Water → HCID 66969318, compound

HRID 1362522Notes

Reaction equation

HRID 1362522 reaction equation
[CH3:1][Si](C)(C)[N-][Si](C)(C)C.[K+].[CH:11]([C:14]1[CH:19]=[CH:18][C:17]([C:20](=O)[CH3:21])=[C:16](OC)[CH:15]=1)([CH3:13])[CH3:12].[OH2:25].[C:26](OCC)(=O)[CH3:27]>[Br-].C([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)C.O1CCCC1.C1(C)C=CC=CC=1>[CH:11]([C:14]1[CH:19]=[CH:18][C:17]([C:20]([CH3:21])=[CH:26][CH3:27])=[C:16]([O:25][CH3:1])[CH:15]=1)([CH3:13])[CH3:12]

Participants

8

Reactant 4

HCID 962WaterHCID 8857Ethyl AcetateHCID 3251421Potassium bis(trimethylsilyl)amideHCID 66968824HCID 66968824, compound

Product 1

HCID 66969318HCID 66969318, compound

Reagents, catalysts & solvents 3

HCID 73727Phosphonium, ethyltriphenyl-, bromide (1:1)CatalystHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

Ethyltriphenylphosphonium bromide (67.49 g, 181.79 mmol) is introduced in 675 ml of tetrahydrofuran. This white suspension is admixed over the course of 30 minutes with potassium hexamethyldisilazide (363.57 ml of a 0.5 M solution in toluene, 181.79 mmol), at a temperature between −5° C. and 0° C. The resulting red suspension is then stirred at room temperature for two and a half hours. Following dropwise addition (35 minutes) of 4′-isopropyl-2′-methoxyacetophenone (23.3 g, 121.19 mmol), in solution in 280 ml of tetrahydrofuran, the temperature rises to 29° C. The orange-brown reaction mixture is stirred at room temperature for four days. The batch is poured into 100 ml of water and admixed with ethyl acetate (250 ml). After 10-minute stirring, the organic phase is separated off and washed with water (40 ml) and brine (40 ml). After drying (Na2SO4) and removal of the solvent on a rotary evaporator, the residue is chromatographed on silica gel (eluent: ethyl acetate/hexane). This isolates more than 100% (26.44 g) of the product as an E/Z mixture, although one of the stereoisomers is predominant.

Workup

  1. customat a temperature between −5° C. and 0° C
  2. customrises to 29° C
  3. stirringThe orange-brown reaction mixture is stirred at room temperature for four days
  4. stirringAfter 10-minute stirring
  5. customthe organic phase is separated off
  6. washwashed with water (40 ml) and brine (40 ml)
  7. customAfter drying
  8. custom(Na2SO4) and removal of the solvent
  9. customon a rotary evaporator
  10. customthe residue is chromatographed on silica gel (eluent: ethyl acetate/hexane)

Sources & evidence

ORD record
ord-5dee497b67684a7ba31f8566e824b13a
Source dataset
uspto-grants-2011_02
Patent number
US07880042B2

Reaction notes

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