Sulfuric Acid → Methyl 2-iodo-3-nitrobenzoate

HRID 33333

Reaction equation

HRID 33333 reaction equation
[I:1][C:2]1[C:10]([N+:11]([O-:13])=[O:12])=[CH:9][CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].S(=O)(=O)(O)O.[CH:19](OC)(OC)OC>CO>[CH3:19][O:5][C:4](=[O:6])[C:3]1[CH:7]=[CH:8][CH:9]=[C:10]([N+:11]([O-:13])=[O:12])[C:2]=1[I:1]

Participants

5

Reactant 3

HCID 1118Sulfuric AcidHCID 9005Trimethyl orthoformateHCID 2209662-Iodo-3-nitrobenzoic acid

Product 1

HCID 264093Methyl 2-iodo-3-nitrobenzoate

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

2-iodo-3-nitro-benzoic acid (61 g, 208 mmol, prepared as described in Org. Syn. Coll. Vol. I, 56-58, and 125-127), sulfuric acid (40.8 g, 416 mmol), and trimethyl orthoformate (88.4 g, 833 mmol) were dissolved in 500 mL dry MeOH. The reaction was refluxed under argon for 20 h. The reaction mixture was concentrated to 100 mL then partitioned between saturated NaHCO3(aq) and CH2Cl2. The layers were separated and the aqueous layer extrated three times with CH2Cl2. The combined organic layers were dried (MgSO4) and concentrated in vacuo. The yellow solid was crystallized from CH2Cl2/hexanes yielding 2-iodo-3-nitro-benzoic acid methyl ester, 57.8 g (90%) as a yellow solid: m.p. 64.0-64.5° C.; 1H NMR (300 MHz, CDCl3) δ 3.99 (s, 3H), 7.54 (app t, J=7.8 Hz, 1H), 7.70 (dd, J=8.1, 1.8 Hz, 1H), 7.77 (dd, J=7.8, 1.8 Hz, 1H).

Workup

  1. temperatureThe reaction was refluxed under argon for 20 h
  2. concentrationThe reaction mixture was concentrated to 100 mL
  3. customthen partitioned between saturated NaHCO3(aq) and CH2Cl2
  4. customThe layers were separated
  5. dry with materialThe combined organic layers were dried (MgSO4)
  6. concentrationconcentrated in vacuo
  7. customThe yellow solid was crystallized from CH2Cl2/hexanes

Sources & evidence

ORD record
ord-67c4bbd805f441dea4733673415f8456
Source dataset
uspto-grants-2008_09
Patent number
US07429578B2

Linked notes

Loading…