnight. After the reaction was completed, the tube was sealed and cooled to room temperature. Adding 5mL of distilled water into the system, and stirring; extraction with diethyl ether (5 mL. Times.3). Combining the organic phases, and removing the solvent by using a rotary evaporator to obtain a crude product; the crude product is poured into 300mL of ethanol for sedimentation, filtered and extracted by a Soxhlet extractor to obtain pure poly 2-methyl-7- (5-methyl-3-octyl thiophene-2-yl) phenanthrene-9, 10-dione as a yellow solid with the separation yield of 87%.
The second method is as follows: 2, 7-Dibromophenanthrene-9, 10-dione (1 mmol, 365 mg), palladium acetate (0.1 mmol,16 mg), potassium carbonate (0.1 mmol,13 mg), pivalic acid (0.1 mmol,10 mg) were weighed into a 25mL tube sealer, magnetons were added, replaced three times with high purity nitrogen, 3-hexylthiophene (1.2 mmol,202 mg) was added to the tube sealer under nitrogen protection, 3mL toluene was screwed up to seal the tube, and the tube was moved into an oil bath at 160℃and stirred, and reacted overnight. After the reaction was completed, the tube was sealed and cooled to room temperature. Adding 5mL of distilled water into the system, and stirring; extraction with diethyl ether (5 mL. Times.3). Combining the organic phases, and removing the solvent by using a rotary evaporator to obtain a crude product; the crude product is poured into 300mL of ethanol for sedimentation, filtered and extracted by a Soxhlet extractor to obtain pure poly 2-methyl-7- (5-methyl-3-octyl thiophene-2-yl) phenanthrene-9, 10-dione as yellow solid with the isolation yield of 93 percent.
Structural identification of structural formula (I-b):
nuclear magnetic resonance data:
1 H NMR(400MHz,Chloroform-d)δ7.92(s,1H),7.84–7.81(m,1H),7.71(s,1H),7.45(s,1H),7.07(s,1H),6.94(s,1H),2.62(s,1H),2.34(s,1H),1.68–1.59(m,2H),1.31(s,9H),0.87–0.83(m,3H)； 13 C NMR(101MHz,Chloroform-d)δ180.03,136.42–135.90(m),135.67(d,J＝8.6Hz),130.64(d,J＝28.0Hz),124.86–124.36(m),124.03,31.71,31.01,30.49,29.36,29.12.
the compounds of formula (I-b) 1 H NMR 13 The C NMR spectra are shown in FIG. 3 and FIG. 4, and the analysis result shows that the obtained target product is correct.
Example 3
Example 3 provides a method for preparing a conjugated polymer containing phenanthrenedione units, which has the following structural formula and preparation method:
the method comprises the following steps: 2, 7-Dibromophenanthrene-9, 10-dione (1 mmol, 365 mg), palladium acetate (0.1 mmol,16 mg), potassium carbonate (0.1 mmol,13 mg), pivalic acid (0.1 mmol,10 mg) were weighed into a 25mL tube sealer, magneton was added, and after three substitutions with high purity nitrogen, 3- (2- (2-methoxyethoxy) ethoxy) thiophene (1.2 mmol,295 mg) was added to the tube sealer under nitrogen protection, 3mL toluene was screwed up, and the tube sealer was moved into an oil bath at 100℃and stirred for overnight reaction. After the reaction was completed, the tube was sealed and cooled to room temperature. Adding 5mL of distilled water into the system, and stirring; extraction with diethyl ether (5 mL. Times.3). Combining the organic phases, and removing the solvent by using a rotary evaporator to obtain a crude product; the crude product is poured into 300mL of normal hexane for sedimentation, filtered and extracted by a Soxhlet extractor to obtain pure poly (2- (3- (2- (2-methoxyethoxy) ethoxy) -5-methylthiophene-2-yl) -7-methylphenanthrene-9, 10-dione) as a yellow solid, and the isolation yield is 90%.
