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

HRID 982907Notes

Reaction equation

HRID 982907 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 18.2%

Reagents, catalysts & solvents 2

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

Procedure

Under an argon stream, CH2Cl2 solvent (0.5 ml) was placed in a two-necked flask beforehand, and thereto was 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 (4.5 ml) over a period of about 1 hour by means of a microfeeder. ZrCl4 (338 mg, 1.45 mmol) was added portionwise every 10 minutes from 5 minutes after the start of dropwise addition of the above mixed solution, 6 times in total. After the completion of the dropwise addition of the mixed solution of the ester and the amine, 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 (28 mg, 18%) and a by-product (34-membered ring; 18 mg, 12%).

Workup

  1. additionbeforehand, and thereto was added dropwise, at 0 to 5° C.
  2. additionafter the start of dropwise addition of the above mixed solution, 6 times in total
  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-33ed17d7310f4693a0a0f4824b8d386d
Source dataset
uspto-grants-2005_03
Patent number
US06861551B2

Reaction notes

Loading…