Benzyl Bromide → 2-Benzyl-1,3-bis(methoxymethoxy)benzene

HRID 1511224Notes

Reaction equation

HRID 1511224 reaction equation
[CH3:1][O:2][CH2:3][O:4][C:5]1[CH:10]=[CH:9][CH:8]=[C:7]([O:11][CH2:12][O:13][CH3:14])[CH:6]=1.[Li]CCCC.[CH2:20](Br)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1>C1COCC1>[CH2:20]([C:6]1[C:7]([O:11][CH2:12][O:13][CH3:14])=[CH:8][CH:9]=[CH:10][C:5]=1[O:4][CH2:3][O:2][CH3:1])[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1

Participants

5

Reactant 3

HCID 7498Benzyl BromideHCID 122226821,3-Bis(methoxymethoxy)benzeneHCID 178418339Butyllithium

Product 1

HCID 251387862-Benzyl-1,3-bis(methoxymethoxy)benzeneYield 30%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-40 °C

Procedure

A solution of 12 (500 mg, 2.52 mmol) in anhydrous THF (2.02 mL) was added dropwise to a solution of nBuLi (2.5 M in hexanes, 1.51 mL, 3.78 mmol) in anhydrous THF (1.65 mL) at room temperature. After 1 hour, the solution was cooled to −40° C. and benzyl bromide (1.22 mL, 10.10 mmol) was added. The resulting solution was warmed to room temperature over 12 hours, and the reaction was quenched by the addition of saturated aqueous NH4Cl. Water (5 mL) was added and the solution was extracted with CH2Cl2 (3×10 mL). Combined organic fractions were dried (Na2SO4), filtered, and concentrated. The residue was purified via column chromatography (SiO2, 4:1; Hexane:EtOAc) to afford 13 as a yellow oil (214 mg, 30%): 1H NMR (CDCl3, 500 MHz) 7.17 (d, J=7.9 Hz, 2H), 7.17-7.12 (m, 2H), 7.06-7.02 (m, 2H), 6.71 (d, J=8.3 Hz, 2H), 5.09 (s, 4H), 4.00 (s, 2H), 3.29 (s, 6H); 13C NMR (CDCl3, 125 MHz) 155.9 (2C), 141.6, 128.5 (2C), 128.0 (2C), 127.5, 125.4, 119.4, 107.7 (2C), 94.3 (2C), 56.0 (2C), 29.1; IR (film) νmax 2953, 2930, 1595, 1470, 1452, 1254, 1153, 1097, 1043, 941, 922, 727, 698 cm−1; HRMS (ESI+) m/z: [M+Na]+ calcd for C17H20O4, 311.1259. found, 311.1201.

Workup

  1. temperatureThe resulting solution was warmed to room temperature over 12 hours
  2. customthe reaction was quenched by the addition of saturated aqueous NH4Cl
  3. additionWater (5 mL) was added
  4. extractionthe solution was extracted with CH2Cl2 (3×10 mL)
  5. dry with materialCombined organic fractions were dried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified via column chromatography (SiO2, 4:1; Hexane:EtOAc)

Sources & evidence

ORD record
ord-39782cf4107b412f97a68df27ddbb1cc
Source dataset
uspto-grants-2012_07
Patent number
US08212011B2

Reaction notes

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