Sodium hydride → trans-Methyl 2-(3-chloro-2-methylphenyl)cyclopropanecarboxylate

HRID 2175312Notes

Reaction equation

HRID 2175312 reaction equation
[I-].[CH3:2][S+](C)(C)=O.[H-].[Na+].[Cl:9][C:10]1[C:11]([CH3:22])=[C:12](/[CH:16]=[CH:17]/[C:18]([O:20][CH3:21])=[O:19])[CH:13]=[CH:14][CH:15]=1>CS(C)=O>[Cl:9][C:10]1[C:11]([CH3:22])=[C:12]([C@@H:16]2[CH2:2][C@H:17]2[C:18]([O:20][CH3:21])=[O:19])[CH:13]=[CH:14][CH:15]=1

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 74498Sulfoxonium, trimethyl-, iodide (1:1)HCID 86712608(E)-Methyl 3-(3-chloro-2-methylphenyl)acrylate

Product 1

HCID 70981958trans-Methyl 2-(3-chloro-2-methylphenyl)cyclopropanecarboxylateYield 39.4%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent2×

Procedure

To a solution of trimethylsulfoxonium iodide (0.157 g, 0.712 mmol) in 1 mL DMSO was added NaH (60% in mineral oil) (0.032 g, 0.807 mmol) portion-wise. The mixture was stirred at room temperature for 30 min, and then a solution (E)-methyl 3-(3-chloro-2-methylphenyl)acrylate (0.1 g, 0.475 mmol) in 1 mL DMSO was added in one portion. The reaction was stirred at room temperature for 16 h. The mixture was partitioned between EtOAc and water. The organic layer was washed with water and brine, dried (MgSO4) and concentrated. The crude material was purified by flash chromatography (0-50% ethyl acetate:hexanes) to afford the title compound (0.042 g, 39% yield) as a clear colorless oil. 1H NMR (500 MHz, CDCl3) δ 7.29-7.24 (d, J=7.8 Hz, 1H), 7.06 (t, J=7.8 Hz, 1H), 6.95 (d, J=7.7 Hz, 1H), 3.79-3.75 (m, 3H), 2.55 (ddd, J=9.1, 6.7, 4.5 Hz, 1H), 2.45 (s, 3H), 1.81 (dt, J=8.4, 4.9 Hz, 1H), 1.64-1.57 (m, 1H), 1.30 (ddd, J=8.4, 6.7, 4.4 Hz, 1H).

Workup

  1. stirringThe reaction was stirred at room temperature for 16 h
  2. customThe mixture was partitioned between EtOAc and water
  3. washThe organic layer was washed with water and brine
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated
  6. customThe crude material was purified by flash chromatography (0-50% ethyl acetate:hexanes)

Sources & evidence

ORD record
ord-37e46d9f8c874032a3f8ad46b99e1574
Source dataset
uspto-grants-2015_06
Patent number
US09062028B2

Reaction notes

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