Benzylamine → HCID 58288264, compound

HRID 1476119Notes

Reaction equation

HRID 1476119 reaction equation
CC(C)([O-])C.[Na+].Br[C:8]1[CH:9]=[C:10]([CH2:15][C:16]([CH3:25])([CH3:24])[C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH:11]=[CH:12][C:13]=1[Cl:14].[CH2:26]([NH2:33])[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1.C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Cl-].[NH4+]>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(OCC)(=O)C.C1(C)C=CC=CC=1>[CH2:26]([NH:33][C:8]1[CH:9]=[C:10]([CH2:15][C:16]([CH3:25])([CH3:24])[C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH:11]=[CH:12][C:13]=1[Cl:14])[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1

Participants

9

Reactant 5

HCID 7504BenzylamineHCID 25517Ammonium ChlorideHCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxideHCID 58288336HCID 58288336, compound

Product 1

HCID 58288264HCID 58288264, compound

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
110 °C

Procedure

Under argon, 1.73 g (17.95 mmol) of sodium tert-butoxide were weighed out into a dry flask, and 40 ml of abs. toluene were added. 5.2 g (14.96 mmol) of tert-butyl 3-(3-bromo-4-chlorophenyl)-2,2-dimethylpropanoate, 1.96 ml (17.95 mmol) of benzylamine, 685 mg (0.75 mmol) of tris(dibenzylideneacetone)dipalladium and 373 mg (0.60 mmol) of (+/−)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl were added in succession. The reaction mixture was stirred at 110° C. for 2.0 h, then cooled to RT and stirred at this temperature overnight. Saturated aqueous ammonium chloride solution and ethyl acetate were then added, and the reaction mixture was filtered off with suction through kieselguhr. After phase separation, the organic phase was washed with saturated ammonium chloride solution and saturated sodium chloride solution, dried over magnesium sulphate and concentrated under reduced pressure. The crude product was purified by preparative HPLC (mobile phase acetonitrile/water). This gave 2.78 g of the title compound (50% of theory).

Workup

  1. temperaturecooled to RT
  2. stirringstirred at this temperature overnight
  3. filtrationthe reaction mixture was filtered off with suction through kieselguhr
  4. customAfter phase separation
  5. washthe organic phase was washed with saturated ammonium chloride solution and saturated sodium chloride solution
  6. dry with materialdried over magnesium sulphate
  7. concentrationconcentrated under reduced pressure
  8. customThe crude product was purified by preparative HPLC (mobile phase acetonitrile/water)

Sources & evidence

ORD record
ord-81723149810f4bed84228861b9be09db
Source dataset
uspto-grants-2015_04
Patent number
US09018414B2

Reaction notes

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