Diisopropylethylamine → HCID 58764141, compound

HRID 859692Notes

Reaction equation

HRID 859692 reaction equation
[Br:1][C:2]1[CH:10]=[CH:9][C:5]([C:6]([OH:8])=O)=[C:4]([CH2:11][CH3:12])[CH:3]=1.[CH:13]([N:16](C(C)C)CC)(C)[CH3:14].F[P-](F)(F)(F)(F)F.N1(OC(N(C)C)=[N+](C)C)C2N=CC=CC=2N=N1>ClCCl.CN(C)C=O>[Br:1][C:2]1[CH:10]=[CH:9][C:5]([C:6]2[O:8][CH:14]=[CH:13][N:16]=2)=[C:4]([CH2:11][CH3:12])[CH:3]=1

Participants

5

Reactant 3

HCID 81531DiisopropylethylamineHCID 9886157Methanaminium, N-((dimethylamino)(3H-1,2,3-triazolo(4,5-b)pyridin-3-yloxy)methylene)-N-methyl-, hexafluorophosphate(1-) (1:1)HCID 106570054-Bromo-2-ethylbenzoic acid

Product 1

HCID 58764141HCID 58764141, compound

Reagents, catalysts & solvents 1

HCID 22350042dichloromethane N,N-dimethylformamideSolvent

Conditions

Temperature
135 °C

Procedure

4-Bromo-2-ethyl-benzoic acid (6.8 g, 30 mmol), diisopropylethylamine (7.8 mL, 44.7 mmol), O-(7-azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyluronium hexafluorophosphate (HATU, 14 g, 37 mmol), and aminoacetaldehyde dimethyl ether (4 mL, 37 mmol) in 2:1 dichlormethane/dimethylformamide (120 mL) 5 h at room temperature. The solution was washed with several portions of water, then 1N HCl(aq) and saturated sodium chloride, dried (Na2SO4), filtered, and concentrated in vacuo to a crude light yellow oil. The residue was redissolved in Eaton's reagent (P2O5 in methanesulfonic acid, 100 mL), and the solution was heated at 135° C. under argon for 6 h. The solution was cooled to room temperature and carefully poured onto ice. The mixture was extracted with dichloromethane, and the organic layer was backwashed with saturated sodium chloride, dried (Na2SO4), filtered, and concentrated in vacuo to a crude oil. The residue was redissolved in ethyl acetate and washed with saturated sodium bicarbonate, then saturated sodium chloride, dried (Na2SO4), filtered, and concentrated in vacuo to pure brown liquid (3.16 g, 44%), 1H NMR (300 MHz, CDCl3): δ ppm 1.24 (t, J=7.54 Hz, 3 H) 3.09 (q, J=7.54 Hz, 2 H) 7.27 (s, 1 H) 7.42 (dd, J=8.38, 1.98 Hz, 1 H) 7.48 (d, J=2.07 Hz, 1 H) 7.74 (s, 1 H) 7.81 (d, J=8.48 Hz, 1 H).

Workup

  1. customat room temperature
  2. washThe solution was washed with several portions of water
  3. dry with material1N HCl(aq) and saturated sodium chloride, dried (Na2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo to a crude light yellow oil
  6. dissolutionThe residue was redissolved in Eaton's reagent (P2O5 in methanesulfonic acid, 100 mL)
  7. temperatureThe solution was cooled to room temperature
  8. additioncarefully poured onto ice
  9. extractionThe mixture was extracted with dichloromethane
  10. dry with materialdried (Na2SO4)
  11. filtrationfiltered
  12. concentrationconcentrated in vacuo to a crude oil
  13. dissolutionThe residue was redissolved in ethyl acetate
  14. washwashed with saturated sodium bicarbonate
  15. dry with materialsaturated sodium chloride, dried (Na2SO4)
  16. filtrationfiltered
  17. concentrationconcentrated in vacuo to pure brown liquid (3.16 g, 44%), 1H NMR (300 MHz, CDCl3): δ ppm 1.24 (t, J=7.54 Hz, 3 H) 3.09 (q, J=7.54 Hz, 2 H) 7.27 (s, 1 H) 7.42 (dd, J=8.38, 1.98 Hz, 1 H) 7.48 (d, J=2.07 Hz, 1 H) 7.74 (s, 1 H) 7.81 (d, J=8.48 Hz, 1 H)

Sources & evidence

ORD record
ord-458d335390b843b481da540fbd871d4e
Source dataset
uspto-grants-2006_12
Patent number
US07151105B2

Reaction notes

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