WO2011155679A1 - A method of controlling the bromination of thiophene derivatives - Google Patents

A method of controlling the bromination of thiophene derivatives 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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bromination
lithium source
derivative according
thiophene
preparing
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French (fr)
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Jae-Suk Lee
A. El-Shehawy Ashraf
Joon-Keun Min
I. Abdo Nabiha
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Gwangju Institute of Science and Technology
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Gwangju Institute of Science and Technology
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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

Provided is a method for regioselective synthesis of a bromoalkylthiophene with improved yield. A 3-alkylthiophene is activated at -78not;C with n-BuLi for about 1.5 hour and then reacted with bromine to give a bromoalkylthiophene with good regioselectivity:

Description

[DESCRIPTION]
[invention Title]
A METHOD OF CONTROLLING THE BROMINATION OF THIOPHENE DERIVATIVES
[Technical Field]
The present disclosure relates to a method for controlling bromination of a thiophene derivative. [Background Art]
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 . synthesized the substance through four reaction steps whereby a TMS group is used as a blocking group and then removed (Loewe, R. S.; Ewbank, P. C . ; Liu, J.; Zhai, L . ; McCullough, R. D. Macromolecules , 2001, 34, 4324) . Another system was introduced to simplify the multi-step reactions. A thiophene intermediate lithiated using Ώ-BuLi was reacted with CBr4. However, due to side reactions and difficulty in purification, the yield was low with 23% (Loewe, R. S . ; Ewbank, P. C . ; Liu, J.; Zhai, L.; cCullough, R. D. Macromolecules , 2001, 34, 4324). Recently, Luscombe et al . used n-BuLi and TMEDA as a base for lithiation and then treated the lithiated intermediate with CBr4. However, after purification, the yield of 2-bromo-4-hexylthiophene was only 11% (Boyd, S. D.; Jen, A. K.-Y.; Luscombe, C. K. Macromolecules, 2009, 42, 9387). [Disclosure]
[Technical Problem]
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.
[Technical Solution]
In one general aspect, 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:
Figure imgf000005_0001
In the above formulae, R is a C1-C12 linear or branched alkyl moiety, an aromatic moiety, or a heterocyclic molecule including at least one heteroatom such as N, S and 0. X is one of N, 0, S and Se. And, n is an integer from 1 to 100.
In another general aspect, 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.
In another general aspect, 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.
In an embodiment, the lithium source may be selected from n-butyllithium, s-butyllithium, t-butyllithium and lithium diisopropylamide, but is not limited thereto.
In another embodiment , the C1-C12 linear or branched alkyl moiety may be selected frombutyl, hexyl, octyl, decyl, ethylhexyl, hexyloxy and octyloxy, but is not limited thereto.
In another embodiment, the aromatic moiety may be selected from phenyl, biphenyl and naphthyl, but is not limited thereto.
In another embodiment, the heterocyclic molecule may be selected from furan, pyridine, thiophene, imidazole and pyrrole, but is not limited thereto.
In an embodiment, the steps (a) and (b) may be performed at -100 °C to 0 °C, specifically at -90 °C to -50 °C.
In another embodiment, after the step (a) and before the step (b) , 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
Figure imgf000006_0001
Figure imgf000006_0002
