Triethylamine → HCID 15171818, compound

HRID 654487Notes

Reaction equation

HRID 654487 reaction equation
[C:1]([C:3]1([CH3:17])[CH2:8][CH2:7][C:6]2[C:9]([CH3:16])=[C:10]([OH:15])[C:11]([CH3:14])=[C:12]([CH3:13])[C:5]=2[O:4]1)#[CH:2].Br[C:19]1[C:20]2[CH:27]=[CH:26][CH:25]=[CH:24][C:21]=2[S:22][CH:23]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(N(CC)CC)C>C(#N)C>[S:22]1[CH:23]=[C:19]([C:2]#[C:1][C:3]2([CH3:17])[CH2:8][CH2:7][C:6]3[C:9]([CH3:16])=[C:10]([OH:15])[C:11]([CH3:14])=[C:12]([CH3:13])[C:5]=3[O:4]2)[C:20]2[CH:27]=[CH:26][CH:25]=[CH:24][C:21]1=2

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 123250Benzo(b)thiophene, 3-bromo-HCID 14478563rac-3,4-dihydro-2-ethynyl-2,5,7,8-tetramethyl-2H-1-benzopyran-6ol

Product 1

HCID 15171818HCID 15171818, compoundYield 45.5%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

A mixture of 4.6 g (20 mmol) of rac-3,4-dihydro-2-ethynyl-2,5,7,8-tetramethyl-2H-1-benzopyran-6-ol, 6.4 g (30 mmol) of 3-bromobenzo[b]thiophene, 0.4 g of triphenylphosphine, 95 mg of cuprous iodide, 6 ml of triethylamine and 150 ml of acetonitrile was degassed with argon for 15 minutes. Palladium acetate, 110 mg, was then added and stirring at room-temperature was continued for 4 days. The solvent was evaporated under reduced pressure and the residue was partitioned between methylene chloride and saturated aqueous sodium bicarbonate solution. The organic layer was separated, dried over sodium sulfate and evaporated. The residue was chromatographed over 200 g of silica gel using methylene chloride/hexane 1:1(v/v) for elution. Crystallization of the combined clean fractions from ether/hexane yielded 3.3 g (45.5%) of colorless crystals with m.p. 123°-124° C. A lower melting modification with m.p. 88°-91° C. was also observed.

Workup

  1. customwas degassed with argon for 15 minutes
  2. additionPalladium acetate, 110 mg, was then added
  3. customThe solvent was evaporated under reduced pressure
  4. customthe residue was partitioned between methylene chloride and saturated aqueous sodium bicarbonate solution
  5. customThe organic layer was separated
  6. dry with materialdried over sodium sulfate
  7. customevaporated
  8. customThe residue was chromatographed over 200 g of silica gel
  9. washfor elution
  10. customCrystallization of the combined clean fractions from ether/hexane

Sources & evidence

ORD record
ord-5f3e06d6f181441c95f457e112375f0e
Source dataset
uspto-grants-1992_07
Patent number
US05132310

Reaction notes

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