Cesium carbonate → 2-(3-(9-Ethyl-9H-imidazo[4,5-c]pyridazin-6-yl)phenyl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine

HRID 1846038Notes

Reaction equation

HRID 1846038 reaction equation
CC1(C)C(C)(C)OB([C:9]2[CH:10]=[C:11]([B:15]3[NH:26][C:25]4[C:27]5[C:21]([CH:22]=[CH:23][CH:24]=4)=[CH:20][CH:19]=[CH:18][C:17]=5[NH:16]3)[CH:12]=[CH:13][CH:14]=2)O1.Cl[C:30]1[C:31]2[N:38]=[CH:37][N:36]([CH2:39][CH3:40])[C:32]=2[N:33]=[N:34][CH:35]=1.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.O.[Pd](Cl)Cl.C(P(C(C)(C)C)[C-]1C=CC=C1)(C)(C)C.[C-]1(P(C(C)(C)C)C(C)(C)C)C=CC=C1.[Fe+2]>[CH2:39]([N:36]1[C:32]2[N:33]=[N:34][CH:35]=[C:30]([C:9]3[CH:10]=[C:11]([B:15]4[NH:26][C:25]5[C:27]6[C:21]([CH:22]=[CH:23][CH:24]=5)=[CH:20][CH:19]=[CH:18][C:17]=6[NH:16]4)[CH:12]=[CH:13][CH:14]=3)[C:31]=2[N:38]=[CH:37]1)[CH3:40]

Participants

7

Reactant 3

HCID 10796Cesium carbonateHCID 552967654-chloro-7-ethyl-7H-imidazo(4,5-c)pyridazineHCID 71306573M-Benzenediboronic acid pinacol ester, 1,8-diaminonaphthalene, protected

Product 1

HCID 867232602-(3-(9-Ethyl-9H-imidazo[4,5-c]pyridazin-6-yl)phenyl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinineYield 83.6%

Reagents, catalysts & solvents 3

HCID 178454861HCID 178454861, compoundCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Procedure

A room temperature solution of 2-[3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl]-2,3-dihydro-1H-1,3-diaza-2-boraphenalene (Preparation 61, 7.8 g, 21.1 mmol), 4-chloro-7-ethyl-7H-imidazo[4,5-c]pyridazine (Preparation 8, 2.6 g, 14.1 mmol) and cesium carbonate (13.8 g, 42.3 mmol) in dioxane (160 mL) and water (13 mL) was degassed. 1,1′-bis(di-tert-butylphosphino) ferrocene palladium dichloride (0.91 g, 1.4 mmol) was then added in one portion and the reaction mixture was again purged with nitrogen gas three times. The resultant solution was then stirred at reflux for 16 hours. The reaction mixture was cooled to room temperature then filtered and concentrated in vacuo. The residue was purified by silica gel column chromatography eluting with CH2Cl2:MeOH, 50:1 to afford the title compound as a yellow solid in 83.6% yield.

Workup

  1. customthe reaction mixture was again purged with nitrogen gas three times
  2. temperatureat reflux for 16 hours
  3. filtrationthen filtered
  4. concentrationconcentrated in vacuo
  5. customThe residue was purified by silica gel column chromatography
  6. washeluting with CH2Cl2

Sources & evidence

ORD record
ord-f532a37def11463fbca486b17840befe
Source dataset
uspto-grants-2015_02
Patent number
US08952008B2

Reaction notes

Loading…