5-Bromosalicylaldehyde → 2-Hydroxy-5-(2-thienyl)benzaldehyde

HRID 430736Notes

Reaction equation

HRID 430736 reaction equation
Br[C:2]1[CH:9]=[C:6]([CH:7]=[O:8])[C:5]([OH:10])=[CH:4][CH:3]=1.C([Sn]([C:24]1[S:25][CH:26]=[CH:27][CH:28]=1)(CCCC)CCCC)CCC>CN(C=O)C.CCOCC>[S:25]1[CH:26]=[CH:27][CH:28]=[C:24]1[C:2]1[CH:9]=[C:6]([CH:7]=[O:8])[C:5]([OH:10])=[CH:4][CH:3]=1

Participants

5

Reactant 2

HCID 728635-BromosalicylaldehydeHCID 27793732-(Tri-n-butylstannyl)thiophene

Product 1

HCID 8284992-Hydroxy-5-(2-thienyl)benzaldehydeYield 66%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

The synthesis of this compound is depicted schematically in FIG. 13. To a mixture of 5-bromosalicylaldehyde (2.847 g, 14.16 mmol) and Cl2Pd(PPh3)2 (0.497 g, 0.708 mmol, 0.05 equiv) was added tributylstannyl thiophene (6.75 mL, 21.24 mmol, 1.5 equiv) in 25 mL of DMF. The reaction mixture was heated at 80° C. 16 h, over which time the reaction color changed from light yellow to dark red. The reaction was cooled, diluted with Et2O and washed with dilute NH4Cl (4×150 mL). The organic layer was collected and filtered through a short silica pad to yield a yellow filtrate. The solvent was removed under reduced pressure to afford a gummy yellow solid, which was transferred to a frit and washed with hexanes. The yellow solid was dried in vacuo to afford 1.895 g (9.28 mmol, 66%) of a yellow powder (mp 102-103° C.). 1H NMR (CDCl3) δ11.01 (s, 1H), 9.96 (s, 1H), 7.80-7.76 (m, 2H), 7.29-7.24 (m, 2H), 7.11-7.07 (dd, 1H), 7.05-7.02 (dd, 1H). 13C NMR (CDCl3) δ196.5, 161.1, 142.7, 134.7, 130.8, 128.3, 127.1, 124.8, 123.0, 120.8, 118.4. MS m/z (204 (M+). HRMS (FAB) found m/z 205.0324 (M+H+); calcd for C11H9O2S m/z 205.0323 (M+H+).

Workup

  1. customThe synthesis of this compound
  2. custom16 h
  3. temperatureThe reaction was cooled
  4. washwashed with dilute NH4Cl (4×150 mL)
  5. customThe organic layer was collected
  6. filtrationfiltered through a short silica pad
  7. customto yield a yellow filtrate
  8. customThe solvent was removed under reduced pressure
  9. customto afford a gummy yellow solid, which
  10. washwashed with hexanes
  11. customThe yellow solid was dried in vacuo

Sources & evidence

ORD record
ord-6b5c8a7023b845468830696c7527bcb6
Source dataset
uspto-grants-2001_11
Patent number
US06323309B1

Reaction notes

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