Nitrogen → Aluminum hydride

HRID 1683299Notes

Reaction equation

HRID 1683299 reaction equation
OS(O)(=O)=O.[H-].[H-].[H-].[H-].[Li+].[Al+3:11].N#N.[AlH3].[CH3:15][N:16]([CH2:18][CH2:19][C:20]1[C:28]2[C:23](=[CH:24][CH:25]=[C:26]([CH2:29][C:30]3[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=3)[CH:27]=2)[NH:22][CH:21]=1)[CH3:17].[C:36]([OH:41])(=[O:40])[C:37]([OH:39])=[O:38]>C1COCC1.CO.CCOCC.O>[AlH3:11].[CH:37]([C:36]([NH2:16])=[O:41])=[O:38].[C:36]([OH:41])(=[O:40])[C:37]([OH:39])=[O:38].[CH3:15][N:16]([CH2:18][CH2:19][C:20]1[C:28]2[C:23](=[CH:24][CH:25]=[C:26]([CH2:29][C:30]3[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=3)[CH:27]=2)[NH:22][CH:21]=1)[CH3:17]

Participants

13

Reactant 6

HCID 947NitrogenHCID 971Oxalic AcidHCID 1118Sulfuric AcidHCID 14488Aluminum hydrideHCID 190428341-(N,N-dimethylamino)-2-(5-benzylindol-3-yl)ethaneHCID 21226445Aluminium lithium hydride

Product 3

HCID 14488Aluminum hydrideHCID 11708045GlyoxamideHCID 190428421-(N,N-dimethylamino)-2-(5-benzylindol-3-yl)ethane oxalate

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of AlH3 was prepared by addition of c.H2SO4 (1.59 g) dropwise to a cooled (ice-bath) suspension of LiAlH4 (1.226 g) in dry THF (82 mL) over 20 min. The mixture was them left to stand under dry N2 for 1 hr to allow the solids to settle. A solution of the glyoxamide (0.59 g, 1.926 mmol) in THF (110 mL) was prepared, and in a N2 atmosphere, the AlH3 solution (55 mL) was added over 5 min. The mixture was stirred for 16 hr and then H2O was added dropwise to quench excess reagent, and the THF was evaporated in vacuo. The residue was partitioned between 1M HCl/CH2Cl12 and after re-extraction of the aqueous layer (2×; CH2Cl2), the combined organic layers were washed with 1M HCl and then saturated aqueous NaCl, dried (MgSO4) and evaporated to a solid. Chromatography (silica gel; CH2Cl2 /EtOH containing 2% concentrated aqueous NH3 ; 0-12%), gave the free base: 1-(N,N-dimethylamino)-2-(5-benzylindol-3-yl)ethane, as a gum, 0.246 g (46%). This was treated with oxalic acid (0.07 g) in MeOH (2 mL) and Et2O added until crystallisation commenced. The product: 1-(N,N-dimethylamino)-2-(5-benzylindol-3-yl)ethane oxalate, was obtained as white granular crystals, 0.191 g (27%), m.p.158°-9° C.

Workup

  1. waitleft
  2. customto quench excess reagent
  3. customthe THF was evaporated in vacuo
  4. customThe residue was partitioned between 1M HCl/CH2Cl12
  5. extractionafter re-extraction of the aqueous layer (2×; CH2Cl2)
  6. washthe combined organic layers were washed with 1M HCl
  7. dry with materialsaturated aqueous NaCl, dried (MgSO4)
  8. customevaporated to a solid
  9. customChromatography (silica gel; CH2Cl2 /EtOH containing 2% concentrated aqueous NH3 ; 0-12%), gave the free base
  10. additionadded until crystallisation

Sources & evidence

ORD record
ord-b4d9cb8f7e7b47d9bc405e474e435971
Source dataset
uspto-grants-1997_06
Patent number
US05637593

Reaction notes

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