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

HRID 982903Notes

Reaction equation

HRID 982903 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[Ti](Cl)(Cl)Cl>[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 45.1%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent3×

Procedure

Under an argon stream, CH2Cl2 solvent (0.1 ml) was placed in a flask beforehand, and thereto were added dropwise, at 0 to 5° C., a mixed solution of dimethyl cis-9-octadecenedioate (141 mg, 0.41 mmol) and Bu3N (230 mg, 1.24 mmol) in CH2Cl2 (1.7 ml) and a solution of TiCl4 (132 μl, 1.20 mmol) in CH2Cl2 (2.0 ml) at the same time over a period of 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 (57 mg, 45%) and a by-product (34-membered ring; 22 mg, 17%).

Workup

  1. additionbeforehand, and thereto were 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-188917c1966149b2aabaef9af2f0bed2
Source dataset
uspto-grants-2005_03
Patent number
US06861551B2

Reaction notes

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