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

HRID 551913Notes

Reaction equation

HRID 551913 reaction equation
[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]

Participants

5

Reactant 3

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

Product 1

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

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
0 °C

Procedure

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).

Workup

  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))

Sources & evidence

ORD record
ord-630d8e51cd1e4d09aa7183f29efb5e8d
Source dataset
uspto-grants-2011_05
Patent number
US07947851B2

Reaction notes

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