Benzenemethanamine, 3,4-dimethyl- → 4-chloro-6-(3,4-dimethyl-benzylamino)-2H-phthalazin-1-one

HRID 1803561Notes

Reaction equation

HRID 1803561 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][C:15]1[CH:16]=[C:17]([CH:20]=[CH:21][C:22]=1[CH3:23])[CH2:18][NH2:19].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:19][CH2:18][C:17]3[CH:20]=[CH:21][C:22]([CH3:23])=[C:15]([CH3:14])[CH:16]=3)[CH:3]=2)[C:8](=[O:12])[NH:7][N:6]=1

Participants

8

Reactant 4

HCID 66888Benzenemethanamine, 3,4-dimethyl-HCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxideHCID 533084876-Bromo-4-chlorophthalazin-1(2H)-one

Product 1

HCID 249485304-chloro-6-(3,4-dimethyl-benzylamino)-2H-phthalazin-1-oneYield 11.6%

Reagents, catalysts & solvents 3

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

Procedure

A mixture 6-bromo-4-chloro-2H-phthalazin-1-one (150 mg, 0.578 mmol), 3,4-dimethylbenzylamine (0.09 mL, 0.636 mmol), Pd2(dba)3 (58 mg, 0.063 mmol), rac-BINAP (104 mg, 0.167 mmol) and NaOtBu (155 mg, 1.613 mmol) in DMA (6 mL) was heated at 85° C. for 1.5 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). Chromatography on silica (EtOAc/hexanes) afforded 4-chloro-6-(3,4-dimethyl-benzylamino)-2H-phthalazin-1-one (21 mg) as a white solid, 1H (400 MHz, d6-DMSO) δ: 2.15 (d, 6H), 4.25 (d, 2H), 6.79 (s, 1H), 7.05 (s, 2H), 7.10 (m, 2H), 7.57 (t, 1H), 7.87 (d, 1H), 12.30 (s, 1H) ppm; m/z (M+1) 313.99.

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-458d82fde1894835b148532f6db4a580
Source dataset
uspto-grants-2013_01
Patent number
US08349836B2

Reaction notes

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