Acetone → 2,6,6-Trimethyl-5-phenyl-7-oxa-2-azabicyclo[3.2.1]octane

HRID 1980093ノート

反応式

HRID 1980093 の反応式
C([Li])CCC.[CH3:6][N:7]1[CH2:12][CH:11]=[C:10]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH2:9][CH2:8]1.[CH3:19][C:20]([CH3:22])=[O:21].Cl>O1CCCC1>[C:13]1([C:10]23[CH2:9][CH:8]([O:21][C:20]2([CH3:22])[CH3:19])[N:7]([CH3:6])[CH2:12][CH2:11]3)[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

参加物

6

反応物 4

HCID 180AcetoneHCID 313Hydrochloric AcidHCID 13881-Methyl-4-phenyl-1,2,3,6-tetrahydropyridineHCID 178418339Butyllithium

生成物 1

HCID 540271932,6,6-Trimethyl-5-phenyl-7-oxa-2-azabicyclo[3.2.1]octane

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

n-Butyllithium (15 ml of 1.5M solution in hexane) was added under nitrogen to a solution of 4.7 g of commercially available 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (II: R1 =Me; R2, R3 =H; R4 =phenyl) in 50 mL of tetrahydrofuran, kept at -10°. The deep red solution was stirred at -10° for 15 min and then transferred in a slow stream into a stirred mixture of 15 mL of acetone and 25 mL of tetrahydrofuran and kept at -70°. Excess 10% hydrochloric acid was added after stirring at -70° for 5 min; the mixture was allowed to come to room temperature, and then washed with toluene. The aqueous layer was made basic with sodium hydroxide and extracted with methylene chloride. Removal of the solvent from the dried solution and short-path distillation of the residue (90°-135° bath temperature, 5×10-4 mm Hg [0.07 Pa]) gave 2.79 g of 5-phenyl-2,6,6-trimethyl-7-oxa-2-azabicyclo[3.2.1]octane (III: R1, R5, R6 =Me; R2, R3 =H, R4 =phenyl) as an oil of ca. 85% purity.

後処理

  1. customkept at -10°
  2. customkept at -70°
  3. stirringafter stirring at -70° for 5 min
  4. customto come to room temperature
  5. washwashed with toluene
  6. extractionextracted with methylene chloride
  7. customRemoval of the solvent
  8. distillationfrom the dried solution and short-path distillation of the residue (90°-135° bath temperature, 5×10-4 mm Hg [0.07 Pa])

出典と根拠

ORDレコード
ord-a348c418a4cf48e2a822e04f63537807
出典データセット
uspto-grants-1984_11
特許番号
US04485109

反応ノート

読み込み中…