Sodium Carbonate → 5-(4-methoxyphenyl)thiophene-2-carbaldehyde

HRID 1497427Notes

Reaction equation

HRID 1497427 reaction equation
Br[C:2]1[S:6][C:5]([CH:7]=[O:8])=[CH:4][CH:3]=1.[CH3:9][O:10][C:11]1[CH:16]=[CH:15][C:14](B(O)O)=[CH:13][CH:12]=1.C([O-])([O-])=O.[Na+].[Na+]>C1(C)C=CC=CC=1.C(O)C.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>[CH3:9][O:10][C:11]1[CH:16]=[CH:15][C:14]([C:2]2[S:6][C:5]([CH:7]=[O:8])=[CH:4][CH:3]=2)=[CH:13][CH:12]=1

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 784285-Bromothiophene-2-carbaldehydeHCID 201262(4-Methoxyphenyl)boronic acid

Product 1

HCID 27978005-(4-methoxyphenyl)thiophene-2-carbaldehyde

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 1140TolueneSolvent

Conditions

Temperature
60 °C

Procedure

To a stirred solution of 5-bromothiophene-2-carbaldehyde (1 g, 5.2 mmol) in toluene (40 mL) and ethanol (20 mL) was added (4-methoxyphenyl)boronic acid (1.59 g, 10.4 mmol), 2M Na2CO3 (14.7 mL), and Pd(PPh3)4 (60 mg, 0.05 mmol). The reaction was purged with argon and heated at 60° C. for about 5 h. The reaction mixture was concentrated, diluted with water (100 mL), and extracted with ethyl acetate (2×200 mL). The combined organic extracts were washed with brine solution (20 mL), the organic layer was dried over Na2SO4 and concentrated under vacuum to obtain crude product. The crude product was purified by flash chromatography (silica gel, 60-120μ) using 10% ethyl acetate in hexane eluent to afford 5-(4-methoxyphenyl)thiophene-2-carbaldehyde as off white solid (1 g, 87.7% yield). 1H NMR (400 MHz, DMSO-d6): δ 9.85 (s, 1H), 7.97 (d, 1H), 7.73 (d, 2H), 7.61 (d, 1H), 7.02 (d, 2H), 3.98 (s, 3H); LC-MS m/z calcd for [M+H]+ 219.04. found 219.3.

Workup

  1. customThe reaction was purged with argon
  2. concentrationThe reaction mixture was concentrated
  3. additiondiluted with water (100 mL)
  4. extractionextracted with ethyl acetate (2×200 mL)
  5. washThe combined organic extracts were washed with brine solution (20 mL)
  6. dry with materialthe organic layer was dried over Na2SO4
  7. concentrationconcentrated under vacuum
  8. customto obtain crude product
  9. customThe crude product was purified by flash chromatography (silica gel, 60-120μ)

Sources & evidence

ORD record
ord-6fbc05ca68104bac80b0b02d70fb855a
Source dataset
uspto-grants-2015_12
Patent number
US09199975B2

Reaction notes

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