Acetic Acid → 5-Hydroxy-7-methyl-6-phenyl-2-naphthalenyl 4-methylbenzenesulfonate

HRID 1992985Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1992985
C([O:4][C:5]1[C:14]2[C:9](=[CH:10][C:11](OC)=[CH:12][CH:13]=2)[CH:8]=[C:7]([CH3:17])[C:6]=1[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)(=O)C.C(O)(=O)C.Br.[C:29]1([CH3:39])[CH:34]=[CH:33][C:32]([S:35]([OH:38])(=[O:37])=[O:36])=[CH:31][CH:30]=1>C(Cl)(Cl)Cl.C(Cl)Cl.N1C=CC=CC=1>[CH3:39][C:29]1[CH:30]=[CH:31][C:32]([S:35]([O:38][C:11]2[CH:12]=[CH:13][C:14]3[C:9](=[CH:8][C:7]([CH3:17])=[C:6]([C:18]4[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=4)[C:5]=3[OH:4])[CH:10]=2)(=[O:36])=[O:37])=[CH:33][CH:34]=1

Komponenten

8

Edukt 4

HCID 176Acetic AcidHCID 260Hydrogen BromideHCID 6101p-Toluenesulfonic acidHCID 685409493-Methyl-6-(methyloxy)-2-phenyl-1-naphthalenyl acetate

Produkt 1

HCID 866166715-Hydroxy-7-methyl-6-phenyl-2-naphthalenyl 4-methylbenzenesulfonateAusbeute 89 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 1049PyridineLösungsmittelHCID 6212ChloroformLösungsmittelHCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

A round-bottomed flask was charged with 3-methyl-6-(methyloxy)-2-phenyl-1-naphthalenyl acetate (6) (5.00 g, 16.34 mmol), acetic acid (100 mL) and 48% aqueous HBr (50 mL). The resultant mixture was stirred between 90° C. and 100° C. for 4 h. The reaction mixture was concentrated under reduced pressure and the residue was neutralized with sat. NaHCO3 (100 mL). The aqueous reaction mixture was extracted with CH2Cl2 (4×150 mL). The combined organic layer was dried (Na2SO4) and concentrated under reduced pressure to afford ˜4.10 g (86%) the crude title product. To a solution of the above obtained crude product (˜1.00 g) in CHCl3 (50 mL) were added pyridine (1 mL), p-toluene sulfonic acid (2 equiv). The resultant mixture was stirred at RT for 36 h. Reaction mixture was diluted with CH2Cl2 (250 mL), washed with 10% aqueous HCl, brine (1×50 mL), and dried (Na2SO4). The organic layer was concentrated under reduced pressure to afford the crude product. The product was purified by SiO2 column chromatography to afford 850 mg (89%) of the title compound (239). 1H NMR (400 MHz, CDCl3): δ 8.08 (d, J=9.2 Hz, 1H), 7.73 (d, J=8.4 Hz, 2H), 7.54 (dd, J1=7.6 Hz, 2H), 7.47 (d, J=7.2 Hz, 1H), 7.39 (d, J=2.0 Hz, 1H), 7.30 (dd, J1=6.4 Hz, J2=6.4 Hz, 4H), 7.22 (br s, 1H), 6.98 and 6.96 (dd, J1=9.2 Hz, J2=2.0 Hz, 1H), 5.25 (s, 1H), 2.44 (s, 3H), 2.16 (s, 3H). LCMS (ESI) m/z 405.22 (M+H)+.

Aufarbeitung

  1. concentrationThe reaction mixture was concentrated under reduced pressure
  2. extractionThe aqueous reaction mixture was extracted with CH2Cl2 (4×150 mL)
  3. dry with materialThe combined organic layer was dried (Na2SO4)
  4. concentrationconcentrated under reduced pressure
  5. customto afford ˜4.10 g (86%) the crude title product
  6. customReaction mixture
  7. washwashed with 10% aqueous HCl, brine (1×50 mL)
  8. dry with materialdried (Na2SO4)
  9. concentrationThe organic layer was concentrated under reduced pressure
  10. customto afford the crude product
  11. customThe product was purified by SiO2 column chromatography

Quellen und Nachweise

ORD-Eintrag
ord-1b4154ef07ed43c8baee6f584e654f42
Quelldatensatz
uspto-grants-2010_01
Patentnummer
US07649093B2

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