Acetic Acid → N,N-dimethyl-4-(5-nitro-1H-indol-3-yl)cyclohex-3-enamine

HRID 552953Notes

Reaction equation

HRID 552953 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]2[C:10](=[CH:11][CH:12]=1)[NH:9][CH:8]=[C:7]2[C:13]1[CH2:18][CH2:17][C:16](=O)[CH2:15][CH:14]=1)([O-:3])=[O:2].Cl.[CH3:21][NH:22][CH3:23].CC(O)=O.[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+]>ClCCCl.[OH-].[Na+]>[CH3:21][N:22]([CH3:23])[CH:16]1[CH2:17][CH2:18][C:13]([C:7]2[C:6]3[C:10](=[CH:11][CH:12]=[C:4]([N+:1]([O-:3])=[O:2])[CH:5]=3)[NH:9][CH:8]=2)=[CH:14][CH2:15]1

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 10473Dimethylamine, hydrochlorideHCID 5049666Sodium triacetoxyborohydrideHCID 573845384-(5-nitro-1H-indol-3-yl)cyclohex-3-en-1-one

Product 1

HCID 44430852N,N-dimethyl-4-(5-nitro-1H-indol-3-yl)cyclohex-3-enamineYield 66%

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolventHCID 14798Sodium HydroxideSolvent

Procedure

A solution of compound 79 (1.0 g, 3.902 mmol) in dry 1,2-dichloroethane (10 mL) was treated with N,N-dimethyl amine hydrochloride (0.31 g, 3.902 mmol), AcOH (0.22 mL, 3.902 mmol), NaBH(OAc)3 (1.24 g, 5.853 mmol) at room temperature and the resulting mixture was stirred for overnight (14 h). The reaction was diluted with 1 N NaOH (30 mL) and product was extracted into ethyl acetate (2 50 mL). The combined ethyl acetate layer was washed with brine (20 mL) and dried (Na2SO4). Solvent was evaporated and crude was purified by column chromatography (2 M NH3 in methanol: CH2Cl2, 1:9) to obtain compound 112 (0.73 g, 66%) as a brown solid. mp 234-236° C.; 1H NMR (DMSO-d6) δ 1.43-1.57 (m, 1H), 1.98-2.06 (m, 1H), 2.12-2.23 (m, 7H), 2.39-2.62 (m, 4H), 6.15 (t, 1H, J=1.5 Hz), 7.54 (d, 1H, J=9.0 Hz), 7.62 (s, 1H), 8.00 (dd, 1H, J=2.1, 9.0 Hz), 8.67 (d, 1H, J=2.1 Hz), 11.82 (s, 1H); ESI-MS m/z (%): 286 (MH+, 100).

Workup

  1. extractionwas extracted into ethyl acetate (2 50 mL)
  2. washThe combined ethyl acetate layer was washed with brine (20 mL)
  3. dry with materialdried (Na2SO4)
  4. customSolvent was evaporated
  5. customcrude was purified by column chromatography (2 M NH3 in methanol: CH2Cl2, 1:9)

Sources & evidence

ORD record
ord-3fd6d09310924eeb9e04f2fdeeaac966
Source dataset
uspto-grants-2011_05
Patent number
US07951940B2

Reaction notes

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