4-Methylmorpholine → 2-(Allyloxy)-N-methoxy-N-methylacetamide

HRID 2060747Notes

Reaction equation

HRID 2060747 reaction equation
S(Cl)(Cl)=O.[CH2:5]([O:8][CH2:9][C:10]([OH:12])=O)[CH:6]=[CH2:7].Cl.[CH3:14][NH:15][O:16][CH3:17].CN1CCOCC1>C1(C)C=CC=CC=1.ClCCl.O>[CH2:5]([O:8][CH2:9][C:10]([N:15]([O:16][CH3:17])[CH3:14])=[O:12])[CH:6]=[CH2:7]

Participants

8

Reactant 4

HCID 79724-MethylmorpholineHCID 24386Thionyl ChlorideHCID 81138Methanamine, N-methoxy-, hydrochloride (1:1)HCID 109970062-(Prop-2-en-1-yloxy)acetic acid

Product 1

HCID 574757612-(Allyloxy)-N-methoxy-N-methylacetamideYield 50%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
65 °C

Procedure

Thionyl chloride (1.5 L) is added in one portion to a solution of 2-(allyloxy)acetic acid (2.2 Kg, 18.9 mol) in toluene (3.0 L), and the mixture is heated at 65° C. under a nitrogen atmosphere for 1 h. The mixture is cooled to room temperature and is added to a solution of N,O-dimethylhydroxylamine hydrochloride (2.1 Kg, 21.5 mol) and N-methyl morpholine (6.5 L, 59.2 mol) in dichloromethane (19 L) at 5° C. The reaction mixture is stirred at 25° C. for 16 h. Water is added, and the reaction mixture is extracted with dichloromethane. The combined organic phase is collected and washed with 1 M HCl (6 L), dried over magnesium sulfate and concentrated under reduced pressure. The residue is purified by silica gel chromatography eluting with ethyl acetate in hexanes to afford the title compound (1.49 Kg, 50%). ES/MS m/e: 160 (M+1).

Workup

  1. temperatureThe mixture is cooled to room temperature
  2. extractionthe reaction mixture is extracted with dichloromethane
  3. customThe combined organic phase is collected
  4. washwashed with 1 M HCl (6 L)
  5. dry with materialdried over magnesium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe residue is purified by silica gel chromatography
  8. washeluting with ethyl acetate in hexanes

Sources & evidence

ORD record
ord-aeea30b8936a48819a70a8f312d1b8dc
Source dataset
uspto-grants-2012_10
Patent number
US08278441B2

Reaction notes

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