Hydrochloric Acid → 4-Bromo-2-fluoro-4'-pentyltolane

HRID 1707888Notes

Reaction equation

HRID 1707888 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5](I)=[C:4]([F:9])[CH:3]=1.[CH2:10]([C:15]1[CH:20]=[CH:19][C:18]([C:21]#[CH:22])=[CH:17][CH:16]=1)[CH2:11][CH2:12][CH2:13][CH3:14].Cl>C(NCC)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:22]#[C:21][C:18]2[CH:19]=[CH:20][C:15]([CH2:10][CH2:11][CH2:12][CH2:13][CH3:14])=[CH:16][CH:17]=2)=[C:4]([F:9])[CH:3]=1

Participants

7

Reactant 3

HCID 313Hydrochloric AcidHCID 27245164-Bromo-2-fluoro-1-iodobenzeneHCID 27751311-Ethynyl-4-pentylbenzene

Product 1

HCID 677422634-Bromo-2-fluoro-4'-pentyltolaneYield 41.3%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8021DiethylamineSolvent

Conditions

Temperature
5 °C

Procedure

4-Bromo-2-fluoro-1-iodobenzene (57 g) was dissolved in diethylamine (66 ml) under nitrogen atmosphere, and then bis(triphenylphosphine)palladium(II) chloride (0.5 g) and copper(I) iodide (0.5 g) were added thereto, followed by stirring. The flask was cooled to 5° C. or lower, and then 4-pentylphenylacetylene (36 g) was added dropwise thereto. After stirring at room temperature for 5 hours, the reaction solution was poured into a mixture of concentrated hydrochloric acid (40 ml) and ice (30 g). After extraction with chloroform, the resultant was washed twice with water, followed by distilling off chloroform therefrom. The residue was distilled under reduced pressure (b.p. 205° to 210° C./3 mmHg), and then recrystallized from a mixed solvent of acetone and methanol to give 4-bromo-2-fluoro-4'-pentyltolane (27 g).

Workup

  1. stirringAfter stirring at room temperature for 5 hours
  2. extractionAfter extraction with chloroform
  3. washthe resultant was washed twice with water
  4. distillationby distilling off chloroform
  5. distillationThe residue was distilled under reduced pressure (b.p. 205° to 210° C./3 mmHg)
  6. customrecrystallized from a mixed solvent of acetone and methanol

Sources & evidence

ORD record
ord-d2e8bc9f38b24806bdd63c57f9dbb160
Source dataset
uspto-grants-1994_10
Patent number
US05356558

Reaction notes

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