Lithium Hexamethyldisilazide → 6-Methoxyquinolin-3-amine

HRID 2421522Notes

Reaction equation

HRID 2421522 reaction equation
Br[C:2]1[CH:3]=[N:4][C:5]2[C:10]([CH:11]=1)=[CH:9][C:8]([O:12][CH3:13])=[CH:7][CH:6]=2.F[B-](F)(F)F.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.C[Si]([N-:36][Si](C)(C)C)(C)C.[Li+]>C1(C)C=CC=CC=1.C(OCC)C.[Pd].[Pd].C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1>[NH2:36][C:2]1[CH:3]=[N:4][C:5]2[C:10]([CH:11]=1)=[CH:9][C:8]([O:12][CH3:13])=[CH:7][CH:6]=2

Participants

7

Reactant 3

HCID 2733832Lithium HexamethyldisilazideHCID 147585873-Bromo-6-methoxyquinolineHCID 44558591Tri-t-butylphosphine fluoroborate

Product 1

HCID 5999396-Methoxyquinolin-3-amine

Reagents, catalysts & solvents 3

HCID 9832798Tris(dibenzylideneacetone) dipalladiumCatalystHCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

Procedure

To a stirred mixture of 3-bromo-6-methoxyquinoline [synthesis given in Tetrahedron (1986), 42, 1475-1485] (2.38 g), tris(dibenzylideneacetone) dipalladium (0) (0.114 g) and tri t-butylphosphine tetrafluoroborate (0.116 g) in toluene (15 ml) under an atmosphere of nitrogen at ambient temperature was added a solution of lithium bistrimethylsilylamide (11.0 ml, 1.0M solution in hexanes). The mixture was stirred for 2 days and the brown suspension diluted with diethyl ether and extracted with 2M aqueous hydrochloric acid (twice) and the acidic fractions combined, washed with diethyl ether and made basic with 2M aqueous sodium hydroxide to give the required product as a brown solid that was used in the next Step without further purification.

Workup

  1. extractionextracted with 2M aqueous hydrochloric acid (twice) and the acidic fractions
  2. washwashed with diethyl ether

Sources & evidence

ORD record
ord-36099860a7fe437e914e14a1229bfd85
Source dataset
uspto-grants-2011_06
Patent number
US07956188B2

Reaction notes

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