Hydrochloric Acid → HCID 58852362, compound

HRID 970727Notes

Reaction equation

HRID 970727 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:9]2[CH2:14][CH2:13][CH:12]([N:15]([CH3:17])[CH3:16])[CH2:11][CH:10]=2)[CH:5]=[C:6]([F:8])[CH:7]=1.C(=[NH:31])(C1C=CC=CC=1)C1C=CC=CC=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(C)([O-])C.[Na+].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].C1(C)C=CC=CC=1>[CH3:16][N:15]([CH3:17])[CH:12]1[CH2:13][CH2:14][C:9]([C:4]2[CH:3]=[C:2]([NH2:31])[CH:7]=[C:6]([F:8])[CH:5]=2)=[CH:10][CH2:11]1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 136809Benzophenone imineHCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxideHCID 58852367HCID 58852367, compound

Product 1

HCID 58852362HCID 58852362, compoundYield 33.5%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

Combine (4-(3-bromo-5-fluoro-phenyl)-cyclohex-3-enyl)-dimethyl-amine (10.8 g, 36.2 mmol), benzhydrylideneamine (7.88 g, 43.5 mmol), toluene (250 mL), BINAP (0.90 g, 1.44 mmol) and sodium t-butoxide (4.87 g, 50.7 mmol) and heat to 90° C. for 10 min. until homogeneous. Add tris(dibenzylideneacetone)dipalladium(0) (0.66 g, 0.72 mmol) and heat to 100° C. for 3 hr. Add 6M HCl solution (60 mL) carefully and continue to heat at 100° C. for 1 hr. Cool to ambient temperature and wash with ethyl acetate (2×100 mL). Basify the aqueous layer with 5N NaOH solution and extract with ethyl acetate (3×250 mL). Dry the organic layer over sodium sulfate, filter and concentrate. Purify the residue by flash chromatography (silica gel, 10% 2M NH3/MeOH in DCM) to obtain 3-(4-dimethylamino-cyclohex-1-enyl)-5-fluoro-phenylamine (2.84 g, 33.5%).

Workup

  1. temperatureCool to ambient temperature
  2. washwash with ethyl acetate (2×100 mL)
  3. extractionBasify the aqueous layer with 5N NaOH solution and extract with ethyl acetate (3×250 mL)
  4. dry with materialDry the organic layer over sodium sulfate
  5. filtrationfilter
  6. concentrationconcentrate
  7. customPurify the residue by flash chromatography (silica gel, 10% 2M NH3/MeOH in DCM)

Sources & evidence

ORD record
ord-568553065ace4890967f75cc4ae168c9
Source dataset
uspto-grants-2007_12
Patent number
US07312236B2

Reaction notes

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