HCID 23591235, compound → HCID 22259816, compound

HRID 1611070Notes

Reaction equation

HRID 1611070 reaction equation
[C:1]1([P:7]2(=[O:14])[CH2:11][CH2:10][CH2:9][CH:8]2[CH2:12]O)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1>C(Cl)Cl>[C:1]1([P:7]2(=[O:14])[CH2:11][CH2:10][CH2:9][C:8]2=[CH2:12])[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

3

Reactant 1

HCID 23591235HCID 23591235, compound

Product 1

HCID 22259816HCID 22259816, compoundYield 75%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

In a 100 ml round bottom 2-neck flask charged with a magnetic stirring bar and 20 ml freshly distilled CH2Cl2, 1.6 g 1-phenyl-2-phospholanemethanol-1-oxide (0.008 mol, mixture of diastereoisomers) was dissolved. The reaction flask was flushed with argon and cooled to 0° C. Subsequently 2.1 ml SOCl2 in 10 ml CH2Cl2 was added dropwise. The resulting yellowish mixture was stirred for 5 h at room temperature, then 20 ml water was added. The mixture was extracted twice with 20 ml CH2Cl2, and the combined organic phases were dried over MgSO4 and filtered. To the resulting filtrate containing crude 2-chloromethyl-1-phenylphospholane 1-oxide (mixture of isomers; 31P NMR (200 MHz) δ: 58.2, 60.3) 1.7 ml DBU was added. The mixture was heated and refluxed overnight. Evaporation of the solvent and flash chromatography of the residue with EtOAc/ethanol 20:1 yielded 1.1 g (75%) 1-phenyl-2-methylenephospholane-1-oxide as a colorless oil. 1H NMR (500 MHz) δ: 1.72-1.89 (m, 1H), 1.94-2.16 (m, 3H), 2.48-2.59 (m, 1H), 2.66-2.78 (m, 1H), 5.74 (dt, 1H, J=2.4, J=17.2), 5.88 (dt, 1H, J=2.1, J=36.6), 7.37-7.48 (m, 3H), 7.63-7.70 (m, 2H); −P NMR (200 MHz) δ: 45.0.

Workup

  1. additionIn a 100 ml round bottom 2-neck flask charged with a magnetic stirring bar
  2. customThe reaction flask was flushed with argon
  3. additionSubsequently 2.1 ml SOCl2 in 10 ml CH2Cl2 was added dropwise
  4. addition20 ml water was added
  5. extractionThe mixture was extracted twice with 20 ml CH2Cl2
  6. dry with materialthe combined organic phases were dried over MgSO4
  7. filtrationfiltered
  8. additionTo the resulting filtrate containing crude 2-chloromethyl-1-phenylphospholane 1-oxide (mixture of isomers; 31P NMR (200 MHz) δ: 58.2, 60.3) 1.7 ml DBU
  9. additionwas added
  10. temperatureThe mixture was heated
  11. temperaturerefluxed overnight
  12. customEvaporation of the solvent and flash chromatography of the residue with EtOAc/ethanol 20:1

Sources & evidence

ORD record
ord-455329abcd4342d1be24c5cef77f5e62
Source dataset
uspto-grants-2006_01
Patent number
US06984744B2

Reaction notes

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