Sodium hydride → Ethyl 9-(2,5-dichlorobenzyl)-9H-beta-carboline-3-carboxylate

HRID 992556Notes

Reaction equation

HRID 992556 reaction equation
[CH:1]1[C:13]2[NH:12][C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[CH:4]=[C:3]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[N:2]=1.[H-].[Na+].[H][H].[Cl:23][C:24]1[CH:31]=[CH:30][C:29]([Cl:32])=[CH:28][C:25]=1[CH2:26]Cl>CN(C=O)C.C(O)(=O)C>[Cl:23][C:24]1[CH:31]=[CH:30][C:29]([Cl:32])=[CH:28][C:25]=1[CH2:26][N:12]1[C:13]2[CH:1]=[N:2][C:3]([C:14]([O:16][CH2:17][CH3:18])=[O:15])=[CH:4][C:5]=2[C:6]2[C:11]1=[CH:10][CH:9]=[CH:8][CH:7]=2

Participants

7

Reactant 4

HCID 24758Sodium hydrideHCID 759762,5-Dichlorobenzyl chlorideHCID 105078Ethyl Beta-Carboline-3-CarboxylateHCID 178418361HCID 178418361, compound

Product 1

HCID 9843845Ethyl 9-(2,5-dichlorobenzyl)-9H-beta-carboline-3-carboxylateYield 986.8%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 6228DimethylformamideSolvent

Procedure

A suspension of ethyl 9H-β-carboline-3-carboxylate (2.40 g, 10 mmol) in anhydrous DMF (20 mL) was cooled in an ice bath under nitrogen. Sodium hydride (420 mg of 60% NaH in mineral oil, 10.5 mmol) was added at once, and the mixture stirred until most of the solids dissolved and hydrogen evolution stopped (approx 10 min). The cool mixture was treated with 2,5-dichlorobenzyl chloride (2.15 g, 1.0 mmol) slowly with stirring, then allowed to warm to room temperature over two hours. The resulting cloudy solution was neutralized with acetic acid, then the solvent was removed in vacuo, affording a tan solid (3.94 g). The crude material was chromatographed on silica gel using a mixture of chloroform and ethyl acetate, affording the title product (1.96 g, 49%). 1H NMR (300 MHz, DMSO-d6) δ9.06 (s, 1 H), 8.96 (s, 1H), 8.48 (d, J=8.0, 1H), 7.55-7.64 (m, 3H), 7.35-7.42 (m, 2H), 6.60 (d,J=2.3, 1H), 5.89 (s, 2H), 4.36 (q, J=6.9, 1H), 1.35 (t, J=7.2, 3H); LRMS calcd for C21H16Cl2N2O2 (M+H) 399, found 399.0.

Workup

  1. temperaturewas cooled in an ice bath under nitrogen
  2. dissolutiondissolved
  3. custom(approx 10 min)
  4. stirringwith stirring
  5. customthe solvent was removed in vacuo

Sources & evidence

ORD record
ord-9624ccf8e94a4d159e8bfe85c8c8992f
Source dataset
uspto-grants-2002_10
Patent number
US06469021B1

Reaction notes

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