2-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl → HCID 67318159, compound

HRID 1042810Notes

Reaction equation

HRID 1042810 reaction equation
[CH3:1][O:2][C:3]1[CH:12]=[C:11]2[C:6]([C:7]([S:13][C:14]3[CH:19]=[CH:18][C:17]([NH2:20])=[CH:16][CH:15]=3)=[CH:8][CH:9]=[N:10]2)=[N:5][CH:4]=1.CC(C)([O-])C.[Na+].COC1C=CC=C(OC)C=1C1C=CC=CC=1P(C1CCCCC1)C1CCCCC1.Cl[C:57]1[N:58]=[N:59][C:60]([C:65]2[CH:70]=[CH:69][C:68]([CH3:71])=[CH:67][CH:66]=2)=[CH:61][C:62]=1[CH2:63][CH3:64]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH2:63]([C:62]1[CH:61]=[C:60]([C:65]2[CH:70]=[CH:69][C:68]([CH3:71])=[CH:67][CH:66]=2)[N:59]=[N:58][C:57]=1[NH:20][C:17]1[CH:18]=[CH:19][C:14]([S:13][C:7]2[C:6]3[C:11](=[CH:12][C:3]([O:2][CH3:1])=[CH:4][N:5]=3)[N:10]=[CH:9][CH:8]=2)=[CH:15][CH:16]=1)[CH3:64]

Participants

6

Reactant 4

HCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylHCID 23676156Sodium t-butoxideHCID 59427300HCID 59427300, compoundHCID 86628667HCID 86628667, compound

Product 1

HCID 67318159HCID 67318159, compound

Reagents, catalysts & solvents 1

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Conditions

Temperature
100 °C

Procedure

A pyrex reaction tube was charged with tris(dibenzylideneacetone)dipalladium (20 mg, 0.021 mmol), 4-(7-methoxy-1,5-naphthyridin-4-ylthio)benzenamine (122 mg, 0.430 mmol), sodium tert-butoxide (99 mg, 1.031 mmol), S-Phos (35 mg, 0.086 mmol), and 3-chloro-4-ethyl-6-p-tolylpyridazine (100 mg, 0.430 mmol). The reaction tube was purged with nitrogen. 1.3 mL of toluene was added, and the tube was sealed. The reaction mixture was heated at 100° C. for 3 h. Upon cooling, the mixture was diluted with 5% iPrOH/EtOAc and washed with water. The organic portion was dried with MgSO4, filtered and concentrated. The crude material was purified by silica gel chromatography (90/10/1 CH2Cl2/MeOH/NH4OH) and reverse phase chromatography (Gilson, 10-95% CH3CN over 15 min) to provide 4-ethyl-N-(4-(7-methoxy-1,5-naphthyridin-4-ylthio)phenyl)-6-p-tolylpyridazin-3-amine as a light yellow solid. MS m/z=480 [M+H]+. Calc'd for C28H25N5OS: 479.60.

Workup

  1. customThe reaction tube was purged with nitrogen
  2. addition1.3 mL of toluene was added
  3. customthe tube was sealed
  4. temperatureUpon cooling
  5. additionthe mixture was diluted with 5% iPrOH/EtOAc
  6. washwashed with water
  7. dry with materialThe organic portion was dried with MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe crude material was purified by silica gel chromatography (90/10/1 CH2Cl2/MeOH/NH4OH)
  11. customphase chromatography (Gilson, 10-95% CH3CN over 15 min)

Sources & evidence

ORD record
ord-d011cd5a7df842b987b0e36e7e43047e
Source dataset
uspto-grants-2013_10
Patent number
US08557816B2

Reaction notes

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