1,2-二溴乙烷 → 2,5-二羧酸-3,4-乙撑二氧噻吩

HRID 47183

反应方程式

HRID 47183 反应方程式
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]

参与物

11

反应物 8

HCID 78391,2-二溴乙烷HCID 11430碳酸钾HCID 14798二甲基对苯二胺二盐酸HCID 1024511,2-二溴己烷HCID 1368802,3-DihydrothiopheneHCID 625399Diethyl 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxylateHCID 44218643,4-乙烯二氧噻吩2 次HCID 50490181,2-Dibromohexadecane

产物 1

HCID 7288412,5-二羧酸-3,4-乙撑二氧噻吩

试剂、催化剂与溶剂 2

HCID 962聚[6-[4-(4-氰基苯基)苯氧基]己基甲基丙烯酸酯]溶剂HCID 6228N,N-二甲基甲酰胺溶剂

实验过程

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.

后处理

  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

来源与证据

ORD记录
ord-0d693ea225024267896906cff1342db4
来源数据集
uspto-grants-2004_03
专利号
US06699633B2

关联笔记

加载中…