Binap, (A+-)- → HCID 24947782, compound

HRID 1667504Notes

Reaction equation

HRID 1667504 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[C:8](=[O:12])[NH:7][N:6]=[C:5]2[Cl:13].Cl.[NH2:15][CH2:16][C:17]1[CH:18]=[C:19]([NH:23][CH2:24][CH2:25][N:26]([CH3:28])[CH3:27])[CH:20]=[CH:21][CH:22]=1.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.CC([O-])(C)C.[Na+]>CC(N(C)C)=O.CCOC(C)=O.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]>[Cl:13][C:5]1[C:4]2[C:9](=[CH:10][CH:11]=[C:2]([NH:15][CH2:16][C:17]3[CH:22]=[CH:21][CH:20]=[C:19]([NH:23][CH2:24][CH2:25][N:26]([CH3:28])[CH3:27])[CH:18]=3)[CH:3]=2)[C:8](=[O:12])[NH:7][N:6]=1

Participants

8

Reactant 4

HCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxideHCID 533084876-Bromo-4-chlorophthalazin-1(2H)-oneHCID 67416686HCID 67416686, compound

Product 1

HCID 24947782HCID 24947782, compoundYield 27.7%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8857Ethyl AcetateSolventHCID 31374DimethylacetamideSolvent

Procedure

A mixture 6-bromo-4-chloro-2H-phthalazin-1-one (204 mg, 0.785 mmol), N-(3-Aminomethyl-phenyl)-N′,N′-dimethyl-ethane-1,2-diamine hydrochloride (198 mg, 0.86 mmol), Pd2(dba)3 (72 mg, 0.0785 mmol), rac-BINAP (162 mg, 0.260 mmol) and NaOtBu (266 mg, 2.77 mmol) in DMA (6 mL) was heated at 85° C. for 3 h. The mixture was allowed to cool, diluted with EtOAc and washed with water. The organic layer was washed with sat.aq. NaHCO3, brine and dried (Na2SO4). Preparatory HPLC afforded 4-chloro-6-[3-(2-dimethylamino-ethylamino)-benzylamino]-2H-phthalazin-1-one hydroformate (81 mg) as a yellow solid. 1H (400 MHz, d6-DMSO) δ: 1.95 (s, 6H), 2.40 (m, 1H), 2.46 (m, 1H), 2.87 (m, 2H), 4.10 (d, 2H), 5.20 (bs, 1H), 6.26 (dd, 1H), 6.34 (d, 1H), 6.37 (s, 1H), 6.62 (s, 1H), 6.82 (t, 1H), 6.93 (dd, 1H), 7.40 (t, 1H), 7.70 (d, 1H), 7.95 (s, 1H), 12.12 (s, 1H) ppm; m/z (M+1) 372.04.

Workup

  1. temperatureto cool
  2. washwashed with water
  3. washThe organic layer was washed with sat.aq
  4. dry with materialNaHCO3, brine and dried (Na2SO4)

Sources & evidence

ORD record
ord-ae2faf5c77874733bab1c8b1c0b991c7
Source dataset
uspto-grants-2011_10
Patent number
US08044041B2

Reaction notes

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