Diethyl Ether → 1-[2-methyl-7-(2,4,6-trimethyl-phenyl)-4,5,6,7-tetrahydro-2H-pyrazolo[3,4-b]pyridine-3-yl]ethanone

HRID 2113799ノート

反応式

HRID 2113799 の反応式
Br[C:2]1[N:3]([CH3:20])[N:4]=[C:5]2[C:10]=1[CH2:9][CH2:8][CH2:7][N:6]2[C:11]1[C:16]([CH3:17])=[CH:15][C:14]([CH3:18])=[CH:13][C:12]=1[CH3:19].C([Li])CCC.CCCCCC.[CH3:32][CH2:33][O:34]CC.C(Cl)(=O)C.[Cl-].[NH4+]>C1COCC1.[Cl-].[Zn+2].[Cl-].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:20][N:3]1[C:2]([C:33](=[O:34])[CH3:32])=[C:10]2[C:5]([N:6]([C:11]3[C:16]([CH3:17])=[CH:15][C:14]([CH3:18])=[CH:13][C:12]=3[CH3:19])[CH2:7][CH2:8][CH2:9]2)=[N:4]1

参加物

10

反応物 6

HCID 3283Diethyl EtherHCID 6367Acetyl chlorideHCID 8058HexaneHCID 25517Ammonium ChlorideHCID 112328983-bromo-2-methyl-7-(2,4,6-trimethylphenyl)-4,5,6,7-tetrahydro-2H-pyrazolo[3,4-b]pyridineHCID 178418339Butyllithium

生成物 1

HCID 598115151-[2-methyl-7-(2,4,6-trimethyl-phenyl)-4,5,6,7-tetrahydro-2H-pyrazolo[3,4-b]pyridine-3-yl]ethanone収率 6.4%

試薬・触媒・溶媒 3

HCID 3007855Zincchloride触媒HCID 178418397HCID 178418397、化合物触媒HCID 8028Tetrahydrofuran溶媒

実験手順

A solution of 3-bromo-2-methyl-7-(2,4,6-trimethyl-phenyl)-4,5,6,7-tetrahydro-2H-pyrazolo[3,4-b]pyridine (1-3; 0.040 g, 1.2 mmol) in 6 mL of dry THF was cooled to −78° C. in a dry ice-acetone bath under an argon atmosphere and treated with n-butyllithium in hexane (0.83 mL, 1.32 mmol). After 10 m a solution of 1 M zinc chloride in ether (3.59 mL, 3.59 mmol) was added. The cooling bath was removed and the reaction stirred at room temperature. After 10 m acetyl chloride (0.113 g, 1.44 mmol) and tetrakis(triphenylphosphine)palladium(0) (28 mg, 0.024 mmol) were added and the brown solution was stirred for 2 hrs. The mixture was poured into 25 mL of saturated ammonium chloride solution, extracted twice with 25 mL portions of ethyl acetate. The combined organic extracts were washed with brine, dried over magnesium sulfate, and evaporated to dryness. The residue was purified on flash chromatography on silica gel eluting with ethyl acetate/hexane (15:85) giving 23 mg (6% yield) of 1-[2-methyl-7-(2,4,6-trimethyl-phenyl)-4,5,6,7-tetrahydro-2H-pyrazolo[3,4-b]pyridine-3-yl]ethanone as a colorless oil: ms (M+H)+=298.

後処理

  1. customThe cooling bath was removed
  2. stirringthe brown solution was stirred for 2 hrs
  3. extractionextracted twice with 25 mL portions of ethyl acetate
  4. washThe combined organic extracts were washed with brine
  5. dry with materialdried over magnesium sulfate
  6. customevaporated to dryness
  7. customThe residue was purified on flash chromatography on silica gel eluting with ethyl acetate/hexane (15:85)

出典と根拠

ORDレコード
ord-e15b6764b1b84d24b0df1f45351bd7f5
出典データセット
uspto-grants-2008_10
特許番号
US07432283B2

反応ノート

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