Water → Ademetionine

HRID 1053539Notes

Reaction equation

HRID 1053539 reaction equation
[CH2:1]([O:21][CH:22]([CH2:30][CH3:31])[C:23]([O:25]C(C)(C)C)=[O:24])[CH2:2][CH2:3][CH2:4]/[CH:5]=[CH:6]\[CH2:7]/[CH:8]=[CH:9]\[CH2:10]/[CH:11]=[CH:12]\[CH2:13]/[CH:14]=[CH:15]\[CH2:16]/[CH:17]=[CH:18]\[CH2:19][CH3:20].FC(F)(F)C(O)=O.O>ClCCl>[CH2:1]([O:21][CH:22]([CH2:30][CH3:31])[C:23]([OH:25])=[O:24])[CH2:2][CH2:3][CH2:4]/[CH:5]=[CH:6]\[CH2:7]/[CH:8]=[CH:9]\[CH2:10]/[CH:11]=[CH:12]\[CH2:13]/[CH:14]=[CH:15]\[CH2:16]/[CH:17]=[CH:18]\[CH2:19][CH3:20]

Participants

5

Reactant 3

HCID 962WaterHCID 6422Trifluoroacetic acidHCID 86665233HCID 86665233, compound

Product 1

HCID 78210211AdemetionineYield 71%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

tert-Butyl 2-((5Z,8Z,11Z,14Z,17Z)-icosa-5,8,11,14,17-pentaen-1-yloxy)butanoate (19.6 g, 45.5 mmol) was dissolved in dichloromethane (200 mL) and placed under nitrogen. Trifluoroacetic acid (50 mL) was added and the reaction mixture was stirred at room temperature for one hour. Water was added and the aqueous phase was extracted twice with dichloromethane. The combined organic extract was washed with brine, dried (Na2SO4), filtered and concentrated. The residue was subjected to flash chromatography on silica gel using increasingly polar mixtures of heptane, ethyl acetate and formic acid (90:10:1→80:20:1) as eluent. Concentration of the appropriate fractions afforded 12.1 g (71% yield) of the title compound as an oil. 1H-NMR (300 MHz, CDCl3): δ 0.90-1.00 (m, 6H), 1.50 (m, 2H), 1.70 (m, 2H), 1.80 (m, 2H), 2.10 (m, 4H), 2.80-2.90 (m, 8H), 3.50 (m, 1H), 3.60 (m, 1H), 3.75 (t, 1H), 5.30-5.50 (m, 10H); MS (electro spray): 373.2 [M-H]−.

Workup

  1. extractionthe aqueous phase was extracted twice with dichloromethane
  2. extractionThe combined organic extract
  3. washwas washed with brine
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. temperatureincreasingly polar mixtures of heptane, ethyl acetate and formic acid (90:10:1→80:20:1) as eluent

Sources & evidence

ORD record
ord-4319ecd86d3d43949dcfa534d808051a
Source dataset
uspto-grants-2016_07
Patent number
US09394228B2

Reaction notes

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