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

HRID 53932

反応式

HRID 53932 の反応式
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]

参加物

6

反応物 4

HCID 8028TetrahydrofuranHCID 31214Ethyl orthoformateHCID 98609Tetrahydro-2-(2-propynyloxy)-2H-pyranHCID 178418443HCID 178418443、化合物

生成物 1

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

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒2 回

実験手順

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 (0.28 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) δ 1.24 (t, J=7 Hz, 6 H), 1.5-1.9 (m, 6 H), 3.5-3.65 (m, 3 H), 3.7-3.9 (m, 3 H), 4.32 (AA', 2 H), 4.81 (m, 1 H), 5.31 (m, 1 H). Mass spectrum: (M+NH4)+ =260.

後処理

  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.)

出典と根拠

ORDレコード
ord-3ad9898b377a40518108ca98b0420cca
出典データセット
uspto-grants-1997_04
特許番号
US05621109

関連ノート

読み込み中…