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

HRID 233058

Reaction equation

HRID 233058 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

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

Sources & evidence

ORD record
ord-f1bb08084ffe426f9a4c432f32f42055
Source dataset
uspto-grants-1997_01
Patent number
US05591846

Linked notes

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