Chlorotrimethylsilane → HCID 59637594, compound

HRID 1254162Notes

Reaction equation

HRID 1254162 reaction equation
[CH3:1][O:2][C:3]1[C:12]2[C:7](=[C:8]([CH3:17])[C:9]([O:15][CH3:16])=[C:10]([O:13][CH3:14])[CH:11]=2)[CH:6]=[C:5]([C:18]([OH:20])=[O:19])[CH:4]=1.[Li]N1C(C)(C)CCCC1(C)C.[CH3:32][Si:33](Cl)([CH3:35])[CH3:34].[OH-].[Na+]>C1COCC1>[CH3:1][O:2][C:3]1[C:12]2[C:7](=[C:8]([CH2:17][Si:33]([CH3:35])([CH3:34])[CH3:32])[C:9]([O:15][CH3:16])=[C:10]([O:13][CH3:14])[CH:11]=2)[CH:6]=[C:5]([C:18]([OH:20])=[O:19])[CH:4]=1

Participants

6

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 14798Sodium HydroxideHCID 51031686HCID 51031686, compoundHCID 178418821HCID 178418821, compound

Product 1

HCID 59637594HCID 59637594, compoundYield 88.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

4,6,7-Trimethoxy-8-methyl-2-naphthoic acid (1) (0.276 g, 1 mmol) is added at −78° C. to a mixture containing the base LTMP (4.2 mmol) and TMSCl (0.998 mL, 5.7 mmol) in anhydrous THF (10 mL). The reaction mixture is stirred at −78° C. for 1 h then gradually heated to ambient temperature over 3 h. After hydrolysis, the reaction mixture is treated with a solution of 2M NaOH (pH 10). The aqueous phase is washed with ethyl ether (2×15 mL), acidified with 2M HCl (pH 1-2) then extracted with dichloromethane (3×20 mL). The combined organic phases are dried over MgSO4, filtered, then concentrated under reduced pressure. The residue is purified by recrystallization (cyclohexane/ethyl acetate) to give 4,6,7-trimethoxy-8-((trimethylsilyl)methyl)-2-naphthoic acid (2) (0.307 g, 88%). 1H NMR (200 MHz, CDCl3): 8.37 (s, 1H), 7.44 (s, 1H), 7.40 (s, 1H), 4.07 (s, 3H, OCH3), 4.03 (s, 3H, OCH3), 3.88 (s, 3H, OCH3), 2.63 (s, 2H, CH2), 0.02 (s, 9H, Si(CH3)3). SMHR, [M+H]+ calculated for C18H25O5Si: 349.1471. Found: 349.1468.

Workup

  1. temperaturethen gradually heated to ambient temperature over 3 h
  2. customAfter hydrolysis
  3. washThe aqueous phase is washed with ethyl ether (2×15 mL)
  4. extractionthen extracted with dichloromethane (3×20 mL)
  5. dry with materialThe combined organic phases are dried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe residue is purified by recrystallization (cyclohexane/ethyl acetate)

Sources & evidence

ORD record
ord-972e1b28fb3b47468639d9e6e91fa73f
Source dataset
uspto-grants-2013_06
Patent number
US08455540B2

Reaction notes

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