Tributylphosphine → 7-[(1-{4-[(4-butylphenyl)ethynyl]phenyl}pentyl)oxy]-2,2-dimethyl-4H-1,3-benzodioxin-4-one

HRID 551913ノート

反応式

HRID 551913 の反応式
[OH:1][C:2]1[CH:3]=[CH:4][C:5]2[C:10](=[O:11])[O:9][C:8]([CH3:13])([CH3:12])[O:7][C:6]=2[CH:14]=1.C(P(CCCC)CCCC)CCC.[CH2:28]([C:32]1[CH:37]=[CH:36][C:35]([C:38]#[C:39][C:40]2[CH:45]=[CH:44][C:43]([CH:46](O)[CH2:47][CH2:48][CH2:49][CH3:50])=[CH:42][CH:41]=2)=[CH:34][CH:33]=1)[CH2:29][CH2:30][CH3:31]>C1(C)C=CC=CC=1>[CH2:28]([C:32]1[CH:37]=[CH:36][C:35]([C:38]#[C:39][C:40]2[CH:45]=[CH:44][C:43]([CH:46]([O:1][C:2]3[CH:3]=[CH:4][C:5]4[C:10](=[O:11])[O:9][C:8]([CH3:12])([CH3:13])[O:7][C:6]=4[CH:14]=3)[CH2:47][CH2:48][CH2:49][CH3:50])=[CH:42][CH:41]=2)=[CH:34][CH:33]=1)[CH2:29][CH2:30][CH3:31]

参加物

5

反応物 3

HCID 13831TributylphosphineHCID 105839507-hydroxy-2,2-dimethyl-4H-benzo[d][1,3]dioxin-4-oneHCID 575545631-{4-[(4-Butylphenyl)ethynyl]phenyl}-1-pentanol

生成物 1

HCID 575545257-[(1-{4-[(4-butylphenyl)ethynyl]phenyl}pentyl)oxy]-2,2-dimethyl-4H-1,3-benzodioxin-4-one収率 64%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

反応条件

温度
0 °C

実験手順

A solution of 7-hydroxy-2,2-dimethyl-4H-1,3-benzodioxin-4-one (363 mg, 1.87 mmol, described in J. Chem. Soc., Perkin Trans. 1, 2000, 4265-4278) and tri-n-butylphosphine (378 mg, 1.87 mmol) in anhydrous toluene (10 mL) was chilled at 0° C. To this solution was added N,N,N′,N′-tetramiethylazodicarboxamide (322 mg, 1.87 mmol) at once and the resulting reaction mixture was stirred 10 min at 0° C. Then 1-{4-[(4-butylphenyl)ethynyl]phenyl}-1-pentanol (461.5 mg; 1.44 mmol; 1.0 eq.) was added and the resulting mixture was stirred overnight at rt. The solvent was removed under reduced pressure and the crude mixture was purified by chromatography on silicagel (EtOAc/c-Hex (1/9)) to give 456 mg (64%) of the title compound. HPLC, Rt: 6.2 min (purity: 97.0%). 1H NMR (CDCl3) δ 7.78 (d, J=8.7 Hz, 1H), 7.50 (d, J=8.3 Hz, 2H), 7.42 (d, J=8.2 Hz, 2H), 7.29 (d, J=8.3 Hz, 2H), 7.15 (d, J=8.3 Hz, 2H), 6.61 (dd, J=2.4 Hz, J=9.0 Hz, 1H), 6.29 (d, J=2.3 Hz, 1H), 5.16-5.07 (m, 1H), 2.61 (t, J=7.8 Hz, 2H), 2.08-1.93 (m, 1H), 1.91-1.75 (m, 1H), 1.73-1.24 (m, 14H), 0.98-0.84 (m, 6H).

後処理

  1. additionTo this solution was added N,N,N′,N′-tetramiethylazodicarboxamide (322 mg, 1.87 mmol) at once and
  2. customthe resulting reaction mixture
  3. stirringthe resulting mixture was stirred overnight at rt
  4. customThe solvent was removed under reduced pressure
  5. customthe crude mixture was purified by chromatography on silicagel (EtOAc/c-Hex (1/9))

出典と根拠

ORDレコード
ord-630d8e51cd1e4d09aa7183f29efb5e8d
出典データセット
uspto-grants-2011_05
特許番号
US07947851B2

反応ノート

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