Bromide ion → HCID 21225112, compound

HRID 1584668Notes

Reaction equation

HRID 1584668 reaction equation
[H-].[Na+].[Na+].[I-].[C:5]([O:14][CH2:15][CH:16]=[CH2:17])(=[O:13])[CH2:6][C:7]([O:9][CH2:10][CH:11]=[CH2:12])=[O:8].Br[CH2:19][CH2:20][CH2:21][C:22]([C:24]1[C:29]([CH3:30])=[CH:28][C:27]([CH3:31])=[CH:26][C:25]=1[CH3:32])=[O:23].OP(O)(O)=O.[Br-].C([O-])(=O)CC([O-])=O>C1COCC1>[CH3:32][C:25]1[CH:26]=[C:27]([CH3:31])[CH:28]=[C:29]([CH3:30])[C:24]=1[C:22](=[O:23])[CH2:21][CH2:20][CH2:19][CH:6]([C:7]([O:9][CH2:10][CH:11]=[CH2:12])=[O:8])[C:5]([O:14][CH2:15][CH:16]=[CH2:17])=[O:13]

Participants

9

Reactant 7

HCID 259Bromide ionHCID 1004Phosphoric AcidHCID 5238Sodium IodideHCID 9084Malonate IonHCID 24758Sodium hydrideHCID 228227Diallyl malonateHCID 212251134-Bromo-1-(2,4,6-trimethylphenyl)butan-1-one

Product 1

HCID 21225112HCID 21225112, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a slurry of NaH (60% in mineral oil, 0.36 g) and NaI (0.55 g) in dry THF (37 mL) was added diallyl malonate (3.2 g, 18.5 mmol). The resulting slurry was stirred at room temp. for 30 min., then 4-bromo-1-(2,4,6-trimethylphenyl)-1-butanone (1.0 g, 3.7mmol) was added. This mixture was heated at the reflux temperature for 18 h, cooled to room temp., and acidified with a 1M H3PO4 solution (10 mL). The resulting mixture was extracted with CH2Cl2 (2×100 mL). The combined organic phases were sequentially washed with a 1M H3PO4 solution (100 mL), and a saturated NaCl solution (50 ml), dried (MgSO4), and concentrated under reduced pressure (kugelrohr, 80° C., (4 mmHg)) to give a crude oil which was further purified using rotary chromatography (SiO2, gradient from 1% EtOAc/hexane to 5% EtOAc/hexane) to give starting bromide (0.34 g) followed by the desired malonate (0.36 g). The resultant compound is illustrated below and was used in the next step without further purification as described in example 1 step 4. ##STR43##

Workup

  1. temperatureThis mixture was heated at the reflux temperature for 18 h
  2. temperaturecooled to room temp.
  3. extractionThe resulting mixture was extracted with CH2Cl2 (2×100 mL)
  4. washThe combined organic phases were sequentially washed with a 1M H3PO4 solution (100 mL)
  5. dry with materiala saturated NaCl solution (50 ml), dried (MgSO4)
  6. concentrationconcentrated under reduced pressure (kugelrohr, 80° C., (4 mmHg))
  7. customto give a crude oil which
  8. customwas further purified
  9. customto give
  10. customwas used in the next step without further purification

Sources & evidence

ORD record
ord-605f0d79c3324f6587f7077bc6b6c09b
Source dataset
uspto-grants-1999_08
Patent number
US05932763

Reaction notes

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