WO2009021639A1 - Verfahren zur herstellung von thiophenoligomeren - Google Patents
Verfahren zur herstellung von thiophenoligomeren Download PDFInfo
- Publication number
- WO2009021639A1 WO2009021639A1 PCT/EP2008/006335 EP2008006335W WO2009021639A1 WO 2009021639 A1 WO2009021639 A1 WO 2009021639A1 EP 2008006335 W EP2008006335 W EP 2008006335W WO 2009021639 A1 WO2009021639 A1 WO 2009021639A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- nickel
- group
- thiophene
- ylene
- mol
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 39
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 title claims description 15
- 229930192474 thiophene Natural products 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- -1 preferably Cl Chemical class 0.000 claims description 59
- 150000001875 compounds Chemical class 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- 150000003577 thiophenes Chemical class 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 125000005549 heteroarylene group Chemical group 0.000 claims description 5
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 claims description 5
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 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 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
- 239000011701 zinc Substances 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 125000006588 heterocycloalkylene group Chemical group 0.000 claims description 3
- 235000021317 phosphate Nutrition 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- 125000002577 pseudohalo group Chemical group 0.000 claims description 3
- 125000001174 sulfone group Chemical group 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 claims description 2
- JTBOBRXTBCQEDC-UHFFFAOYSA-N 1,3-bis(1-adamantyl)imidazolidin-1-ium;chloride Chemical compound [Cl-].C1C(C2)CC(C3)CC2CC13[NH+]1CCN(C23CC4CC(CC(C4)C2)C3)C1 JTBOBRXTBCQEDC-UHFFFAOYSA-N 0.000 claims description 2
- HOOKQVAAJVEFHV-UHFFFAOYSA-N 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-1-ium;chloride Chemical compound [Cl-].CC1=CC(C)=CC(C)=C1N1C[NH+](C=2C(=CC(C)=CC=2C)C)CC1 HOOKQVAAJVEFHV-UHFFFAOYSA-N 0.000 claims description 2
- VMSBCZLYJOAVIG-UHFFFAOYSA-N 3,4-dichloro-2-pyridin-2-ylpyridine;nickel Chemical compound [Ni].ClC1=CC=NC(C=2N=CC=CC=2)=C1Cl VMSBCZLYJOAVIG-UHFFFAOYSA-N 0.000 claims description 2
- 229930194542 Keto Natural products 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 2
- 125000000262 haloalkenyl group Chemical group 0.000 claims description 2
- 125000000232 haloalkynyl group Chemical group 0.000 claims description 2
- 125000003106 haloaryl group Chemical group 0.000 claims description 2
- 125000005216 haloheteroaryl group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000000468 ketone group Chemical group 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 2
- QEKXARSPUFVXIX-UHFFFAOYSA-L nickel(2+);triphenylphosphane;dibromide Chemical compound [Ni+2].[Br-].[Br-].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 QEKXARSPUFVXIX-UHFFFAOYSA-L 0.000 claims description 2
- KFBKRCXOTTUAFS-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].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 KFBKRCXOTTUAFS-UHFFFAOYSA-N 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 125000005353 silylalkyl group Chemical group 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- SRDMJILINNZFLI-UHFFFAOYSA-L CC.Cl[Ni]Cl Chemical compound CC.Cl[Ni]Cl SRDMJILINNZFLI-UHFFFAOYSA-L 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- VBXJWRFADSRGDI-UHFFFAOYSA-L dichloronickel propane Chemical compound CCC.Cl[Ni]Cl VBXJWRFADSRGDI-UHFFFAOYSA-L 0.000 claims 1
