Diiodomethane → Methyl 4-cyano-5-iodo-2-methylbenzoate

HRID 906153Notes

Reaction equation

HRID 906153 reaction equation
N[C:2]1[C:3]([C:13]#[N:14])=[CH:4][C:5]([CH3:12])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].[I:15]CI.N(OCCC(C)C)=O>C1COCC1.[Cu](I)I>[C:13]([C:3]1[C:2]([I:15])=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[C:5]([CH3:12])[CH:4]=1)#[N:14]

Participants

6

Reactant 3

HCID 6346DiiodomethaneHCID 8053Isoamyl NitriteHCID 67402842Methyl 5-amino-4-cyano-2-methylbenzoate

Product 1

HCID 67402433Methyl 4-cyano-5-iodo-2-methylbenzoateYield 76%

Reagents, catalysts & solvents 2

HCID 83717Copper iodideCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
85 °C

Procedure

To a solution of methyl 5-amino-4-cyano-2-methylbenzoate (5.0 g, 0.0262 mol) in THF (100 mL) was added copper iodide (5.0 g, 0.0262 mol), diiodomethane (10.5 mL, 0.131 mol) and isoamyl nitrite (10.5 mL, 0.0786 mol). The reaction mixture was heated to 85° C. and stirred for 3 h, at which time it was cooled to room temperature. The heterogeneous mixture was filtered through a bed of celite, and the filter cake rinsed with ethyl acetate. The filtrate was concentrated and the residue was purified by flash chromatography (100% hexanes to 2% diethyl ether in hexanes), then triturated with hexanes to afford methyl 4-cyano-5-iodo-2-methylbenzoate (3.7 g, 76%) as a white powder. 1H NMR (400 MHz, CDCl3): 8.39 (s, 1H), 7.50 (s, 1H), 3.94 (s, 3H), 2.56 (s, 3H).

Workup

  1. temperaturewas cooled to room temperature
  2. filtrationThe heterogeneous mixture was filtered through a bed of celite
  3. washthe filter cake rinsed with ethyl acetate
  4. concentrationThe filtrate was concentrated
  5. customthe residue was purified by flash chromatography (100% hexanes to 2% diethyl ether in hexanes)
  6. customtriturated with hexanes

Sources & evidence

ORD record
ord-2da5dd2b902a4f8d9051d38270da3cf1
Source dataset
uspto-grants-2011_09
Patent number
US08012956B2

Reaction notes

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