Diisopropylethylamine → 2-(2,2-Dimethyl-5-oxo-[1,3]dioxolan-4-ylidene)-N-(4-fluoro-2-methylsulfanyl-benzyl)-N-methyl-acetamide

HRID 2214669Notes

Reaction equation

HRID 2214669 reaction equation
[F:1][C:2]1[CH:10]=[CH:9][C:5]([CH2:6][NH:7][CH3:8])=[C:4]([S:11][CH3:12])[CH:3]=1.C(N(C(C)C)CC)(C)C.[CH3:22][C:23]1([CH3:33])[O:27][C:26](=[CH:28][C:29](Cl)=[O:30])[C:25](=[O:32])[O:24]1>C(Cl)Cl>[CH3:22][C:23]1([CH3:33])[O:27][C:26](=[CH:28][C:29]([N:7]([CH2:6][C:5]2[CH:9]=[CH:10][C:2]([F:1])=[CH:3][C:4]=2[S:11][CH3:12])[CH3:8])=[O:30])[C:25](=[O:32])[O:24]1

Participants

5

Reactant 3

HCID 81531DiisopropylethylamineHCID 21947442(4-Fluoro-2-methylsulfanyl-benzyl)-methyl-amineHCID 85435482(2,2-Dimethyl-5-oxo-[1,3]dioxolan-4-ylidene)-acetyl chloride

Product 1

HCID 696563232-(2,2-Dimethyl-5-oxo-[1,3]dioxolan-4-ylidene)-N-(4-fluoro-2-methylsulfanyl-benzyl)-N-methyl-acetamideYield 89%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of (4-fluoro-2-methylsulfanyl-benzyl)-methyl-amine (1.3 g) and diisopropylethylamine (1.74 mL, 10 mmol) in CH2Cl2 (60 mL) was added (2,2-dimethyl-5-oxo-[1,3]dioxolan-4-ylidene)-acetyl chloride (1.1 g, 6 mmol). After 1 h, the reaction mixture was concentrated and the resulting residue was taken up in ether (100 mL), washed with 1N HCl (10 mL) and brine (10 mL). The organic layer was dried over anhydrous Na2SO4, filtered and concentrated to give a viscous yellow oil. Flash chromatography on a silica gel column with 3:2 hexanes/EtOAc followed by 2:3 hexanes/EtOAc gave the desired product as a 1:1 mixture of E and Z isomers 1.8123 g, 89% yield). 1HNMR (500 MHz, CDCl3) δ: 7.17 (0.5H, dd, J=8.54, 6.11 Hz), 7.00 (0.5H, dd, J=8.55, 5.8 Hz), 6.94–6.89 (1H, m), 6.83–6.77 (1H, m), 6.17 (0.5H, s), 6.04 (0.5H, s), 4.68 (1H, s), 4.51 (1H, s), 2.98 (1.5H, s), 2.97 (1.5H, s), 2.48 (1.5H, s), 2.45 (1.5H, s), 1.72 (3H, s), 1.67 (3H, s). MS calcd for C16H19FNO4S (M+H): 340.1. found: 340.3.

Workup

  1. concentrationthe reaction mixture was concentrated
  2. washwashed with 1N HCl (10 mL) and brine (10 mL)
  3. dry with materialThe organic layer was dried over anhydrous Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customto give a viscous yellow oil

Sources & evidence

ORD record
ord-37f169f19e114d4b9b592170c3cfd2f4
Source dataset
uspto-grants-2006_09
Patent number
US07109186B2

Reaction notes

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