- 150000002431 hydrogen Chemical group 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 230000007246 mechanism Effects 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 150000002902 organometallic compounds Chemical class 0.000 description 4
- 238000010626 work up procedure Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005442 molecular electronic Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 125000000160 oxazolidinyl group Chemical group 0.000 description 2
- 125000003386 piperidinyl group Chemical group 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 125000003363 1,3,5-triazinyl group Chemical group N1=C(N=CN=C1)* 0.000 description 1
- NREOZXRFNFCTHM-UHFFFAOYSA-N 1,3-bis[2,6-di(propan-2-yl)phenyl]imidazolidin-1-ium;chloride Chemical compound [Cl-].CC(C)C1=CC=CC(C(C)C)=C1N1C[NH+](C=2C(=CC=CC=2C(C)C)C(C)C)CC1 NREOZXRFNFCTHM-UHFFFAOYSA-N 0.000 description 1
- KDCBVVQAMMXRFB-UHFFFAOYSA-N 1,4,7,10,13-pentazacyclopentadecane Chemical compound C1CNCCNCCNCCNCCN1 KDCBVVQAMMXRFB-UHFFFAOYSA-N 0.000 description 1
- QBPPRVHXOZRESW-UHFFFAOYSA-N 1,4,7,10-tetraazacyclododecane Chemical class C1CNCCNCCNCCN1 QBPPRVHXOZRESW-UHFFFAOYSA-N 0.000 description 1
- CIBAIKDMTBNPNQ-UHFFFAOYSA-N 1,4,7-thiadiazonane Chemical compound C1CNCCSCCN1 CIBAIKDMTBNPNQ-UHFFFAOYSA-N 0.000 description 1
- ITWBWJFEJCHKSN-UHFFFAOYSA-N 1,4,7-triazonane Chemical compound C1CNCCNCCN1 ITWBWJFEJCHKSN-UHFFFAOYSA-N 0.000 description 1
- PQNPKQVPJAHPSB-UHFFFAOYSA-N 1,4,7-trithionane Chemical compound C1CSCCSCCS1 PQNPKQVPJAHPSB-UHFFFAOYSA-N 0.000 description 1
- MDAXKAUIABOHTD-UHFFFAOYSA-N 1,4,8,11-tetraazacyclotetradecane Chemical compound C1CNCCNCCCNCCNC1 MDAXKAUIABOHTD-UHFFFAOYSA-N 0.000 description 1
- 125000005940 1,4-dioxanyl group Chemical group 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 1
- NSYFIAVPXHGRSH-UHFFFAOYSA-N 2,5-dibromo-3-hexylthiophene Chemical compound CCCCCCC=1C=C(Br)SC=1Br NSYFIAVPXHGRSH-UHFFFAOYSA-N 0.000 description 1
- JEDHEMYZURJGRQ-UHFFFAOYSA-N 3-hexylthiophene Chemical compound CCCCCCC=1C=CSC=1 JEDHEMYZURJGRQ-UHFFFAOYSA-N 0.000 description 1
- 125000004648 C2-C8 alkenyl group Chemical group 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical class CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- GROYGRZSTCDMEM-UHFFFAOYSA-L dichloronickel 2-diphenylphosphanylpropan-2-yl(diphenyl)phosphane Chemical compound [Ni](Cl)Cl.C1(=CC=CC=C1)P(C1=CC=CC=C1)C(C)(C)P(C1=CC=CC=C1)C1=CC=CC=C1 GROYGRZSTCDMEM-UHFFFAOYSA-L 0.000 description 1
- WDQZIRSDNFWMAE-UHFFFAOYSA-L dichloronickel;1-diphenylphosphanylethyl(diphenyl)phosphane Chemical compound Cl[Ni]Cl.C=1C=CC=CC=1P(C=1C=CC=CC=1)C(C)P(C=1C=CC=CC=1)C1=CC=CC=C1 WDQZIRSDNFWMAE-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 238000006894 reductive elimination reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000003507 tetrahydrothiofenyl group Chemical group 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical class C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 150000003751 zinc Chemical class 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
Definitions
- the present invention relates to a process for the preparation of oligothiophenes.
