Formaldehyde → HCID 23591235, compound

HRID 1611069Notes

Reaction equation

HRID 1611069 reaction equation
[C:1]1([P:7]2(=[O:12])[CH2:11][CH2:10][CH2:9][CH2:8]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH2:13]=[O:14].C1(C)C=CC=CC=1>C1COCC1>[C:1]1([P:7]2(=[O:12])[CH2:8][CH2:9][CH2:10][CH:11]2[CH2:13][OH:14])[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

5

Reactant 3

HCID 712FormaldehydeHCID 1140Toluene2×HCID 6019914963-91-12×

Product 1

HCID 23591235HCID 23591235, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-20 °C

Procedure

In a 1 l round bottom 2-neck flask charged a with a magnetic stirring bar, 23.4 g 1-phenylphospholane-1-oxide (0.11 mol) was dissolved in 300 ml freshly distilled THF, and 10.4 g dry paraformaldehyde was added. The reaction flask was flushed with argon and cooled to −20° C. Subsequently 100 ml phenyllithium solution in cyclohexane/diethylether 7:3 (1.8M) was added in one portion. The resulting mixture was stirred until the temperature reached +10° C. and additionally 5 minutes at that temperature. Then 10 g NH4Cl was added. The mixture was filtered, concentrated, and the residue purified by flash chromatography (EtOAc, followed by EtOAc/methanol 10:1). Yields: 2.5 g substrate (1-phenylphospholane-1-oxide) (11%), 11.7 g (43%) trans-1-phenyl-2-phospholanemethanol-1-oxide as white crystals, m.p. 109-110° C. (toluene); 1H NMR (500 MHz) δ: 1.70-1.85 (m, 1H), 1.95-2.30 (m, 6H), 3.90-4.00 (m, 2H), 4.19 (t, 1H, J=6.1), 7.45-7.55 (m, 3H), 7.70-7.76 (m, 2H); 31P NMR (200 MHz) δ: 63.3; and 2.2 g (8%) cis-1-phenyl-2-phospholanemethanol-1-oxide, white crystals, m.p. 149-151° C. (toluene); 1H NMR (500 MHz) δ: 1.46-1.57 (m, 1H), 2.02-2.22 (m, 4H), 2.28-2.42 (m, 1H), 2.44-2.58 (m, 1H), 3.32-3.49 (m, 2H), 3.76 (t, 1H, J=5.7), 7.46-7.51 (m, 2H.), 7.52-7.57 (m, 1H), 7.67-7.73 (m, 2H); 31P NMR (200 MHz) δ: 62.7.

Workup

  1. additionIn a 1 l round bottom 2-neck flask charged a with a magnetic stirring bar
  2. additionwas added
  3. customThe reaction flask was flushed with argon
  4. additionSubsequently 100 ml phenyllithium solution in cyclohexane/diethylether 7:3 (1.8M) was added in one portion
  5. additionThen 10 g NH4Cl was added
  6. filtrationThe mixture was filtered
  7. concentrationconcentrated
  8. customthe residue purified by flash chromatography (EtOAc, followed by EtOAc/methanol 10:1)
  9. customYields

Sources & evidence

ORD record
ord-70de063ac42449e083393a7a7f2c903b
Source dataset
uspto-grants-2006_01
Patent number
US06984744B2

Reaction notes

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