Ethyl Acetate → HCID 86653776, compound

HRID 1528131Notes

Reaction equation

HRID 1528131 reaction equation
[CH2:1]([O:8][C:9]1[C:14]([CH3:15])=[C:13]([CH3:16])[C:12]([O:17][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)=[C:11]([CH3:25])[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Br:26]Br.CCOC(C)=O.CCCCCCC>COCCOC>[Br:26][C:10]1[C:11]([CH3:25])=[C:12]([O:17][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C:13]([CH3:16])=[C:14]([CH3:15])[C:9]=1[O:8][CH2:1][C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 8900HeptaneHCID 24408Bromine2×HCID 86653775HCID 86653775, compound

Product 1

HCID 86653776HCID 86653776, compound

Reagents, catalysts & solvents 1

HCID 80711,2-DimethoxyethaneSolvent3×

Procedure

A solution of 2,5-bis(benzyloxy)-3,4,6-trimethylbenzene in 100 mL DME (5 g, 15.0 mmol) was treated with a solution of Br2 (0.85 mL, 16.5 mmol, 1.1 equiv.) in 10 mL DME (1.6 M) over ten minutes. The reaction was judged incomplete by HPLC. Additional Br2 in DME (0.42 mL, 1.31 g, 8.19 mmol, 0.55 equiv.) was added and stirred overnight. The reaction was treated with 200 mL EtOAc, which dissolved the crystals, and washed with H2O until the aqueous washings were colorless (3×100 mL). The combined aqueous layers were back extracted with EtOAc (3×50 mL) and the combined organics washed 2×100 mL saturated NaCl, dried over Na2SO4 and concentrated to a brown solid. The solid was adsorbed onto silica and purified by flash chromatography (gradient elution 2-20% EtOAc/heptane) to give a yellow solid. The solid was suspended into heptane, stirred overnight, filtered and the filter cake rinsed with heptane. The resulting white powder was dried in vacuo and yielded 3.31 g of 2-bromo-1,4-bis(benzyloxy)-3,5,6-trimethylbenzene as a white powder. 1H NMR (400 MHz, CDCl3) δ=7.57 (d, 2H), 7.48 (d, 2H), 7.44-7.36 (m, 6H), 4.87 (s, 2H), 4.74 (s, 2H), 2.41 (s, 3H), 2.24 (s, 3H), 2.20 (s, 3H) ppm.

Workup

  1. dissolutiondissolved the crystals
  2. washwashed with H2O until the aqueous washings
  3. extractionThe combined aqueous layers were back extracted with EtOAc (3×50 mL)
  4. washthe combined organics washed 2×100 mL saturated NaCl
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated to a brown solid
  7. custompurified by flash chromatography (gradient elution 2-20% EtOAc/heptane)
  8. customto give a yellow solid
  9. stirringstirred overnight
  10. filtrationfiltered
  11. washthe filter cake rinsed with heptane
  12. customThe resulting white powder was dried in vacuo

Sources & evidence

ORD record
ord-2a642af61524400fbdb860e8da625ca5
Source dataset
uspto-grants-2015_07
Patent number
US09090576B2

Reaction notes

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