- OFETs Simple structuring and integration of OFETs into integrated organic semiconductor circuits makes possible low-cost solutions for smart cards or price tags, which hitherto can not be realized with the aid of silicon technology due to the price and lack of flexibility of the silicon components. Also, OFETs could be used as switching elements in large area flexible matrix displays.
- All compounds have continuous conjugated units and are subdivided into conjugated polymers and conjugated oligomers depending on their molecular weight and structure.
- a distinction is usually oligomers of polymers in that oligomers usually have a narrow molecular weight distribution and a molecular weight to about 10,000 g / mol (Da), whereas polymers usually have a correspondingly higher molecular weight and a broader molecular weight distribution.
- Da g / mol
- polymers usually have a correspondingly higher molecular weight and a broader molecular weight distribution.
- it makes more sense to differentiate on the basis of the number of repeating units since a monomer unit can certainly reach a molecular weight of 300 to 500 g / mol, as for example in (3,3 "-dihexyl) -quarterthiophene.
- the most important semiconducting poly- or oligomers include the oligothiophenes whose monomer unit is e.g. 3-hexylthiophene.
- oligothiophenes whose monomer unit is e.g. 3-hexylthiophene.
- the polymerization in a catalytic cycle is started by the Kumada method (cross-coupling metathesis reaction) using a nickel catalyst (preferably Ni (dppp) Cl 2 ).
- the polymers are generally obtained via Soxhlet purifications of the necessary purity.
- the chain length largely depends on the number of active catalyst centers and the amount of monomer, the molecular weight being broadened by statistical distribution of the monomer onto the growing chains.
- the growing chain is predominantly coordinated to a nickel center.
- the object of the present invention was therefore to provide a method which at least partially overcomes the disadvantages mentioned and enables the production, in particular the large-scale production of oligothiophenes with the lowest possible catalyst concentration.
- a method for the polymerization of at least one thiophene derivative having at least two leaving groups to oligomers is proposed, wherein the polymerization by means of a thiophene-organometallic compound and at least one catalyst, characterized in that the method at a catalyst concentration (based on the molar amount of the thiophene derivative used) of> 0.01 - ⁇ 0.95 mol% and a temperature of> 105 ° C - ⁇ 155 ° C is performed.
- oligomers means in particular thiophene derivatives having a chain length of chain lengths with n> 2 to ⁇ 20 monomer units, preferably from> 3 to ⁇ 12, more preferably from> 4 to ⁇ 10 and most preferably from> 5 to ⁇ 8.
- the molecular weight of the oligothiophenes obtainable by the process is from the molecular weight of the monomeric thiophene derivative from> 800 to ⁇ 6000, preferably from> 900 to ⁇ 5000, more preferably from> 1000 to ⁇ 3000, most preferably from> 1000 to ⁇ 2500 ,
- the process at a catalyst concentration (based on the molar amount of the thiophene derivative used) of> 0.05 - ⁇ 0.85 mol%, preferably> 0.15 - ⁇ 0.75 mol%, further preferably of> 0 , 25 - ⁇ 0.55 mol%, and most preferably> 0.35 - ⁇ 0.45 mol%.
- the process proceeds at a temperature of> 110 ° C - ⁇ 150 ° C, more preferably> 115 ° C - ⁇ 145 ° C, and most preferably> 120 ° C - ⁇ 140 ° C.
- the reaction takes place at elevated pressures, preferably at> 1-30 bar, in particular at> 2-15 bar and particularly preferably in the range of> 4-10 bar.
- thiophene derivative is understood to mean both mono-, di- or polysubstituted and unsubstituted thiophene.
- thiophene derivatives which are alkyl-substituted, particularly preferably 3-alkyl-substituted thiophene derivatives.
- the term "leaving group” is understood in particular to mean any group which is protected by means of a metal or an organometallic compound Forming a thiophene-organometallic compound is able to react.
