1,3-Dichloroacetone → 4-Chloromethyl-4-hydroxy-2-isopropyoxazoline

HRID 1861174Notes

Reaction equation

HRID 1861174 reaction equation
[C:1]([NH2:6])(=[O:5])[CH:2]([CH3:4])[CH3:3].[Cl:7][CH2:8][C:9]([CH2:11]Cl)=[O:10].C([O-])(O)=O.[Na+].[O-]S([O-])(=O)=O.[Mg+2]>CC(C)=O>[Cl:7][CH2:8][C:9]1([OH:10])[CH2:11][O:5][C:1]([CH:2]([CH3:4])[CH3:3])=[N:6]1

Participants

6

Reactant 4

HCID 107931,3-DichloroacetoneHCID 24083Sulfuric acid magnesium salt (1:1)HCID 68424IsobutyramideHCID 516892Sodium Bicarbonate

Product 1

HCID 107498144-Chloromethyl-4-hydroxy-2-isopropyoxazolineYield 46%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

To a solution of isobutyramide (9.876 g, 0.1122 mol) in acetone (130 mL) was added 1,3-dichloroacetone (10.0 g, 0.0748 mol), NaHCO3 (9.429 g, 0.1122 mol), and MgSO4 (18.01 g, 0.1496 mol). The mixture was heated at reflux under argon for 63 hrs, then cooled to room temperature, vacuum filtered, and concentrated in vacuo to a dark brown semi-solid. The residue was purified by SiO2 flash chromatography using a gradient of EtOAc/CH2Cl2 (5%, 10%, 20%, 40%) to obtain the desired product as an orange liquid (6.06 g, 0.0341 mol, 46%): 1H NMR (CDCl3) δ 1.20-1.28 (m, 6H), 2.56-2.72 (m, 1H), 3.70 (s, 2H), 4.18 (d, J=9.6 Hz, 1H), 4.38 (d, J=9.6 Hz, 1H). Mass spectrum: (M+H)+=178, 180.

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux under argon for 63 hrs
  3. filtrationvacuum filtered
  4. concentrationconcentrated in vacuo to a dark brown semi-solid
  5. customThe residue was purified by SiO2 flash chromatography

Sources & evidence

ORD record
ord-631add9a0bd3430d9f2fc2db1e281776
Source dataset
uspto-grants-2003_03
Patent number
US06531610B1

Reaction notes

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