Methyl Salicylate → HCID 54767384, compound

HRID 336113Notes

Reaction equation

HRID 336113 reaction equation
[OH:1][C:2]1[CH:11]=[CH:10][CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].C([O-])([O-])=O.[K+].[K+].Br[CH2:19][C:20]1[CH:25]=[CH:24][C:23]([B:26]2[O:34][C:31]([CH3:33])([CH3:32])[C:28]([CH3:30])([CH3:29])[O:27]2)=[CH:22][CH:21]=1>C(#N)C>[CH3:32][C:31]1([CH3:33])[C:28]([CH3:29])([CH3:30])[O:27][B:26]([C:23]2[CH:22]=[CH:21][C:20]([CH2:19][O:1][C:2]3[CH:11]=[CH:10][CH:9]=[CH:8][C:3]=3[C:4]([O:6][CH3:7])=[O:5])=[CH:25][CH:24]=2)[O:34]1

Participants

5

Reactant 3

HCID 4133Methyl SalicylateHCID 11430Potassium CarbonateHCID 37345062-(4-(Bromomethyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Product 1

HCID 54767384HCID 54767384, compoundYield 77%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
70 °C

Procedure

To 5 ml, of acetonitrile was added methyl 2-hydroxybenzoate (85 μL, 0.66 mmol), K2CO3 (273 mg, 2.0 mmol), and 4-bromomethylphenyl boronic acid pinacol ester (217 mg, 0.73 mmol). The reaction was heated to 70° C. under nitrogen overnight. After removal of the solvent via rotary evaporation, the resulting oil was brought up in EtOAc and washed with a saturated sodium bicarbonate solution to remove starting materials. The organic layer was dried over MgSO4, filtered and concentrated. The product was purified on a silica gel column eluting with 5% EtOAc in hexanes to yield B1 as a white solid in 77% yield (186 mg, 0.5 mmol). 1H NMR (400 MHz, CDCl3) δ=7.85-7.81 (m, 3H), 7.49 (d, J=7.6 Hz, 2H), 7.40 (dt, J1=8.4 Hz, J2=1.8 Hz, 1H), 7.00-6.96 (m, 2H), 5.20 (s, 2H), 3.90 (s, 3H), 1.35 (s, 12H). 13C NMR (100 MHz, CDCl3) δ=140.2, 135.2, 133.6, 132.0, 126.2, 121.0, 120.8, 114.0, 84.0, 70.7, 52.3, 25.1. ESI-MS(+): m/z 368.82 [M+H]+, 385.69 [M+NH4]+.

Workup

  1. customAfter removal of the solvent
  2. customvia rotary evaporation
  3. washwashed with a saturated sodium bicarbonate solution
  4. customto remove
  5. dry with materialThe organic layer was dried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe product was purified on a silica gel column
  9. washeluting with 5% EtOAc in hexanes

Sources & evidence

ORD record
ord-4c6bdb851e284014a56701b5d981f6cc
Source dataset
uspto-grants-2014_11
Patent number
US08889638B2

Reaction notes

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