Sodium hydride → Methyl 2-(4-(4-bromophenyl)-4-(hydroxymethyl)cyclohexylidene)acetate

HRID 881716Notes

Reaction equation

HRID 881716 reaction equation
[H-].[Na+].[CH3:3][O:4][C:5]([CH2:7]P(OC)(OC)=O)=[O:6].[Br:14][C:15]1[CH:20]=[CH:19][C:18]([C:21]2([CH2:28][OH:29])[CH2:26][CH2:25][C:24](=O)[CH2:23][CH2:22]2)=[CH:17][CH:16]=1>CO>[Br:14][C:15]1[CH:16]=[CH:17][C:18]([C:21]2([CH2:28][OH:29])[CH2:26][CH2:25][C:24](=[CH:7][C:5]([O:4][CH3:3])=[O:6])[CH2:23][CH2:22]2)=[CH:19][CH:20]=1

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 80029Trimethyl phosphonoacetateHCID 867008224-(4-Bromophenyl)-4-(hydroxymethyl)cyclohexanone

Product 1

HCID 86700824Methyl 2-(4-(4-bromophenyl)-4-(hydroxymethyl)cyclohexylidene)acetateYield 86.3%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a round bottom flask containing methanol (60 ml) was added sodium hydride (0.78 g, 19.37 mmol) portion-wise at room temperature under stirring, Trimethyl phosphonoacetate (2.58 ml, 17.88 mmol) was added drop-wise and the resulting mixture was stirred at room temperature for 30 minutes. To this mixture was then added 4-(4-bromophenyl)-4-(hydroxymethyl)cyclohexanone (4.22 g, 14.90 mmol) in several portions and stirred at room temperature for overnight. The reaction mixture was then quenched with a saturated solution of ammonium chloride and subsequently concentrated to remove excess methanol. The residue was taken in saturated ammonium chloride solution and extracted twice with EtOAc. The combined organic portion was dried over sodium sulfate and concentrated to afford a crude product. Column purification afforded the title compound as viscous oil (4.36 g, 86% yield). LC/MS, ESI-MS: non-ionizable, RT: 1.32 (Condition E).

Workup

  1. stirringthe resulting mixture was stirred at room temperature for 30 minutes
  2. customThe reaction mixture was then quenched with a saturated solution of ammonium chloride
  3. concentrationsubsequently concentrated
  4. customto remove excess methanol
  5. extractionextracted twice with EtOAc
  6. dry with materialThe combined organic portion was dried over sodium sulfate
  7. concentrationconcentrated
  8. customto afford a crude product
  9. customColumn purification

Sources & evidence

ORD record
ord-d302e30d45c54b549ea239be04c069cc
Source dataset
uspto-grants-2015_03
Patent number
US08993619B2

Reaction notes

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