Dimethylformamide → 4-{Cycloheptylidene[4-(5-hydroxy-1-pentyn-1-yl)phenyl]methyl}phenol

HRID 1716150ノート

反応式

HRID 1716150 の反応式
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8](=[C:16]2[CH2:23][CH2:22]CC[CH2:19][CH2:18][CH2:17]2)[C:9]2[CH:14]=[CH:13][C:12]([OH:15])=[CH:11][CH:10]=2)=[CH:4][CH:3]=1.[CH:24](N(CC)C(C)C)(C)C.[CH2:33](O)[CH2:34][CH2:35][C:36]#C.[NH4+].[Cl-].CN([CH:44]=[O:45])C>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I.O>[C:16]1(=[C:8]([C:5]2[CH:6]=[CH:7][C:2]([C:33]#[C:34][CH2:35][CH2:36][CH2:44][OH:45])=[CH:3][CH:4]=2)[C:9]2[CH:14]=[CH:13][C:12]([OH:15])=[CH:11][CH:10]=2)[CH2:23][CH2:22][CH2:24][CH2:19][CH2:18][CH2:17]1

参加物

9

反応物 5

HCID 6228DimethylformamideHCID 25517Ammonium ChlorideHCID 793464-Pentyn-1-olHCID 81531DiisopropylethylamineHCID 686544754-[(4-Bromophenyl)(cyclooctylidene)methyl]phenol

生成物 1

HCID 111992024-{Cycloheptylidene[4-(5-hydroxy-1-pentyn-1-yl)phenyl]methyl}phenol収率 45%

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418476HCID 178418476、化合物触媒HCID 962Water溶媒

反応条件

温度
80 °C

実験手順

To a degassed solution of 4-[(4-bromophenyl)(cycloheptylidene)methyl]phenol (9) (0.20 g, 0.56 mmol) in DMF (5 mL) were added Pd(PPh3)2Cl2 (40 mg, 0.06 mmol), CuI (11 mg, 0.06 mmol), N,N-diisopropylethylamine (0.45 mL, 2.52 mmol) and 4-pentyn-1-ol (0.11 mL, 1.12 mmol). The reaction mixture was stirred at 80° C. overnight, poured into saturated aqueous NH4Cl (15 mL) and water (5 mL), extracted with ethyl acetate (3×50 mL). The combined organic phase was washed with water, brine, dried over Na2SO4, filtered, and the filtrate was concentrated to give the crude product as brown oil. The crude product was purified by chromatography on a silica gel column eluted with a gradient from hexanes to 45% EtOAc in hexanes to give a light brown solid. The solid was triturated with hot hexanes containing 1% MeOH to afford 91 mg (45%) of the title compound (240) as beige solid. mp 125-126° C. 1H NMR (400 MHz, DMSO-d6): δ 1.49 (bs, 8H), 1.60-1.70 (m, 2H), 2.10-2.25 (m, 4H), 2.41 (t, J=7.0 Hz, 2H), 3.40-3.50 (m, 2H), 4.49 (t, J=5.2 Hz, 1H), 6.65 (d, J=8.4 Hz, 2H), 6.88 (d, J=8.4 Hz, 2H), 7.04 (d, J=8.0 Hz, 2H), 7.26 (d, J=8.2 Hz, 2H), 9.27 (s, 1H). LCMS (ESI): m/z 361 (M+H)+, 359 (M−H)−.

後処理

  1. extractionextracted with ethyl acetate (3×50 mL)
  2. washThe combined organic phase was washed with water, brine
  3. dry with materialdried over Na2SO4
  4. filtrationfiltered
  5. concentrationthe filtrate was concentrated
  6. customto give the crude product as brown oil
  7. customThe crude product was purified by chromatography on a silica gel column
  8. washeluted with a gradient from hexanes to 45% EtOAc in hexanes
  9. customto give a light brown solid
  10. customThe solid was triturated with hot hexanes containing 1% MeOH

出典と根拠

ORDレコード
ord-247ff2397474489b9c69a8f7fe2e313b
出典データセット
uspto-grants-2010_09
特許番号
US07799828B2

反応ノート

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