Chemical Properties
Off-white to cream powder
Uses
p-Toluenesulfonic anhydride has been employed as reagent in palladium-catalyzed allylic alkenylation of allylic alcohols with
n-butyl acrylate.
Reactions
Used as Reagent for tosylation.
p-Toluenesulfonic anhydride is a reliable way for the tosylation of many nucleophiles, primarily, for alcohols. The regent is a shelf-stable, well-soluble solid and “softer” electrophile than p-toluenesulfonyl chloride. Lipophilic alcohols can be easily tosylated in a very economical and eco-friendly way simply by using Ts2O in water without any catalyst. The tosylation can be realized in a few minutes under microwave assistance, giving p-toluenesulfonic acid as the only byproduct
[1]. Besides, it can be applied as an additive in palladium-catalyzed allylic alkenylation of allylic alcohols.
General Description
p-Toluenesulfonic anhydride acts as electrophilic species and activates 2-deoxy-sugar hemiacetals
in situ, which reacts stereoselectively with nucleophilic acceptors to afford β-anomers.
Chemical Reactivity
4-Toluenesulfonic anhydride has a high chemical reactivity towards common nucleophilic reagents. It can undergo sulfonylation reaction with alcohol hydroxyl groups or amine compounds under alkaline conditions.
Synthesis
Add p-toluenesulfonic acid and an m-phosphorous compound used as raw materials into a reaction kettle, dropwise adding thionyl chloride while stirring. Controlling the temperature in the reaction kettle at 68-76 ℃ and heating to perform condensation after dropwise addition; inputting water and hydrochloric acid into the reaction kettle, cooling to 0 ℃. The reaction solution generated in the previous step was drawn into the water, vacuum filtration was performed, and centrifuging was used to obtain a crude product, p-toluenesulfonic anhydride. Furthermore, it was inputting ethyl acetate, performing heating reflux, and freezing to perform crystallization, thus obtaining the qualified finished product.
References
[1] OLIVERIO M, COSTANZO P, PAONESSA R, et al. Catalyst-free tosylation of lipophilic alcohols in water†[J]. RSC Advances, 2012, 8: 2548-2552. DOI:10.1039/C2RA23067D.
