Pyridine → HCID 21265377, compound

HRID 2256777Notes

Reaction equation

HRID 2256777 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([OH:9])[CH:5]=[CH:6][C:7]=1[F:8].CN(C)[CH:12]=[O:13].N1C=CC=CC=1.[Br:21][C:22]1[CH:30]=[CH:29][CH:28]=[CH:27][C:23]=1C(Cl)=O>O>[Br:21][C:22]1[CH:30]=[CH:29][C:28]([C:12]([O:9][C:4]2[CH:5]=[CH:6][C:7]([F:8])=[C:2]([F:1])[CH:3]=2)=[O:13])=[CH:27][CH:23]=1

Participants

6

Reactant 4

HCID 1049PyridineHCID 6228DimethylformamideHCID 235422-Bromobenzoyl chlorideHCID 759273,4-Difluorophenol

Product 1

HCID 21265377HCID 21265377, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
70 °C

Procedure

120 g of thionyl chloride was added to 100 g of 4-bromobenzoic acid and the mixture was heated at 90° C. while stirring for 6 hours. After the reaction, an excess amount of thionyl chloride was removed by evaporation. 85 g of bromobenzoic acid chloride was obtained at a distillation temperature range of 190°-200° C. by vacuum distillation at about 20 mmHg. A solution prepared from 50 g of 3,4-difluorophenol, 150 ml of dimethylformamide, and 31 g of pyridine was added dropwise to the bromobenzoic acid chloride over about one hour while stirring at a temperature below 30° C. The mixture was then heated to 70° C. and stirred for 10 hours, and poured into a 10-fold amount of water to produce crystals. The crystals were collected by filtration, washed with dilute HCl and then water, dried in vacuum at 40° C., and recrystallized from ethyl acetate to obtain 50 g of 3,4-difluorophenyl 4-bromobenzoate. To this were added 25 g of 4-n-propylphenylacetylene, 0.11 g of bis(triphenylphosphine)palladium(II) chloride, 0.12 g of copper iodide, 0.96 g of triphenylphosphine, and 320 ml of triethylamine, followed by stirring for 10 hours while heating at 90° C. After the reaction, the reaction product was poured into a 10-fold amount of water to produce crystals. The crystals were collected by filtration, washed with water, dried in vacuum at 40° C., and recrystallized from a mixed solvent of ethyl acetate and methanol to obtain 43 g of 3,4-difluorophenyl 4-[2-(4-propylphenyl)ethynyl]benzoate of the following formula. ##STR9##

Workup

  1. stirringstirred for 10 hours
  2. customto produce crystals
  3. filtrationThe crystals were collected by filtration
  4. washwashed with dilute HCl
  5. dry with materialwater, dried in vacuum at 40° C.
  6. customrecrystallized from ethyl acetate

Sources & evidence

ORD record
ord-5384f5adf8db4e66a62051616240316d
Source dataset
uspto-grants-1997_08
Patent number
US05656198

Reaction notes

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