Sodium Azide → tert-Butyl 6-(2-azidoethyl)-1,4,5,6-tetrahydroazepino[4,5-b]indole-3(2H)-carboxylate

HRID 1356273Notes

Reaction equation

HRID 1356273 reaction equation
CS(O[CH2:6][CH2:7][N:8]1[C:16]2[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=2[C:10]2[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:9]1=2)(=O)=O.[N-:29]=[N+:30]=[N-:31].[Na+]>CN(C=O)C.CCOC(C)=O>[N:29]([CH2:6][CH2:7][N:8]1[C:16]2[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=2[C:10]2[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:9]1=2)=[N+:30]=[N-:31]

Participants

5

Reactant 2

HCID 33557Sodium AzideHCID 22396678tert-Butyl 6-{2-[(methylsulfonyl)oxy]ethyl}-1,4,5,6-tetrahydroazepino[4,5-b]indole-3(2H)-carboxylate

Product 1

HCID 22396936tert-Butyl 6-(2-azidoethyl)-1,4,5,6-tetrahydroazepino[4,5-b]indole-3(2H)-carboxylateYield 94.3%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
60 °C

Procedure

tert-Butyl 6-{2-[(methylsulfonyl)oxy]ethyl }-1,4,5,6-tetrahydroazepino[4,5-b]indole-3(2H)-carboxylate (0.224 g, 0.549 mmol) and NaN3 (0.357 g, 5.49 mmol, 10.0 equiv.) were dissolved in DMF (2.5 mL) and the solution was stirred at 60° C. under N2 for 14.5 h. The reaction mixture was taken up in EtOAc and washed with water (2×15 mL). The aqueous layers were back extracted with EtOAc (25 mL). The combined organic layers were washed with brine (10 mL), dried over MgSO4, filtered and concentrated. The crude product (0.214 g) was chromatographed (SiO2 25 g, eluted with 3:1 hexane:EtOAc) to give tert-butyl 6-(2-azidoethyl)-1,4,5, 6-tetrahydroazepino[4,5-b]indole-3(2H)-carboxylate (0.184 g) in 94% yield. 1H NMR (300 MHz, CDCl3) δ 1.51, 2.99-3.10, 3.60, 3.66-3.84, 4.26, 7.14, 7.21, 7.27, 7.51; MS (ESI+) for Cl9H25N5O2 m/z 356.2 (M+H)+.

Workup

  1. washwashed with water (2×15 mL)
  2. extractionThe aqueous layers were back extracted with EtOAc (25 mL)
  3. washThe combined organic layers were washed with brine (10 mL)
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude product (0.214 g) was chromatographed
  8. wash(SiO2 25 g, eluted with 3:1 hexane:EtOAc)

Sources & evidence

ORD record
ord-b35b62400331493ab5752f39d69aa1e7
Source dataset
uspto-grants-2003_07
Patent number
US06586421B2

Reaction notes

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