N,N'-Dimethylethylenediamine → HCID 59632790, compound

HRID 2369031Notes

Reaction equation

HRID 2369031 reaction equation
[CH3:1]NCCNC.C[Al](C)C.[Cl:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[C:18]1[N:22]([C:23]2[CH:24]=[N:25][C:26]([C:29]3[CH:34]=[CH:33][CH:32]=[C:31]([S:35]([CH3:38])(=[O:37])=[O:36])[CH:30]=3)=[CH:27][CH:28]=2)[N:21]=[C:20]([C:39](OC)=[O:40])[CH:19]=1>C1(C)C=CC=CC=1>[Cl:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[C:18]1[N:22]([C:23]2[CH:24]=[N:25][C:26]([C:29]3[CH:34]=[CH:33][CH:32]=[C:31]([S:35]([CH3:38])(=[O:37])=[O:36])[CH:30]=3)=[CH:27][CH:28]=2)[N:21]=[C:20]([C:39](=[O:40])[CH3:1])[CH:19]=1

Participants

5

Reactant 3

HCID 8070N,N'-DimethylethylenediamineHCID 16682925TrimethylaluminumHCID 59632546HCID 59632546, compound

Product 1

HCID 59632790HCID 59632790, compoundYield 22.1%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

To a stirred solution of N,N′-dimethylethylenediamine (56 μL, 0.52 mmol) in toluene (3 mL, anhyd) at 0° C. was added dropwise a 2.0M solution of trimethylaluminum in hexanes (0.75 mL, 1.5 mmol). After addition was complete the flask was removed from the ice-water bath and allowed to warm to ambient temperature. After 50 min the reaction mixture was charged slowly with a solution of methyl 5-(2-chlorophenyl)-1-{6-[3-(methylsulfonyl)phenyl]pyridin-3-yl}-1H-pyrazole-3-carboxylate (0.22 g, 0.47 mmol) in toluene (3 mL, anhyd) and then heated at reflux. After 90 min the reaction mixture was allowed to cool to ambient temperature and quenched by addition of 1N HCl. The resulting mixture was extracted with EtOAc (2×50 mL). The combined extracts were washed with brine, dried (Na2SO4), concentrated and purified by chromatography (silica, EtOAc/Hex, 30:70 to 60:40) to yield the title compound (47 mg, 22%) as a white solid. 1H-NMR (DCM-d2): δ 8.65 (m, 1H), 8.57 (m, 1H), 8.30 (m, 1H), 7.99 (m, 1H), 7.79-7.87 (m, 2H), 7.71 (m, 1H), 7.36-7.47 (m, 4H), 7.02 (s, 1H), 3.09 (s, 3H), 2.68 (s, 3H); MS(ES): 452 [M+H]+.

Workup

  1. additionAfter addition
  2. customwas removed from the ice-water bath
  3. temperatureanhyd) and then heated
  4. temperatureat reflux
  5. temperatureto cool to ambient temperature
  6. customquenched by addition of 1N HCl
  7. extractionThe resulting mixture was extracted with EtOAc (2×50 mL)
  8. washThe combined extracts were washed with brine
  9. dry with materialdried (Na2SO4)
  10. concentrationconcentrated
  11. custompurified by chromatography (silica, EtOAc/Hex, 30:70 to 60:40)

Sources & evidence

ORD record
ord-faaeb9a6900f4415b0dff8903c8ef952
Source dataset
uspto-grants-2014_04
Patent number
US08703805B2

Reaction notes

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