The second method is as follows: 2, 7-Dibromophenanthrene-9, 10-dione (1 mmol, 365 mg), palladium acetate (0.1 mmol,16 mg), potassium carbonate (0.1 mmol,13 mg), pivalic acid (0.1 mmol,10 mg) were weighed into a 25mL tube sealer, magneton was added, and after three substitutions with high purity nitrogen, 3- (2- (2-methoxyethoxy) ethoxy) thiophene (1.2 mmol,295 mg) was added to the tube sealer under nitrogen protection, 3mL toluene was screwed up, and the tube sealer was moved into an oil bath at 160℃and stirred for overnight reaction. After the reaction was completed, the tube was sealed and cooled to room temperature. Adding 5mL of distilled water into the system, and stirring; extraction with diethyl ether (5 mL. Times.3). Combining the organic phases, and removing the solvent by using a rotary evaporator to obtain a crude product; the crude product is poured into 300mL of normal hexane for sedimentation, filtered and extracted by a Soxhlet extractor to obtain pure poly (2- (3- (2- (2-methoxyethoxy) ethoxy) -5-methylthiophene-2-yl) -7-methylphenanthrene-9, 10-dione) as a yellow solid, and the isolation yield is 94%.
Structural identification of structural formula (I-c):
nuclear magnetic resonance data:
1 H NMR(400MHz,Chloroform-d)δ8.38(s,1H),8.13(s,1H),7.97(d,J＝8.2Hz,1H),7.83–7.71(m,2H),7.17(s,1H),6.80(d,J＝37.2Hz,1H),4.43(s,5H),3.89(s,1H),3.81–3.79(m,1H),3.70–3.62(m,4H),3.52(s,1H),3.34(d,J＝15.4Hz,3H)； 13 C NMR(101MHz,Chloroform-d)δ138.89,133.42,131.98,130.93,127.96,125.86(d,J＝13.3Hz),124.85,124.53,124.28,119.77,118.42,72.05,71.12,70.86,70.62,70.08,59.16.
the compounds of the formula (I-c) 1 H NMR 13 The C NMR spectra are shown in FIG. 5 and FIG. 6, and the analysis result shows that the obtained target product is correct.
Example 4
Example 4 provides a method for preparing a conjugated polymer containing phenanthrenedione units, which has the following structural formula and preparation method:
the method comprises the following steps: 2, 7-Dibromophenanthrene-9, 10-dione (1 mmol, 365 mg), palladium acetate (0.1 mmol,16 mg), potassium carbonate (0.1 mmol,13 mg), pivalic acid (0.1 mmol,10 mg) were weighed into a 25mL tube sealer, magnetons were added, and after three substitutions with high purity nitrogen, 3-decyl thiophene [3,2-b ] thiophene (1.2 mmol,336 mg), 3mL toluene were added to the tube sealer under nitrogen protection, the tube sealer was screwed, and it was transferred into an oil bath pot at 100℃and stirred, and reacted overnight. After the reaction was completed, the tube was sealed and cooled to room temperature. Adding 5mL of distilled water into the system, and stirring; extraction with diethyl ether (5 mL. Times.3). Combining the organic phases, and removing the solvent by using a rotary evaporator to obtain a crude product; the crude product is poured into 300mL of ethanol for sedimentation, filtered and extracted by a Soxhlet extractor to obtain pure poly (2- (3-decyl-5-methyldienyl [3,2-b ] thiophene-2-yl) -7-methylphenanthrene anthracene-9, 10-dione) as a yellow solid, and the isolation yield is 90%.
The second method is as follows: 2, 7-Dibromophenanthrene-9, 10-dione (1 mmol, 365 mg), palladium acetate (0.1 mmol,16 mg), potassium carbonate (0.1 mmol,13 mg), pivalic acid (0.1 mmol,10 mg) were weighed into a 25mL tube sealer, magnetons were added, and after three substitutions with high purity nitrogen, 3-decyl thiophene [3,2-b ] thiophene (1.2 mmol,336 mg), 3mL toluene was added to the tube sealer under nitrogen protection, the tube sealer was screwed, and it was transferred into an oil bath pot at 160℃and stirred, and reacted overnight. After the reaction was completed, the tube was sealed and cooled to room temperature. Adding 5mL of distilled water into the system, and stirring; extraction with diethyl ether (5 mL. Times.3). Combining the organic phases, and removing the solvent by using a rotary evaporator to obtain a crude product; the crude product is poured into 300mL of ethanol for sedimentation, filtered and extracted by a Soxhlet extractor to obtain pure poly (2- (3-decyl-5-methyldienyl [3,2-b ] thiophene-2-yl) -7-methylphenanthrene anthracene-9, 10-dione) as yellow solid, and the isolation yield is 93%.