- Particularly preferred leaving groups are halogens, sulfates, sulfonates and diazo groups.
- the at least one thiophene derivative contains at least two different leaving groups. This may be useful for achieving better regioselectivity of the polymer in many applications of the present invention.
- the leaving groups of the at least one thiophene derivative are identical.
- thiophene-organometallic compound is understood in particular to mean a compound in which at least one metal-carbon bond to one of the carbon atoms on the thiophene heterocycle is present.
- organometallic compound is understood in particular to mean an alkylmetalorganic compound.
- Preferred metals within the at least one thiophene-organometallic compound are tin, magnesium, zinc and boron. It should be understood that within the present invention, boron is also considered to be a metal. In the event that the process according to the invention proceeds with the participation of boron, the leaving group is preferably selected from the group comprising MgBr, MgI, MgCl, Li or mixtures thereof.
- organometallic compounds which are used in the process according to the invention are preferably organometallic Sn compounds, for example tributyltin chloride, or Zn compounds, for example activated zinc (Zn *) or borane compounds, for example B ( OMe) 3 or B (OH) 3 , or Mg compounds, particularly preferably organometallic Mg compounds, particularly preferably Grignard compounds of the formula R-Mg-X,
- R is alkyl, very particularly preferably C2-alkyl
- X is halogen, more preferably Cl, Br or I, and most preferably Br.
- the term "catalyst” is understood in particular to mean a catalytically active metal compound.
- the at least one catalyst contains nickel and / or palladium. This has been found to be favorable in many application examples of the present invention.
- the at least one catalyst particularly preferably contains at least one compound selected from the group of nickel and palladium catalysts with ligands selected from the group consisting of tri-tert-butylphosphine, triadamantylphosphine, 1,3-bis (2,4,6-trimethylphenyl) imidazolidinium chloride, 1,3-bis (2,6-diisopropylphenyl) imidazolidinium chloride or 1,3-diadamantylimidazolidinium chloride or mixtures thereof; To-
- alkyl linear and branched C 1 -C 8 -alkyls
- long-chain alkyls linear and branched C5-C20 alkyls
- alkenyl C2-C8 alkenyl
- cycloalkyl C3-C8-cycloalkyl
- alkoxy Cl-C6-alkoxy
- Alkylene selected from the group comprising:
- methylene 1, 1 -ethylene; 1,2-ethylene; 1,1-propylidene; 1,2-propylene; 1,3-propylene; 2,2-propylidenes; butan-2-ol-l, 4-diyl; propan-2-ol-l, 3-diyl; 1, 4-butylenes; cyclohexane-l, l-diyl; cyclohexane-l, 2-diyl; cyclohexane-1,3-diyl; cyclohexane-l, 4-diyl; cyclopentane-l, l-diyl; cyclopentane-l, 2-diyl; and cyclopentane-1,3-diyl, aryl: selected from aromatics having a molecular weight below 300Da.
- arylenes selected from the group comprising: 1,2-phenylenes; 1,3-phenylenes; 1, 4-phenylene; 1,2-naphthalenylenes; 1,3-naphtalenylene; 1,4-naphthalenylenes; 2,3-naphtalenylene; 1-hydroxy-2,3-phenylene; 1-hydroxy-2,4-phenylene; 1-hydroxy-2,5-phenylene; and 1-hydroxy-2,6-phenylene,
- heteroaryl selected from the group comprising: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; thiophenyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be linked to the compound via any atom in the ring of the selected heteroaryl.
