Triethylamine → 7-Nitro-1,2,4,5-tetrahydro-benzo[d]azepin-3-carboxylic acid dimethylamide

HRID 1040823Notes

Reaction equation

HRID 1040823 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].[CH2:19]([N:21]([CH2:24]C)[CH2:22]C)C.C(Cl)(=[O:28])N>C(Cl)Cl>[CH3:19][N:21]([CH3:24])[C:22]([N:14]1[CH2:15][CH2:16][C:10]2[CH:9]=[C:8]([N+:5]([O-:7])=[O:6])[CH:18]=[CH:17][C:11]=2[CH2:12][CH2:13]1)=[O:28]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 68048Carbamic chlorideHCID 855770687-Nitro-2,3,4,5-tetrahydro-1H-benzo[d]azepine nitrate

Product 1

HCID 672639377-Nitro-1,2,4,5-tetrahydro-benzo[d]azepin-3-carboxylic acid dimethylamideYield 85%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

7-Nitro-2,3,4,5-tetrahydro-1H-benzo[d]azepine nitric acid salt (100 mg, 0.394 mmol) was dissolved CH2Cl2 and triethylamine (119 mg, 166 μL, 1.182 mmol, 3.0 eq) followed by carbamoyl chloride (46.4 mg, 39.7 μL, 0.433 mmol, 1.1 eq) were added. The reaction was stirred at room temperature for 4 hours and then concentrated under reduced pressure. Purification by silica gel chromatography using a gradient of 0-5% MeOH/CH2Cl2 as the eluting solvent to obtain 7-nitro-1,2,4,5-tetrahydro-benzo[d]azepin-3-carboxylic acid dimethylamide as a light orange oil (88 mg, 85%). LCMS (m/e) 264 (M+1); 1H-NMR (CDCl3, 400 MHz) δ 8.01-7.95 (m, 2H), 7.26 (d, 1H, J=9.3 Hz), 3.45-3.39 (m, 4H), 3.11-3.04 (m, 4H), 2.84 (s, 3H), 2.83 (s, 3H).

Workup

  1. additionwere added
  2. concentrationconcentrated under reduced pressure
  3. customPurification by silica gel chromatography

Sources & evidence

ORD record
ord-3e4dfd148853407099cc58d3259da74c
Source dataset
uspto-grants-2013_10
Patent number
US08552186B2

Reaction notes

Loading…