WO2011155679A1 - Procédé permettant de maîtriser la bromation de dérivés de thiophène - Google Patents

Procédé permettant de maîtriser la bromation de dérivés de thiophène Download PDF

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Publication number
WO2011155679A1
WO2011155679A1 PCT/KR2010/008891 KR2010008891W WO2011155679A1 WO 2011155679 A1 WO2011155679 A1 WO 2011155679A1 KR 2010008891 W KR2010008891 W KR 2010008891W WO 2011155679 A1 WO2011155679 A1 WO 2011155679A1
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WO
WIPO (PCT)
Prior art keywords
bromination
lithium source
derivative according
thiophene
preparing
Prior art date
Application number
PCT/KR2010/008891
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English (en)
Inventor
Jae-Suk Lee
A. El-Shehawy Ashraf
Joon-Keun Min
I. Abdo Nabiha
Original Assignee
Gwangju Institute Of Science And Technology
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.)
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Application filed by Gwangju Institute Of Science And Technology filed Critical Gwangju Institute Of Science And Technology
Publication of WO2011155679A1 publication Critical patent/WO2011155679A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
    • C07D333/10—Thiophene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/12—Radicals substituted by halogen atoms or nitro or nitroso radicals

Definitions

  • the present disclosure relates to a method for controlling bromination of a thiophene derivative.
  • Oligo- and polythiophenes have received substantial attention as potential materials in organic semiconductor devices. Especially, since alkylthiophenes are precursors to polythiophene synthesis , there is a need for the synthesis of bromoalkylthiophenes . Bromoalkylthiophenes are used in many reactions including Kumada, Stille and Suzuki couplings. Since head-to-tail or tail-to-tail regioisomers are synthesized depending on the position of bromine, synthesis of 2-bromo-4-alkylthiophene is required to attain good regioregularity with regularly arranged alkyl chains. McCullough et al .
  • the present disclosure is directed to providing a method for preparing bromothiophene in high yield through a one-pot synthesis, thereby overcoming the problems of low yield and complicated reaction steps associated with the existing bromothiophene syntheses.
  • the present disclosure provides a method for controlling bromination of a thiophene derivative, including: (a) reacting a thiophene derivative of Chemical Formula 2 with a lithium source in a reactor; and (b) adding bromine to the reactor for bromination, wherein a molar ratio of the lithium source and bromine is controlled such that a compound of Chemical Formula 3 or 4 is produced as a main product:
  • the present disclosure provides a method for preparing a bromothiophene derivative of Chemical Formula 3, including: (a) reacting a thiophene derivative of Chemical Formula 2 with a lithium source in a reactor; and (b) adding bromine to the reactor for bromination, wherein a molar ratio of the lithium source and bromine is 0.8-1.5 : 1.
  • the present disclosure provides a method for preparing a bromothiophene derivative of Chemical Formula 4, including: (a) reacting a thiophene derivative of Chemical Formula 2 with a lithium source in a reactor; and (b) adding bromine to the reactor for bromination, wherein a molar ratio of the lithium source and bromine is 1.6-3 : 1.
  • the lithium source may be selected from n-butyllithium, s-butyllithium, t-butyllithium and lithium diisopropylamide, but is not limited thereto.
  • the aromatic moiety may be selected from phenyl, biphenyl and naphthyl, but is not limited thereto.
  • the heterocyclic molecule may be selected from furan, pyridine, thiophene, imidazole and pyrrole, but is not limited thereto.
  • the steps (a) and (b) may be performed at -100 °C to 0 °C, specifically at -90 °C to -50 °C.
  • a reaction product of the step (a) may be activatedby stirring.
  • the stirring for activation may be performed for 10 minutes to 3 hours .
  • Examples of the compound of Chemical Formula 2 include but are not limited thereto.
  • the compound of Chemical Formula 2 may be a 3-alkylthiophene
  • the compound of Chemical Formula 3 may be a 2-bromo-4-alkylthiophene .
  • the present disclosure allows the synthesis of 2-bromo-3-hexylthiophene with high regioselectivity and high yield through a one-pot synthesis. It will be effectively prepared into head-to-head, tail-to-tail and head-to-tail dihexyl-2 , 2 ' -bithiophene oligomers through Kumada, Suzuki and Stille couplings, thus being easily applicable to organic semiconductors .
  • Fig. 1 shows a 1 H-NMR spectrum of 2-bromo-4-butylthiophene
  • Fig. 2 shows a 13 C-NMR spectrum of 2-bromo-4-butylthiophene
  • Fig. 3 shows a 1 H-NMR spectrum of 2-bromo-4-hexylthiophene
  • Fig. 4 shows a C-NMR spectrum of 2-bromo-4-hexylthiophene
  • Fig. 5 shows a 1 H-N R spectrum of 2-bromo-4-octylthiophene ;
  • Fig. 6 shows a 13 C-NMR spectrum of 2-bromo-4-octylthiophene .
  • the present disclosure is directed to synthesizing a 2-bromo-4-alkylthiophene with high yield through a one-pot process .