Structural identification of structural formula (I-d):
nuclear magnetic resonance data:
1 H NMR(400MHz,Chloroform-d)δ7.90–7.76(m,1H),7.63(s,1H),7.54(s,1H),7.38(s,1H),7.33(s,1H),7.23(s,1H),6.97(s,1H),2.78–2.53(m,2H),1.79–1.72(m,2H),1.27(s,16H),0.89(s,3H)； 13 C NMR(101MHz,Chloroform-d)δ179.91(d,J＝45.3Hz),140.02,136.12(d,J＝19.9Hz),135.46,131.03,130.78,128.52,126.58,125.04–124.19(m),123.71,122.10,32.04,29.50,14.26.
the compounds of the formula (I-d) 1 H NMR 13 The C NMR spectra are shown in FIG. 7 and FIG. 8, and the analysis result shows that the obtained target product is correct.
Example 5
Example 5 provides a method for preparing a conjugated polymer containing phenanthrenedione units, which has the following structural formula and preparation method:
the method comprises the following steps: 2, 7-Dibromophenanthrene-9, 10-dione (1 mmol, 365 mg), palladium acetate (0.1 mmol,16 mg), potassium carbonate (0.1 mmol,13 mg), pivalic acid (0.1 mmol,10 mg) were weighed into a 25mL tube sealer, magnetons were added, and after three substitutions with high purity nitrogen, thiophene-3-carboxylic acid ethyl ester (1.2 mmol,187 mg) was added to the tube sealer under nitrogen protection, 3mL toluene was screwed into the tube sealer, and the tube sealer was moved into an oil bath at 100℃and stirred, and reacted overnight. After the reaction was completed, the tube was sealed and cooled to room temperature. Adding 5mL of distilled water into the system, and stirring; extraction with diethyl ether (5 mL. Times.3). Combining the organic phases, and removing the solvent by using a rotary evaporator to obtain a crude product; the crude product is poured into 300mL of ethanol for sedimentation, filtered and extracted by a Soxhlet extractor to obtain pure poly (5-methyl-2- (7-methyl-9, 10-dioxo-9, 10-dihydrophenanthrene-2-yl) thiophene-3-carboxylic acid ethyl ester as yellow solid, and the separation yield is 88%.
The second method is as follows: 2, 7-Dibromophenanthrene-9, 10-dione (1 mmol, 365 mg), palladium acetate (0.1 mmol,16 mg), potassium carbonate (0.1 mmol,13 mg), pivalic acid (0.1 mmol,10 mg) were weighed into a 25mL tube sealer, magnetons were added, and after three substitutions with high purity nitrogen, thiophene-3-carboxylic acid ethyl ester (1.2 mmol,187 mg) was added to the tube sealer under nitrogen protection, 3mL toluene was screwed into the tube sealer, and the tube sealer was moved into an oil bath at 160℃and stirred, and reacted overnight. After the reaction was completed, the tube was sealed and cooled to room temperature. Adding 5mL of distilled water into the system, and stirring; extraction with diethyl ether (5 mL. Times.3). Combining the organic phases, and removing the solvent by using a rotary evaporator to obtain a crude product; the crude product is poured into 300mL of ethanol for sedimentation, filtered and extracted by a Soxhlet extractor to obtain pure poly (5-methyl-2- (7-methyl-9, 10-dioxo-9, 10-dihydrophenanthrene-2-yl) thiophene-3-carboxylic acid ethyl ester as yellow solid, and the separation yield is 90%.
