Triethylamine → 4-[(3-Aminophenyl)ethynyl]-phenyl Trifluoromethyl Sulfide

HRID 1030869Notes

Reaction equation

HRID 1030869 reaction equation
[F:1][C:2]([S:5][C:6]1[CH:11]=[CH:10][C:9](Br)=[CH:8][CH:7]=1)([F:4])[F:3].C(N(CC)CC)C.[NH2:20][C:21]1[CH:22]=[C:23]([C:27]#[CH:28])[CH:24]=[CH:25][CH:26]=1>CCOCC.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[F:1][C:2]([S:5][C:6]1[CH:11]=[CH:10][C:9]([C:28]#[C:27][C:23]2[CH:24]=[CH:25][CH:26]=[C:21]([NH2:20])[CH:22]=2)=[CH:8][CH:7]=1)([F:4])[F:3]

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 104682Benzenamine, 3-ethynyl-HCID 7364134-(Trifluoromethylthio)bromobenzene

Product 1

HCID 198210804-[(3-Aminophenyl)ethynyl]-phenyl Trifluoromethyl SulfideYield 62%

Reagents, catalysts & solvents 3

HCID 11776TriphenylphosphineCatalystHCID 10122028Bis(triphenylphosphine)palladiumCatalystHCID 3283Diethyl EtherSolvent

Conditions

Temperature
75 °C

Procedure

A multinecked flask as described in Example 1 was charged with 5.4 g (0.021 mol) of p-bromophenyl trifluoromethyl sulfide, 75 ml of dried, degassed triethylamine, 2.46 g (0.021 mol) of 3-aminophenylacetylene, 0.048 g (0.068 mmol) of bis(triphenylphosphine) palladium II chloride, 0.0148 g (0.564 mmol) of triphenylphosphine, and 0.03 g (0.157 mmol) of cuprous iodide. The reaction mixture was heated at 75° C. for 20 hours after which gas chromatography showed the reaction to be complete. The mixture was cooled to room temperature and diluted with 75 ml of ether. Filtration of the insoluble triethylamine hydrobromide salt by-product followed by concentration of the filtrate gave the crude product in near quantitative yield as an off-white solid. Short path distillation of the crude product under reduced pressure gave 3.9 g (0.013 mol, 62% yield) of the purified product as a white solid.

Workup

  1. customA multinecked flask as described in Example 1
  2. customof dried
  3. customthe reaction
  4. temperatureThe mixture was cooled to room temperature
  5. filtrationFiltration of the insoluble triethylamine hydrobromide salt by-product
  6. customgave the crude product in near quantitative yield as an off-white solid
  7. distillationShort path distillation of the crude product under reduced pressure

Sources & evidence

ORD record
ord-449573d4fe6e435fa02cbff10b507c72
Source dataset
uspto-grants-1992_04
Patent number
US05107026

Reaction notes

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