EP2178943A1 - Procédé de préparation d'oligomères de thiophène - Google Patents

Procédé de préparation d'oligomères de thiophène

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Publication number
EP2178943A1
EP2178943A1 EP08785276A EP08785276A EP2178943A1 EP 2178943 A1 EP2178943 A1 EP 2178943A1 EP 08785276 A EP08785276 A EP 08785276A EP 08785276 A EP08785276 A EP 08785276A EP 2178943 A1 EP2178943 A1 EP 2178943A1
Authority
EP
European Patent Office
Prior art keywords
nickel
group
thiophene
ylene
mol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08785276A
Other languages
German (de)
English (en)
Inventor
Björn HENNINGER
Frank Rauscher
Leslaw Mleczko
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer Intellectual Property GmbH
Original Assignee
Bayer Technology Services GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Technology Services GmbH filed Critical Bayer Technology Services GmbH
Publication of EP2178943A1 publication Critical patent/EP2178943A1/fr
Withdrawn legal-status Critical Current

Links

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:

Abstract

La présente invention concerne un procédé de synthèse d'oligothiophènes à des températures élevées et à de faibles concentrations en catalyseurs.
EP08785276A 2007-08-14 2008-08-01 Procédé de préparation d'oligomères de thiophène Withdrawn EP2178943A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007038449A DE102007038449A1 (de) 2007-08-14 2007-08-14 Verfahren zur Herstellung von Thiophenoligomeren
PCT/EP2008/006335 WO2009021639A1 (fr) 2007-08-14 2008-08-01 Procédé de préparation d'oligomères de thiophène

Publications (1)

Publication Number Publication Date
EP2178943A1 true EP2178943A1 (fr) 2010-04-28

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EP08785276A Withdrawn EP2178943A1 (fr) 2007-08-14 2008-08-01 Procédé de préparation d'oligomères de thiophène

Country Status (9)

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US (1) US8394916B2 (fr)
EP (1) EP2178943A1 (fr)
JP (1) JP2010535823A (fr)
KR (1) KR20100049067A (fr)
CN (1) CN101809059B (fr)
CA (1) CA2696173A1 (fr)
DE (1) DE102007038449A1 (fr)
TW (1) TWI421272B (fr)
WO (1) WO2009021639A1 (fr)

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JP5645430B2 (ja) * 2010-03-08 2014-12-24 清水　真 チオフェン化合物の製造方法
DE102010062961A1 (de) 2010-12-13 2012-06-14 Bayer Technology Services Gmbh Carboxylierung von Poly-/Oligothiophenen
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
WO2019241192A1 (fr) * 2018-06-13 2019-12-19 Abbott Diabetes Care Inc. Matériaux de membrane insensibles à la température et capteurs d'analyte les contenant

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Also Published As

Publication number Publication date
DE102007038449A1 (de) 2009-02-19
CA2696173A1 (fr) 2009-02-19
US8394916B2 (en) 2013-03-12
TWI421272B (zh) 2014-01-01
WO2009021639A1 (fr) 2009-02-19
CN101809059A (zh) 2010-08-18
CN101809059B (zh) 2012-08-29
KR20100049067A (ko) 2010-05-11
US20100190945A1 (en) 2010-07-29
TW200916499A (en) 2009-04-16
JP2010535823A (ja) 2010-11-25

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