p-Toluenesulfonic acid → 2-Propanol, 1-chloro-3-[(tetrahydro-2H-pyran-2-yl)oxy]-

HRID 977792

Reaction equation

HRID 977792 reaction equation
[OH:1][CH2:2][CH:3]([O:6][CH:7]1[CH2:12][CH2:11][CH2:10][CH2:9][O:8]1)[CH2:4][Cl:5].[CH2:13](C1OC1)[Cl:14].C(OCC(O)CCl)(=O)C.C(OC(CCl)CO)(=O)C.O1C=CCCC1.C1(C)C=CC(S(O)(=O)=O)=CC=1.C(OCC(OC1CCCCO1)CCl)(=O)C.O1CCCCC1OCC(OC(=O)C)CCl.C(=O)([O-])[O-].[K+].[K+]>[Fe](Cl)(Cl)Cl.CO.C(O)(=O)C>[OH:1][CH2:2][CH:3]([O:6][CH:7]1[CH2:12][CH2:11][CH2:10][CH2:9][O:8]1)[CH2:4][Cl:5].[O:8]1[CH2:9][CH2:10][CH2:11][CH2:12][CH:7]1[O:6][CH2:3][CH:2]([OH:1])[CH2:13][Cl:14]

Participants

14

Reactant 9

HCID 6101p-Toluenesulfonic acidHCID 7835EpichlorohydrinHCID 80803,4-dihydro-2H-pyranHCID 11430Potassium CarbonateHCID 980693-Chloro-2-hydroxypropyl acetateHCID 136667621-Hydroxy-2-(tetrahydropyran-2-yl)oxy-3-chloropropaneHCID 159164011-Chloro-3-hydroxypropan-2-yl acetateHCID 19048387HCID 19048387, compoundHCID 19048416HCID 19048416, compound

Product 2

HCID 113214982-Propanol, 1-chloro-3-[(tetrahydro-2H-pyran-2-yl)oxy]-HCID 136667621-Hydroxy-2-(tetrahydropyran-2-yl)oxy-3-chloropropane

Reagents, catalysts & solvents 3

HCID 24380Iron chloride (FeCl3)CatalystHCID 176Acetic AcidSolventHCID 887MethanolSolvent

Procedure

1-hydroxy-2-(tetrahydropyran-2-yl)oxy-3-chloropropane can be prepared by the following scheme: epichlorohydrin is reacted with acetic acid in the presence of a catalytic amount of iron trichloride to give a mixture of 1-acetyloxy-3-chloropropan-2-ol and 2-acetyloxy-3-chloropropan-1-ol, the major component. The mixture is treated with dihydropyran in the presence of p-toluenesulfonic acid for five hours at 25° C. to give a mixture of 1-acetyloxy-2-(tetrahydropyran-2-yl)oxy-3-chloropropane and 1-(tetrahydropyranyloxy)-2-acetyloxy-3-chloropropane. The mixture is added to a rapidly stirred mixture of aqueous methanol and potassium carbonate at 25° C. and stirred for two hours. Evaporation of the methanol, extraction and drying yields a mixture 1-hydroxy-2-(tetrahydropyran-2-yl)oxy-3-chloropropane and 1-(tetrahydropyran-2-yl)oxy-2-hydroxy-3-chloropropane. Fractional vacuum distillation yields pure 1-hydroxy-2-(tetrahydropyran-2-yl)-oxy-3-chloro-propane since the minor impurity is converted into the more volatile epoxy compound during the distillation procedure.

Workup

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  2. customto give
  3. customEvaporation of the methanol, extraction
  4. customdrying

Sources & evidence

ORD record
ord-b4654c1742964587b06371c1c348a591
Source dataset
uspto-grants-1997_03
Patent number
US05614638

Linked notes

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