Cesium carbonate → 4-(3,5-dimethylpyridin-4-yl)-N-(diphenylmethylene)-3,5-dimethyl-benzenamine

HRID 1169528Notes

Reaction equation

HRID 1169528 reaction equation
[CH3:1][C:2]1[CH:3]=[N:4][CH:5]=[C:6]([CH3:24])[C:7]=1[C:8]1[C:13]([CH3:14])=[CH:12][C:11](OS(C(F)(F)F)(=O)=O)=[CH:10][C:9]=1[CH3:23].C([O-])([O-])=O.[Cs+].[Cs+].[C:31](=[NH:44])([C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1)[C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1>C1COCC1.CC([O-])=O.CC([O-])=O.[Pd+2].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1>[CH3:1][C:2]1[CH:3]=[N:4][CH:5]=[C:6]([CH3:24])[C:7]=1[C:8]1[C:13]([CH3:14])=[CH:12][C:11]([N:44]=[C:31]([C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)=[CH:10][C:9]=1[CH3:23]

Participants

7

Reactant 3

HCID 10796Cesium carbonateHCID 136809Benzophenone imineHCID 585105243,5-Dimethyl-4-[2,6-dimethyl-4-(trifluoromethylsulfonyloxy)phenyl]pyridine

Product 1

HCID 595503324-(3,5-dimethylpyridin-4-yl)-N-(diphenylmethylene)-3,5-dimethyl-benzenamineYield 97.7%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 634876Binap, (A+-)-CatalystHCID 8028TetrahydrofuranSolvent

Procedure

A flame-dried sealable Schlenk tube was charged with triflate 8 (0.359 g, 1.00 mmol), Cs2CO3 (0.456 g, 1.40 mmol), Pd(OAc)2 (6.7 mg, 0.030 mmol), and BINAP (28.2 mg, 0.0450 mmol). The tube was evacuated and then backfilled with N2. Next, a solution of benzophenone imine (0.224 g, 1.20 mmol) in dry THF (4 mL) was added with stirring under an N2 flow. The Schlenk tube was sealed, the mixture was degassed by three freeze-thaw cycles, and backfilled with N2. The mixture was then stirred at 65° C. for 15 h. The reaction mixture was next cooled to room temperature, diluted with methylene chloride (40 mL), filtered, and the filtrate was concentrated in vacuo. The resulting yellow solid was purified by flash chromatography on silica gel, eluting with 1:1 hexane: ethyl acetate, to give 0.381 g (97.7%) of the title compound as a colorless solid: mp 44-45° C.; 1H NMR (400 MHz, CD2Cl2): δ 8.305 (s, 2H), 7.774 (d, 2H, J=8.0 Hz), 7.494-7.408 (m, 3H), 7.271 (m, 3H), 7.144 (d, 2H, J=6.8 Hz), 6.476 (s, 2H), 1.828 (s, 6H), 1.706 (s, 6H); 13C NMR (100 MHz, CD2Cl2): δ 168.647, 151.523, 148.783, 148.611, 140.013, 136.737, 135.099, 132.206, 131.678, 131.114, 130.040, 129.685, 128.912, 128.583, 128.038, 120.459, 19.842, 16.594; MS(ESI): m/z 391.5 [(M+H)+, 100]; Anal. Calcd. for C28H26N2: C, 86.12; H, 6.71; N, 7.17. Found; C, 85.86; H, 6.74; N, 7.17.

Workup

  1. customThe tube was evacuated
  2. customThe Schlenk tube was sealed
  3. customthe mixture was degassed by three freeze-thaw cycles
  4. stirringThe mixture was then stirred at 65° C. for 15 h
  5. additiondiluted with methylene chloride (40 mL)
  6. filtrationfiltered
  7. concentrationthe filtrate was concentrated in vacuo
  8. customThe resulting yellow solid was purified by flash chromatography on silica gel
  9. washeluting with 1:1 hexane

Sources & evidence

ORD record
ord-fba5f1ca6ddd40c6bf95fc79e14f1bb2
Source dataset
uspto-grants-2010_11
Patent number
US07824582B2

Reaction notes

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