Dichloromethane → 2-Methoxy-7-oxo-6,7,8,9-tetrahydro-5H-benzocycloheptene-6,8-dicarboxylic acid diethyl ester

HRID 1687539Notes

Reaction equation

HRID 1687539 reaction equation
C(Cl)Cl.Br[CH2:5][C:6]1[CH:11]=[CH:10][C:9]([O:12][CH3:13])=[CH:8][C:7]=1[CH2:14]Br.[O:16]=[C:17]([CH2:24][C:25]([O:27][CH2:28][CH3:29])=[O:26])[CH2:18][C:19]([O:21][CH2:22][CH3:23])=[O:20].[Cl-].[NH4+]>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.C(=O)(O)[O-].[Na+].O>[CH2:28]([O:27][C:25]([CH:24]1[C:17](=[O:16])[CH:18]([C:19]([O:21][CH2:22][CH3:23])=[O:20])[CH2:14][C:7]2[CH:8]=[C:9]([O:12][CH3:13])[CH:10]=[CH:11][C:6]=2[CH2:5]1)=[O:26])[CH3:29]

Participants

8

Reactant 4

HCID 6344Dichloromethane2×HCID 25517Ammonium ChlorideHCID 66045Diethyl acetonedicarboxylateHCID 105417861,2-Bis(bromomethyl)-4-methoxybenzene

Product 1

HCID 672639952-Methoxy-7-oxo-6,7,8,9-tetrahydro-5H-benzocycloheptene-6,8-dicarboxylic acid diethyl ester

Reagents, catalysts & solvents 3

HCID 67553Tetrabutylammonium IodideCatalystHCID 962WaterSolventHCID 516892Sodium BicarbonateSolvent

Procedure

From an adapted procedure in Helvetic Chimica Acta, 2001, 84, 2051-2063, to a stirred solution of Tetra-n-butylammonium iodide (12.1 g, 0.0326 mol) in 0.6 M of Sodium bicarbonate in Water (300 mL) and Methylene chloride (130 mL, 2.1 mol) was added a solution of 1,2-Bis-bromomethyl-4-methoxy-benzene (16.00 g, 0.05442 mol) and 3-Oxopentanedioic acid, diethyl ester (14.31 g, 0.07075 mol) in Methylene chloride (40 mL, 0.6 mol). The solution was stirred vigorously at room temperature for 20 h. Saturated ammonium chloride solution was added to the reaction mixture. The product was extracted with ethyl acetate (3×100 mL). The ethyl acetate extracts were washed with water and brine, then dried over magnesium sulfate, filtered and concentrated in vacuo to a yellow oil. The oil was triturated with ether and a precipitate crashed out of solution and was removed by filtration (tetrabutylammonium salts). The filtrate was concentrated to an oil (20.0 grams, 100%) that was carried on to the next step without further purification.

Workup

  1. extractionThe product was extracted with ethyl acetate (3×100 mL)
  2. washThe ethyl acetate extracts were washed with water and brine
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo to a yellow oil
  6. customThe oil was triturated with ether
  7. customwas removed by filtration (tetrabutylammonium salts)
  8. concentrationThe filtrate was concentrated to an oil (20.0 grams, 100%) that
  9. customwas carried on to the next step without further purification

Sources & evidence

ORD record
ord-a3c53f7e14c147628421c874fffe4881
Source dataset
uspto-grants-2012_04
Patent number
US08148391B2

Reaction notes

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