Hydrochloric Acid → (Tetrahydro-2H-pyran-4-yl)methyl 4-methylbenzenesulfonate

HRID 538629Notes

Reaction equation

[O:1]1[CH2:6][CH2:5][CH:4]([CH2:7][OH:8])[CH2:3][CH2:2]1.[OH-].[Na+].[C:11]1([CH3:21])[CH:16]=[CH:15][C:14]([S:17](Cl)(=[O:19])=[O:18])=[CH:13][CH:12]=1.Cl.CC1CCCCC1>CC1CCCO1>[O:1]1[CH2:6][CH2:5][CH:4]([CH2:7][O:8][S:17]([C:14]2[CH:15]=[CH:16][C:11]([CH3:21])=[CH:12][CH:13]=2)(=[O:19])=[O:18])[CH2:3][CH2:2]1

Participants

Conditions

Temperature: 32.5 °C

Procedure

To 97 g (810 mmol) of (tetrahydro-pyran-4-yl)-methanol in 2-methyltetrahydrofuran (190 mL) are added 165 mL of 50% aq. NaOH solution. To this stirred suspension is added dropwise with cooling a solution of p-toluene-sulfonylchloride (283 g, 1.46 mol) in 2-methyltetrahydrofuran (280 mL). The reaction is stirred at 30-35° C. for 18 h. The suspension is poured into a mixture of ice-water (280 mL) and aq. HCl solution (37%, 203 mL). After addition of methylcyclohexane (1.4 L) and further ice-water (0.2 L), the reaction mixture is stirred for 2 h in an ice-bath. The resulting crystalline precipitate is isolated by filtration and washed with methylcyclohexane (0.5 L) and water (0.5 L). Drying under reduced pressure at 40° C. gave 216 g of toluene-4-sulfonic acid tetrahydro-pyran-4-ylmethyl ester. Yield: 99%; ESI-MS: 271 [M+H]+

Workup

additionTo this stirred suspension is added dropwise
stirringthe reaction mixture is stirred for 2 h in an ice-bath
customThe resulting crystalline precipitate is isolated by filtration
washwashed with methylcyclohexane (0.5 L) and water (0.5 L)
customDrying under reduced pressure at 40° C.

Sources & evidence

ORD record: ord-8ea29db611614204bca07ed801ef6bb2
Source dataset: uspto-grants-2014_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08865744B1

Reaction notes

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