Structural identification of structural formula (I-e):
nuclear magnetic resonance data:
1 H NMR(400MHz,Chloroform-d)δ8.23(s,1H),8.10(d,J＝14.9Hz,1H),7.96(s,1H),7.85(s,1H),7.77(s,1H),7.52(d,J＝18.0Hz,1H),7.28(d,J＝19.4Hz,1H),4.40–4.19(m,2H),1.37–1.21(m,3H)； 13 C NMR(101MHz,Chloroform-d)δ179.75,163.02,139.05,137.60,136.31,133.20,131.89,130.51,126.03,125.16,124.23–124.07(m),61.06,27.13,14.27.
compounds of formula (I-e) 1 H NMR 13 The C NMR spectra are shown in FIG. 9 and FIG. 10, and the analysis result shows that the obtained target product is correct.
Example 6
Example 6 provides a method for preparing a conjugated polymer containing phenanthrenedione units, which has the following structural formula and preparation method:
the method comprises the following steps: 2, 7-Dibromophenanthrene-9, 10-dione (1 mmol, 365 mg), palladium acetate (0.1 mmol,16 mg), potassium carbonate (0.1 mmol,13 mg), pivalic acid (0.1 mmol,10 mg) were weighed into a 25mL tube sealer, magnetons were added, and after three substitutions with high purity nitrogen, 3, 4-bis (2- (2-methoxyethoxy) ethoxy) thiophene (1.2 mmol,320 mg) was added to the tube sealer under nitrogen protection, 3mL toluene was screwed up, and the tube sealer was moved into an oil bath at 100℃and stirred, and reacted overnight. After the reaction was completed, the tube was sealed and cooled to room temperature. Adding 5mL of distilled water into the system, and stirring; extraction with diethyl ether (5 mL. Times.3). Combining the organic phases, and removing the solvent by using a rotary evaporator to obtain a crude product; the crude product is poured into 300mL of normal hexane for sedimentation, and is filtered and extracted by a Soxhlet extractor to obtain pure poly (2- (3, 4-bis (2- (2-methoxyethoxy) ethoxy) -5-methylthiophene-2-yl) -7-methylphenanthrene-9, 10-dione, yellow solid, and the separation yield is 86%.
The second method is as follows: 2, 7-Dibromophenanthrene-9, 10-dione (1 mmol, 365 mg), palladium acetate (0.1 mmol,16 mg), potassium carbonate (0.1 mmol,13 mg), pivalic acid (0.1 mmol,10 mg) were weighed into a 25mL tube sealer, magnetons were added, and after three substitutions with high purity nitrogen, 3, 4-bis (2- (2-methoxyethoxy) ethoxy) thiophene (1.2 mmol,320 mg) was added to the tube sealer under nitrogen protection, 3mL toluene was screwed up, and the tube sealer was moved into an oil bath at 160℃and stirred, and reacted overnight. After the reaction was completed, the tube was sealed and cooled to room temperature. Adding 5mL of distilled water into the system, and stirring; extraction with diethyl ether (5 mL. Times.3). Combining the organic phases, and removing the solvent by using a rotary evaporator to obtain a crude product; the crude product is poured into 300mL of normal hexane for sedimentation, and is filtered and extracted by a Soxhlet extractor to obtain pure poly (2- (3, 4-bis (2- (2-methoxyethoxy) ethoxy) -5-methylthiophene-2-yl) -7-methylphenanthrene-9, 10-dione, yellow solid, and the separation yield is 92%.
Structural identification of structural formula (I-f):
nuclear magnetic resonance data:
1 H NMR(400MHz,Chloroform-d)δ8.57(d,J＝5.4Hz,2H),8.47–8.44(m,2H),8.20(s,2H),3.97–3.91(m,4H),2.99–2.94(m,5H),2.48(s,8H),2.10(s,6H)； 13 C NMR(101MHz,Chloroform-d)δ179.57(d,J＝15.6Hz),139.10(d,J＝20.9Hz),132.95,127.30(d,J＝10.8Hz),125.83,124.15,121.53,112.51,71.98,70.65,59.10.
the compounds of formula (I-f) 1 H NMR 13 The C NMR spectra are shown in FIG. 11 and FIG. 12, and the analysis result shows that the obtained target product is correct.
