Formic Acid → HCID 12162157, compound

HRID 393972Notes

Reaction equation

HRID 393972 reaction equation
[C:1]([C:5]1[CH:10]=[C:9]([C:11]([CH3:14])([CH3:13])[CH3:12])[CH:8]=[C:7]([CH:15]([C:22]2[CH:27]=[CH:26][C:25]([C:28]#[N:29])=[CH:24][CH:23]=2)N2CCCCC2)[C:6]=1O)([CH3:4])([CH3:3])[CH3:2].[CH:31]([OH:33])=[O:32]>C1(C)C=CC=CC=1>[C:11]([C:9]1[CH:10]=[C:5]([C:1]([CH3:4])([CH3:3])[CH3:2])[C:6]2[O:32][C:31](=[O:33])[CH:15]([C:22]3[CH:23]=[CH:24][C:25]([C:28]#[N:29])=[CH:26][CH:27]=3)[C:7]=2[CH:8]=1)([CH3:14])([CH3:13])[CH3:12]

Participants

4

Reactant 2

HCID 284Formic AcidHCID 22648343HCID 22648343, compound

Product 1

HCID 12162157HCID 12162157, compoundYield 79.4%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
140 °C

Procedure

A solution of 11.33 g (28.0 mmol) of compound (206), prepared according to Example 3a, in 150 ml of dry toluene is degassed using argon and then 33.6 mg (0.057 mmol) of dichloro-[1,3-bis(diphenylphosphino)propane]palladium(II) and 4.22 ml (112 mmol) of formic acid are added. The autoclave is flushed with carbon monoxide and sealed, and a carbon monoxide pressure of 6 bar is then applied. The reaction mixture is maintained at 140° C. for 14 hours. After cooling to room temperature, the reaction mixture is poured into water and extracted three times using ethyl acetate. The organic phases are combined, dried over sodium sulfate and concentrated using a vacuum rotary evaporator. Filtration of the residue on silica gel using ethyl acetate and crystallisation of the pure fractions from methanol yields 7.72 g (79%) of compound (106) (Table 1), m.p. 136-137° C. Molecular weight C23H25NO2 (347.46). Analysis, calculated: C 79.51; H 7.25; N 4.03%. Analysis, found: C 79.36; H 6.98; N 3.82%. 1HNMR (300 MHz, CDCl3, ppm): 1.23 (s, 9H); 1.36 (s, 9H); 4.83 (s, 1H); 6.95 (m, 1H); 7.31 (m, 3H); 7.61 (d, 2H).

Workup

  1. customis degassed
  2. customThe autoclave is flushed with carbon monoxide
  3. customsealed
  4. temperatureAfter cooling to room temperature
  5. additionthe reaction mixture is poured into water
  6. extractionextracted three times
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated
  9. customa vacuum rotary evaporator
  10. filtrationFiltration of the residue on silica gel
  11. customethyl acetate and crystallisation of the pure fractions from methanol

Sources & evidence

ORD record
ord-6ca9e9ac37fd4bc281db4d5f8956413a
Source dataset
uspto-grants-2004_10
Patent number
US06809208B2

Reaction notes

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