P-Xylene → 3,5-Diacetoxy-4'-chloroacetoxy stilbene

HRID 2236334Notes

Reaction equation

HRID 2236334 reaction equation
CC1C=CC(C)=CC=1.[C:9]([O:12][C:13]1[CH:14]=[C:15]([CH:19]=[C:20]([O:22][C:23](=[O:25])[CH3:24])[CH:21]=1)[C:16](Cl)=O)(=[O:11])[CH3:10].[Cl:26][CH2:27][C:28]([O:30][C:31]1[CH:38]=[CH:37][C:34]([CH:35]=C)=[CH:33][CH:32]=1)=[O:29].CN1CCOCC1>[Pd].[Cl-].C(C1C=CC=C(C(C)C)C=1[NH+]1CCN(C2C(C(C)C)=CC=CC=2C(C)C)C1)(C)C.CCOC(C)=O>[C:9]([O:12][C:13]1[CH:14]=[C:15]([CH:16]=[CH:35][C:34]2[CH:33]=[CH:32][C:31]([O:30][C:28](=[O:29])[CH2:27][Cl:26])=[CH:38][CH:37]=2)[CH:19]=[C:20]([O:22][C:23](=[O:25])[CH3:24])[CH:21]=1)(=[O:11])[CH3:10]

Participants

8

Reactant 4

HCID 7809P-XyleneHCID 79724-MethylmorpholineHCID 11368883(3-Acetyloxy-5-carbonochloridoylphenyl) acetateHCID 593017254-Chloroacetoxystyrene

Product 1

HCID 722512213,5-Diacetoxy-4'-chloroacetoxy stilbeneYield 69.4%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 184547821,3-BIS(2,6-DIISOPROPYLPHENYL)imidazoLIDINIUM-CHLORIDECatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
120 °C

Procedure

A 10 mL round bottom flask was charged with p-xylene (4 mL), Pd II catalyst (4.5 mg, 0.02 mmol), 1,3-bis-(2,6-diisopropylphenyl) imidazolinium chloride (8.6 mg, 0.02 mmol), 3,5-diacetoxybenzoyl chloride (0.7695 g, 3 mmol), 4-chloroacetoxystyrene (0.393 g, 2 mmol), and N-methyl morpholine (0.276 g, 2.4 mmol). The mixture was stirred at 120° C. for 3.5 h under nitrogen atmosphere. Then it was cooled to room temperature and EtOAc was added and filtered. The filtrate was washed with brine and dried over Na2SO4. Then it was filtered and purified via flash chromatography and gave the product (0.54 g, 69.4%) as white solid. Data are: 1H NMR (CDCl3, 300 MHz) δ 7.47 (d, 2H, J=8.7 Hz), 7.14-7.10 (m, 4H), 6.99 (q, 2H, J=16.2 Hz), 6.83 (t, 1H, J=2.1 Hz), 4.29 (s, 2H), 2.29 (s, 6H); 13C NMR (CDCl3, 75 MHz) δ 169.1, 165.9, 151.4, 150.1, 139.5, 135.1, 129.5, 127.9, 127.7, 121.6, 117.1, 114.7, 41.0, 21.2; HRMS (EI+) found 388.0710 M+, calcd 388.0714 for C20H17ClO6.

Workup

  1. temperatureThen it was cooled to room temperature
  2. filtrationfiltered
  3. washThe filtrate was washed with brine
  4. dry with materialdried over Na2SO4
  5. filtrationThen it was filtered
  6. custompurified via flash chromatography

Sources & evidence

ORD record
ord-cdb29232d2e541f8b7a48eb7d9f309dc
Source dataset
uspto-grants-2010_05
Patent number
US07714161B2

Reaction notes

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