Binap, (A+-)- → HCID 58447296, compound

HRID 1803588Notes

Reaction equation

HRID 1803588 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].[CH3:14][N:15]([CH2:17][C:18]1[CH:19]=[C:20]([CH:23]=[CH:24][CH:25]=1)[CH2:21][NH2:22])[CH3:16].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:22][CH2:21][C:20]3[CH:23]=[CH:24][CH:25]=[C:18]([CH2:17][N:15]([CH3:16])[CH3:14])[CH:19]=3)[CH:3]=2)[C:8](=[O:12])[NH:7][N:6]=1

Participants

8

Reactant 4

HCID 634876Binap, (A+-)-HCID 162280701-[3-(Aminomethyl)phenyl]-N,N-dimethylmethanamineHCID 23676156Sodium t-butoxideHCID 533084876-Bromo-4-chlorophthalazin-1(2H)-one

Product 1

HCID 58447296HCID 58447296, compoundYield 24.3%

Reagents, catalysts & solvents 3

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

Procedure

A mixture 6-bromo-4-chloro-2H-phthalazin-1-one (156 mg, 0.601 mmol), 3-dimethylaminomethylbenzylamine (110 mg, 0.67 mmol), Pd2(dba)3 (49 mg, 0.0535 mmol), rac-BINAP (108 mg, 0.173 mmol) and NaOtBu (143 mg, 1.488 mmol) in DMA (5 mL) was heated at 85° C. for 1 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-dimethylaminomethyl-benzylamino)-2H-phthalazin-1-one hydroformate (50 mg) as a pale brown solid. 1H (400 MHz, d6-DMSO) δ: 2.21 (s, 6H), 3.46 (s, 2H), 4.51 (d, 2H), 6.90 (s, 1H), 7.25 (m, 2H), 7.36 (m, 2H), 7.40 (s, 1H), 7.77 (t, 1H), 8.02 (s, 1H), 8.27 (s, 1H), 12.42 (s, 1H), ppm; m/z (M+1) 343.05.

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-a716fbe92b504246a927b4c0e19f21e3
Source dataset
uspto-grants-2013_01
Patent number
US08349836B2

Reaction notes

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