Nitrogen → HCID 54471613, compound

HRID 1914515Notes

Reaction equation

HRID 1914515 reaction equation
Cl.NC[CH2:4][C:5]1[CH:6]=[C:7](B(O)O)[CH:8]=[CH:9][CH:10]=1.Br[C:15]1[CH:20]=[CH:19][C:18]([C:21]([F:24])([F:23])[F:22])=[CH:17][CH:16]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].[N:33]#N>C(COC)OC.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[F:22][C:21]([F:24])([F:23])[C:18]1[CH:19]=[CH:20][C:15]([C:9]2[CH:8]=[CH:7][CH:6]=[C:5]([CH2:4][NH2:33])[CH:10]=2)=[CH:16][CH:17]=1

Participants

8

Reactant 4

HCID 947NitrogenHCID 62657Potassium Phosphate, TribasicHCID 67872Benzene, 1-bromo-4-(trifluoromethyl)-HCID 57461337HCID 57461337, compound

Product 1

HCID 54471613HCID 54471613, compoundYield 69%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent2×HCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
120 °C

Procedure

In a screw top flask 3-aminoethylphenylboronic acid hydrochloride (10.0 g, 53.4 mmol), 4-bromobenzotrifluoride (12.0, 53.4 mmol) and potassium phosphate (34.0 g, 160.2 mmol) were combined in dimethoxyethane (50 mL) and water (10 mL). The flask was flushed with N2 and tetrakis(triphenylphosphine)palladium (3.10 g, 2.67 mmol) was added. The flask was sealed and heated to 120° C. for 12 hours. The reaction mixture was cooled to rt and H2O (100 mL) was added and the resulting mixture was extracted with EtOAc (3×25 mL). The organic phases were combined, washed with brine (20 mL), dried with Na2SO4, filtered, concentrated and purified by flash column chromatography (0%-20% of a 10% NH3 in CH2Cl2 in CH2Cl2) providing the desired product as a brown oil (8.7 g, 69%). MS (ESI): mass calcd. for C14H12F3N, 251.25; m/z found 252.1 [M+H]+. 1H NMR (500 MHz, DMSO) δ 7.90 (d, J=8.1, 2H), 7.82 (d, J=8.2, 2H), 7.71 (s, 1H), 7.56 (d, J=7.5, 1H), 7.44 (t, J=7.5, 1H), 7.39 (d, J=7.5, 1H), 3.79 (s, 2H), 1.86 (s, 2H).

Workup

  1. additionwas added
  2. customThe flask was sealed
  3. temperatureThe reaction mixture was cooled to rt
  4. extractionthe resulting mixture was extracted with EtOAc (3×25 mL)
  5. washwashed with brine (20 mL)
  6. dry with materialdried with Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. custompurified by flash column chromatography (0%-20% of a 10% NH3 in CH2Cl2 in CH2Cl2)

Sources & evidence

ORD record
ord-d714f5f78f7c4f85bb7f01f1d36d7f76
Source dataset
uspto-grants-2013_12
Patent number
US08614201B2

Reaction notes

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