tert-Butanol → 1,1-Dimethylethyl 3-bromo-5-iodobenzoate

HRID 852522Notes

Reaction equation

HRID 852522 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:8]=[C:9]([I:11])[CH:10]=1)[C:5]([OH:7])=[O:6].Cl.CN(C)CCCN=C=NCC.[C:24](O)([CH3:27])([CH3:26])[CH3:25]>C(Cl)Cl.CN(C1C=CN=CC=1)C>[C:24]([O:6][C:5](=[O:7])[C:4]1[CH:8]=[C:9]([I:11])[CH:10]=[C:2]([Br:1])[CH:3]=1)([CH3:27])([CH3:26])[CH3:25]

Participants

6

Reactant 3

HCID 6386tert-ButanolHCID 27239391,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochlorideHCID 51825203-Bromo-5-iodobenzoic acid

Product 1

HCID 574859731,1-Dimethylethyl 3-bromo-5-iodobenzoateYield 86.3%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalyst2×HCID 6344DichloromethaneSolvent

Procedure

To a solution of 3-bromo-5-iodo-benzoic acid (D7) (50 g, 153 mmol, 1 equiv) in CH2Cl2 (500 ml) was added 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride (30.8 g, 160 mmol, 1.05 equiv), DMAP (14 g, 114 mmol, 0.75 equiv) and tert-butanol (90 ml, 917 mmol, 6 equiv). The resulting mixture was stirred at room temperature for 48 h. DMAP (4.67 g, 38 mmol, 0.25 equiv) was then added and the solution was stirred for another 24 h then concentrated in vacuo. The residue was dissolved in AcOEt and washed sequentially with 2N aqueous HCl solution, 1N aqueous NaOH solution and brine, dried over MgSO4 and concentrated in vacuo to give 3-bromo-5-iodo-benzoic acid tert-butyl ester (D8b) (50.6 g, 86%) as a brown solid.

Workup

  1. stirringthe solution was stirred for another 24 h
  2. concentrationthen concentrated in vacuo
  3. dissolutionThe residue was dissolved in AcOEt
  4. washwashed sequentially with 2N aqueous HCl solution, 1N aqueous NaOH solution and brine
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-5221abb6ed364bd79389160a11680dea
Source dataset
uspto-grants-2007_08
Patent number
US07253198B2

Reaction notes

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