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

HRID 1992985Notes

Reaction equation

HRID 1992985 reaction equation
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

Participants

8

Reactant 4

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

Product 1

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

Reagents, catalysts & solvents 3

HCID 1049PyridineSolventHCID 6212ChloroformSolventHCID 6344DichloromethaneSolvent

Procedure

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)+.

Workup

  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

Sources & evidence

ORD record
ord-1b4154ef07ed43c8baee6f584e654f42
Source dataset
uspto-grants-2010_01
Patent number
US07649093B2

Reaction notes

Loading…