3,4-Dichlorobenzaldehyde → 3-(3,4-Dichlorophenylmethylene)-1-(4-fluorobenzenesulfonyl)-5-methyl-2-pyrrolidinone

HRID 2086918Notes

Reaction equation

HRID 2086918 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([N:11]2[CH:15]([CH3:16])[CH2:14][CH2:13][C:12]2=[O:17])(=[O:10])=[O:9])=[CH:4][CH:3]=1.C[Si]([N-][Si](C)(C)C)(C)C.[Na+].[Cl:28][C:29]1[CH:30]=[C:31]([CH:34]=[CH:35][C:36]=1[Cl:37])[CH:32]=O>C1COCC1.Cl>[Cl:28][C:29]1[CH:30]=[C:31]([CH:32]=[C:13]2[CH2:14][CH:15]([CH3:16])[N:11]([S:8]([C:5]3[CH:4]=[CH:3][C:2]([F:1])=[CH:7][CH:6]=3)(=[O:10])=[O:9])[C:12]2=[O:17])[CH:34]=[CH:35][C:36]=1[Cl:37]

Participants

6

Reactant 3

HCID 227103,4-DichlorobenzaldehydeHCID 2724254Sodium bis(trimethylsilyl)amideHCID 227253831-(4-Fluorobenzenesulfonyl)-5-methyl-2-pyrrolidinone

Product 1

HCID 698945963-(3,4-Dichlorophenylmethylene)-1-(4-fluorobenzenesulfonyl)-5-methyl-2-pyrrolidinoneYield 7.3%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

A flame dried flask was charged with 332 mg 1-(4-fluorobenzenesulfonyl)-5-methyl-2-pyrrolidinone (prepared above, 1.29 mmol, 1.0 equiv) and 10 mL THF under N2. The solution was cooled to −78° C. followed by the addition of 1.68 mL of a 1.0 M solution of sodium bis(trimethylsilyl)amide (1.68 mmol, 1.3 equiv). The solution was allowed to stir for an additional 40 min followed by the addition of 271 mg 3,4-dichlorobenzaldehyde (1.54 mmol, 1.2 equiv) in 2 mL THF. After stirring an additional 10 min, the solution was diluted with 10 mL 0.1 N HCl and allowed to warm to rt. The solution was then extracted (3×Et2O), washed with brine, dried (MgSO4), and concentrated under reduced pressure. Purification via flash chromatography (SiO2, 1% MeOH/CH2Cl2) gave the product 3-(3,4-dichlorophenylmethylene)-1-(4-fluorobenzenesulfonyl)-5-methyl-2-pyrrolidinone as a white foam (39 mg, 0.0937 mmol, 7%). 1H NMR (DMSO, 400 MHz) δ 8.28 (m, 2 H), 7.96 (d, J=2 Hz, 1H), 7.85 (d, J=8.4 Hz, 1 H), 7.70-7.63 (m, 3 H), 7.45 (t, J=2.9 Hz, 1 H), 4.86 (m, 1 H), 3.59 (m, 1 H), 2.92 (m, 1 H), 1.56 (d, J=6.0 Hz, 3 H).

Workup

  1. customA flame dried flask
  2. stirringAfter stirring an additional 10 min
  3. temperatureto warm to rt
  4. extractionThe solution was then extracted (3×Et2O)
  5. washwashed with brine
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated under reduced pressure
  8. customPurification via flash chromatography (SiO2, 1% MeOH/CH2Cl2)

Sources & evidence

ORD record
ord-99c6a02242b841fb91d7c06593181c2e
Source dataset
uspto-grants-2004_04
Patent number
US06727267B2

Reaction notes

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