Water → Ethyl 6-amino-9-(3-chlorobenzyl)-9H-beta-carboline-3-carboxylate

HRID 891021Notes

Reaction equation

HRID 891021 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:27]=[CH:28][CH:29]=1)[CH2:5][N:6]1[C:18]2[CH:17]=[N:16][C:15]([C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:14][C:13]=2[C:12]2[C:7]1=[CH:8][CH:9]=[C:10]([N+:24]([O-])=O)[CH:11]=2.C1COCC1.O.CN(C=O)C>C(O)(=O)C.[Cl-].[Ti+3].[Cl-].[Cl-]>[NH2:24][C:10]1[CH:11]=[C:12]2[C:7](=[CH:8][CH:9]=1)[N:6]([CH2:5][C:4]1[CH:27]=[CH:28][CH:29]=[C:2]([Cl:1])[CH:3]=1)[C:18]1[CH:17]=[N:16][C:15]([C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:14][C:13]2=1

Participants

7

Reactant 4

HCID 962WaterHCID 6228DimethylformamideHCID 8028TetrahydrofuranHCID 21883399Ethyl 9-(3-chlorobenzyl)-6-nitro-9H-beta-carboline-3-carboxylate

Product 1

HCID 21883389Ethyl 6-amino-9-(3-chlorobenzyl)-9H-beta-carboline-3-carboxylateYield 28%

Reagents, catalysts & solvents 2

HCID 10313229titanium(III) trichlorideCatalystHCID 176Acetic AcidSolvent

Procedure

A solution of ethyl 9-(3-chlorobenzyl)-6-nitro-9H-β-carboline-3-carboxylate (2.7 g, 6.59 mmol) and titanium(III) chloride (36 mL, 20% solution, 46.75 mmol) in a mixture of acetic acid (54 mL), THF (180 mL), water (54 mL) and DMF (10 mL) was stirred for 5 hours at ambient temperature. The reaction mixture was quenched with water (200 mL), and extracted with ethyl acetate (100 mL). The pH of the water layer was adjusted to 7 with saturated Na2CO3 aqueous solution. Then, the resulting precipitate was filtered and dried in vacuo. The product was extracted from the precipitate with CHCl3 in a Soxhlet extractor and purified by chromatography with ethyl acetate to provide the title compound (0.70 g, yield 27.8%). 1H NMR (DMSO-d6): δ 9.06 (s, 1H), 8.70 (s, 1H), 7.50 (d, 1H, J=8.0 Hz), 7.45 (s, 1H), 7.27–7.31 (m, 3H), 7.09 (s, 1H), 7.01 (d, 1H, J=8.0 Hz), 5.75 (s, 2H), 5.05 (s, 2H), 4.36 (q, 2H, J=7.0 Hz), 1.35 (t, 3H, J=7.0 Hz). LCMS (APCI, M+H+): 380.1/382.1=3/1.

Workup

  1. customThe reaction mixture was quenched with water (200 mL)
  2. extractionextracted with ethyl acetate (100 mL)
  3. filtrationThen, the resulting precipitate was filtered
  4. customdried in vacuo
  5. extractionThe product was extracted from the precipitate with CHCl3 in a Soxhlet extractor
  6. custompurified by chromatography with ethyl acetate

Sources & evidence

ORD record
ord-d3955beca72442a7900e613818dc4c37
Source dataset
uspto-grants-2006_02
Patent number
US07001912B2

Reaction notes

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