Methanesulfonic Acid → 3-(1-Adamantyl)-4,5-methylenedioxybromobenzene

HRID 508670Notes

Reaction equation

HRID 508670 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]2[O:8][CH2:9][O:10][C:4]=2[CH:3]=1.[C:11]12(O)[CH2:20][CH:15]3[CH2:16][CH:17]([CH2:19][CH:13]([CH2:14]3)[CH2:12]1)[CH2:18]2.CS(O)(=O)=O>>[C:11]12([C:6]3[C:5]4[O:8][CH2:9][O:10][C:4]=4[CH:3]=[C:2]([Br:1])[CH:7]=3)[CH2:20][CH:15]3[CH2:16][CH:17]([CH2:19][CH:13]([CH2:14]3)[CH2:12]1)[CH2:18]2

Participants

4

Reactant 3

HCID 6395Methanesulfonic AcidHCID 641521-AdamantanolHCID 758311-Bromo-3,4-(methylenedioxy)benzene

Product 1

HCID 194297023-(1-Adamantyl)-4,5-methylenedioxybromobenzeneYield 86%

Procedure

A mixture of 4-bromo-1,2-methylenedioxybenzene (2.00 g, 9.95 mmol), 1-adamantanol (1.52 g, 9.95 mmol), and MeSO3H (5 mL) was stirred for 1 h. The resulting solution was quenched with H2O (40 mL) and extracted with EtOAc (110 mL). The extract was washed with 0.5 N NaOH, sat. NaHCO3, and brine and dried. The residue obtained on concentration was purified on silica gel (hexane) to give 2.86 g (86%) of 4-(1-adamantyl)-6-bromobenzo[1,3]dioxole as a white solid, mp 135-136° C. IR 2901, 2843, 1435, 1189 cm−1; 1H NMR δ (CDCl3) 1.76 (bs, 6H, AdCH2), 1.98 (bs, 6H, AdCH2), 2.06 (bs, 3H, AdCH), 5.93 (s, 2H, CH2), 6.84 (s, 1H, 7-ArH), 6.86 ppm (s, 1H, 5-ArH).

Workup

  1. customThe resulting solution was quenched with H2O (40 mL)
  2. extractionextracted with EtOAc (110 mL)
  3. washThe extract was washed with 0.5 N NaOH, sat. NaHCO3, and brine
  4. customdried
  5. customThe residue obtained on concentration
  6. customwas purified on silica gel (hexane)

Sources & evidence

ORD record
ord-836acf3b6c2944deb3b75e09dcf11d1e
Source dataset
uspto-grants-2015_08
Patent number
US09096544B2

Reaction notes

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