- heteroarylenes selected from the group comprising: pyridinediyl; quinolindiyl; pyrazodiyl; pyrazoldiyl; triazolediyl; pyrazinediyl, thiophenediyl; and imidazolediyl, wherein the heteroarylene functions as a bridge in the compound via any atom in the ring of the selected heteroaryl, especially preferred are: pyridine-2,3-diyl; pyridin-2,4-diyl; pyridin-2,5-diyl; pyridine-2,6-diyl; pyridine-3,4-diyl; pyridine-3,5-diyl; quinolin-2,3-diyl; quinolin-2,4-diyl; quinoline-2, 8-diyl; isoquinoline-1, 3-diyl; isoquinoline-l, 4-diyl; pyrazole-1, 3-di
- heterocycloalkylenes selected from the group comprising: piperidin-1,2-ylenes; piperidin-2,6-ylene; piperidin-4,4-ylidene; l, 4-piperazin-l, 4-ylene; l, 4-piperazin-2,3-ylene; 1, 4-piperazine-2,5-ylene; 1, 4-piperazine-2,6-ylene; 1, 4-piperazine-1,2-ylene; 1,4-piperazine-1,3-ethylene; 1, 4-piperazine-1, 4-ylene; tetrahydrothiophen-2,5-ylene; tetrahydrothiophen-3,4-ylene; tetrahydrothiophen-2,3-ylene; tetrahydrofuran-2,5-ylene; tetrahydrofuran-3,4-ylene; tetrahydrofuran-2,3-ylene; pyrrolidine-2,5-ylene; pyrrolidin-3,4-ylene; pyrrolidin-2
- heterocycloalkyl selected from the group comprising: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1,4-piperazinyl; tetrahydrothiophenyl; tetrahydrofuranyl; 1,4,7-triazacyclononanyl; 1,4,8,11-tetraazacyclotetradecanyl; 1,4,7,10,13-pentaazacyclopentadecanyl; l, 4-diaza-7-thiacyclononanyl; 1,4-diaza-7-oxa-cyclononanyl; 1,4,7,10-tetraazacyclododecanyl; 1, 4-dioxanyl; 1,4,7-trithiacyclononanyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl may be linked to the compound via any atom in the
- halogen selected from the group comprising: F; Cl; Br and I,
- haloalkyl selected from the group consisting of mono-, di-, tri-, poly- and perhalogenated linear and branched C 1 -C 8 -alkyl,
- pseudohalogen selected from the group consisting of -CN, -SCN, -OCN, N3, -CNO, -SeCN.
- alkyl linear and branched C 1 -C 6 -alkyl
- long-chain alkyls linear and branched C5-C10 alkyl, preferably C6-C8 alkyl,
- alkenyl C3-C6 alkenyl
- cycloalkyl C6-C8-cycloalkyl
- alkoxy Cl-C4-alkoxy
- long-chain alkoxy linear and branched C5-C10 alkoxy, preferably linear C6-C8 alkoxy
- Alkylene selected from the group comprising: methylenes; 1,2-ethylene; 1,3-propylene; butan-2-ol-1,4-diyl; 1, 4-butylenes; cyclohexane-l, l-diyl; cyclohexane-l, 2-diyl; cyclohexane-l, 4-diyl; cyclopentane-1, 1-diyl; and cyclopentane-1, 2-diyl,
- Aryl selected from the group comprising: phenyl; biphenyl; naphthalenyl; anthracenyl; and phenanthrenyl,
- Arylene selected from the group comprising: 1, 2-phenylene; 1,3-phenylenes; 1,4-phenylene; 1,2-naphthalenylenes; 1,4-naphthalenylene; 2,3-naphthalenylenes and 1-hydroxy-2,6-phenylenes,
- Heteroarylene thiophene, pyrrole, pyridine, pyridazine, pyrimidine, indole, thienothiophene,
- Halogen selected from the group comprising: Br and Cl, more preferably Br.
- the at least one thiophene derivative contains at least one compound of the general formula:
- R is selected from the group consisting of hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy and / or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, haloalkyl, aryl, arylenes, haloaryl, heteroaryl, heteroarylenes, Heterocycloalkylenes, heterocycloalkyl, haloheteroaryl, alkenyl,
- the first and / or the second solution contain a solvent selected from the group of aliphatic hydrocarbons, e.g. Alkanes, in particular pentane, hexane, cyclohexane or heptane, unsubstituted or substituted aromatic hydrocarbons, such as. Benzene, toluene and xylenes, as well as ether group-containing compounds, e.g. Diethyl ether, tert-butyl methyl ether, dibutyl ether, amyl ether, dioxane and tetrahydrofuran (THF) and solvent mixtures of the abovementioned groups.
