Bromoacetic Acid → HCID 12462879, compound

HRID 1908701Notes

Reaction equation

HRID 1908701 reaction equation
P([O-])([O:5][CH2:6][CH3:7])OCC.[H-].[Na+].Br[CH2:12][C:13]([OH:15])=O.[C:16]1(=[O:22])[CH2:21][CH2:20][CH2:19][CH2:18][CH2:17]1>COCCOC>[OH:15][C:13]1[CH:12]=[C:18]2[C:17]([C:6](=[O:5])[CH2:7][C:16]3([O:22]2)[CH2:21][CH2:20][CH2:19][CH2:18][CH2:17]3)=[CH:16][CH:21]=1

Participants

6

Reactant 4

HCID 6227Bromoacetic AcidHCID 7967CyclohexanoneHCID 24758Sodium hydrideHCID 3780918Diethylphosphite

Product 1

HCID 12462879HCID 12462879, compound

Reagents, catalysts & solvents 1

HCID 80711,2-DimethoxyethaneSolvent2×

Procedure

To a solution of diethyl phosphite (4 mL, 31.0 mmol) in 1,2-dimethoxyethane (100 mL) was added 60% NaH (3.72 g, 93 mmol). When gas evolution had mostly ceased (10 min), a solution of bromoacetic acid (4.3 g, 30.9 mmol) in 1,2-dimethoxyethane (30 mL) was added slowly. When gas evolution had again ceased, cyclohexanone (3.2 mL, 30.9 mmol) was added dropwise. The reaction mixture was stirred at room temperature for 1 h, then was quenched with ethanol (5 mL) and was poured into ice water. The aqueous layer was washed with ether, acidified to pH 4 with conc. HCl, and then extracted with ether. The extracts were dried over Na2SO4, filtered and were evaporated in vacuo. The title compound was afforded as a yellow-orange oil, which was mixed in POCl3 (25 mL, 268.2 mmol) with resorcinol (3.39 g, 30.8 mmol) and ZnCl2 (5.9 g, 43.3 mmol). The mixture was stirred at room temperature for 5.5 h and was then poured onto ice. Extraction with ethyl acetate, followed by drying over Na2SO4, filtration and evaporation in vacuo, afforded the crude product as a dark orange oil. Chromatography on silica gel (7:3 hexane-ethyl acetate, eluant) yielded the title compound as an off-white solid, 3.14 g (44%). 1H NMR (300 MHz, DMSO-d6) δ 10.47 (br, 1H), 7.56 (d, J=8.5 Hz, 1H), 6.43 (m, 1H), 6.28 (d, J=2.4 Hz, 1H), 2.63 (s, 2H), 1.44-1.87 (m, 10H). MS (DCI+) m/z 233 (M+H).

Workup

  1. custom(10 min)
  2. customwas quenched with ethanol (5 mL)
  3. additionwas poured into ice water
  4. washThe aqueous layer was washed with ether
  5. extractionextracted with ether
  6. dry with materialThe extracts were dried over Na2SO4
  7. filtrationfiltered
  8. customwere evaporated in vacuo

Sources & evidence

ORD record
ord-3419cdb8ff5b4b20a3bbe4f18201755a
Source dataset
uspto-grants-2013_12
Patent number
US08598220B2

Reaction notes

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