4-Toluenesulfonyl chloride → Methyl 4-(2-cyano-1-{[(4-methylphenyl)sulfonyl]oxy}vinyl)benzoate

HRID 1926023Notes

Reaction equation

HRID 1926023 reaction equation
[C:1]([CH2:3][C:4]([C:6]1[CH:15]=[CH:14][C:9]([C:10]([O:12][CH3:13])=[O:11])=[CH:8][CH:7]=1)=[O:5])#[N:2].[C:16]1([CH3:26])[CH:21]=[CH:20][C:19]([S:22](Cl)(=[O:24])=[O:23])=[CH:18][CH:17]=1.C(N(CC)CC)C>ClCCl>[C:1]([CH:3]=[C:4]([C:6]1[CH:15]=[CH:14][C:9]([C:10]([O:12][CH3:13])=[O:11])=[CH:8][CH:7]=1)[O:5][S:22]([C:19]1[CH:20]=[CH:21][C:16]([CH3:26])=[CH:17][CH:18]=1)(=[O:24])=[O:23])#[N:2]

Participants

5

Reactant 3

HCID 73974-Toluenesulfonyl chlorideHCID 8471TriethylamineHCID 736021Methyl 4-(cyanoacetyl)benzoate

Product 1

HCID 86615759Methyl 4-(2-cyano-1-{[(4-methylphenyl)sulfonyl]oxy}vinyl)benzoateYield 97.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a mixture of methyl 4-(cyanoacetyl)benzoate (10.29 g), p-toluenesulfonyl chloride (11.58 g) and dichloromethane (110 mL) was added dropwise triethylamine (7.68 g) under ice-cooling. After stirring under ice-cooling for 2.5 hrs, the mixture was diluted with dichloromethane (100 mL), washed with water (150 mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent, hexane:methyl acetate=9:1→1:1) to give the title compound (17.60 g) as a mixture of (E)-form and (Z)-form (6:5).

Workup

  1. temperaturecooling
  2. temperaturecooling for 2.5 hrs
  3. washwashed with water (150 mL)
  4. dry with materialdried over anhydrous magnesium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified by silica gel column chromatography (eluent, hexane:methyl acetate=9:1→1:1)

Sources & evidence

ORD record
ord-06ffba59c10841ac9c3c11ed80ca8005
Source dataset
uspto-grants-2012_05
Patent number
US08178543B2

Reaction notes

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