- aliphatic hydrocarbons e.g. Alkanes, in particular pentane, hexane, cyclohexane or heptane
- unsubstituted or substituted aromatic hydrocarbons such as. Benzene, toluene and xylenes
- Solvents containing ether groups are preferably used in the process according to the invention. Very particular preference is tetrahydrofuran. However, it is also possible and preferred for many embodiments of the present invention to use as solvent mixtures of two or more of these solvents. For example, mixtures of the preferred solvent may be tetrahydrofuran and alkanes, e.g. Hexane (e.g., contained in commercially available solutions of starting products such as organometallic compounds). It is important in the context of the invention that the solvent, the solvents or mixtures thereof be chosen so that the thiophene derivatives used or the polymerization-active monomers are present in dissolved form in the first solution. Also suitable for the workup are halogenated aliphatic hydrocarbons, such as methylene chloride and chloroform.
- a hydrolyzing solvent is added to the polymerization solution to terminate the reaction ("quenching"), preferably an alkyl alcohol, more preferably ethanol or methanol, most preferably methanol.
- the workup is preferably carried out so that the precipitated product is filtered off, washed with the precipitant and then taken up in a solvent.
- purification in the soxhlet can be carried out, preferably using nonpolar solvents, such as e.g. Hexane can be used as extractant.
- nonpolar solvents such as e.g. Hexane
- the oligomers prepared according to the method are also distinguished by the presence of one or two leaving groups at the chain end, which in the further course can serve as substitution sites for functionalizations or end-capping reactions.
- reaction takes place with a thiophene derivative having only one leaving group.
- the thiophene derivative having only one leaving group has a further functionalizable radical, preferably in the 5-position, which is preferably selected from the group phosphoalkyl, phosphonates, phosphates, phosphine, Phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonates, sulphates, sulphones or mixtures thereof has proven to be advantageous for many applications of the present invention.
- the inventive method is characterized in particular in many applications by the possibility of targeted adjustment of a desired average chain length as well as the production of products with a narrow molecular weight distribution.
- oligothiophenes obtainable by the process according to the invention.
- Oligothiophenes having a narrow molecular weight distribution with a polydispersity index PDI of> 1 to ⁇ 3, preferably PDI ⁇ 2, particularly preferably PDI> 1.1 to ⁇ 1.7, are preferably obtained here.
- Example 1 is to be understood as illustrative only and not as a limitation of the present invention, which is defined purely by the claims.
- Ni (dppp) Cl 2 0.04 wt.%, Equivalent to 0.5 mol.%
- both starting material streams are mixed by the use of a ⁇ mixer (Ehrmitz) and subsequently conveyed through a reaction capillary (1/16 ”) and subsequently through a further residence reactor (sandwich reactor (Ehrmitz))
- the capillary takes place at room temperature, in the residence reactor, on the other hand, 140 ° C.
- the total pressure is 6 bar in the system and is maintained at the reactor outlet via a pressure-holding valve
- the total residence time is 25 minutes, whereby it divides into the reaction capillary and in about 7 minutes About 18 minutes in the residence reactor.
- reaction solution is added to methanol and the precipitated solid is filtered off. The solid is then extracted with hexane. The desired oligomer is obtained from the evaporated-in hexane phase.
- the structure and the educts corresponded to the example according to the invention, except that a catalyst concentration of 1 -mol% was selected.
