Pyridine → HCID 11335795, compound

HRID 1065612Notes

Reaction equation

HRID 1065612 reaction equation
[Br:1]Br.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH2:22]([O:24][P:25]([CH:30](O)[C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)(=[O:29])[O:26][CH2:27][CH3:28])[CH3:23].N1C=CC=CC=1>C(Cl)Cl>[CH2:22]([O:24][P:25]([CH:30]([Br:1])[C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)(=[O:29])[O:26][CH2:27][CH3:28])[CH3:23]

Participants

6

Reactant 4

HCID 1049PyridineHCID 11776TriphenylphosphineHCID 24408BromineHCID 238674diethoxyphosphoryl-phenyl-methanol

Product 1

HCID 11335795HCID 11335795, compoundYield 72.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent4×

Procedure

90 g of bromine, dissolved in 250 ml of methylene chloride, were added dropwise to a solution of 131 g (0.5 mole) of triphenylphosphine in 500 ml of methylene chloride at 30° to 35° C., moisture being excluded. The mixture was subsequently stirred at room temperature for 1 hour, a solution of 122 g (0.5 mole) of α-hydroxybenzyl-phosphonic acid diethyl ester in 250 ml of methylene chloride was then added dropwise at -20° C. in the course of 1 hour, the mixture was subsequently stirred at -20° C. for 1 hour and 40 g of pyridine, dissolved in 250 ml of methylene chloride, were then added dropwise at -20° C. in the course of one hour. The mixture was subsequently stirred for 20 hours, whereupon the temperature rose slowly to +20° C. The reaction mixture was transferred to a pear-shaped flask and the solvent was distilled off under a waterpump vacuum. The residue was extracted by stirring with one liter of ether and the undissolved triphenylphosphine oxide was filtered off (120 g of triphenylphosphine oxide=86% of theory). The mother liquor was concentrated in vacuo and the residue distilled under a high vacuum. 112 g (72% of theory) of α-bromobenzylphosphonic acid diethyl ester were obtained as a light yellow oil with a boiling point of 110° C./0.01 mm Hg and a purity of 95.9% (gas chromatogram).

Workup

  1. stirringthe mixture was subsequently stirred at -20° C. for 1 hour
  2. additionwere then added dropwise at -20° C. in the course of one hour
  3. stirringThe mixture was subsequently stirred for 20 hours, whereupon the temperature
  4. customrose slowly to +20° C
  5. customThe reaction mixture was transferred to a pear-shaped flask
  6. distillationthe solvent was distilled off under a waterpump vacuum
  7. extractionThe residue was extracted
  8. stirringby stirring with one liter of ether
  9. filtrationthe undissolved triphenylphosphine oxide was filtered off (120 g of triphenylphosphine oxide=86% of theory)
  10. concentrationThe mother liquor was concentrated in vacuo
  11. distillationthe residue distilled under a high vacuum

Sources & evidence

ORD record
ord-27ebc92d75904881bcbb14a612cfe065
Source dataset
uspto-grants-1982_05
Patent number
US04330482

Reaction notes

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