Chloroiodomethane → Methyl 3-cyano-4-hydroxybenzoate

HRID 1436194Notes

Reaction equation

HRID 1436194 reaction equation
O[C:2]1C=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1I.ClCI.C([Zn][CH2:19][CH3:20])C.[NH4+:21].[Cl-].[NH4+].[OH-:24]>ClCCCl.CCOC(C)=O>[C:2]([C:3]1[CH:4]=[C:5]([CH:10]=[CH:19][C:20]=1[OH:24])[C:6]([O:8][CH3:9])=[O:7])#[N:21]

Participants

8

Reactant 5

HCID 11644ChloroiodomethaneHCID 14923Ammonium HydroxideHCID 25517Ammonium ChlorideHCID 11346465Methyl 4-hydroxy-3-iodobenzoateHCID 178418750HCID 178418750, compound

Product 1

HCID 11769089Methyl 3-cyano-4-hydroxybenzoateYield 30%

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

Compound 2 (5.56 g, 24.0 mmol) was combined with chloroiodomethane (5.59 mL, 76.8 mmol) and dissolved in 1,2-dichloroethane (35 mL) under an atmosphere of nitrogen. The solution was cooled to 0° C. with an ice bath and diethyl zinc (38.4 mL, 1.0 M in hexanes, 38.4 mmol) was added over 10 minutes. The resulting mixture was stirred for 30 minutes and allowed to warm to room temperature. It was cooled to 0° C. with an ice bath, and saturated aqueous NH4Cl (150 mL) was added, followed by concentrated aqueous NH4OH (25 mL) and EtOAc (200 mL). The layers were separated and the aqueous phase was extrated with additional EtOAc (2×100 mL). The organic phases were combined, dried (Na2SO4) and concentrated to a crude oil which was purified using silica gel (100% hexanes). Compound 3 (1.76 g, 7.2 mmol, 30% yield) was a colorless oil which was characterized using 1H NMR.

Workup

  1. temperatureto warm to room temperature
  2. temperatureIt was cooled to 0° C. with an ice bath
  3. customThe layers were separated
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated to a crude oil which
  6. customwas purified

Sources & evidence

ORD record
ord-db2964acaa224bfeb79c982c91ff5140
Source dataset
uspto-grants-2009_11
Patent number
US07618981B2

Reaction notes

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