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Benzaldehyde → [2,4-Bis(methoxymethoxy)-6-(2-methoxyethyl)phenyl]phenylmethanol

HRID 499864
Notes
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Reaction equation

HRID 499864 reaction equation
[CH3:1][O:2][CH2:3][O:4][C:5]1[C:6](Br)=[C:7]([CH2:15][CH2:16][O:17][CH3:18])[CH:8]=[C:9]([O:11][CH2:12][O:13][CH3:14])[CH:10]=1.C([Li])CCC.CCCCCC.[CH:31](=[O:38])[C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1.[Cl-].[NH4+]>O1CCCC1>[CH3:1][O:2][CH2:3][O:4][C:5]1[CH:10]=[C:9]([O:11][CH2:12][O:13][CH3:14])[CH:8]=[C:7]([CH2:15][CH2:16][O:17][CH3:18])[C:6]=1[CH:31]([C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)[OH:38]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

7

Reactant 5

HCID 240BenzaldehydeHCID 8058HexaneHCID 25517Ammonium ChlorideHCID 231164713,5-Bis(methoxymethoxy)-2-bromo-1-(2-methoxyethyl)benzeneHCID 178418339Butyllithium

Product 1

HCID 23116486[2,4-Bis(methoxymethoxy)-6-(2-methoxyethyl)phenyl]phenylmethanol
Yield 53%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

3,5-Bis(methoxymethoxy)-2-bromo-1-(2-methoxyethyl)-benzene (5.3 g, 16 mmol) obtained in Example 1, Step 4 was dissolved in tetrahydrofuran (0.10 L). After the solution was cooled to −78° C., a 1.6 mol/L solution of n-butyllithium in hexane (30 mL, 48 mmol) was added thereto, followed by stirring for 5 minutes. Benzaldehyde (6.4 mL, 62 mmol) was added to the reaction mixture, followed by stirring for 1 hour. To the reaction mixture was added a saturated aqueous solution of ammonium chloride (30 mL), and the mixture was extracted with ethyl acetate (0.30 L). The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (ethyl acetate/hexane=1/9-1/2) to obtain [2,4-bis(methoxymethoxy)-6-(2-methoxyethyl)phenyl]phenyl-methanol (3.0 g, 53%). Then, [2,4-bis(methoxymethoxy)-6-(2-methoxyethyl)phenyl]phenylmethanol (3.0 g, 8.4 mmol) was dissolved in dichloromethane (50 mL), and Molecular Sieves 4 (7.9 g) and pyridinium dichromate (7.9 g, 21 mmol) were added thereto, followed by stirring at room temperature for 5 hours. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (ethyl acetate/hexane=1/9-1/2) to obtain 2,4-bis(methoxymethoxy)-6-(2-methoxyethyl)phenyl=phenyl=ketone (2.9 g, 96%).

Workup

  1. stirringby stirring for 1 hour
  2. extractionthe mixture was extracted with ethyl acetate (0.30 L)
  3. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  4. concentrationconcentrated under reduced pressure
  5. customThe resulting residue was purified by silica gel column chromatography (ethyl acetate/hexane=1/9-1/2)

Sources & evidence

ORD record
ord-a10ea36789c3416e879c24a163ff6b87
Source dataset
uspto-grants-2010_08
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US07767693B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes