Hydrochloric Acid → HCID 58611869, compound

HRID 2375210Notes

Reaction equation

HRID 2375210 reaction equation
[O:1]=[C:2]([O:14]C1CCCCO1)[CH2:3][C:4]1[CH:13]=[CH:12][C:7]([C:8]([O:10][CH3:11])=[O:9])=[CH:6][CH:5]=1.Br[CH2:22][CH2:23][CH2:24][CH2:25][CH2:26]Br.[H-].[Na+].Cl>CN(C)P(=O)(N(C)C)N(C)C.O1CCOCC1.O.C(OCC)(=O)C>[CH3:11][O:10][C:8]([C:7]1[CH:6]=[CH:5][C:4]([C:3]2([C:2]([OH:14])=[O:1])[CH2:26][CH2:25][CH2:24][CH2:23][CH2:22]2)=[CH:13][CH:12]=1)=[O:9]

Participants

9

Reactant 4

HCID 313Hydrochloric AcidHCID 81001,5-DibromopentaneHCID 24758Sodium hydrideHCID 58611847HCID 58611847, compound

Product 1

HCID 58611869HCID 58611869, compoundYield 68.6%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 12679HexamethylphosphoramideSolventHCID 312751,4-DioxaneSolvent

Procedure

The crude methyl 4-[2-oxo-2-(tetrahydro-2H-pyran-2-yl-oxy)ethyl]benzoate (E12) (1.64 g) (0.671 g, 3.45 mmol)) and 1,5-dibromopentane (1.200 g, 5.21 mmol) were dissolved in dry hexamethylphosphoric triamide (6 ml) and the mixture was cooled in an ice bath. To the cooled solution, a 60% suspension of NaH in mineral oil (0.425 g, 10.62 mmol) was added and the reaction mixture was stirred at ice bath temperature for 15 minutes and 1.5 hours at room temperature. The reaction mixture was diluted with dioxane (20 ml) and water (15 ml), and the pH of the medium was brought to pH 1 with conc. HCl (3 ml). The reaction mixture was stirred for 20 minutes and poured into ethyl acetate (100 ml). The organic layer was washed with 2N HCl (2×50 ml), brine (50 ml), and dried (Na2SO4). The solvents were evaporated and the residue was chromatographed on silicagel (50 g) with toluene-ethyl acetate-acetic acid (8:2:0.1) as eluent to give the title compound (0.621 g, 68.5% based on E11) as a white solid. 1H NMR (CDCl3, HMDSO) δ: 0.94-2.09 (8H, m); 2.25-2.65 (2H, m); 3.88 (3H, s); 7.49 (2H, d, J=8.6 Hz); 7.96 (2H, d, J=8.6 Hz); 10.07 (1H, br s).

Workup

  1. temperaturethe mixture was cooled in an ice bath
  2. custom1.5 hours
  3. customat room temperature
  4. stirringThe reaction mixture was stirred for 20 minutes
  5. washThe organic layer was washed with 2N HCl (2×50 ml), brine (50 ml)
  6. dry with materialdried (Na2SO4)
  7. customThe solvents were evaporated
  8. customthe residue was chromatographed on silicagel (50 g) with toluene-ethyl acetate-acetic acid (8:2:0.1) as eluent

Sources & evidence

ORD record
ord-67f1b98ad27d4a28a0f03649a71a4dd7
Source dataset
uspto-grants-2008_12
Patent number
US07465719B2

Reaction notes

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