The present embodiment is only for explanation of the present invention and is not to be construed as limiting the present invention, and modifications to the present embodiment, which may not creatively contribute to the present invention as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present invention.
Claims (10)
1. A preparation method for synthesizing a conjugated polymer containing phenanthrenedione units through direct functionalization of C-H bonds is characterized by comprising the following steps: the method comprises the following steps:
reacting a compound of formula II with a compound of formula III in the presence of a palladium catalyst, an acid additive, a base additive, a catalyst ligand and an organic solvent to obtain a compound of formula I;
wherein the structural formula of the compounds of formulae I-III is as follows:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 Independently selected from hydrogen, halogen, substituted boric acid, borate or unsubstituted C 1～10 Alkyl, substituted or unsubstituted C 6～20 Aryl, substituted or unsubstituted C 1～10 Alkoxy, carboxyl, C 2～10 Any one of an ester group, a substituted or unsubstituted amino group, an acyl group, a cyano group, a nitro group, a hydroxyl group, or an azide group;is arylene, heteroarylene, or a bond; n is more than or equal to 5.
2. The method for preparing the conjugated polymer containing phenanthrenedione units by direct functionalization through C-H bonds according to claim 1, wherein the method comprises the following steps: the saidIs C 3 ～C 16 Arylene or C of (2) 3 ～C 16 Heteroarylene group.
3. The method for preparing the conjugated polymer containing phenanthrenedione units by direct functionalization through C-H bonds according to claim 1, wherein the method comprises the following steps: the catalyst ligand is a bidentate ligand which can coordinate with palladium ions.
4. The method for preparing the conjugated polymer containing phenanthrenedione units by direct functionalization through C-H bonds according to claim 1, wherein the method comprises the following steps: the palladium catalyst is one or more of palladium acetate, palladium chloride, tetraphenylphosphine palladium and di (tri-tert-butylphosphine) palladium.
5. The method for preparing the conjugated polymer containing phenanthrenedione units by direct functionalization through C-H bonds according to claim 1, wherein the method comprises the following steps: the acid additive is one or more of hydrochloric acid, acetic acid, pivalic acid, phosphoric acid, formic acid, carbonic acid, hydrofluoric acid, cyanic acid, thiocyanic acid, nitrous acid and hypochlorous acid.
6. The method for preparing the conjugated polymer containing phenanthrenedione units by direct functionalization through C-H bonds according to claim 1, wherein the method comprises the following steps: the alkali additive is one or more of sodium hydroxide, sodium bicarbonate, sodium carbonate, potassium hydroxide, potassium carbonate, ammonia water, ammonium chloride, barium hydroxide and calcium hydroxide.
7. The method for preparing the conjugated polymer containing phenanthrenedione units by direct functionalization through C-H bonds according to claim 1, wherein the method comprises the following steps: the organic solvent is one or more of dichloroethane, dichloromethane, chloroform, tetrahydrofuran, dioxane, benzene, toluene, benzotrifluoride, acetonitrile, ethyl acetate, diethyl ether, methyl tert-butyl ether, n-hexane, cyclohexane and petroleum ether.
8. The method for preparing the conjugated polymer containing phenanthrenedione units by direct functionalization through C-H bonds according to claim 1, wherein the method comprises the following steps: the mol ratio of the compound of the formula II to the compound of the formula III is 1:1-1.5.
9. The method for preparing the conjugated polymer containing phenanthrenedione units by direct functionalization through C-H bonds according to claim 1, wherein the method comprises the following steps: the reaction time of the preparation method is 12-36 h, and the reaction temperature is 80-180 ℃.
10. The method for preparing the conjugated polymer containing phenanthrenedione units by direct functionalization through C-H bonds according to claim 1, wherein the method comprises the following steps: the conjugated polymer containing phenanthrenedione units is synthesized and then subjected to a purification step, wherein the purification step comprises concentration, chemical precipitation or Soxhlet extraction.
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