Ethynylcyclohexane → Cyclohexylmethyl 5-(cyclohexylethynyl)furan-2-carboxylate

HRID 63322

Reaction equation

HRID 63322 reaction equation
Br[C:2]1[O:6][C:5]([C:7]([O:9][CH2:10][CH:11]2[CH2:16][CH2:15][CH2:14][CH2:13][CH2:12]2)=[O:8])=[CH:4][CH:3]=1.[C:17]([CH:19]1[CH2:24][CH2:23][CH2:22][CH2:21][CH2:20]1)#[CH:18]>CCN(CC)CC.[Cu]I>[CH:19]1([C:17]#[C:18][C:2]2[O:6][C:5]([C:7]([O:9][CH2:10][CH:11]3[CH2:16][CH2:15][CH2:14][CH2:13][CH2:12]3)=[O:8])=[CH:4][CH:3]=2)[CH2:24][CH2:23][CH2:22][CH2:21][CH2:20]1

Participants

5

Reactant 2

HCID 70263EthynylcyclohexaneHCID 86694615Cyclohexylmethyl 5-bromofuran-2-carboxylate

Product 1

HCID 86694616Cyclohexylmethyl 5-(cyclohexylethynyl)furan-2-carboxylate

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8471TriethylamineSolvent

Procedure

A mixture of cyclohexylmethyl 5-bromofuran-2-carboxylate (0.63 g, 2.19 mmol) and ethynylcyclohexane (0.32 g, 2.96 mmol) in Et3N (10 mL) was degassed by bubbling Ar. CuI (0.023 g, 0.119 mmol) and PdCl2(Ph3P)2 (0.0412 g, 0.0587 mmol) were added and the reaction mixture was degassed by alternating vac/Ar three 3 times. The reaction mixture was stirred at +70° C. under Ar overnight and concentrated under reduced pressure. The residue was partitioned between hexanes and aqueous NH4Cl (25%) and aqueous layer was extracted twice with hexanes. Combined organic layers were washed with brine, treated with activated charcoal and dried over anhydrous MgSO4. Concentration under reduced pressure gave cyclohexylmethyl 5-(cyclohexylethynyl)furan-2-carboxylate as an orange solid which was used directly in the next step without additional purification. Yield (0.75 g, quant.); 1H NMR (400 MHz, CDCl3) δ 7.10 (d, J=3.9 Hz, 1H), 6.50 (d, J=3.9 Hz, 1H), 4.10 (d, J=6.4 Hz, 2H), 1.56-2.66 (m, 1H), 1.63-1.84 (m, 9H), 1.42-1.60 (m, 4H), 1.10-1.40 (m, 6H), 0.96-1.10 (m, 2H).

Workup

  1. customwas degassed
  2. customby bubbling Ar
  3. customthe reaction mixture was degassed
  4. concentrationconcentrated under reduced pressure
  5. customThe residue was partitioned between hexanes and aqueous NH4Cl (25%) and aqueous layer
  6. extractionwas extracted twice with hexanes
  7. washCombined organic layers were washed with brine
  8. additiontreated with activated charcoal
  9. dry with materialdried over anhydrous MgSO4
  10. concentrationConcentration under reduced pressure

Sources & evidence

ORD record
ord-ee60ea3880d24478967c8fa9c727501a
Source dataset
uspto-grants-2016_09
Patent number
US09447078B2

Linked notes

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