Pyridine → HCID 21265377, compound

HRID 1740673Notes

Reaction equation

HRID 1740673 reaction equation
[Br:1][C:2]1[CH:10]=[CH:9][CH:8]=[CH:7][C:3]=1C(Cl)=O.[F:11][C:12]1[CH:13]=[C:14]([OH:19])[CH:15]=[CH:16][C:17]=1[F:18].CN(C)[CH:22]=[O:23].N1C=CC=CC=1>O>[Br:1][C:2]1[CH:10]=[CH:9][C:8]([C:22]([O:19][C:14]2[CH:15]=[CH:16][C:17]([F:18])=[C:12]([F:11])[CH:13]=2)=[O:23])=[CH:7][CH:3]=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 by vacuum distillation at about 20 mmHg in a distillation temperature range of 190-200° C. The bromobenzoic acid chloride was added dropwise to a solution prepared from 50 g of 3,4-difluorophenol, 150 ml of dimethylformamide, and 31 g of pyridine 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 40 g of 4-propylcyclohexylphenylacetylene, 0.11 g of bis(triphenylphosphine)palladium(II) chloride, 0.12 g of copper iodide, 0.96 g of triphenylphosphine, and 400 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 a compound of the following formula. This compound had a nematic liquid crystal phase, a C-N point (crystal-nematic phase transition temperature) of 104° C., and an N-I point of 235° C. The IR spectrum of this compound had peaks (cm-1) at 3030, 2921, 2217, 1735, 1518, 1246, 1178, 1145, and 1107. ##STR33##

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-8c3cb39ef3874eb8b0db477057773454
Source dataset
uspto-grants-1999_10
Patent number
US05972244

Reaction notes

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