Allyl bromide → 1-Allyl-cyclohexane-1,3-dicarboxylic acid diethyl ester

HRID 2199447Notes

Reaction equation

HRID 2199447 reaction equation
C(N[CH:5]([CH3:7])[CH3:6])(C)C.[Li]CCCC.CN1C(=O)N(C)CCC1.[CH2:22]([O:24][C:25]([CH:27]1[CH2:32][CH2:31][CH2:30][CH:29]([C:33]([O:35][CH2:36][CH3:37])=[O:34])[CH2:28]1)=[O:26])[CH3:23].C(Br)C=C>C1COCC1>[CH2:36]([O:35][C:33]([C:29]1([CH2:7][CH:5]=[CH2:6])[CH2:30][CH2:31][CH2:32][CH:27]([C:25]([O:24][CH2:22][CH3:23])=[O:26])[CH2:28]1)=[O:34])[CH3:37]

Participants

7

Reactant 5

HCID 7841Allyl bromideHCID 7912DiisopropylamineHCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-HCID 143870Diethyl cyclohexane-1,3-dicarboxylateHCID 178418339Butyllithium

Product 1

HCID 671086101-Allyl-cyclohexane-1,3-dicarboxylic acid diethyl esterYield 100.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To a cooled solution (−78° C.) of N,N-diisopropylamine (272 mL, 1.94 mol) in anhydrous THF (1.4 L) was added n-BuLi (1.6 M in hexane, 1.21 L, 1.94 mol) over the period of one hour and 20 minutes. The mixture was stirred at 0° C. for one hour and again cooled down to −78° C. DMPU (834 mL, 6.92 mol) was added dropwise, followed by the addition of the solution of cyclohexane-1,3-dicarboxylic acid diethyl ester from step 1 (316 g, 1.38 mol) in THF (400 mL). The mixture was stirred at −78° C. for 2.5 hours, and then allyl bromide (132 mL, 1.52 mol) was added. The mixture was warmed up to rt slowly and stirred at rt overnight. The mixture was quenched with ice-cold aqueous HCl (1 N, 1 L), diluted with ethyl acetate (30 mL) and extracted. The organic layer was washed with water (4×1.5 L), brine, dried over Na2SO4 and concentrated under reduced pressure to afford 371 g of the title compound as a thick oil, which was used in the next step without further purification.

Workup

  1. temperatureagain cooled down to −78° C
  2. stirringThe mixture was stirred at −78° C. for 2.5 hours
  3. temperatureThe mixture was warmed up to rt slowly
  4. stirringstirred at rt overnight
  5. customThe mixture was quenched with ice-cold aqueous HCl (1 N, 1 L)
  6. additiondiluted with ethyl acetate (30 mL)
  7. extractionextracted
  8. washThe organic layer was washed with water (4×1.5 L), brine
  9. dry with materialdried over Na2SO4
  10. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-030aa680f3454506902ebc46910ad992
Source dataset
uspto-grants-2016_06
Patent number
US09359297B2

Reaction notes

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