Potassium Carbonate → HCID 502056, compound

HRID 841099Notes

Reaction equation

HRID 841099 reaction equation
[OH:1][C:2]1[CH:11]=[C:10]([O:12][C:13](=[O:18])[C:14]([CH3:17])([CH3:16])[CH3:15])[CH:9]=[C:8]2[C:3]=1[C:4]([CH2:20][CH2:21][CH3:22])=[CH:5][C:6](=[O:19])[O:7]2.C(=O)([O-])[O-].[K+].[K+].Cl[C:30]([CH3:34])([CH3:33])[C:31]#[CH:32]>CC(=O)CC.CN(C=O)C.[I-].C([N+](CCCC)(CCCC)CCCC)CCC.[Cl-].[Cl-].[Zn+2]>[CH3:33][C:30]1([CH3:34])[O:1][C:2]2[C:3]3[C:4]([CH2:20][CH2:21][CH3:22])=[CH:5][C:6](=[O:19])[O:7][C:8]=3[CH:9]=[C:10]([O:12][C:13](=[O:18])[C:14]([CH3:16])([CH3:17])[CH3:15])[C:11]=2[CH:32]=[CH:31]1

Participants

8

Reactant 3

HCID 11430Potassium CarbonateHCID 706791-Butyne, 3-chloro-3-methyl-HCID 12017526HCID 12017526, compound

Product 1

HCID 502056HCID 502056, compoundYield 73%

Reagents, catalysts & solvents 4

HCID 67553Tetrabutylammonium IodideCatalystHCID 3007855ZincchlorideCatalystHCID 6228DimethylformamideSolventHCID 6569Methyl Ethyl KetoneSolvent

Conditions

Temperature
60 °C

Procedure

To a suspension of compound 7b (304 mg, 1 mmol) in 2-butanone (13 mL) and DMF (1.3 mL) was added potassium carbonate (346 mg, 2.5 mmol), 3-chloro-3-methyl-1-butyne (0.56 mL, 5 mmol) and tetrabutylammonium iodide (360 mg, 1 mmol). The reaction mixture was heated to 60° C. for 1 h, then anhydrous ZnCl2 (1.0 M solution in ether, 1.3 mL) was added. The reaction mixture was heated to 70° C. for 26 h, then cooled to r.t., quenched with saturated aqueous NH4Cl (25 mL), and extracted with ethyl acetate (2×75 mL). The organic solutions were combined, washed with brine, dried (Na2SO4), and concentrated. The crude product obtained was purified by silica gel chromatography (8:1 hexane/ethyl acetate) to obtain 5b as a yellow solid (270 mg, 73%). mp: 65-68° C.; Rf: 0.54 (4:1 hexane/ethyl acetate); 1H NMR (CDCl3) 1.04 (3H, d, J=7.2 Hz), 1.39 (9H, s), 1.52 (6H, s), 1.66-1.71 (2H, m), 2.90 (2H, t, J=7.8 Hz), 5.62 (1H, d, J=10.2 Hz), 6.07 (1H, s), 6.30 (1H, d, J=10.2 Hz), 6.62 (1H, s); 13C NMR (CDC13) 13.8, 22.9, 26.9, 27.8, 38.3, 39.3, 78.1, 103.5, 107.9, 110.9, 113.4, 115.9, 129.1, 148.9, 152.0, 155.1, 157.4, 160.6, 176.2; IR (film): 2967, 1750, 1616, 1364, 1142 cm−1; MS m/e 371 (M+1); Anal. Calcd. for C22H26O5: C, 71.33; H, 7.07. Found: C, 71.08; H, 7.35.

Workup

  1. temperatureThe reaction mixture was heated to 70° C. for 26 h
  2. temperaturecooled to r.t.
  3. customquenched with saturated aqueous NH4Cl (25 mL)
  4. extractionextracted with ethyl acetate (2×75 mL)
  5. washwashed with brine
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated
  8. customThe crude product obtained
  9. customwas purified by silica gel chromatography (8:1 hexane/ethyl acetate)

Sources & evidence

ORD record
ord-777d8053d56041b584195a0ca901d6db
Source dataset
uspto-grants-2002_04
Patent number
US06369241B1

Reaction notes

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