Water → Methyl 17-oxocycloheptadec-8-ene-1-carboxylate

HRID 982906Notes

Reaction equation

HRID 982906 reaction equation
[C:1]([O:23]C)(=O)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8]/[CH:9]=[CH:10]\[CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][C:18]([O:20][CH3:21])=[O:19].N(CCCC)(CCCC)CCCC.O>C(Cl)Cl.[Cl-].[Cl-].[Cl-].[Cl-].[Zr+4]>[CH3:21][O:20][C:18]([CH:17]1[CH2:16][CH2:15][CH2:14][CH2:13][CH2:12][CH2:11][CH:10]=[CH:9][CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][CH2:2][C:1]1=[O:23])=[O:19]

Participants

6

Reactant 3

HCID 962WaterHCID 7622TributylamineHCID 11198603Dimethyl cis-9-octadecenedioate

Product 1

HCID 69720201Methyl 17-oxocycloheptadec-8-ene-1-carboxylateYield 28%

Reagents, catalysts & solvents 2

HCID 9856075Zirconium chloride (ZrCl4), (T-4)-CatalystHCID 6344DichloromethaneSolvent2×

Procedure

Under an argon stream, to a suspension of ZrCl4 (338 mg, 1.45 mmol) in CH2Cl2 (1.0 ml) were added dropwise, at 0 to 5° C., a mixed solution of dimethyl cis-9-octadecenedioate (170 mg, 0.50 mmol) and Bu3N (278 mg, 1.50 mmol) in CH2Cl2 (4.0 ml) over a period of about 1 hour by means of a microfeeder. The whole was further mixed at the same temperature for 15 minutes. Water was added to the reaction mixture and the resulting mixture was stirred and then extracted with ether. The organic layer was washed with water and saturated brine, and then dried over anhydrous sodium sulfate. After the evaporation of the solvent under reduced pressure, the crude product was purified by silica gel chromatography (hexane/ethyl acetate=20/1→10/1) to obtain the aimed product (43 mg, 28%) and a by-product (34-membered ring; 6 mg, 4%).

Workup

  1. additionwere added dropwise, at 0 to 5° C.
  2. additionThe whole was further mixed at the same temperature for 15 minutes
  3. extractionextracted with ether
  4. washThe organic layer was washed with water and saturated brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. customAfter the evaporation of the solvent under reduced pressure
  7. customthe crude product was purified by silica gel chromatography (hexane/ethyl acetate=20/1→10/1)

Sources & evidence

ORD record
ord-4ac245b5d0f94da19091fe4ea5178529
Source dataset
uspto-grants-2005_03
Patent number
US06861551B2

Reaction notes

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