Diisopropylamine → Methyl 3-iodo-4-(3-methyl-but-2-enylamino)-benzoate

HRID 392228Notes

Reaction equation

HRID 392228 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[NH2:13][C:14]1[CH:23]=[CH:22][C:17]([C:18]([O:20][CH3:21])=[O:19])=[CH:16][C:15]=1[I:24].Br[CH2:26][CH:27]=[C:28]([CH3:30])[CH3:29]>O1CCCC1.CCCCCC.[Cl-].[Na+].O>[I:24][C:15]1[CH:16]=[C:17]([CH:22]=[CH:23][C:14]=1[NH:13][CH2:26][CH:27]=[C:28]([CH3:30])[CH3:29])[C:18]([O:20][CH3:21])=[O:19]

Participants

8

Reactant 4

HCID 7912DiisopropylamineHCID 700922-Butene, 1-bromo-3-methyl-HCID 4104649Methyl 4-amino-3-iodobenzoateHCID 178418339Butyllithium

Product 1

HCID 22663311Methyl 3-iodo-4-(3-methyl-but-2-enylamino)-benzoate

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
0 °C

Procedure

A solution of diisopropylamine (2.8 ml) in tetrahydrofuran (25 ml), under nitrogen, cooled to −10° C. was treated with butyl lithium in hexane (12.4 ml, 1.6M). The solution was added slowly via a syringe to a cooled to solution of methyl 4-amino-3-iodobenzoate (5 g, prepared according to the procedure of M. L. Hill, Tetrahedron, 1990, 46, page 4587) in tetrahydrofuran (100 ml), under nitrogen and at −78° C. The mixture was allowed to warm to 0° C. and after stirring for a further 10 minutes the mixture was cooled to −78° C. and then treated with 4-bromo-2-methyl-2-butene (2.49 ml). The reaction mixture was allowed to warm to room temperature over 1.5 hours then poured into saturated brine (100 ml). The organic layer was separated and the aqueous phase was extracted with ethyl acetate (100 ml). the combined organic phases were evaporated and the residue was subjected to flash chromatography on silica eluting with a mixture of ethyl acetate and petroleum ether (1:9, v/v) to give the title compound (5 g).

Workup

  1. additionThe solution was added slowly via a syringe to
  2. customprepared
  3. customat −78° C
  4. temperaturewas cooled to −78° C.
  5. temperatureto warm to room temperature over 1.5 hours
  6. customThe organic layer was separated
  7. extractionthe aqueous phase was extracted with ethyl acetate (100 ml)
  8. customthe combined organic phases were evaporated
  9. additionthe residue was subjected to flash chromatography on silica eluting with a mixture of ethyl acetate and petroleum ether (1:9, v/v)

Sources & evidence

ORD record
ord-f3da4775d2b943328cd70dc898dfe903
Source dataset
uspto-grants-2004_10
Patent number
US06800645B1

Reaction notes

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