Propargyl bromide → 7-Nitro-3-prop-2-ynyl-2,3,4,5-tetrahydro-1H-benzo[d]azepine

HRID 1687125Notes

Reaction equation

HRID 1687125 reaction equation
[N+]([O-])(O)=O.[N+:5]([C:8]1[CH:18]=[CH:17][C:11]2[CH2:12][CH2:13][NH:14][CH2:15][CH2:16][C:10]=2[CH:9]=1)([O-:7])=[O:6].C([O-])([O-])=O.[Cs+].[Cs+].[CH2:25](Br)[C:26]#[CH:27]>CC(C)=O>[N+:5]([C:8]1[CH:18]=[CH:17][C:11]2[CH2:12][CH2:13][N:14]([CH2:27][C:26]#[CH:25])[CH2:15][CH2:16][C:10]=2[CH:9]=1)([O-:7])=[O:6]

Participants

5

Reactant 3

HCID 7842Propargyl bromideHCID 10796Cesium carbonateHCID 855770687-Nitro-2,3,4,5-tetrahydro-1H-benzo[d]azepine nitrate

Product 1

HCID 866338797-Nitro-3-prop-2-ynyl-2,3,4,5-tetrahydro-1H-benzo[d]azepineYield 83.3%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

7-Nitro-2,3,4,5-tetrahydro-1H-benzo[d]azepine nitric acid salt (1.0 g, 3.94 mmol) was dissolved in acetone (100 mL) followed by addition of Cs2CO3 (3.84 g, 11.82 mmol, 3.0 eq) and propargyl bromide (80% in toluene) (463 μL, 4.33 mmol, 1.1 eq). The reaction was stirred at room temperature for 24 hours. The solution was then concentrated under reduced pressure and the residue was taken up in CH2Cl2 (100 mL) and washed with water (100 mL). The organic layer was dried (sodium sulfate), filtered, and concentrated under reduced pressure. Purification by silica gel chromatography using a gradient of 0-10% MeOH/CH2Cl2 as the eluting solvent to obtain 7-nitro-3-prop-2-ynyl-2,3,4,5-tetrahydro-1H-benzo[d]azepine as a yellow solid (756 mg, 83%). m.p.=122-125° C.; LCMS (m/e) 231 (M+1); 1H-NMR (CDCl3, 400 MHz) δ 8.05-7.98 (m, 2H), 7.30-7.23 (m, 1H), 3.49-3.43 (m, 2H), 3.13-3.02 (m, 4H), 2.84-2.71 (m, 4H), 2.26-2.22 (m, 1H).

Workup

  1. concentrationThe solution was then concentrated under reduced pressure
  2. washwashed with water (100 mL)
  3. dry with materialThe organic layer was dried (sodium sulfate)
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. customPurification by silica gel chromatography

Sources & evidence

ORD record
ord-c8c1403b6a204667b4bfd7609ee3395b
Source dataset
uspto-grants-2012_04
Patent number
US08148391B2

Reaction notes

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