2,4-Dichlorobenzaldehyde → alpha-[1-(4-Methylphenyl)ethenyl]-2,4-dichlorobenzenemethanol

HRID 1248991Notes

Reaction equation

HRID 1248991 reaction equation
C(C1C=C(C(C)C)C=C(C(C)C)C=1S(NN=[C:21]([C:23]1[CH:28]=[CH:27][C:26]([CH3:29])=[CH:25][CH:24]=1)[CH3:22])(=O)=O)(C)C.C[Li].[Cl:32][C:33]1[CH:40]=[C:39]([Cl:41])[CH:38]=[CH:37][C:34]=1[CH:35]=[O:36]>O1CCCC1>[CH3:29][C:26]1[CH:27]=[CH:28][C:23]([C:21]([CH:35]([C:34]2[CH:37]=[CH:38][C:39]([Cl:41])=[CH:40][C:33]=2[Cl:32])[OH:36])=[CH2:22])=[CH:24][CH:25]=1

Participants

5

Reactant 3

HCID 134042,4-DichlorobenzaldehydeHCID 867411431-(4-Methylphenyl)ethanone 2,4,6-triisopropylbenzenesulphonylhydrazoneHCID 178418348HCID 178418348, compound

Product 1

HCID 20225865alpha-[1-(4-Methylphenyl)ethenyl]-2,4-dichlorobenzenemethanol

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 1-(4-methylphenyl)ethanone-2,4,6-triisopropylbenzenesulfonylhydrazone (6.54 g) in tetrahydrofuran (80 ml) at -70° C. was dropwise added a solution of methyl lithium (25 ml, 1.3M in ether) while stirring and maintaining the temperature of the mixture below -60° C. After 10 minutes the reaction mixture was allowed to warm to room temperature. When evolution of nitrogen from the reaction mixture ceased, a solution of 2,4-dichlorobenzaldehyde (3.48 g) in tetrahydrofuran (10 ml) was rapidly added. After stirring for 1 hour at room temperature the reaction was quenched with a saturated aqueous ammonium chloride solution. The reaction mixture was concentrated under reduced pressure. The resulting residue was dissolved in ethyl acetate, washed with saturated aqueous sodium hydrogen carbonate, washed with water, dried over anhydrous magnesium sulphate and concentrated under reduced pressure to yield an oil. The oil was chromatographed on silica gel eluting with ethyl acetate-hexane (3:97) to yield α-[1-(4-methylphenyl)ethenyl]-2,4-dichlorobenzenemethanol δ (CDCl3): 1.86 (1H,d, J=5 Hz), 2.64-2.78 (1H, dd, J=13.5 Hz, J=10 Hz), 2.92-3.04 (1H,dd, J=15 Hz, J=5 Hz), 4.8 (1H,m), 5.38 (2H,d, J=6 Hz) and 7.16-7.5 (10H,m) as a yellow oil (2.1 g) having the formula: ##STR13##

Workup

  1. temperaturemaintaining the temperature of the mixture below -60° C
  2. stirringAfter stirring for 1 hour at room temperature the reaction
  3. customwas quenched with a saturated aqueous ammonium chloride solution
  4. concentrationThe reaction mixture was concentrated under reduced pressure
  5. dissolutionThe resulting residue was dissolved in ethyl acetate
  6. washwashed with saturated aqueous sodium hydrogen carbonate
  7. washwashed with water
  8. dry with materialdried over anhydrous magnesium sulphate
  9. concentrationconcentrated under reduced pressure
  10. customto yield an oil
  11. customThe oil was chromatographed on silica gel eluting with ethyl acetate-hexane (3:97)

Sources & evidence

ORD record
ord-18f79f9603ee458087ce6d540d60c2e6
Source dataset
uspto-grants-1986_12
Patent number
US04628104

Reaction notes

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