Chlorotrimethylsilane → 2-Trimethylsilanyl-naphthalene-1,4-dicarboxylic acid diisopropyl ester

HRID 221941Notes

Reaction equation

HRID 221941 reaction equation
CC1CCCN(C)C1(C)C.C([Li])CCC.CCCCCC.Cl[Si:23]([CH3:26])([CH3:25])[CH3:24].[CH:27]([O:30][C:31]([C:33]1[C:42]2[C:37](=[CH:38][CH:39]=[CH:40][CH:41]=2)[C:36]([C:43]([O:45][CH:46]([CH3:48])[CH3:47])=[O:44])=[CH:35][CH:34]=1)=[O:32])([CH3:29])[CH3:28].[Cl-].[NH4+]>C1COCC1>[CH:46]([O:45][C:43]([C:36]1[C:37]2[C:42](=[CH:41][CH:40]=[CH:39][CH:38]=2)[C:33]([C:31]([O:30][CH:27]([CH3:29])[CH3:28])=[O:32])=[CH:34][C:35]=1[Si:23]([CH3:26])([CH3:25])[CH3:24])=[O:44])([CH3:48])[CH3:47]

Participants

8

Reactant 6

HCID 6397ChlorotrimethylsilaneHCID 8058HexaneHCID 25517Ammonium ChlorideHCID 187617721,2,2,3-TetramethylpiperidineHCID 57332763Naphthalene-1,4-dicarboxylic acid diisopropyl esterHCID 178418339Butyllithium

Product 1

HCID 594887872-Trimethylsilanyl-naphthalene-1,4-dicarboxylic acid diisopropyl esterYield 34.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

Under a nitrogen stream, to a solution of tetramethylpiperidine (0.39 mL, 2.311 mmol) in THF (1.8 mL) was added a solution of n-butyllithium in n-hexane (2.67 M, 0.87 mL, 2.323 mmol) under ice cooling, and the resultant solution was stirred for 10 minutes at the same temperature. The solution was cooled to −78° C., and then chlorotrimethylsilane (2.47 mL, 19.325 mmol) and a solution of naphthalene-1,4-dicarboxylic acid diisopropyl ester (0.58 g, 1.931 mmol) in THF (2 mL) were added thereto. The temperature of the solution was raised over 1 hour to room temperature, and then to the solution was added saturated aqueous ammonium chloride to stop the reaction. The resultant mixture was twice extracted with dichloromethane. After drying the organic layer over anhydrous magnesium sulfate, solvent was removed by distillation under reduced pressure. The resulting residue was purified by silica gel column chromatography (developing solution=ethyl acetate:n-hexane (1:9)), to thereby obtain the titled compound (246 mg, 34%).

Workup

  1. temperatureThe temperature of the solution was raised over 1 hour to room temperature
  2. customthe reaction
  3. extractionThe resultant mixture was twice extracted with dichloromethane
  4. dry with materialAfter drying the organic layer over anhydrous magnesium sulfate, solvent
  5. customwas removed by distillation under reduced pressure
  6. customThe resulting residue was purified by silica gel column chromatography (developing solution=ethyl acetate:n-hexane (1:9))

Sources & evidence

ORD record
ord-cfac9f5661a940b8b11729c54f2796fb
Source dataset
uspto-grants-2012_06
Patent number
US08207134B2

Reaction notes

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