Methylamine → HCID 67267332, compound

HRID 598088Notes

Reaction equation

HRID 598088 reaction equation
[CH3:1][C:2]1[CH:7]=[C:6]([CH3:8])[CH:5]=[CH:4][C:3]=1[C:9]1[CH:18]=[CH:17][CH:16]=[C:15]([N+:19]([O-:21])=[O:20])[C:10]=1[C:11](OC)=[O:12].[OH-].[Na+].CN.F[P-](F)(F)(F)(F)F.[N:33]1(OC(N(C)C)=[N+](C)C)[C:37]2C=CC=CC=2N=N1.C(N(C(C)C)CC)(C)C>CO.O1CCCC1.O.C(OCC)(=O)C>[CH3:1][C:2]1[CH:7]=[C:6]([CH3:8])[CH:5]=[CH:4][C:3]=1[C:9]1[CH:18]=[CH:17][CH:16]=[C:15]([N+:19]([O-:21])=[O:20])[C:10]=1[C:11]([NH:33][CH3:37])=[O:12]

Participants

10

Reactant 5

HCID 6329MethylamineHCID 14798Sodium HydroxideHCID 81531DiisopropylethylamineHCID 2733084Methanaminium, N-((1H-benzotriazol-1-yloxy)(dimethylamino)methylene)-N-methyl-, hexafluorophosphate(1-) (1:1)HCID 67267092HCID 67267092, compound

Product 1

HCID 67267332HCID 67267332, compoundYield 30%

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent2×

Conditions

Temperature
65 °C

Procedure

To a mixture containing 0.32 g (1.12 mmol) of methyl 2-(2,4-dimethylphenyl)-6-nitrobenzoate in methanol (2.2 ml), tetrahydrofuran (3.5 ml) and water (3.5 ml) was added 0.18 g (4.5 mmol) of sodium hydroxide. The reaction was allowed to stir at 65° C. for 12 h. The solution was cooled, diluted with ethyl acetate (10 mL) and water (10 mL) and shaken vigorously. The aqueous layer was separated, acidified to pH=3 and extracted with ethyl acetate (3×). The combined ethyl acetate layers were washed with brine, dried (Na2SO4), filtered and concentrated. The residue was then dissolved in tetrahydrofuran (10 mL) and methylamine (0.14 g, 2.2 mmol), O-(benzotriazol-1-yl)-N,N,N′,N′-tetramethyluronium hexafluorophosphate (HBTU) (0.62 g, 1.66 mmol), and diisopropylethylamine (0.28 mL, 2.2 mmol) were added. The reaction was allowed to stir at room temperature for 12 h. The reaction was diluted with ethyl acetate and washed with saturated sodium bicarbonate. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent and purification of the residue via biotage eluting with 30% ethyl acetate/hexanes gave 0.095 g (30%) of product.

Workup

  1. temperatureThe solution was cooled
  2. stirringshaken vigorously
  3. customThe aqueous layer was separated
  4. extractionextracted with ethyl acetate (3×)
  5. washThe combined ethyl acetate layers were washed with brine
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. dissolutionThe residue was then dissolved in tetrahydrofuran (10 mL)
  10. stirringto stir at room temperature for 12 h
  11. washwashed with saturated sodium bicarbonate
  12. dry with materialThe organic phase was dried over magnesium sulfate
  13. filtrationFiltration, removal of solvent and purification of the residue via biotage
  14. washeluting with 30% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-1ed8a7e6dd4248408b1f64585dc45b11
Source dataset
uspto-grants-2011_03
Patent number
US07897607B2

Reaction notes

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