Thionyl Chloride → 1,1'-Sulfinylbis(3,4-di-tert-butoxybenzene)

HRID 725287Notes

Reaction equation

HRID 725287 reaction equation
[C:1]([O:5][C:6]1[CH:7]=[C:8](Cl)[CH:9]=[CH:10][C:11]=1[O:12][C:13]([CH3:16])([CH3:15])[CH3:14])([CH3:4])([CH3:3])[CH3:2].[Mg].[S:19](Cl)(Cl)=[O:20]>C1COCC1>[C:1]([O:5][C:6]1[CH:7]=[C:8]([S:19]([C:8]2[CH:9]=[CH:10][C:11]([O:12][C:13]([CH3:14])([CH3:15])[CH3:16])=[C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])[CH:7]=2)=[O:20])[CH:9]=[CH:10][C:11]=1[O:12][C:13]([CH3:16])([CH3:15])[CH3:14])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 24386Thionyl ChlorideHCID 5462224MagnesiumHCID 21458933HCID 21458933, compound

Product 1

HCID 538105471,1'-Sulfinylbis(3,4-di-tert-butoxybenzene)Yield 64%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A Grignard reagent was conventionally prepared using 3,4-di-tert-butoxyphenyl chloride, magnesium, and THF and further reacted with thionyl chloride, obtaining bis(3,4-di-tert-butoxyphenyl) sulfoxide in a yield of 64%. Then 58.9 g (0.12 mol) of bis(3,4-di-tert-butoxyphenyl) sulfoxide was dissolved in 120 g of THF and cooled in an ice water bath. Then 12.1 g (0.12 mol) of triethylamine was added thereto and 68.3 g (0.31 mol) of trimethylsilyl triflate was added dropwise in a controlled manner at less 10° C. To this solution, a Grignard reagent which was conventionally prepared using 61.6 g (0.24 mol) of 1,2-di-tert-butoxy-4-chlorobenzene, 5.8 g (0.24 mol) of magnesium, and 100 g of THF was added dropwise in a controlled manner at less 10° C. With the reaction temperature controlled at 0° to 10° C., reaction ripening was carried out for 30 minutes. A 20% ammonium chloride aqueous solution, 700 g, was added to the reaction solution to terminate reaction, followed by separation. 300 g of chloroform was added to the organic layer. The organic layer was washed twice using 300 g of water and then evaporated, obtaining an oily residue. The oily residue was worked up by column chromatography (silica gel, eluent: chloroform/methanol), obtaining tris(3,4-di-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate of 99% purity in a yield of 20%. The final percent yield of this two-steps synthesis process was 13%.

Sources & evidence

ORD record
ord-4118ac1c1a684deeb6782aab67bf532c
Source dataset
uspto-grants-1998_01
Patent number
US05705702

Reaction notes

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