Nitromethane → HCID 22720618, compound

HRID 1582458Notes

Reaction equation

HRID 1582458 reaction equation
[CH:1]([C:3]1[C:11]2[CH:10]=[CH:9][CH:8]=[CH:7][C:6]=2[N:5]2[CH2:12][CH2:13][N:14]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:15][CH2:16][C:4]=12)=O.C([O-])(=O)C.[NH4+].[N+:29]([CH3:32])([O-:31])=[O:30]>O>[N+:29](/[CH:32]=[CH:1]/[C:3]1[C:11]2[CH:10]=[CH:9][CH:8]=[CH:7][C:6]=2[N:5]2[CH2:12][CH2:13][N:14]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:15][CH2:16][C:4]=12)([O-:31])=[O:30]

Participants

5

Reactant 3

HCID 6375NitromethaneHCID 517165Ammonium AcetateHCID 22720322HCID 22720322, compound

Product 1

HCID 22720618HCID 22720618, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A solution of tert-butyl 11-formyl-1,2,4,5-tetrahydro-3H-[1,4]diazepino[1,7-a]indole-3-carboxylate (314 gm, 1.0 mmol) in nitromethane (1 mL) is treated with ammonium acetate (23 mg, 0.3 mmol) and heated to reflux. After 18 hrs, the resulting dark brown solution is cooled to rt, diluted with water (15 mL), and extracted twice with dichloromethane (20 mL). The combined organics are washed with brine (15 mL), dried over MgSO4, filtered, and concentrated to give a crude solid. This material is purified by LC (230-400 silica gel) eluting with 10:40:50 ethyl acetate/dichloromethane/heptane to afford 240 mg of tert-butyl 11-[(E)-2-nitroethenyl]-1,2,4,5-tetrahydro-3H-[1,4]diazepino[1,7-a]indole-3-carboxylate as a bright yellow solid, mp 227-230° C. IR (drift) 1692, 1621, 1493, 1472, 1419, 1323, 1310, 1302, 1291, 1277, 1259, 1248, 1198, 1164, 751 cm−1; MS (EI) m/z 357 (M+).

Workup

  1. temperatureheated to reflux
  2. extractionextracted twice with dichloromethane (20 mL)
  3. washThe combined organics are washed with brine (15 mL)
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customto give a crude solid
  8. customThis material is purified by LC (230-400 silica gel)
  9. washeluting with 10:40:50 ethyl acetate/dichloromethane/heptane

Sources & evidence

ORD record
ord-d2ea30a3c68d46e1b43a456021470def
Source dataset
uspto-grants-2004_05
Patent number
US06734301B2

Reaction notes

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