Triethylamine → (3aR,7R,7aR)-4,4-diphenyl-7-fluoro-2-[1-imino-2-(2-methoxyphenyl)ethyl]perhydroisoindole

HRID 2400024ノート

反応式

HRID 2400024 の反応式
Cl.[C:2]1([C:8]2([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[CH2:16][CH2:15][C@@H:14]([F:17])[C@@H:13]3[C@H:9]2[CH2:10][NH:11][CH2:12]3)[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(N(CC)CC)C.F[B-](F)(F)F.[CH3:36][O:37][C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][C:39]=1[CH2:44][C:45](=[NH:49])OCC.C(=O)([O-])[O-].[K+].[K+]>ClCCl>[C:18]1([C:8]2([C:2]3[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=3)[CH2:16][CH2:15][C@@H:14]([F:17])[C@@H:13]3[C@H:9]2[CH2:10][N:11]([C:45](=[NH:49])[CH2:44][C:39]2[CH:40]=[CH:41][CH:42]=[CH:43][C:38]=2[O:37][CH3:36])[CH2:12]3)[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=1

参加物

6

反応物 4

HCID 8471TriethylamineHCID 11430Potassium CarbonateHCID 67746156(3aR, 7R,7aR)-4,4-diphenyl-7-fluoroperhydroisoindole hydrochlorideHCID 86749006Ethyl (2-methoxyphenyl)acetimidate tetrafluoroborate

生成物 1

HCID 54395804(3aR,7R,7aR)-4,4-diphenyl-7-fluoro-2-[1-imino-2-(2-methoxyphenyl)ethyl]perhydroisoindole収率 27.8%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

実験手順

A solution of 0.6 g of (3aR,7R,7aR)-4,4-diphenyl-7-fluoroperhydroisoindole hydrochloride and 0.51 cm3 of triethylamine in 10 cm3 of dry dichloromethane is added to a solution of 0.41 g of ethyl (2-methoxyphenyl)-acetimidate tetrafluoroborate in 10 cm3 of dry dichloromethane. The reaction mixture is refluxed for 3 hours. It is then treated, after re-equilibrating to room temperature, with 5 cm3 of a 10% aqueous solution of potassium carbonate; the organic phase is washed with 10 cm3 of distilled water, dried over magnesium sulphate and concentrated to dryness under reduced pressure (2.7 kPa). The residue is chromatographed on a silica gel column (particle size 0.04-0.06 mm, diameter 2 cm, height 20 cm), eluting under a nitrogen pressure of 0.6 bar with an ethyl acetate, acetic acid and water mixture (15/1/1 by volume) and collecting fractions of 25 cm3. Fractions 24 to 38 are pooled and concentrated to dryness under reduced pressure (2.7 kPa). The residue is taken up in 40 cm3 of dichloromethane, washed with 10 cm3 of a saturated aqueous solution of potassium carbonate and then with 10 cm3 of a saturated aqueous solution of sodium chloride. The organic phase is dried over magnesium sulphate and concentrated to dryness under reduced pressure (2.7 kPa). The residue is crystallized from isopropyl oxide. The crystals are drained and dried. 0.18 g of (3aR,7R,7aR)-4,4-diphenyl-7-fluoro-2-[1-imino-2-(2-methoxyphenyl)ethyl]perhydroisoindole is obtained in the form of white crystals, melting point 184° C., with decomposition.

後処理

  1. temperatureThe reaction mixture is refluxed for 3 hours
  2. additionIt is then treated
  3. customto room temperature
  4. washthe organic phase is washed with 10 cm3 of distilled water
  5. dry with materialdried over magnesium sulphate
  6. concentrationconcentrated to dryness under reduced pressure (2.7 kPa)
  7. customThe residue is chromatographed on a silica gel column (particle size 0.04-0.06 mm, diameter 2 cm, height 20 cm)
  8. washeluting under a nitrogen pressure of 0.6 bar with an ethyl acetate, acetic acid and water mixture (15/1/1 by volume)
  9. customcollecting fractions of 25 cm3
  10. concentrationconcentrated to dryness under reduced pressure (2.7 kPa)
  11. washwashed with 10 cm3 of a saturated aqueous solution of potassium carbonate
  12. dry with materialThe organic phase is dried over magnesium sulphate
  13. concentrationconcentrated to dryness under reduced pressure (2.7 kPa)
  14. customThe residue is crystallized from isopropyl oxide
  15. customdried

出典と根拠

ORDレコード
ord-d1011f8e78ec43e1be789f33b31b8c31
出典データセット
uspto-grants-1995_09
特許番号
US05451601

反応ノート

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