- a polymer was obtained with the following data:
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Abstract
Description
Claims
Priority Applications (5)
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CA2696173A CA2696173A1 (en) | 2007-08-14 | 2008-08-01 | Method for the production of thiophene oligomers |
JP2010520454A JP2010535823A (ja) | 2007-08-14 | 2008-08-01 | チオフェンオリゴマーの製造法 |
CN2008801029067A CN101809059B (zh) | 2007-08-14 | 2008-08-01 | 噻吩低聚物的制备方法 |
EP08785276A EP2178943A1 (de) | 2007-08-14 | 2008-08-01 | Verfahren zur herstellung von thiophenoligomeren |
US12/668,899 US8394916B2 (en) | 2007-08-14 | 2008-08-01 | Method for the production of thiophene oligomers |
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DE102007038449A DE102007038449A1 (de) | 2007-08-14 | 2007-08-14 | Verfahren zur Herstellung von Thiophenoligomeren |
DE102007038449.3 | 2007-08-14 |
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US (1) | US8394916B2 (de) |
EP (1) | EP2178943A1 (de) |
JP (1) | JP2010535823A (de) |
KR (1) | KR20100049067A (de) |
CN (1) | CN101809059B (de) |
CA (1) | CA2696173A1 (de) |
DE (1) | DE102007038449A1 (de) |
TW (1) | TWI421272B (de) |
WO (1) | WO2009021639A1 (de) |
Cited By (2)
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CN102190666A (zh) * | 2010-03-08 | 2011-09-21 | 清水真 | 噻吩化合物的制备方法 |
DE102010062961A1 (de) | 2010-12-13 | 2012-06-14 | Bayer Technology Services Gmbh | Carboxylierung von Poly-/Oligothiophenen |
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JP5585916B2 (ja) * | 2011-01-28 | 2014-09-10 | 国立大学法人山形大学 | ポリチオフェン類の製造方法、及び新規なチオフェンモノマー |
AU2019284481B2 (en) * | 2018-06-13 | 2022-07-14 | Abbott Diabetes Care Inc. | Temperature-insensitive membrane materials and analyte sensors containing the same |
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- 2007-08-14 DE DE102007038449A patent/DE102007038449A1/de not_active Withdrawn
-
2008
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- 2008-08-01 EP EP08785276A patent/EP2178943A1/de not_active Withdrawn
- 2008-08-01 WO PCT/EP2008/006335 patent/WO2009021639A1/de active Application Filing
- 2008-08-01 CA CA2696173A patent/CA2696173A1/en not_active Abandoned
- 2008-08-01 CN CN2008801029067A patent/CN101809059B/zh not_active Expired - Fee Related
- 2008-08-01 JP JP2010520454A patent/JP2010535823A/ja active Pending
- 2008-08-01 US US12/668,899 patent/US8394916B2/en not_active Expired - Fee Related
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Cited By (4)
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CN102190666A (zh) * | 2010-03-08 | 2011-09-21 | 清水真 | 噻吩化合物的制备方法 |
CN102190666B (zh) * | 2010-03-08 | 2014-09-17 | 清水真 | 噻吩化合物的制备方法 |
DE102010062961A1 (de) | 2010-12-13 | 2012-06-14 | Bayer Technology Services Gmbh | Carboxylierung von Poly-/Oligothiophenen |
WO2012080074A1 (de) | 2010-12-13 | 2012-06-21 | Bayer Technology Services Gmbh | Carboxylierung von poly-/oligothiophenen |
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CN101809059B (zh) | 2012-08-29 |
US8394916B2 (en) | 2013-03-12 |
TWI421272B (zh) | 2014-01-01 |
CA2696173A1 (en) | 2009-02-19 |
DE102007038449A1 (de) | 2009-02-19 |
US20100190945A1 (en) | 2010-07-29 |
CN101809059A (zh) | 2010-08-18 |
TW200916499A (en) | 2009-04-16 |
JP2010535823A (ja) | 2010-11-25 |
EP2178943A1 (de) | 2010-04-28 |
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