Cesium carbonate → HCID 118114595, compound

HRID 1050567Notes

Reaction equation

HRID 1050567 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2([C:11]([F:14])([F:13])[F:12])[CH2:10][CH2:9]2)=[CH:4][CH:3]=1.[C:15](=[O:22])([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])[NH2:16].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.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]>[F:12][C:11]([F:14])([F:13])[C:8]1([C:5]2[CH:6]=[CH:7][C:2]([NH:16][C:15](=[O:22])[O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[CH:3][CH:4]=2)[CH2:10][CH2:9]1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 77922tert-Butyl carbamateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 509985581-Bromo-4-[1-(trifluoromethyl)cyclopropyl]benzene

Product 1

HCID 118114595HCID 118114595, compound

Reagents, catalysts & solvents 2

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

Conditions

Temperature
115 °C

Procedure

1-Bromo-4-(1-(trifluoromethyl)cyclopropyl)benzene (1.00 g, 3.77 mmol) was mixed with tert-butyl carbamate (1.77 g, 15.1 mmol), Pd2(dba)3 (350 mg, 0.38 mmol), XantPhos (650 mg, 1.13 mmol), fine-powder cesium carbonate (7.40 g, 22.6 mmol) in 80 mL dioxane. The mixture was degassed using nitrogen stream for 5 min, and stirred in 115° C. bath under nitrogen atmosphere for 7 hours. It was cooled to RT, diluted with 200 mL EtOAc, well stirred, filtered using ChemGlass OP-6602-12 disposable funnel, concentrated in vacuo, and subjected to silica flash column using 0 to 1% MeOH in DCM to isolate tert-butyl 4-(1-(trifluoromethyl)cyclopropyl)phenylcarbamate. It was treated with 1:1 DCM/TFA (10 mL/10 mL) at RT for 10 min, concentrated in vacuo, taken into chloroform, washed with 1N NaOH (aq) and water, dried, concentrated and subjected to silica flash column to isolate 4-(1-(trifluoromethyl)cyclopropyl)aniline (330) (300 mg, 40%).

Workup

  1. customThe mixture was degassed
  2. customfor 5 min
  3. temperatureIt was cooled to RT
  4. additiondiluted with 200 mL EtOAc
  5. stirringwell stirred
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-3c9bb605850443e88eff8266a944d28b
Source dataset
uspto-grants-2016_07
Patent number
US09382246B2

Reaction notes

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