Formic Acid → 3-Methoxybenzaldehyde

HRID 1411220Notes

Reaction equation

HRID 1411220 reaction equation
C(N(CC)CC)C.C(O)=O.[CH3:11][O:12][C:13]1[CH:14]=[C:15]([CH:18]=[CH:19][C:20]=1OS(C(F)(F)F)(=O)=O)[CH:16]=[O:17]>CC([O-])=O.CC([O-])=O.[Pd+2].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[Fe+2].CN(C=O)C>[CH3:11][O:12][C:13]1[CH:14]=[C:15]([CH:18]=[CH:19][CH:20]=1)[CH:16]=[O:17]

Participants

7

Reactant 3

HCID 284Formic AcidHCID 8471TriethylamineHCID 108029624-Formyl-2-methoxyphenyl trifluoromethanesulfonate

Product 1

HCID 115693-Methoxybenzaldehyde

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

To a round-bottomed flask equipped with magnetic stirring bar was charged DMF (5 mL) and triethylamine (2.81 g, 27.8 mmol). Next, 98% formic acid (1.28 g, 27.8 mmol) was added dropwise over 1 min. Then, 2a (1 g, 3.5 mmol) was added followed by Pd(OAc)2 (30 mg, 0.13 mmol) and DPPF (150 mg, 0.27 mmol). All the solids dissolved to give a clear orange solution. The mixture was then heated to 80° C. and after about 15 min a yellow solid precipitated. The mixture was cooled to room temperature and filtered. The filtrate was partitioned between Et2O (25 mL) and H2O (25 mL). The organic layer was further washed with H2O (25 mL) followed by brine. The organic phase was dried over anhydrous MgSO4 and evaporated under reduced pressure to yield a brown oil. Distillation under reduced pressure (0.1 torr) gave 3a as a colorless, mobile liquid (400 mg, 85%), lit. bp. 121° C./14 torr. 1H NMR (CDCl3): δ 9.97 (s, 1H), 7.47-7.42 (m, 2H), 7.39-7.37 (m, 1H), 7.20-7.14 (m, 1H), 3.86 (s, 3H); 13C NMR (CDCl3): δ 192.29, 160.38, 138.03, 130.22, 123.71, 121.70, 112.28, 55.67. Anal. Calcd for C8H8O2: C, 70.57; H, 5.92. Found: C, 70.27; H, 5.95.

Workup

  1. customTo a round-bottomed flask equipped with magnetic stirring bar
  2. dissolutionAll the solids dissolved
  3. customto give a clear orange solution
  4. customprecipitated
  5. temperatureThe mixture was cooled to room temperature
  6. filtrationfiltered
  7. customThe filtrate was partitioned between Et2O (25 mL) and H2O (25 mL)
  8. washThe organic layer was further washed with H2O (25 mL)
  9. dry with materialThe organic phase was dried over anhydrous MgSO4
  10. customevaporated under reduced pressure
  11. customto yield a brown oil
  12. distillationDistillation under reduced pressure (0.1 torr)

Sources & evidence

ORD record
ord-c6d131ff815349a2bf1ece9f543e8e28
Source dataset
uspto-grants-2014_12
Patent number
US08921614B1

Reaction notes

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