3-Iodopyridine → 3-{[4-(Difluoromethoxy)phenyl]ethynyl}pyridine

HRID 271126

反応式

HRID 271126 の反応式
I[C:2]1[CH:3]=[N:4][CH:5]=[CH:6][CH:7]=1.[F:8][CH:9]([F:19])[O:10][C:11]1[CH:16]=[CH:15][C:14]([C:17]#[CH:18])=[CH:13][CH:12]=1>C(N(CC)CC)C.C(#N)C.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.[Cu](I)I>[F:8][CH:9]([F:19])[O:10][C:11]1[CH:16]=[CH:15][C:14]([C:17]#[C:18][C:2]2[CH:3]=[N:4][CH:5]=[CH:6][CH:7]=2)=[CH:13][CH:12]=1

参加物

7

反応物 2

HCID 707143-IodopyridineHCID 27784971-(Difluoromethoxy)-4-ethynylbenzene

生成物 1

HCID 689973503-{[4-(Difluoromethoxy)phenyl]ethynyl}pyridine

試薬・触媒・溶媒 4

HCID 83717Copper iodide触媒HCID 178418397HCID 178418397、化合物触媒HCID 6342Acetonitrile溶媒HCID 8471Triethylamine溶媒

実験手順

A solution of 3-iodopyridine (205 mg, 1.0 mg) in triethylamine was treated with tetrakis(triphenylphosphine)palladium (80 mg, 0.069 mmol), copper iodide (18 mg, 0.097 mmol) and a solution of 1-(difluoromethoxy)-4-ethynylbenzene (168 mg, 1.0 mmol) in acetonitrile at room temperature, heated at 60° C. for 1 h, cooled and concentrated to dryness to afford 3-{[4-(difluoromethoxy)phenyl]ethynyl}pyridine as a residue. The residue (240 mg) was dissolved in acetone, treated sequentially with a solution of NaHCO3 (50 mg) and MgSO4 (180 mg) in H2O and KMnO4 (327 mg), stirred for 10 minutes at room temperature and extracted with 1/1 Et2O/hexane. The combined extracts were concentrated to dryness to give 1-[4-(difluoromethoxy)phenyl]-2-pyridin-3-ylethane-1,2-dione. A mixture of 1-[4-(difluoromethoxy)phenyl]-2-pyridin-3-ylethane-1,2-dione (230 mg), N-methylguanidine hydrochloride (155 mg) and Na2CO3 (240 mg) in ethanol was heated at reflux temperature for 1.5 h. and concentrated in vacuo. The resultant residue was purified by chromatography (silica gel, EtOAc/2.0 M NH3 in EtOH: 97/3) to give the title compound (130 mg) as a solid, mp: 173-175° C., identified by NMR and mass spectral analyses. MS (+) APPI: 333 (M+H)+.

後処理

  1. temperaturecooled
  2. concentrationconcentrated to dryness

出典と根拠

ORDレコード
ord-695f4f05c4c74eaa83bf5fc3b7c06da8
出典データセット
uspto-grants-2008_11
特許番号
US07452885B2

関連ノート

読み込み中…