  • the present disclosure is also directed to selectively controlling the position where a 3-alkylthiophene is brominated with butyllithium and Br 2 .
  • the present disclosure provides a new synthesis method of a bromoalkylthiophene through regioselective bromination.
  • a new system is introduced instead of reacting alone with NBS or Br 2 .
  • a 3-alkylthiophene was activated using n-BuLi at, for example, -78 °C for controlling the selective lithiation on the second position on the 3-alkylthiophene . Then, after dropping bromine for 20 minutes , the reactor was heated slowly to room temperature. After purification, a 2-bromo-4-alkylthiophene was obtained with the high yield of 93%.
  • a specific example of the 2-bromo-4-alkylthiophene may be represented by Chemical Formula 1 :
  • the bromination of the alkylthiophene may be performed by mono- or dibromination .
  • the position where bromination occurs may be controlled through an appropriate stoichiometric amount of a lithium source and Br2.
  • the stoichiometric amount means the amount of the lithium source or Br2 required preparing the mono- or dibromo product .
  • the alkylthiophene may be reacted by contacting with n-BuLi for 0.5-5 hours and contacting with Br 2 for 1-24 hours.
  • the reaction may be performed at -100 to 0 °C.
  • the reaction may be performed without an additional solvent. However, an extra solvent may be added if desired. In this case, the solvent can be removed after the reaction is completed through a common separation process, e.g. by distillation or evaporation, from the final bromination product.
  • Schemes 1 and 2 respectively show a general case and a case where the reactant is the compound of Chemical Formula 1.
  • the reaction mixture was warmed to room temperature by removing the cooling bath, poured into ice cold water and extracted with diethyl ether.
  • the organic layer was washed successively with 3% Na 2 S 2 0 3 (30 mL) , water and 10% NaCl (50 mL) , and was dried over anhydrous Na 2 SC> .
  • the solvent was removed under reduced pressure and the resulting light yellow oil was purified by flash column chromatography on neutralized silica gel with hexane . Apale-yellow liquid substance was obtained. The yield was 90%.
  • 3-Hexylthiophene (1.68 g) was added to a dry THF solvent in a 3-bulb flask. Then, under argon gas atmosphere, the temperature was lowered to -78 °C. After adding 2.5 M n-BuLi/hexane ( ⁇ 4 mL) dropwise over 1.5 hours, the resulting solution was activated by stirring at -78 °C for about 1 hour. At the same temperature, a solution of bromine (1.68 g) and THF (5 mL) was slowly added for about 15 minutes. The mixture was stirred for 20 minutes and a few drops of an aqueous methanolic solution of sodium thiosulfate were added at -78 °C .
  • the reaction mixture was warmed to room temperature by removing the cooling bath, poured into ice cold water and extracted with diethyl ether.
  • the organic layer was washed successively with 3% Na 2 S 2 0 3 (30 mL) , water and 10% NaCl (50 mL) , and was dried over anhydrous Na 2 S0 4 .
  • the solvent was removed under reduced pressure and the resulting light yellow oil was purified by flash column chromatography on neutralized silica gel with hexane to afford a colorless oil. ' The yield was 93%.
  • 3-Octylthiophene (1.96 g) was added to a dry THF solvent in a 3-bulb flask. Then, under argon gas atmosphere, the temperature was lowered to -78 °C. After adding 2.5 M n-BuLi/hexane ( ⁇ 4 mL) dropwise over 1.5 hours, the resulting solution was activated by stirring at -78 °C for about 1 hour. At the same temperature, a solution of bromine (1.68 g) and THF (5 mL) was slowly added for about 15 minutes. The mixture was stirred for 20 minutes and a few drops of an aqueous methanolic solution of sodium thiosulfate were added at -78 °C .
  • the reaction mixture was warmed to room temperature by removing the cooling bath, poured into ice cold water and extracted with diethyl ether .
  • the organic layer was washed successively with 3% Na 2 S 2 0 3 (30 mL) , water and 10% NaCl (50 mL) , and was dried over anhydrous Na 2 S0 4 .
  • the solvent was removed under reduced pressure and the resulting light yellow oil was purified by flash column chromatography on neutralized silica gel with hexane. A colorless substance was obtained. The yield was 92%.
  • the mixture was stirred for 20 minutes and a few drops of an aqueous methanolic solution of sodium thiosulfate were added at -78 °C .
  • the reaction mixture was warmed to room temperature by removing the cooling bath, poured into ice cold water and extracted with diethyl ether.
  • the organic layer was washed successively with 3% Na 2 S 2 C>3 (30 mL) , water and 10% NaCl (50 mL) , and was dried over anhydrous Na 2 S0 4 .
  • the solvent was removed under reduced pressure and the resulting light yellow oil was purified by flash column chromatography on neutralized silica gel with hexane . A colorless substance was obtained. The yield was 90%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