but are not limited thereto.
In an embodiment, the compound of Chemical Formula 2 may be a 3-alkylthiophene, and the compound of Chemical Formula 3 may be a 2-bromo-4-alkylthiophene .
Other features and aspects will be apparent from the following detailed description, the drawings, and the claims.
[Advantageous Effects]
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 .
[Description of Drawings]
The above and other objects, features and advantages of the present disclosure will become apparent from the following description of certain exemplary embodiments given in conjunction with the accompanying drawings, in which:
Fig. 1 shows a 1H-NMR spectrum of 2-bromo-4-butylthiophene ;
Fig. 2 shows a 13C-NMR spectrum of 2-bromo-4-butylthiophene;
Fig. 3 shows a 1H-NMR spectrum of 2-bromo-4-hexylthiophene; Fig. 4 shows a C-NMR spectrum of 2-bromo-4-hexylthiophene ; Fig. 5 shows a 1H-N R spectrum of 2-bromo-4-octylthiophene ; and
Fig. 6 shows a 13C-NMR spectrum of 2-bromo-4-octylthiophene .
[Best Mode]
Hereinafter, the embodiments of the present disclosure will be described in detail.
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 Br2.
The present disclosure provides a new synthesis method of a bromoalkylthiophene through regioselective bromination. To control the position where bromination occurs, a new system is introduced instead of reacting alone with NBS or Br2.
As will be described in detail in the following examples, 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 :
Figure imgf000009_0001
where RisaCi-C^linearor branched alkyl moiety, or an aromatic moiety .
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 .
For example, the alkylthiophene may be reacted by contacting with n-BuLi for 0.5-5 hours and contacting with Br2 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.
[Scheme 1]
Figure imgf000010_0001
Figure imgf000010_0002
(I sol ate yi eld - 93%) (Ti ace s)
[Mode for Invention]
The examples and experiments will now be described. The following examples and experiments are for illustrative purposes only and not intended to limit the scope of the present disclosure.
Example 1
3-Butylthiophene (1.40 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% Na2S203 (30 mL) , water and 10% NaCl (50 mL) , and was dried over anhydrous Na2SC> . 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%.
Example 2
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% Na2S203 (30 mL) , water and 10% NaCl (50 mL) , and was dried over anhydrous Na2S04. 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%.
Example 3
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% Na2S203 (30 mL) , water and 10% NaCl (50 mL) , and was dried over anhydrous Na2S04. 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%.
Example 4
3-Hexyl-2- ( 4-hexylthiophene-2-yl ) thiophene (3.4 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% Na2S2C>3 (30 mL) , water and 10% NaCl (50 mL) , and was dried over anhydrous Na2S04. 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%.
The present application contains subject matter related to Korean Patent Application No. 10-2010-0055518, filed in the Korean Intellectual Property Office on June 11, 2010, the entire contents of which is incorporated herein by reference.
Those skilled in the art will appreciate that the conceptions and specific embodiments disclosed in the foregoing description may be readily utilized as a basis for modifying, or designing other embodiments for carrying out the same purposes of the present disclosure. Those skilled in the art will also appreciate that such equivalent embodiments do not depart from the spirit and scope of the disclosure as set forth in the appended claims.

