Potassium Carbonate → HCID 502055, compound

HRID 841098Notes

Reaction equation

HRID 841098 reaction equation
[OH:1][C:2]1[CH:11]=[C:10]([O:12][C:13](=[O:16])[CH2:14][CH3:15])[CH:9]=[C:8]2[C:3]=1[C:4]([CH2:18][CH2:19][CH3:20])=[CH:5][C:6](=[O:17])[O:7]2.C([O-])([O-])=O.[K+].[K+].Cl[C:28]([CH3:32])([CH3:31])[C:29]#[CH:30]>CC(=O)CC.CN(C=O)C.[I-].C([N+](CCCC)(CCCC)CCCC)CCC.[Cl-].[Cl-].[Zn+2]>[CH3:31][C:28]1([CH3:32])[O:1][C:2]2[C:3]3[C:4]([CH2:18][CH2:19][CH3:20])=[CH:5][C:6](=[O:17])[O:7][C:8]=3[CH:9]=[C:10]([O:12][C:13](=[O:16])[CH2:14][CH3:15])[C:11]=2[CH:30]=[CH:29]1

Participants

8

Reactant 3

HCID 11430Potassium CarbonateHCID 706791-Butyne, 3-chloro-3-methyl-HCID 5494875HCID 5494875, compound

Product 1

HCID 502055HCID 502055, compoundYield 27.3%

Reagents, catalysts & solvents 4

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

Conditions

Temperature
70 °C

Procedure

To a solution of 7-propionate 7a (0.83 g, 3.0 mmol) in 2-butanone (40 mL) and DMF (4 mL) were added tetrabutylammonium iodide (1.11 g, 3 rnmol), K2CO3 (1.04 g, 7.5 mmol), and 3-chloro-3-methyl-1-butyne (1.11 g, 3 mmol). The reaction mixture was heated at 60° C. for 1 h before ZnCl2 (3.9 mL of 1.0 M solution in ether, 3.9 mmol) was added. The temperature was then raised to 70° C. and maintained at that temperature for 21 h. The reaction mixture was cooled to room temperature and quenched with saturated aqueous NH4Cl (100 mL). The mixture was extracted with EtOAc (100 mL×2) and the combined organic layers were washed with brine (100 mL) and dried over Na2SO4. Evaporation of the solvent gave the crude product (1.9 g). After column chromtographic purification, 280 mg (27.1% yield) of the desired product 5a was obtained as a waxy solid. 1H NMR (DMSO-d6) 1.00 (3H, t, J=7.2 Hz), 1.16 (3H, t, J=7.5 Hz); 1.47 (6H, s), 1.61 (2H, m), 2.71 (2H, q, J=7.5 Hz), 2.89 (2H, t, J=7.8), 5.84 (1H, d, J=9.9 Hz), 6.17 (1H, s), 6.41 (1H, d, J=10.2 Hz); 13C NMR (DMSO-d6) 8.6, 13.7, 22.8, 26.6, 27.2, 37.4, 78.3, 103.6, 107.2, 110.8, 113.4, 115.5, 130.1, 148.5, 151.4, 154.4, 156.9, 159.3, 172.2; IR 1767 (s and sharp), 1723 (s and sharp), 1616 (s and sharp) cm−1; MS m/e 343 (M+1); Anal. Calcd. for C20H22O5: C, 70.16; H, 6.47. Found: C, 70.37; H, 6.51.

Workup

  1. additionwas added
  2. temperaturemaintained at that temperature for 21 h
  3. temperatureThe reaction mixture was cooled to room temperature
  4. customquenched with saturated aqueous NH4Cl (100 mL)
  5. extractionThe mixture was extracted with EtOAc (100 mL×2)
  6. washthe combined organic layers were washed with brine (100 mL)
  7. dry with materialdried over Na2SO4
  8. customEvaporation of the solvent
  9. customgave the crude product (1.9 g)
  10. customAfter column chromtographic purification

Sources & evidence

ORD record
ord-df3ee4ff4e2e4ecbb50f4e8bcaf68f69
Source dataset
uspto-grants-2002_04
Patent number
US06369241B1

Reaction notes

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