Reaction #511516

Reaction equation

hydrochloric acid

2-methacryloyloxy-5-oxo-4-oxa-tricyclo[4.2.1.03,7]-non-9-ylcarbonyl chloride

triphenylsulfonium 1,1-difluoro-2-hydroxy-ethanesulfonate

triethylamine

→

triphenylsulfonium 1,1-difluoro-2-(9-methacryloyloxy-4-oxo-5-oxatricyclo[4.2.1.03,7]-non-2-ylcarbonyloxy)-ethane-1-sulfonate

Yield 61.0%

Solvents

methylene chloride

methylene chloride

Conditions

Workup

1. 1
   workup.ADDITIONwas added at a temperature below 5° C.
2. 2
   Washwashed with water, from which methylene chloride
3. 3
   workup.DISTILLATIONwas distilled off in vacuum
4. 4
   workup.ADDITION30 g of methyl isobutyl ketone was added to the residue, from which the residual water
5. 5
   workup.DISTILLATIONwas distilled off in vacuum together with methyl isobutyl ketone
6. 6
   OtherThe resulting residue was purified by silica gel chromatography

Procedure

To 2.8 g (10 mmol) of the 2-methacryloyloxy-5-oxo-4-oxa-tricyclo[4.2.1.03,7]-non-9-ylcarbonyl chloride were added 4.2 g (10 mmol) of triphenylsulfonium 1,1-difluoro-2-hydroxy-ethanesulfonate in Synthesis Example 1-13 and 20 g of methylene chloride. To the mixture under ice cooling, a solution containing 1.0 g (10 mmol) of triethylamine and 0.25 g (2 mmol) of N,N-dimethylaminopyridine in 5 g of methylene chloride was added at a temperature below 5° C., and the resulting mixture was stirred for 2 hours at room temperature. Thereafter, 11 g of 5% dilute hydrochloric acid was added to the reaction mixture. The organic layer was taken out and washed with water, from which methylene chloride was distilled off in vacuum. 30 g of methyl isobutyl ketone was added to the residue, from which the residual water was distilled off in vacuum together with methyl isobutyl ketone. The resulting residue was purified by silica gel chromatography, obtaining the target compound, triphenylsulfonium 1,1-difluoro-2-(9-methacryloyloxy-4-oxo-5-oxatricyclo[4.2.1.03,7]-non-2-ylcarbonyloxy)-ethane-1-sulfonate. Colorless solids, 4.0 g (yield 61%). The compound has the following structure.

Source