Benzyl Bromide → Methyl 2-(benzyloxy)-4-iodobenzoate

HRID 1522915Notes

Reaction equation

HRID 1522915 reaction equation
C([O-])([O-])=O.[K+].[K+].[I:7][C:8]1[CH:9]=[C:10]([OH:18])[C:11](=[CH:16][CH:17]=1)[C:12]([O:14][CH3:15])=[O:13].[CH2:19](Br)[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1>CC#N>[CH2:19]([O:18][C:10]1[CH:9]=[C:8]([I:7])[CH:17]=[CH:16][C:11]=1[C:12]([O:14][CH3:15])=[O:13])[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1

Participants

5

Reactant 3

HCID 7498Benzyl BromideHCID 11430Potassium CarbonateHCID 11380407Methyl 4-iodosalicylate

Product 1

HCID 66990993Methyl 2-(benzyloxy)-4-iodobenzoateYield 99%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
80 °C

Procedure

Solid K2CO3 (76.1 g, 0.55 mol) was added to a solution of methyl 4-iodosalicylate (1) (76.5 g, 0.28 mol) in MeCN (550 mL) at RT. Benzyl bromide (32.7 mL, 0.28 mol) was added via syringe, and the resulting reaction mixture was warmed to 80° C. and stirred overnight. The reaction mixture was then cooled to RT and filtered subsequently to remove insoluble salts, which were washed further with EtOAc. The filtrate was concentrated in vacuo, before re-dissolving the residue in fresh EtOAc and filtering a second time. The filtrate was concentrated in vacuo to provide an oil which solidified upon standing to yield 2 (99%, 100.5 g) as a beige solid that required no further purification. 1H NMR (500 MHz, CDCl3, 25° C.): δ=7.54 (d, J=8.0 Hz, 1H), 7.49 (d, J=7.5 Hz, 2H), 7.43-7.35 (m, 4H), 7.33 (t, J=7.5 Hz, 1H), 5.15 (s, 2H), 3.89 (s, 3H) ppm. 13C NMR (126 MHz, CDCl3, 25° C.): δ=166.3, 158.4, 136.2, 133.1, 130.1, 128.8, 128.1, 127.0, 123.3, 120.3, 100.0, 71.0, 52.3 ppm. HRMS (ESI) calculated for C15H14IO3: m/z=367.9909 ([M+H]+); Found m/z=367.9893.

Workup

  1. customthe resulting reaction mixture
  2. temperatureThe reaction mixture was then cooled to RT
  3. filtrationfiltered subsequently
  4. customto remove insoluble salts, which
  5. washwere washed further with EtOAc
  6. concentrationThe filtrate was concentrated in vacuo
  7. dissolutionbefore re-dissolving the residue in fresh EtOAc
  8. filtrationfiltering a second time
  9. concentrationThe filtrate was concentrated in vacuo
  10. customto provide an oil which

Sources & evidence

ORD record
ord-c77f5122f4304cebb0164bc835f15565
Source dataset
uspto-grants-2015_07
Patent number
US09078922B2

Reaction notes

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