L'invention porte sur un procédé pour la synthèse régiosélective d'un bromoalkylthiophène présentant un rendement amélioré. Un 3-alkylthiophène est activé à -78°C avec du n-BuLi pendant environ 1,5 heure, puis est amené à réagir avec du brome pour donner un bromoalkylthiophène présentant une bonne régiosélectivité.
PCT/KR2010/008891 2010-06-11 2010-12-13 Procédé permettant de maîtriser la bromation de dérivés de thiophène WO2011155679A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2010-0055518 2010-06-11
KR1020100055518A KR101268026B1 (ko) 2010-06-11 2010-06-11 싸이오펜 유도체의 브롬화도 조절방법

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Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7253292B2 (en) 2001-05-15 2007-08-07 Basell Polyolefine Gmbh Synthesis of cyclopentadiene derivatives

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
EL-SHEHAWY, ASHRAF A. ET AL.: "A selective and direct synthesis of 2-bromo- 4-alkylthiophenes: Convenient and straightforward approaches for the synthesis of head-to- tail (HT) and tail-to-tail (TT) dihexyl-2,20-bithiophenes.", TETRAHEDRON LETTERS, vol. 51, 25 June 2010 (2010-06-25), pages 4526 - 4529 *
FACCHETTI, ANTONIO ET AL.: "n-Type Building Blocks for Organic Electronics: A Homologous Family of Fluorocarbon-Substituted Thiophene Oligomers with High Carrier Mobility.", ADVANCED MATERIALS, vol. 15, 2003, pages 33 - 38 *
FULLER, LANCE S. ET AL.: "Thienothiophenes. Part 2.1 Synthesis, metallation and bromine->lithium exchange reactions of thieno[3,2-b]thiophene and its polybromo derivatives.", J. CHEM. SOC., PERKIN TRANS., vol. 1, 1997, pages 3465 - 3470 *
KANATO, HIROKI ET AL.: "Synthesis and Photophysical Properties of Ferrocene- Oligothiophene-Fullerene Triads.", JOURNAL OF ORGGNIC CHEMISTRY, vol. 69, 2004, pages 7183 - 7189 *
LI, YUNING ET AL.: "Poly(2,5-bis(2-thienyl)-3,6-dialkylthieno[3,2-b]- thiophene)s-High-Mobility Semiconductors for Thin-Film Transistors.", ADVANCED MATERIALS, vol. 18, 2006, pages 3029 - 3032 *
LIM, EUNHEE ET AL.: "Relationship between the Liquid Crystallinity and Field- Effect-Transistor Behavior of Fluorene-Thiophene-Based Conjugated Copolymers.", JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY 2006, vol. 44, 2006, pages 4709 - 4721 *
MEIJERE, ARMIN DE ET AL.: "1,3-Bicyclo[1.I.1]pentanediyl: The Shortest Rigid Linear Connector of Phenylated Photochromic Units and a 1,5-Dimethoxy-9,10-di(phenylethynyl)anthracene Fluorophore.", CHEMISTRY-A EUROPEAN JOURNAL, vol. 13, 2007, pages 2503 - 2516 *

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KR101268026B1 (ko) 2013-05-27

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