Claims

[CLAIMS]
[Claim l]
Amethod for controlling the degree of bromination in a thiophene derivative, comprising:
reacting a thiophene derivative of Chemical Formula 2 with a lithium source in a reactor; and
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 :
Figure imgf000014_0001
where R is a C1-C12 linear or branched alkyl moiety, an aromatic moiety, or a heterocyclic molecule including at least one atom selected from N, S and 0; X is selected from N, 0, S and Se; and n is an integer from 0 to 100.
[Claim 2]
The method for controlling the degree of bromination in a thiophene derivative according to claim 1 , wherein the lithium source is selected from n-butyllithium, s-butyllithium, t-butyllithium and lithium diisopropylamide .
[Claim 3]
The method for controlling the degree of bromination in a thiophene derivative according to claim 1, wherein the C1-C12 linear or branched alkyl moiety is selected from butyl , hexyl, octyl, decyl, ethylhexyl, hexyloxy and octyloxy.
[Claim 4]
The method for controlling the degree of bromination in a thiophene derivative according to claim 1, wherein the aromatic moiety is selected from phenyl, biphenyl and naphthyl .
[Claim 5]
The method for controlling the degree of bromination in a thiophene derivative according to claim 1, wherein the heterocyclic molecule is selected from furan, pyridine, thiophene, imidazole and pyrrole.
[Claim 6]
The method for controlling the degree of bromination in a thiophene derivative according to claim 1, wherein the reaction of the thiophene derivative with the lithium source and the bromination are performed at -100 °C to 0 °C.
[Claim 7]
The method for controlling the degree of bromination in a thiophene derivative according to claim 1, wherein the reaction of the thiophene derivative with the lithium source and the bromination are performed at-90 °C to -50 °C.
[Claim 8]
The method for controlling the degree of bromination in a thiophene derivative according to claim 1, which further comprises, after the reaction of the thiophene derivative with the lithium source and before the bromination, stirring a reaction product resulting from the reaction of the thiophene derivative with the lithium source for 10 minutes to 3 hours for activation.
[Claim 9]
A method for preparing a bromothiophene derivative of Chemical Formula 3, comprising:
reacting a thiophene derivative of Chemical Formula 2 with a lithium source in a reactor; and
adding bromine to the reactor for bromination,
wherein a molar ratio of the lithium source and bromine is
0.8-1.5.: 1:
Figure imgf000017_0001
where R is a C1-C12 linear or branched alkyl moiety, an aromatic moiety, or a heterocyclic molecule including at least one atom selected from N, S and 0; X is selected from N, 0, S and Se; and n is an integer from 0 to 100.
[Claim 10]
A method for preparing a bromothiophene derivative of Chemical Formula 4, comprising:
reacting a thiophene derivative of Chemical Formula 2 with a lithium source in a reactor; and
adding bromine to the reactor for bromination,
wherein a molar ratio of the lithium source and bromine is 1.6-3 : 1:
Figure imgf000018_0001
where R is a C1-C12 linear or branched alkyl moiety, an aromatic moiety, or a heterocyclic molecule including at least one atom selected from N, S and 0; X is selected from N, 0, S and Se; and n is an integer from 0 to 100.
[Claim 11]
The method for preparing a bromothiophene derivative according to claim 9 or 10, wherein the lithium source is selected from n-butyllithium, s-butyllithium, t-butyllithium and lithium diisopropylamide .
[Claim 12]
The method for preparing a bromothiophene derivative according to claim 9 or 10, wherein the C1-C12 linear or branched alkyl moiety is selected from butyl, hexyl, octyl, decyl, ethylhexyl, hexyloxy and octyloxy.
[Claim 13]
The method for preparing a bromothiophene derivative according to claim 9 or 10, wherein the aromatic moiety is selected from phenyl , biphenyl and naphthyl .
[Claim 14]
The method for preparing a bromothiophene derivative according to claim 9 or 10, wherein the heterocyclic molecule is selected from furan, pyridine, thiophene, imidazole and pyrrole.
[Claim 15]
The method for preparing a bromothiophene derivative according to claim 9, wherein the molar ratio of the lithium source and bromine is 0.9-1.2 : 1.
[Claim 16]
The method for preparing a bromothiophene derivative according to claim 10, wherein the molar ratio of the lithium source and bromine is 2-3 : 1.
[Claim 17]
The method for preparing a bromothiophene derivative according to claim 9 or 10, wherein the reaction of the thiophene derivative with the lithium source and the bromination are performed at -100 °C to 0 °C.
[Claim 18]
The method for preparing a bromothiophene derivative according to claim 9 or 10, wherein the reaction of the thiophene derivative with the lithium source and the bromination are performed at-90 °C to -50 °C.
[Claim 19]
The method for preparing a bromothiophene derivative according to claim 9 or 10, which further comprises, after the reaction of the thiophene derivative with the lithium source and before the bromination, stirring a reaction product resulting from the reaction of the thiophene derivative with the lithium source for 10 minutes to 3 hours for activation.
[Claim 20]
The method for preparing a bromothiophene derivative according to claim, wherein the compound of Chemical Formula 2 is a 3-alkylthiophene and the compound of Chemical Formula 3 is a 2-bromo-4-alkylthiophene .
PCT/KR2010/008891 2010-06-11 2010-12-13 A method of controlling the bromination of thiophene derivatives Ceased WO2011155679A1 (en)

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