Pyridine → 2-(4-Nitrobenzyl)-1,3,2-dioxaphosphinane 2-oxide

HRID 1599397Notes

Reaction equation

HRID 1599397 reaction equation
C(Cl)(=O)C(Cl)=O.[N+:7]([C:10]1[CH:20]=[CH:19][C:13]([CH2:14][P:15](=[O:18])([OH:17])[OH:16])=[CH:12][CH:11]=1)([O-:9])=[O:8].N1C=C[CH:24]=[CH:23][CH:22]=1>O1CCCC1>[N+:7]([C:10]1[CH:20]=[CH:19][C:13]([CH2:14][P:15]2(=[O:16])[O:17][CH2:24][CH2:23][CH2:22][O:18]2)=[CH:12][CH:11]=1)([O-:9])=[O:8]

Participants

5

Reactant 3

HCID 1049PyridineHCID 65578Oxalyl chlorideHCID 5180708(4-Nitro-benzyl)-phosphonic acid

Product 1

HCID 113458932-(4-Nitrobenzyl)-1,3,2-dioxaphosphinane 2-oxideYield 26.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

Oxalyl chloride (22.09 g) was added dropwise to a mixture of 4-nitrobenzylphosphonic acid (17.99 g), pyridine (13.76 g) and tetrahydrofuran (500 ml) at -78° C. After the mixture was stirred at -78° C. for 30 minutes and then at room temperature for 1.5 hours, the insoluble solid was filtered off. The filtrate was concentrated under reduced pressure, and the residual oily substance was dissolved in tetrahydrofuran (500 ml). To this solution, a solution of 1,3-propanediol (2.58 g) in acetonitrile (30 ml) was added dropwise at -78° C. over a 15-minute period. Then, pyridine (5.62 g) was added dropwise at -78° C. over a 5-minute period, and the mixture was stirred at room temperature for 15 hours. After the insoluble solid was filtered off, the filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with ethyl acetate-chloroform-methanol (10:10:1, v/v) to yield 2-(4-nitrobenzyl)-1,3,2-dioxaphosphorinane-2-oxide (5.62 g, 26%), which was then recrystallized from ethanol-hexane to yield colorless needles having a melting point of 144° to 145° C.

Workup

  1. waitat room temperature for 1.5 hours
  2. filtrationthe insoluble solid was filtered off
  3. concentrationThe filtrate was concentrated under reduced pressure
  4. dissolutionthe residual oily substance was dissolved in tetrahydrofuran (500 ml)
  5. additionTo this solution, a solution of 1,3-propanediol (2.58 g) in acetonitrile (30 ml) was added dropwise at -78° C. over a 15-minute period
  6. additionThen, pyridine (5.62 g) was added dropwise at -78° C. over a 5-minute period
  7. stirringthe mixture was stirred at room temperature for 15 hours
  8. filtrationAfter the insoluble solid was filtered off
  9. concentrationthe filtrate was concentrated under reduced pressure
  10. washeluted with ethyl acetate-chloroform-methanol (10:10:1

Sources & evidence

ORD record
ord-0eb66f2699a84724af525053f1e80f03
Source dataset
uspto-grants-1998_04
Patent number
US05741784

Reaction notes

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