Methanol → Methyl 5-oxo-5,6,7,8-tetrahydronaphthalene-1-carboxylate

HRID 1004445ノート

反応式

HRID 1004445 の反応式
[CH3:1][OH:2].CC(C)(C)CCN[C:8]([C:10]1[C:19]2[CH2:18][CH2:17][CH:16](CCN3CCC(C4C=CC=CC=4)CC3)[C:15](=[O:34])[C:14]=2[CH:13]=[CH:12][CH:11]=1)=[O:9].C(N(CC)CC)C>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CN(C=O)C>[CH3:1][O:2][C:8]([C:10]1[C:19]2[CH2:18][CH2:17][CH2:16][C:15](=[O:34])[C:14]=2[CH:13]=[CH:12][CH:11]=1)=[O:9]

参加物

7

反応物 3

HCID 887MethanolHCID 8471TriethylamineHCID 18794702N-(3,3-Dimethylbutyl)-5,6,7,8-tetrahydro-6-[2-(4-phenyl-1-piperidinyl)ethyl]-5-oxo-1-naphthalenecarboxamide

生成物 1

HCID 12284900Methyl 5-oxo-5,6,7,8-tetrahydronaphthalene-1-carboxylate収率 90%

試薬・触媒・溶媒 3

HCID 812191,3-Bis(diphenylphosphino)propane触媒HCID 167845palladium(II) acetate触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
80 °C

実験手順

A 450-mL Parr bomb was charged with methanol (81 mL), DMF (160 mL), compound 2 (24.0 g, 81.6 mmol), palladium acetate (549 mg, 2.45 mmol), 1,3-bis(diphenylphosphino)-propane (1.01 g, 2.45 mmol), and triethylamine (23 mL, 163 mmol). The bomb was purged with carbon monoxide using 2 fill/vent cycles. The bomb was repressurized to 150 psi and was heated to 80° C. for 3 hours. During this time additional CO was admitted to maintain the pressure at 150 psi. The bomb was cooled to room temperature and vented. A second identical run was made. The combined reactions were diluted with methylene chloride (2 L), washed with water (4×800 mL), dried (MgSO4) and concentrated in vacuo to a black solid. Chromatography (flash, silica, 120 mm dia×20 cm, 2% ethyl acetate/methylene chloride) provided semi-pure product. Recrystallization of this material from hot hexanes in 2 crops followed by chromatography of the final mothor liquors (silica gel, methylene chloride (700 mL) then 2% ethyl acetate/methylene chloride) provided a total of 30.3 g (90%) of the title compound.

後処理

  1. customThe bomb was purged with carbon monoxide using 2 fill/vent cycles
  2. temperatureto maintain the pressure at 150 psi
  3. temperatureThe bomb was cooled to room temperature
  4. additionThe combined reactions were diluted with methylene chloride (2 L)
  5. washwashed with water (4×800 mL)
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated in vacuo to a black solid
  8. customChromatography (flash, silica, 120 mm dia×20 cm, 2% ethyl acetate/methylene chloride) provided semi-pure product
  9. customRecrystallization of this material from hot hexanes in 2 crops

出典と根拠

ORDレコード
ord-b5391f0ba54b4f22a602f601305abfca
出典データセット
uspto-grants-2000_04
特許番号
US06048877

反応ノート

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