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(Di)chlorination of phosphoricphosphonic acid ester

What is the best way to do this reaction to form the dichloride as an reactive intermediate when the substituent R is acid sensitive?

enter image description here

In the literature the reaction is either performed with PCl5, a mixture of POCl3 and PCl5, SOCl2 or Oxalylchloride + TMSBr. This goes for ethyl or isopropyl moieties, I also saw an example for benzyl. I think my best shot would be SOCl2 which is as I know more reactive than oxalylchloride and because it is a liquid, while PCl5 (can't be evaporated so easy) is a solid and my compound may not be stable to TMSBr, because it is suspected to be sensitive to TMS+ cation.

All of these reagents will generate acid when they have contact to trace water. These reactions are all performed under schlenk conditions, still usually I see back reactions to the hydrolysis product. Is the only viable strategy to remove the excess of chlorination agent in vacuo or is there the possibility to perform a quenching step that does not release acid while keeping the dichloride intact?

For example when I use oxalyl chloride, to produce an phosphorus acid chloride, the removal at the rotivap is often not complete. I doubt, that there is the possibility to perform this reaction from the start under basic conditions?

(Di)chlorination of phosphoric acid ester

What is the best way to do this reaction to form the dichloride when the substituent R is acid sensitive?

enter image description here

In the literature the reaction is either performed with PCl5, a mixture of POCl3 and PCl5, SOCl2 or Oxalylchloride + TMSBr. I think my best shot would be SOCl2 which is as I know more reactive than oxalylchloride and because it is a liquid, while PCl5 (can't be evaporated so easy) is a solid and my compound may not be stable to TMSBr, because it is suspected to be sensitive to TMS+ cation.

All of these reagents will generate acid when they have contact to trace water. These reactions are all performed under schlenk conditions, still usually I see back reactions to the hydrolysis product. Is the only viable strategy to remove the excess of chlorination agent in vacuo or is there the possibility to perform a quenching step that does not release acid while keeping the dichloride intact?

For example when I use oxalyl chloride, to produce an phosphorus acid chloride, the removal at the rotivap is often not complete. I doubt, that there is the possibility to perform this reaction from the start under basic conditions?

(Di)chlorination of phosphonic acid ester

What is the best way to do this reaction to form the dichloride as an reactive intermediate when the substituent R is acid sensitive?

enter image description here

In the literature the reaction is either performed with PCl5, a mixture of POCl3 and PCl5, SOCl2 or Oxalylchloride + TMSBr. This goes for ethyl or isopropyl moieties, I also saw an example for benzyl. I think my best shot would be SOCl2 which is as I know more reactive than oxalylchloride and because it is a liquid, while PCl5 (can't be evaporated so easy) is a solid and my compound may not be stable to TMSBr, because it is suspected to be sensitive to TMS+ cation.

All of these reagents will generate acid when they have contact to trace water. These reactions are all performed under schlenk conditions, still usually I see back reactions to the hydrolysis product. Is the only viable strategy to remove the excess of chlorination agent in vacuo or is there the possibility to perform a quenching step that does not release acid while keeping the dichloride intact?

For example when I use oxalyl chloride, to produce an phosphorus acid chloride, the removal at the rotivap is often not complete. I doubt, that there is the possibility to perform this reaction from the start under basic conditions?

Source Link
raptorlane
raptorlane
  • 799
  • 1
  • 12

(Di)chlorination of phosphoric acid ester

What is the best way to do this reaction to form the dichloride when the substituent R is acid sensitive?

enter image description here

In the literature the reaction is either performed with PCl5, a mixture of POCl3 and PCl5, SOCl2 or Oxalylchloride + TMSBr. I think my best shot would be SOCl2 which is as I know more reactive than oxalylchloride and because it is a liquid, while PCl5 (can't be evaporated so easy) is a solid and my compound may not be stable to TMSBr, because it is suspected to be sensitive to TMS+ cation.

All of these reagents will generate acid when they have contact to trace water. These reactions are all performed under schlenk conditions, still usually I see back reactions to the hydrolysis product. Is the only viable strategy to remove the excess of chlorination agent in vacuo or is there the possibility to perform a quenching step that does not release acid while keeping the dichloride intact?

For example when I use oxalyl chloride, to produce an phosphorus acid chloride, the removal at the rotivap is often not complete. I doubt, that there is the possibility to perform this reaction from the start under basic conditions?