N,N-Dimethylethylenediamine → HCID 71230972, compound

HRID 2172683Notes

Reaction equation

HRID 2172683 reaction equation
[F:1][C:2]([F:18])([F:17])[C:3]1[O:7][N:6]=[C:5]([C:8]2[CH:16]=[CH:15][C:11]([C:12]([OH:14])=O)=[CH:10][CH:9]=2)[N:4]=1.CCOC(C(C#N)=NOC(N1CCOCC1)=[N+](C)C)=O.F[P-](F)(F)(F)(F)F.CCN(C(C)C)C(C)C.[CH3:55][N:56]([CH3:60])[CH2:57][CH2:58][NH2:59]>C(Cl)Cl>[CH3:55][N:56]([CH3:60])[CH2:57][CH2:58][NH:59][C:12](=[O:14])[C:11]1[CH:10]=[CH:9][C:8]([C:5]2[N:4]=[C:3]([C:2]([F:1])([F:18])[F:17])[O:7][N:6]=2)=[CH:16][CH:15]=1

Participants

6

Reactant 4

HCID 66053N,N-DimethylethylenediamineHCID 81531DiisopropylethylamineHCID 104914054-[5-(Trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzoic acidHCID 75951468(1-Cyano-2-ethoxy-2-oxoethylidenaminooxy)dimethylamino-morpholino-carbenium hexafluorophosphate

Product 1

HCID 71230972HCID 71230972, compoundYield 79.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a suspension of Intermediate 12b (1 g, 3.87 mmol) in DCM (20 ml) was added COMU (1.891 g, 4.26 mmol) and DIPEA (0.812 ml, 4.65 mmol). The yellow solution was stirred for 2 min at rt and turned red. 2-Dimethylaminoethylamine (0.518 ml, 4.65 mmol) was added and the reaction mixture was stirred at reflux for 1 hr. After cooling to rt, the mixture was washed with water, saturated aqueous NH4Cl and extrated with EtOAc. The organic layer was dried over Na2SO4 and the solvent was removed in vacuo. The crude product was purified by flash chromatography (ISCO CombiFlash Rf, 120 g silicagel; A=dichloromethane, B=DCM:7N NH3 in MeOH (9:1), 2% hold for 5 min, gradient to 50% B over 15 min). Fractions containing the product where combined to yield 1.355 g. The final product (1.015 g) was obtained after crystallisation from heptane as a white solid.

Workup

  1. stirringthe reaction mixture was stirred
  2. temperatureat reflux for 1 hr
  3. temperatureAfter cooling to rt
  4. washthe mixture was washed with water, saturated aqueous NH4Cl
  5. dry with materialThe organic layer was dried over Na2SO4
  6. customthe solvent was removed in vacuo
  7. customThe crude product was purified by flash chromatography (ISCO CombiFlash Rf, 120 g silicagel
  8. waitA=dichloromethane, B=DCM:7N NH3 in MeOH (9:1), 2% hold for 5 min
  9. waitgradient to 50% B over 15 min)
  10. additionFractions containing the product where
  11. customto yield 1.355 g

Sources & evidence

ORD record
ord-939cd4ccdd5a47ceae382044c987c40e
Source dataset
uspto-grants-2015_06
Patent number
US09056843B2

Reaction notes

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