Cesium carbonate → HCID 178428369, compound

HRID 1783700Notes

Reaction equation

HRID 1783700 reaction equation
[N+]([C:4]1[CH:5]=[C:6]2[C:11](=[CH:12][CH:13]=1)[C:10](=[O:14])[N:9]([C:15]1[CH:20]=[CH:19][C:18]([C:21]([CH3:24])([CH3:23])[CH3:22])=[CH:17][CH:16]=1)[N:8]=[C:7]2[NH:25][C:26]1[N:27](C(C)(C)C)[N:28]=[C:29]([CH3:31])[CH:30]=1)([O-])=O.[N+](C1C=C2C(C(NC3N(C(C)(C)C)N=C(C)C=3)=N[N:45](C3C=CC(C(C)(C)C)=CC=3)[C:46]2=[O:49])=CC=1)([O-])=O.BrC1C2C(=CC=C([N+]([O-])=O)C=2)C(=O)N(C2C=CC(C(C)(C)C)=CC=2)N=1.BrC1C2C(=CC([N+]([O-])=O)=CC=2)C(=O)N(C2C=CC(C(C)(C)C)=CC=2)N=1.C(N1C(N)=CC(C)=N1)(C)(C)C.C(=O)([O-])[O-].[Cs+].[Cs+].C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1>O1CCOCC1.C(Cl)Cl.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]>[C:21]([C:18]1[CH:17]=[CH:16][C:15]([N:9]2[C:10](=[O:14])[C:11]3[C:6](=[CH:5][CH:4]=[C:13]([NH:45][CH:46]=[O:49])[CH:12]=3)[C:7]([NH:25][C:26]3[NH:27][N:28]=[C:29]([CH3:31])[CH:30]=3)=[N:8]2)=[CH:20][CH:19]=1)([CH3:22])([CH3:23])[CH3:24]

Participants

11

Reactant 7

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 7372001-tert-Butyl-3-methyl-1H-pyrazol-5-amineHCID 21106559HCID 21106559, compoundHCID 21106560HCID 21106560, compoundHCID 21106579HCID 21106579, compoundHCID 21106588HCID 21106588, compound

Product 1

HCID 178428369HCID 178428369, compound

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 6344DichloromethaneSolventHCID 312751,4-DioxaneSolvent

Procedure

6-Nitro-4-(2-tert-butyl-5-methyl-2H-pyrazol-3-ylamino)-2-(4-tert-butyl-phenyl)-2H-phthalazin-1-one and 7-Nitro-4-(2-tert-butyl-5-methyl-2H-pyrazol-3-ylamino)-2-(4-tert-butyl-phenyl)-2H-phthalazin-1-one: 4.56 g of a 1:1 mixture of 4-Bromo-2-(4-tert-butyl-phenyl)-6-nitro-2H-phthalazin-1-one and 4-Bromo-2-(4-tert-butyl-phenyl)-7-nitro-2H-phthalazin-1-one in 45 ml dry dioxane were reacted with 2.605 g 1-(tert.butyl)-3-methyl-1H-pyrazole-5-ylamine, 5.526 g cesium carbonate, 311 mg tris-(dibenzylideneacetone)-dipalladium and 393 mg 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene under nitrogen at 80 C. After 2 hrs HPLC indicated complete conversion and the mixture was cooled to RT, diluted with 150 ml DCM and washed twice with diluted HCl. The organic phase was dried and evaporated and the residue chromatographed on silica eluting first heptane and subsequently with heptane/EtOAc 8:2. The first eluting product was the 6-nitro isomer (1.82 g), the second eluting product was the 7-nitro isomer (2.05 g).

Workup

  1. washwashed twice with diluted HCl
  2. customThe organic phase was dried
  3. customevaporated
  4. customthe residue chromatographed on silica eluting first heptane and subsequently with heptane/EtOAc 8:2

Sources & evidence

ORD record
ord-3b5cbdaddb17473fa653398223052303
Source dataset
uspto-grants-2009_03
Patent number
US07501410B2

Reaction notes

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