Heptane → HCID 86653776, compound

HRID 1020873Notes

Reaction equation

HRID 1020873 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.CCCCCCC>COC>[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

5

Reactant 3

HCID 8900HeptaneHCID 24408Bromine2×HCID 86653775HCID 86653775, compound

Product 1

HCID 86653776HCID 86653776, compound

Reagents, catalysts & solvents 1

HCID 8254Dimethyl EtherSolvent3×

Procedure

In 100 mL dimethyl ether (DME) was dissolved 1,4-bis(benzyloxy)-3,5,6-trimethylbenzene prepared as in step 1(5 g, 15.0 mmol) which 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 via a dropping funnel. 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. A white solid precipitated from the solution during the night. The reaction was treated with 200 mL EtOAc, which dissolved the solid, 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. HPLC 97.8% at 215 nm, did not ionize; 1H NMR (400 MHz, CDCl3) d=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. customA white solid precipitated from the solution during the night
  2. additionThe reaction was treated with 200 mL EtOAc, which
  3. dissolutiondissolved the solid
  4. washwashed with H2O until the aqueous washings
  5. extractionThe combined aqueous layers were back extracted with EtOAc (3×50 mL)
  6. washthe combined organics washed 2×100 mL saturated NaCl
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated to a brown solid
  9. custompurified by flash chromatography (gradient elution 2-20% EtOAc/heptane)
  10. customto give a yellow solid
  11. stirringstirred overnight
  12. filtrationfiltered
  13. washthe filter cake rinsed with heptane
  14. customThe resulting white powder was dried in vacuo

Sources & evidence

ORD record
ord-f906c0c5b96a45a28dc1dde03e24d359
Source dataset
uspto-grants-2014_05
Patent number
US08716486B2

Reaction notes

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