Aluminium lithium hydride → HCID 178522949, compound

HRID 1168189Notes

Reaction equation

HRID 1168189 reaction equation
[Cl:1][C:2]1[CH:26]=[CH:25][C:5]([CH2:6][NH:7][C:8]([C:10]2[N:11]=[N:12][C:13]3[C:18]([C:19]=2[OH:20])=[CH:17][C:16]([C:21](OC)=[O:22])=[CH:15][CH:14]=3)=[O:9])=[CH:4][CH:3]=1.[H-].[Al+3].[Li+].[H-].[H-].[H-]>C1COCC1>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([CH2:6][NH:7][C:8]([C:10]2[N:11]=[N:12][C:13]3[C:18]([C:19]=2[OH:20])=[CH:17][C:16]([CH2:21][OH:22])=[CH:15][CH:14]=3)=[O:9])=[CH:25][CH:26]=1

Participants

4

Reactant 2

HCID 21226445Aluminium lithium hydrideHCID 178497403HCID 178497403, compound

Product 1

HCID 178522949HCID 178522949, compoundYield 52%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a suspension of methyl 3-{[(4-chlorobenzyl)amino]carbonyl}-4-hydroxy-6-cinnolinecarboxylate (Prep 5, 0.48 g) in 40 mL THF is added lithium aluminum hydride (2.60 μL) dropwise. The reaction turns a dark green color. After 1 h, the reaction is quenched carefully with water, 15% NaOH, and water again. The reaction is filtered to remove aluminum salts. The filtrate is concentrated and the resulting residue is dissolved in CH2Cl2/MeOH and adsorbed onto silica. Purification by chromatography (eluent CH2Cl2 (1L), 0.5% MeOH/CH2Cl2 (1L), 1% MeOH/CH2Cl2 (1L), 2% MeOH/CH2Cl2 (1L), 3% MeOH/CH2Cl2 (1L), 4% MeOH/CH2Cl2 (1L), 5% MeOH/CH2Cl2 (2L), 5.5% MeOH/CH2Cl2 (2L)) affords the desired product (0.23 g, 52%). Physical characteristics are as follows: m.p. 296-298° C.; 1H NMR (300 MHz, DMSO-d6) δ10.12, 8.14, 7.84, 7.74, 7.41, 5.50, 4.66, 4.56; IR (drift) 2922, 2873, 1647, 1602, 1555, 1490, 1358, 1183, 1022, 930, 919, 836, 808, 722, 684 cm−1; MS (FAB) m/z 344 (MH+), 346, 344, 287, 229, 153, 133, 125, 121, 107, 103; HRMS (FAB) calcd for C17H14ClN3O3+H1 344.0802, found 344.0805.

Workup

  1. customthe reaction is quenched carefully with water, 15% NaOH, and water again
  2. filtrationThe reaction is filtered
  3. customto remove aluminum salts
  4. concentrationThe filtrate is concentrated
  5. dissolutionthe resulting residue is dissolved in CH2Cl2/MeOH
  6. customPurification by chromatography (eluent CH2Cl2 (1L), 0.5% MeOH/CH2Cl2 (1L), 1% MeOH/CH2Cl2 (1L), 2% MeOH/CH2Cl2 (1L), 3% MeOH/CH2Cl2 (1L), 4% MeOH/CH2Cl2 (1L), 5% MeOH/CH2Cl2 (2L), 5.5% MeOH/CH2Cl2 (2L))

Sources & evidence

ORD record
ord-4625ed64e45748e4adfa01cfc363db42
Source dataset
uspto-grants-2003_09
Patent number
US06624160B2

Reaction notes

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