4-Bromo-2-chloro-alpha,alpha,alpha-trifluorotoluene → HCID 22345177, compound

HRID 584048Notes

Reaction equation

HRID 584048 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([Cl:12])=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:7]=1.[CH2:13]([N:16]1[CH2:21][CH2:20][NH:19][CH2:18][CH2:17]1)[CH2:14][CH3:15].CC(C)([O-])C.[Na+]>O1CCOCC1.CCOCC.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:12][C:5]1[CH:4]=[CH:3][C:2]([N:19]2[CH2:20][CH2:21][N:16]([CH2:13][CH2:14][CH3:15])[CH2:17][CH2:18]2)=[CH:7][C:6]=1[C:8]([F:11])([F:10])[F:9]

Participants

7

Reactant 3

HCID 679594-Bromo-2-chloro-alpha,alpha,alpha-trifluorotolueneHCID 415812Piperazine, 1-propyl-, hydrochloride (1:2)HCID 23676156Sodium t-butoxide

Product 1

HCID 22345177HCID 22345177, compound

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 3283Diethyl EtherSolventHCID 312751,4-DioxaneSolvent

Procedure

A mixture of 5-bromo-2-chlorobenzotrifluoride (0.2 g, 0.85 mmol), n-propyl piperazine (0.15 g, 1.17 mmol), sodium tert-butoxide (0.134 g) dppf (14 mg) and [Pd2(dba)3 (10 mg) in dioxane (5 ml) was heated under argon at 100° C. for 24 h. After cooling to room temperature, the reaction mixture was taken up in Et2O (40-50 ml) and washed with brine (15-20 ml). The organic fraction was dried (MgSO4), filtered and evaporated to dryness. The crude material was purified by flash chromatography on silica gel using CH2Cl2:MeOH (9:1 (v/v)). The amine was converted into the HCl-salt and recrystallized from ethanol/diethylether; m.p. 268° C. (HCl); MS m/z (rel. intensity, 70 eV)) 307 (M+, 6), 279 (33), 277 (98), 70 (bp), 56 (40). Rf=0.35 (EtOAc)

Workup

  1. washwashed with brine (15-20 ml)
  2. dry with materialThe organic fraction was dried (MgSO4)
  3. filtrationfiltered
  4. customevaporated to dryness
  5. customThe crude material was purified by flash chromatography on silica gel
  6. customrecrystallized from ethanol/diethylether

Sources & evidence

ORD record
ord-6f6026024f43412abe986aebbcc78006
Source dataset
uspto-grants-2005_08
Patent number
US06924374B2

Reaction notes

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