1,2-Dibromoethane → 2,3-Dihydro-thieno(3,4-b)(1,4)dioxin-5,7-dicarboxylic acid

HRID 47183

反応式

HRID 47183 の反応式
S1C=CCC1.[C:6]([O-:9])([O-:8])=O.[K+].[K+].C1OC2C(=CSC=2)OC1.BrCCBr.BrCC(Br)CCCCCCCCCCCCCC.BrCC(Br)CCCC.[C:51]([C:56]1[S:57][C:58](C(OCC)=O)=[C:59]2[O:64][CH2:63][CH2:62][O:61][C:60]=12)([O:53]CC)=[O:52].[OH-].[Na+]>O.CN(C=O)C>[C:6]([C:58]1[S:57][C:56]([C:51]([OH:53])=[O:52])=[C:60]2[O:61][CH2:62][CH2:63][O:64][C:59]=12)([OH:9])=[O:8]

参加物

11

反応物 8

HCID 78391,2-DibromoethaneHCID 11430Potassium CarbonateHCID 14798Sodium HydroxideHCID 102451Hexane, 1,2-dibromo-HCID 1368802,3-DihydrothiopheneHCID 625399Diethyl 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxylateHCID 44218643,4-Ethylenedioxythiophene2 回HCID 50490181,2-Dibromohexadecane

生成物 1

HCID 7288412,3-Dihydro-thieno(3,4-b)(1,4)dioxin-5,7-dicarboxylic acid

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6228Dimethylformamide溶媒

実験手順

The salt either 5 or 6 is dissolved in water and acidified with 1 Molar HCI added slowly dropwise with constant stirring until the solution becomes acidic. Immediately following, thick white precipitate falls out. After filtration, the precipitate is washed with water and air-dried to give 2,5-dicarbethoxy-3,4-dihydroxythiophene (Z). The salt either (5, 2.5 grams) or 6 can be alkylated directly or the dihydrothiophene derivative (7) can be suspended in the appropriate 1,2-dihaloalkane or substituted 1,2-dihaloalkane and refluxed for 24 hours in the presence of anhydrous K2CO3 in anhydrous DMF. To prepare EDOT, either 1,2-dicholorethane (commercially available from Aldrich) or 1,2-dibromoethane (commercially from Aldrich) is used. To prepare the various substituted EDOT derivatives the appropriate 1,2-dibromoalkane is used, such as 1-dibromodecane, 1,2-dibromohexadecane (prepared from 1-hexadecene and bromine), 1,2-dibromohexane, other reported 1,2-dibromoalkane derivatives, and the like. The resulting 2,5-dicarbethoxy-3,4-ethylenedioxythiophene or 2,5-dicarbethoxy-3,4-alkylenedioxythiophene is refluxed in base, for example 10 percent aqueous sodium hydroxide solution for 1 to 2 hours, and the resulting insoluble material is collected by filtration. This material is acidified with 1 Normal HCl and recrystallized from methanol to produce either 2,5-dicarboxy-3,4-ethylenedioxythiophene or the corresponding 2,5-dicarboxy-3,4-alkylenedioxythiophene. The final step to reduce the carboxylic acid functional groups to hydrogen to produce the desired monomer is given in the references above.

後処理

  1. additionadded slowly dropwise
  2. filtrationAfter filtration
  3. washthe precipitate is washed with water
  4. customair-dried
  5. customto give 2,5-dicarbethoxy-3,4-dihydroxythiophene (Z)
  6. customTo prepare the
  7. filtrationthe resulting insoluble material is collected by filtration
  8. customrecrystallized from methanol

出典と根拠

ORDレコード
ord-0d693ea225024267896906cff1342db4
出典データセット
uspto-grants-2004_03
特許番号
US06699633B2

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