Toluene → 2-Acetyl-1-benzyl-4-methoxy-6,7,8,9-tetrahydro-1h-benz[g]indole

HRID 489110노트

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HRID 489110 반응식
[CH2:1]([N:8]1[C:16]2[C:11](=[C:12]([O:21][CH3:22])[CH:13]=[C:14]3[CH2:20][CH2:19][CH2:18][CH2:17][C:15]3=2)[CH:10]=[C:9]1[C:23](OCC)=[O:24])C1C=CC=CC=1.[C:28]1(C)[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1.[OH-].[Na+].O1CCC[CH2:38]1>C(OCC)C.C(=O)(O)[O-].[Na+].[CH3-].C[Al+]C.[CH-]1C=CC=C1.[CH-]1C=CC=C1.[Cl-].[Ti+3]>[C:23]([C:9]1[N:8]([CH2:1][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[C:16]2[C:11]([CH:10]=1)=[C:12]([O:21][CH3:22])[CH:13]=[C:14]1[CH2:20][CH2:19][CH2:18][CH2:17][C:15]=21)(=[O:24])[CH3:38]

참가 물질

8

반응물 4

HCID 1140TolueneHCID 8028TetrahydrofuranHCID 14798Sodium HydroxideHCID 112106971-Benzyl-2-carboethoxy-4-methoxy-6,7,8,9-tetrahydro-1h-benz[g]indole

생성물 1

HCID 114730712-Acetyl-1-benzyl-4-methoxy-6,7,8,9-tetrahydro-1h-benz[g]indole수율 73%

시약·촉매·용매 3

HCID 53384502mu-Chlorobis(eta5-cyclopentadienyl)(dimethylaluminum)-mu-methylenetitanium촉매HCID 3283Diethyl Ether용매HCID 516892Sodium Bicarbonate용매

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온도
2 °C

실험 절차

To a solution of 1-benzyl-2-carboethoxy-4-methoxy-6,7,8,9-tetrahydro-1H-benz[g]indole (1.01 g, 2.77 mmol) in tetrahydrofuran (8 mL) cooled to 0° C. was added 0.5 M Tebbe Reagent in toluene (6.5 mL, 3.3 mmol). The mixture was stirred for 1 h at 2° C. then diluted with diethyl ether (32 mL) and treated with 2 N aqueous sodium hydroxide solution (2 mL) over 30 min. The mixture was diluted with excess saturated sodium bicarbonate solution and filtered through a pad of silica gel. The filtrate was concentrated in vacuo and the resulting residue triturated with 1:1 ether/hexanes. The resulting material was dissolved in 4:1 acetone/methylene chloride (5 mL) and treated with 1 N hydrochloric acid (1 mL). After standing for 20 min the mixture was diluted with saturated sodium bicarbonate solution, concentrated in vacuo, and partitioned between methylene chloride and water. The organic layer was separated, dried (sodium sulfate), filtered, and concentrated in vacuo. Purification of the residue by chromatography (silica gel, methylene chloride) provided 673 mg (73%) of the title compound as a brown film. 1H NMR (CDCl3) δ 7.49 (s, 1H), 7.15 (m, 3H), 6.78 (d, J=7 Hz, 2H), 6.24 (s, 1H), 6.11 (bs, 2H), 3.91 (s, 3H), 2.95 (m, 2H), 2.84 (m, 2H), 2.52 (s, 2H), 1.69 (m, 4H); MS ES+ m/e 334 (p+1); IR (KBr, cm−1) 3400, 2813, 1593, 1292.

후처리

  1. filtrationfiltered through a pad of silica gel
  2. concentrationThe filtrate was concentrated in vacuo
  3. customthe resulting residue triturated with 1:1 ether/hexanes
  4. dissolutionThe resulting material was dissolved in 4:1 acetone/methylene chloride (5 mL)
  5. additiontreated with 1 N hydrochloric acid (1 mL)
  6. waitAfter standing for 20 min
  7. additionthe mixture was diluted with saturated sodium bicarbonate solution
  8. concentrationconcentrated in vacuo
  9. custompartitioned between methylene chloride and water
  10. customThe organic layer was separated
  11. dry with materialdried (sodium sulfate)
  12. filtrationfiltered
  13. concentrationconcentrated in vacuo
  14. customPurification of the residue by chromatography (silica gel, methylene chloride)

출처 및 근거

ORD 기록
ord-edf823ae0f8d4a87b69b8c97ff8ee2da
출처 데이터셋
uspto-grants-2005_12
특허 번호
US06974831B2

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