3-Bromophenol → HCID 71029053, compound

HRID 1028332Notes

Reaction equation

HRID 1028332 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([OH:8])[CH:5]=[CH:6][CH:7]=1.[CH3:9][C:10]1([CH3:19])[O:15][CH2:14][C:13]([CH3:18])([CH2:16]O)[CH2:12][O:11]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>C1COCC1>[CH3:9][C:10]1([CH3:19])[O:15][CH2:14][C:13]([CH3:18])([CH2:16][O:8][C:4]2[CH:5]=[CH:6][CH:7]=[C:2]([Br:1])[CH:3]=2)[CH2:12][O:11]1

Participants

6

Reactant 4

HCID 115633-BromophenolHCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 3737095-Hydroxymethyl-2,2,5-trimethyl-1,3-dioxane

Product 1

HCID 71029053HCID 71029053, compoundYield 85%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-2 °C

Procedure

To a mechanically stirred mixture of 3-bromophenol (26.14 g, 0.1511 mol), 2,2,5-trimethyl-5-hydroxymethyl-1,3-dioxane (31.98 g, 0.20 mol), triphenylphosphine (59.32 g, 0.226 mol), and THF (250 ml) cooled to −2° C., a solution of diisopropyl azodicarboxylate (DIAD), 4.6 ml, 0.2265 mol) in THF (50 ml) was added drop-wise over 45 minutes, and the mixture was allowed to warm up to room temperature. After 3 days, the THF was removed, and the residue was stirred in a mixture of toluene and heptane (1:1, 300 ml) and filtered. The solids were washed with the same mixture of solvents (200 ml), and the combined filtrates were washed with dilute sodium hydroxide solution, water, and saturated sodium chloride solution, before being dried and concentrated. The residue was chromatographed over silica gel. Elution with toluene-heptane (1:1) removed some unreacted triphenylphosphine. The product came in toluene-heptane (3:1) eluates, and on standing with pentane, solidified, 40.69 g (85% yield), m.p. 67-70° C. Mass spec: m/z 314, 316 (M+). Anal Calcd for C14H19BrO3: C, 53.34; H, 6.08; Br, 25.35%. Found: C, 53.37; H, 5.97; Br, 25.35%.

Workup

  1. temperatureto warm up to room temperature
  2. customthe THF was removed
  3. filtrationfiltered
  4. washThe solids were washed with the same mixture of solvents (200 ml)
  5. washthe combined filtrates were washed with dilute sodium hydroxide solution, water, and saturated sodium chloride solution
  6. custombefore being dried
  7. concentrationconcentrated
  8. customThe residue was chromatographed over silica gel
  9. washElution with toluene-heptane (1:1)
  10. customremoved some unreacted triphenylphosphine

Sources & evidence

ORD record
ord-de092c5e965b4193a82379c8f2c993d3
Source dataset
uspto-grants-2014_05
Patent number
US08735528B1

Reaction notes

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