Sodium Carbonate → 3-Bromo-2-methoxy-5-phenylthiophene

HRID 1828319Notes

Reaction equation

HRID 1828319 reaction equation
[Br:1][C:2]1[CH:6]=[C:5](Br)[S:4][C:3]=1[O:8][CH3:9].C(=O)=O.CO.B(OCCCC)(OCCCC)OCCCC.C([O-])([O-])=O.[Na+].[Na+].I[C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCCCCC.C1COCC1>[Br:1][C:2]1[CH:6]=[C:5]([C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[S:4][C:3]=1[O:8][CH3:9]

Participants

9

Reactant 5

HCID 10340Sodium CarbonateHCID 11575IodobenzeneHCID 12712Tributyl borateHCID 117779883,5-Dibromo-2-methoxythiopheneHCID 21973728Carbon dioxide methanol

Product 1

HCID 220661523-Bromo-2-methoxy-5-phenylthiophene

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
70 °C

Procedure

250 ml of anhydrous THF was added into 24 g (88 mmol) of 3,5-dibromo-2-methoxythiophene and was cooled to be −78° C. with dry ice-methanol. Then, 56 ml (92 mmol) of a solution containing 15% n-butylithium hexane was slowly dripped into it. After being stirred for 1 hour, 32 ml (123 mmol) of tri-n-butyl borate was slowly dripped into it and stirred for 2 hours. After being returned to a room temperature, 90 ml of 20 wt % Na2CO3, 18 g (88 mmol) of iodobenzene, and 4.4 g (0.36 mmol) of Pd(Ph3P)4 were added to the solution and refluxed for 5 hours at 70° C. The reaction solution was extracted with ether, washed with a salt solution, and dried with addition of magnesium sulfate. The dried extract was condensed after removing magnesium sulfate by filtration. By developing the product with hexane on a silica gel column, a colorless solid 3-bromo-2-methoxy-5-phenylthiophene was obtained (Rf=0.35). The yield was 15 g in weight and 63% in percentage.

Workup

  1. temperaturewas cooled
  2. stirringstirred for 2 hours
  3. customAfter being returned to a room temperature
  4. extractionThe reaction solution was extracted with ether
  5. washwashed with a salt solution
  6. dry with materialdried with addition of magnesium sulfate
  7. extractionThe dried extract
  8. customcondensed
  9. customafter removing magnesium sulfate
  10. filtrationby filtration

Sources & evidence

ORD record
ord-35edab39d0084952ba68a0891fefd2a5
Source dataset
uspto-grants-2006_06
Patent number
US07057054B2

Reaction notes

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