p-Toluenesulfonyl azide → (1E)-1-diazo-1-dimethoxyphosphorylpropan-2-one

HRID 2251983Notes

Reaction equation

HRID 2251983 reaction equation
[H-].[Na+].[CH3:3][O:4][P:5]([CH2:9][C:10](=[O:12])[CH3:11])(=[O:8])[O:6][CH3:7].S([N:23]=[N+:24]=[N-])(C1C=CC(C)=CC=1)(=O)=O>C1C=CC=CC=1.O1CCCC1>[CH3:3][O:4][P:5]([C:9](=[N+:23]=[N-:24])[C:10](=[O:12])[CH3:11])(=[O:8])[O:6][CH3:7]

Participants

6

Reactant 3

HCID 13661p-Toluenesulfonyl azideHCID 24758Sodium hydrideHCID 77872Dimethyl (2-oxopropyl)phosphonate

Product 1

HCID 136023029(1E)-1-diazo-1-dimethoxyphosphorylpropan-2-oneYield 92.3%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolvent3×HCID 8028TetrahydrofuranSolvent

Procedure

To sodium hydride (188 mg of a 60% solution in mineral oil, 113 mg clean, 4.70 mmol) in 14 mL of benzene and 2.5 mL of tetrahydrofuran, add the (2-Oxo-propyl)-phosphonic acid dimethyl ester (743 mg, 618 μL, 4.48 mmol) as a solution in 5 mL of benzene at 0° C. dropwise. The mix remains white and produces some gas. After 1 h at 0° C., add tosyl azide (940 mg, 4.70 mmol) as a solution in 2.5 mL of benzene and remove the bath. After 2.3 hours, pour the mix through a plug of Celite® with tetrahydrofuran, benzene and ether. Concentrate and apply to a 4 mm chromatotron plate and elute with 100 mL of Hexanes, and then 200 mL of 20:80 EtOAc/Hexanes, 30:70 EtOAc/Hexanes, 50:50 Hexanes/EtOAc, 85:15 EtOAc/Hexanes and 250 ml of EtOAc to provide 794 mg of (1-Diazo-2-oxo-propyl)-phosphonic acid dimethyl ester as a yellow solid. This material may be used directly. Exact Mass 192.03: mass spectrum (aspci): m/z=165.0 (M+1 (—N2).

Workup

  1. customproduces some gas
  2. customremove the bath
  3. waitAfter 2.3 hours
  4. additionpour the
  5. additionmix through a plug of Celite® with tetrahydrofuran, benzene and ether
  6. concentrationConcentrate and apply to a 4 mm chromatotron plate
  7. washelute with 100 mL of Hexanes

Sources & evidence

ORD record
ord-ee16758d3fb943dfbc05593a80b3c935
Source dataset
uspto-grants-2008_01
Patent number
US07320994B2

Reaction notes

Loading…