Cesium carbonate → HCID 58197945, compound

HRID 473020Notes

Reaction equation

HRID 473020 reaction equation
Br[C:2]1[CH:10]=[C:9]2[C:5]([CH2:6][C:7]3([CH2:21][CH2:20][C:15]4[CH:16]=[N:17][N:18]=[CH:19][C:14]=4[CH2:13][CH2:12]3)[C:8]2=[O:11])=[CH:4][CH:3]=1.Br[C:23]1[CH:31]=[C:30]2[C:26]([CH2:27][C:28]3([CH2:42][CH2:41][CH2:40][C:35]4[CH:36]=[N:37][N:38]=[CH:39][C:34]=4[CH2:33]3)[C:29]2=[O:32])=[CH:25][CH:24]=1.[C:43]([C:45]1[CH:46]=[C:47](B(O)O)[CH:48]=[CH:49][CH:50]=1)#[N:44].C([O-])([O-])=O.[Cs+].[Cs+]>C(Cl)Cl.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O.O1CCOCC1>[O:11]=[C:8]1[C:9]2[C:5](=[CH:4][CH:3]=[C:2]([C:49]3[CH:50]=[C:45]([CH:46]=[CH:47][CH:48]=3)[C:43]#[N:44])[CH:10]=2)[CH2:6][C:7]21[CH2:12][CH2:13][C:14]1[CH:19]=[N:18][N:17]=[CH:16][C:15]=1[CH2:20][CH2:21]2.[O:32]=[C:29]1[C:30]2[C:26](=[CH:25][CH:24]=[C:23]([C:49]3[CH:50]=[C:45]([CH:46]=[CH:47][CH:48]=3)[C:43]#[N:44])[CH:31]=2)[CH2:27][C:28]21[CH2:42][CH2:41][CH2:40][C:35]1[CH:36]=[N:37][N:38]=[CH:39][C:34]=1[CH2:33]2

Participants

10

Reactant 4

HCID 10796Cesium carbonateHCID 27343253-Cyanophenylboronic acidHCID 58197479HCID 58197479, compoundHCID 58198039HCID 58198039, compound

Product 2

HCID 58197945HCID 58197945, compoundHCID 58198255HCID 58198255, compound

Reagents, catalysts & solvents 4

HCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
110 °C

Procedure

A 10 mL microwave tube was charged with a mixture of 6′-bromo-5,6,8,9-tetrahydrospiro[cyclohepta[d]pyridazine-7,2′-inden]-1′(3′H)-one and 6′-bromo-5,7,8,9-tetrahydrospiro[cyclohepta[d]pyridazine-6,2′-inden]-1′(3′H)-one (0.1646 g), obtained as described above, 3-cyanophenylboronic acid (0.2530 g, 1.7 mmol), Cs2CO3 (0.6177 g, 1.9 mmol), 1,4-dioxane (4 mL), water (1 mL), and PdCl2(PPh3)2 (0.0360 g, 0.05 mmol). The tube was heated in a CEM microwave reactor at 110° C. for 30 min. The reaction mixture was diluted with CH2Cl2 and dried over Na2SO4. After the solvent was evaporated under reduced pressure, the residue was purified by reversed-phase HPLC (SunFire™ Prep C18 OBD™ 5 μm 19×50 mm column, 10%→90% MeOH/H2O, 0.1% CF3COOH over 8 min and then 90% MeOH/H2O, 0.1% CF3COOH over 2 min, flow rate 20 mL/min) to afford 0.0281 g of 3-(1′-oxo-1′,3′,5,6,8,9-hexahydrospiro[cyclohepta[d]pyridazine-7,2′-inden]-6′-yl)benzonitrile and 0.0925 g of 3-(1′-oxo-1′,3′,5,7,8,9-hexahydrospiro[cyclohepta[d]pyridazine-6,2′-inden]-6′-yl)benzonitrile.

Workup

  1. customobtained
  2. dry with materialdried over Na2SO4
  3. customAfter the solvent was evaporated under reduced pressure
  4. customthe residue was purified by reversed-phase HPLC (SunFire™ Prep C18 OBD™ 5 μm 19×50 mm column, 10%
  5. customover 8 min

Sources & evidence

ORD record
ord-bb940e08508a4fdea6f25d0af74d0713
Source dataset
uspto-grants-2014_01
Patent number
US08633212B2

Reaction notes

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