Tetrahydrofuran → 2-[(4,4-Diethoxy-2-butyn-1-yl)oxy]tetrahydropyran

HRID 742157Notes

Reaction equation

HRID 742157 reaction equation
C([Mg]Br)C.C1COCC1.[CH2:10]([O:13][CH:14]1[CH2:19][CH2:18][CH2:17][CH2:16][O:15]1)[C:11]#[CH:12].[CH2:20]([O:22][CH:23](OCC)[O:24][CH2:25][CH3:26])[CH3:21]>C1(C)C=CC=CC=1>[CH2:20]([O:22][CH:23]([O:24][CH2:25][CH3:26])[C:12]#[C:11][CH2:10][O:13][CH:14]1[CH2:19][CH2:18][CH2:17][CH2:16][O:15]1)[CH3:21]

Participants

6

Reactant 4

HCID 8028TetrahydrofuranHCID 31214Ethyl orthoformateHCID 98609Tetrahydro-2-(2-propynyloxy)-2H-pyranHCID 178418443HCID 178418443, compound

Product 1

HCID 136446252-[(4,4-Diethoxy-2-butyn-1-yl)oxy]tetrahydropyranYield 79%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

A 1M solution of ethylmagnesium bromide in THF (200 ml, 0.2 mol) was treated with 29 ml (0.2 mol) of a solution of 3,4,5,6-tetrahydro-2-(2-propynyloxy)-2H-pyran in toluene, while maintaining ambient temperature through use of a cool water bath. The resulting solution was stirred for 4 h and treated with 47 ml (.28 mol) of a solution of triethylorthoformate in toluene, while maintaining ambient temperature with a cool water bath. The resulting solution was heated to 85° C. for 8 h, allowing the removal of THF by distillation. After being allowed to cool, the resulting solution was poured into 500 ml of ice-water containing 29 g of NH4OAc, extracted with two portions of ether, dried over K2CO3, and concentrated in vacuo. The residue was distilled at ca. 0.5 mm Hg pressure (b.p. 103°-108° C.) to provide 39.5 g (79%) of the desired compound. 1H NMR (CDCl3)δ1.24 (t, J=7 Hz, 6H), 1.5-1.9 (m, 6H), 3.5-3.65 (m, 3H), 3.7-3.9 (m, 3H), 4.32 (AA', 2H), 4.81 (m, 1H), 5.31 (m, 1H). Mass spectrum: (M+NH4)+ ==260.

Workup

  1. temperaturewhile maintaining ambient temperature with a cool water bath
  2. temperatureThe resulting solution was heated to 85° C. for 8 h
  3. customthe removal of THF
  4. distillationby distillation
  5. temperatureto cool
  6. additionthe resulting solution was poured into 500 ml of ice-water containing 29 g of NH4OAc
  7. extractionextracted with two portions of ether
  8. dry with materialdried over K2CO3
  9. concentrationconcentrated in vacuo
  10. distillationThe residue was distilled at ca. 0.5 mm Hg pressure (b.p. 103°-108° C.)

Sources & evidence

ORD record
ord-fa7e99b1fe764aa8a4df784c1bbfff0b
Source dataset
uspto-grants-1996_09
Patent number
US05552558

Reaction notes

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