Cesium carbonate → 1552271-08-5

HRID 2175391Notes

Reaction equation

HRID 2175391 reaction equation
[NH2:1][C:2]1[CH:3]=[CH:4][C:5](Br)=[C:6]([CH:9]=1)[C:7]#[N:8].[CH:11]1(B(O)O)[CH2:13][CH2:12]1.C([O-])([O-])=O.[Cs+].[Cs+].C1(P(C2CCCCC2)C2CCCCC2)CCCCC1>CC([O-])=O.CC([O-])=O.[Pd+2].O.C1(C)C=CC=CC=1>[NH2:1][C:2]1[CH:3]=[CH:4][C:5]([CH:11]2[CH2:13][CH2:12]2)=[C:6]([CH:9]=1)[C:7]#[N:8]

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 75806TricyclohexylphosphineHCID 8172085-amino-2-bromobenzonitrileHCID 2760897Cyclopropylboronic acid

Product 1

HCID 867213231552271-08-5

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

5-amino-2-bromobenzonitrile (5.0 g, 25.4 mmol), cyclopropylboronic acid (4.36 g, 50.8 mmol), Cs2CO3 (49.62 g, 152.3 mmol), and tricyclohexylphosphine (2.85 g, 10.2 mmol) were weighed out and added to a large reaction tube with magnetic stir bar. Toluene (120 mL) and water (40 mL) were added, and the reaction was subjected to vigorous sub-surface nitrogen sparging. Pd(OAc)2 (1.14 g, 5.1 mmol) was weighed out and added, the tube was sealed under nitrogen, and the reaction was heated overnight at 110° C. This was then filtered with water and ethyl acetate washings. The combined washings were treated with saturated aqueous NaHCO3 and the layers were separated. The aqueous was extracted 4 more times with ethyl acetate, and the combined organic layer was washed twice with brine and dried over sodium sulfate. After filtration, concentration, and drying on the high vacuum, 7.65 g was obtained of 5-amino-2-cyclopropylbenzonitrile containing tricyclohexylphosphine derived byproducts. This was used without further purification.

Workup

  1. additionadded to a large reaction tube with magnetic stir bar
  2. additionadded
  3. customthe tube was sealed under nitrogen
  4. filtrationThis was then filtered with water and ethyl acetate washings
  5. additionThe combined washings were treated with saturated aqueous NaHCO3
  6. customthe layers were separated
  7. extractionThe aqueous was extracted 4 more times with ethyl acetate
  8. washthe combined organic layer was washed twice with brine
  9. dry with materialdried over sodium sulfate
  10. filtrationAfter filtration, concentration
  11. customdrying on the high vacuum

Sources & evidence

ORD record
ord-229c03f2fc0046ff9dceff746180862b
Source dataset
uspto-grants-2015_06
Patent number
US09062068B2

Reaction notes

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