Benzaldehyde → HCID 22000958, compound

HRID 1976342Notes

Reaction equation

HRID 1976342 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:6]=[CH:7][CH:8]=1)[NH2:5].[CH3:9][C:10]([OH:14])(C#C)[CH3:11].[CH:15](=O)[C:16]1C=CC=CC=1.C(O)(=O)C1C=CC=CC=1.[OH-].[Na+]>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(C)C=CC=CC=1.C(N(CC)CC)C>[CH3:9][CH:10]([CH3:11])[OH:14].[NH2:5][C:4]1[CH:3]=[C:2]([C:15]#[CH:16])[CH:8]=[CH:7][CH:6]=1

Participants

10

Reactant 5

HCID 240BenzaldehydeHCID 243Benzoic AcidHCID 82582-Methyl-3-butyn-2-olHCID 115623-BromoanilineHCID 14798Sodium Hydroxide

Product 1

HCID 22000958HCID 22000958, compound

Reagents, catalysts & solvents 4

HCID 11776TriphenylphosphineCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 1140TolueneSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 3-bromoaniline (1.72 g, 10 mmol), 2-methyl-3-butyn-2-ol (1.1 g, 13 mmol), benzaldehyde (0.3 g, 2.8 mmol, containing some benzoic acid impurity), triethylamine (3 g), toluene (3 g), dichlorobis(triphenylphosphine)palladium (15 mg), and triphenylphosphine (80 mg) was deaerated by bubbling nitrogen and heated to 80° C. and treated with Cul (10 mg). This mixture was refluxed for 7 hours. The cooled reaction mixture was treated with aq NaOH (3 mL, 5 mM). The aqueous phase was separated and the organic phase was distilled to remove TEA with more toluene being added. The resulting toluene solution was treated with aq HCl (5 mL, 9%). After 30 min the aqueous phase was separated and basified with 50% NaOH. The precipitated solid was filtered and dried to afford 1.2 g of 3-aminophenylacetylene dimethylcarbinol.

Workup

  1. customby bubbling nitrogen
  2. additiontreated with Cul (10 mg)
  3. temperatureThis mixture was refluxed for 7 hours
  4. customThe cooled reaction mixture
  5. customThe aqueous phase was separated
  6. distillationthe organic phase was distilled
  7. customto remove TEA with more toluene being
  8. additionadded
  9. additionThe resulting toluene solution was treated with aq HCl (5 mL, 9%)
  10. customAfter 30 min the aqueous phase was separated
  11. filtrationThe precipitated solid was filtered
  12. customdried

Sources & evidence

ORD record
ord-d9eff64f486443b98b405c475b62e052
Source dataset
uspto-grants-2001_05
Patent number
US06225499B1

Reaction notes

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