Dimethylformamide → 2-Chloro-5,5-dimethyl-1-cyclohexenecarbaldehyde

HRID 1920487Notes

Reaction equation

HRID 1920487 reaction equation
CN(C)[CH:3]=[O:4].O=P(Cl)(Cl)[Cl:8].[CH3:11][C:12]1([CH3:19])[CH2:17][CH2:16][C:15](=O)[CH2:14][CH2:13]1>C(Cl)Cl>[Cl:8][C:15]1[CH2:16][CH2:17][C:12]([CH3:19])([CH3:11])[CH2:13][C:14]=1[CH:3]=[O:4]

Participants

5

Reactant 3

HCID 6228Dimethylformamide2×HCID 24813Phosphorus oxychlorideHCID 138166Cyclohexanone, 4,4-dimethyl-

Product 1

HCID 137424062-Chloro-5,5-dimethyl-1-cyclohexenecarbaldehyde

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of N,N-dimethylformamide (1.37 eq.) in CH2Cl2 (1.5 vol.) was cooled to 0° C. and then POCl3 (1.25 eq.) was added slowly to the N,N-dimethylformamide solution at below 25° C. The resulting solution was allowed to warm up to room temperature. A solution of 4,4-dimethylcyclohexanone (1.00 eq.) in CH2Cl2 (1.4 vol.) was added slowly to the above solution at below 30° C., and then the reaction mixture was stirred at 45° C. overnight. The reaction mixture was quenched into a cooled 10% sodium acetate solution (30.0 vol.) at below 15° C., followed by a CH2Cl2 rinse (4.6 vol.). The quenched mixture was stirred while allowing it to warm up to room temperature. The organic layer was separated and then aqueous layer was extracted with CH2Cl2 (7.6 vol.×3). The organic layer and CH2Cl2 extracts were combined and concentrated to give a solution and the solution was used in the next step without purification. 1H NMR (400 MHz, CDCl3) δ 10.1 (1H, s, CHO) 1H NMR (400 MHz, CDCl3) δ 10.1 (1H, s, CHO), 2.61-2.57 (2H, m), 2.09 (2H, s), 1.54-1.51 (2H, m), 0.95 (6H, s).

Workup

  1. customThe reaction mixture was quenched into a cooled 10% sodium acetate solution (30.0 vol.) at below 15° C.
  2. washrinse (4.6 vol.)
  3. stirringThe quenched mixture was stirred
  4. temperatureto warm up to room temperature
  5. customThe organic layer was separated
  6. extractionaqueous layer was extracted with CH2Cl2 (7.6 vol.×3)
  7. concentrationconcentrated
  8. customto give a solution
  9. customthe solution was used in the next step without purification

Sources & evidence

ORD record
ord-9df48770775b4b2eb1088bce810a9fb3
Source dataset
uspto-grants-2012_05
Patent number
US08168784B2

Reaction notes

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