2,6-Dibromopyridine → Methyl 4-(6-bromo(2-pyridyl))-5-methylthiothiophene-2-carboxylate

HRID 2298598Notes

Reaction equation

HRID 2298598 reaction equation
C[Sn]([C:5]1[CH:6]=[C:7]([C:11]([O:13][CH3:14])=[S:12])[S:8][C:9]=1[CH3:10])(C)C.[Br:15][C:16]1[CH:21]=[CH:20][CH:19]=[C:18](Br)[N:17]=1>CN(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>[Br:15][C:16]1[N:17]=[C:18]([C:5]2[CH:6]=[C:7]([C:11]([O:13][CH3:14])=[S:12])[S:8][C:9]=2[CH3:10])[CH:19]=[CH:20][CH:21]=1

Participants

5

Reactant 2

HCID 122742,6-DibromopyridineHCID 86758668Methyl 4-(1,1-dimethyl-1-stannaethyl)-5-methylthiothiophene-2-carboxylate

Product 1

HCID 86758669Methyl 4-(6-bromo(2-pyridyl))-5-methylthiothiophene-2-carboxylateYield 42.4%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
120 °C

Procedure

Methyl 4-(1,1-dimethyl-1-stannaethyl)-5-methylthiothiophene-2-carboxylate (195 mg, 0.56 mmol) as prepared in previous step, and 2,6-dibromopyridine (398 mg, 1.7 mmol) were taken in anhydrous DMF (2 mL). To this mixture tetrakistriphenylphosphine-palladium (20 mg) was added and heated at 120° C. for 24 h. DMF was removed under vacuum and the residue was purified by preparative silica gel thin-layer chromatography to give 78 mg (41%) of methyl 4-(6-bromo(2-pyridyl))-5-methylthiothiophene-2-carboxylate as a solid. 1H-NMR (CDCl3; 300 MHz) δ2.60 (S, 3H), 3.78 (s, 3H), 7.19 (S, 1H), 7.47 (dd, J=1.09 and 7.67 Hz, 1H)), 7.58 (t, J=7.70, 1H), 7.65 (dd, J=1.12 and 7.43 Hz, 1H).

Workup

  1. customDMF was removed under vacuum
  2. customthe residue was purified by preparative silica gel thin-layer chromatography

Sources & evidence

ORD record
ord-8ff9b008a1f6420387417e4a6dd62578
Source dataset
uspto-grants-2002_12
Patent number
US06492403B1

Reaction notes

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