1,4-Dibromobenzene → (4-Bromophenyl)diphenylphosphine

HRID 1706855Notes

Reaction equation

HRID 1706855 reaction equation
C([Li])CCC.Br[C:7]1[CH:12]=[CH:11][C:10]([Br:13])=[CH:9][CH:8]=1.Cl[P:15]([C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1>CCCCCC.O1CCCC1>[C:22]1([P:15]([C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=2)[C:7]2[CH:12]=[CH:11][C:10]([Br:13])=[CH:9][CH:8]=2)[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=1

Participants

6

Reactant 3

HCID 78041,4-DibromobenzeneHCID 66180ChlorodiphenylphosphineHCID 178418339Butyllithium

Product 1

HCID 69773(4-Bromophenyl)diphenylphosphineYield 29.5%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

To 1.0 mole of n-butyllithium in hexane at -78° C. under an inert atmosphere is added dropwise and with efficient stirring 236 g of p-dibromobenzene in dry tetrahydrofuran (total volume 500 ml). The resulting solution is stirred at -78° C. for 1 hour, then treated dropwise at this temperature with 220.5 g of chlorodiphenylphosphine. When this addition is complete, the mixture is allowed to warm to room temperature, then solvent is removed under vacuum. The residue is triturated with two 400-ml portions of methanol, then distilled through a Vigreux column. The cut with bp 165°-170° C. (0.15 mm) is recrystallized from ethanol to give 100.5 g of p-diphenylphosphinobromobenzene, mp 78°-80° C.

Workup

  1. additionWhen this addition
  2. temperatureto warm to room temperature
  3. customsolvent is removed under vacuum
  4. customThe residue is triturated with two 400-ml portions of methanol
  5. distillationdistilled through a Vigreux column
  6. customThe cut with bp 165°-170° C. (0.15 mm) is recrystallized from ethanol

Sources & evidence

ORD record
ord-d8a098a446d54d16b695cf279a8d27bf
Source dataset
uspto-grants-1980_06
Patent number
US04209468

Reaction notes

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