2,6-Di-tert-butyl-4-methylphenol → HCID 70005765, compound

HRID 1860526Notes

Reaction equation

HRID 1860526 reaction equation
[C:1]1([C:11](Cl)=[O:12])[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[CH:3][CH:2]=1.[CH3:14][O:15][C:16](=[O:44])[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][C@H:23]1[C@H:27]([CH:28]=[CH:29][Sn](CCCC)(CCCC)CCCC)[CH2:26][CH2:25][C:24]1=[O:43].C(C1C=C(C)C=C(C(C)(C)C)C=1O)(C)(C)C>C1(C)C=CC=CC=1.C(OCC)(=O)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>[CH3:14][O:15][C:16](=[O:44])[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][C@@H:23]1[C:24](=[O:43])[CH2:25][CH2:26][C@H:27]1[CH:28]=[CH:29][C:11]([C:1]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[CH:3][CH:2]=1)=[O:12]

Participants

7

Reactant 3

HCID 314042,6-Di-tert-butyl-4-methylphenolHCID 701461-Naphthalenecarbonyl chlorideHCID 70006201HCID 70006201, compound

Product 1

HCID 70005765HCID 70005765, compound

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
100 °C

Procedure

A solution of tetrakis(triphenylphosphine)palladium(0) (97 mg, 0.084 mmol) in dry toluene (10 mL) was evacuated under vacuum and was purged with carbon monoxide (3×). Naphthalene-1-carbonyl chloride (320 mg, 1.68 mmol) was added followed by addition of trans-7-[2-oxo-5-(2-tributylstannanyl-vinyl)-cyclopentyl)-heptanoic acid methyl ester (the compound of Preparation 1, Step D, 1.0 g, 1.85 mmol) and 2,6-di-tert-butyl-4-methylphenol (few crystals). The mixture was heated at 100° C. under an atmosphere of carbon monoxide for 24 h. The mixture was cooled to room temperature, diluted with ethyl acetate, and the insolubles were removed by filtration through a pad of Celite®. The filtrate was washed with 10% aqueous ammonium hydroxide, dried (magnesium sulfate), filtered, and concentrated. Purification by flash chromatography (hexanes to 20% ethyl acetate in hexanes) provided the title compound of Step A (162 mg). 1H NMR (CDCl3, 250 MHz) d 8.31 (m, 1H), 8.00 (d, 1H), 7.91 (m, 1H), 7.70 (dd, 1H), 7.55 (m, 3H), 6.91-6.71 (m, 2H), 3.68 (s, 3H), 2.75 (m, 1H), 2.42-2.11 (m, 5H), 2.00 (m, 1H), 1.81-1.20 (m, 9H), 1.94 (t, 2H); MS 407 (M+1), 424 (M+18).

Workup

  1. customwas purged with carbon monoxide (3×)
  2. temperatureThe mixture was cooled to room temperature
  3. customthe insolubles were removed by filtration through a pad of Celite®
  4. washThe filtrate was washed with 10% aqueous ammonium hydroxide
  5. dry with materialdried (magnesium sulfate)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customPurification by flash chromatography (hexanes to 20% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-87763a5d48f445048bfb895b97a7daca
Source dataset
uspto-grants-2003_03
Patent number
US06531485B2

Reaction notes

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