Ethyl Acetate → HCID 22396780, compound

HRID 1356328Notes

Reaction equation

HRID 1356328 reaction equation
[Cl:1][C:2]1[C:10]2[N:9]([CH2:11][C:12](OCC)=[O:13])[C:8]3[CH2:17][CH2:18][N:19]([C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[CH2:20][CH2:21][C:7]=3[C:6]=2[CH:5]=[CH:4][C:3]=1[Cl:29].[Li+].[BH4-].[OH-].[Na+].CCOC(C)=O>C1COCC1.O>[Cl:1][C:2]1[C:10]2[N:9]([CH2:11][CH2:12][OH:13])[C:8]3[CH2:17][CH2:18][N:19]([C:22]([O:24][C:25]([CH3:27])([CH3:26])[CH3:28])=[O:23])[CH2:20][CH2:21][C:7]=3[C:6]=2[CH:5]=[CH:4][C:3]=1[Cl:29]

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 14798Sodium HydroxideHCID 4148881Lithium borohydride2×HCID 22396717HCID 22396717, compound

Product 1

HCID 22396780HCID 22396780, compoundYield 64%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of tert-butyl 7,8-dichloro-6-(2-ethoxy-2-oxoethyl)-1,4,5,6-tetrahydroazepino[4,5-b]indole-3(2H)-carboxylate (3.0 g, 6.8 mmol) in dry THF (30 mL) was cooled to 0° C. Then, LiBH4 (0.74 g, 34 mmol) was added and the reaction was allowed to warm slowly to rt. Additional LiBH4 (0.30 g, 14 mmol) was added after 24 h. After another 7 h, the reaction was diluted with H2O (75 mL) followed by addition of 10% aqueous NaOH and extraction with EtOAc (3×100 mL). The combined organic extracts were washed with brine, dried over Na2SO4, decanted, and concentrated. The crude product was purified by column chromatography (Biotage, 40M, SIM) with heptane/EtOAc (1:1) followed by crystallization from EtOAc/heptane gave 1.7 g (64%) of a white solid: mp 149.0-149.5° C.; TR (diffuse reflectance) 3420, 2974, 1665, 1482, 1468, 1445, 1414, 1365, 1334, 1240, 1220, 1168, 1151, 1122, 900 cm−1; MS (EI) m/z 398 (M+), 398, 342, 298, 270, 268, 258, 256, 212, 57, 56; Anal. Calcd for C19H24Cl2N2O3: C, 57.15; H, 6.06; N, 7.01; found: C, 57.31; H, 6.10; N, 6.98.

Workup

  1. washThe combined organic extracts were washed with brine
  2. dry with materialdried over Na2SO4
  3. customdecanted
  4. concentrationconcentrated
  5. customThe crude product was purified by column chromatography (Biotage, 40M, SIM) with heptane/EtOAc (1:1)
  6. customfollowed by crystallization from EtOAc/heptane

Sources & evidence

ORD record
ord-df3bbd9e2d7f47d68a6456e99644cc87
Source dataset
uspto-grants-2003_07
Patent number
US06586421B2

Reaction notes

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