Water → 1-(3-Benzyloxy-4-nitrobenzyl)-1,2,4,5-tetrahydrobenzo[c]azepin-3-one

HRID 660567Notes

Reaction equation

HRID 660567 reaction equation
[CH2:1]([O:8][C:9]1[CH:10]=[C:11]([CH:25]=[CH:26][C:27]=1[N+:28]([O-:30])=[O:29])[CH2:12][CH:13]1[C:22]2[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=2)[CH2:16][CH2:15][C:14]1=[N:23]O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.P(Cl)(Cl)(Cl)(Cl)Cl.[OH2:37]>C(Cl)(Cl)Cl>[CH2:1]([O:8][C:9]1[CH:10]=[C:11]([CH:25]=[CH:26][C:27]=1[N+:28]([O-:30])=[O:29])[CH2:12][CH:13]1[C:22]2[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=2[CH2:16][CH2:15][C:14](=[O:37])[NH:23]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 962WaterHCID 24819Phosphorus pentachlorideHCID 866325751-(3-Benzyloxy-4-nitrobenzyl)-3,4-dihydro-1H-naphthalen-2-one Oxime

Product 1

HCID 688425281-(3-Benzyloxy-4-nitrobenzyl)-1,2,4,5-tetrahydrobenzo[c]azepin-3-one

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

A solution of 1-(3-benzyloxy-4-nitrobenzyl)-3,4-dihydro-1H-naphthalen-2-one oxime (600 mg, 1.49 mmol) in 10 mL CHCl3 is cooled to −50° C. PCl5 (310 mg, 1.49 mmol) is added portionwise over 10 minutes to maintain the temperature below −30° C. The suspension is stirred until it becomes a solution then is warmed to RT and stirred for 2 hours. Water is added and the solution is extracted with CH2Cl2. The organic layer is washed with water, 5% NaOH and brine then is dried over MgSO4. The solvent is removed under reduced pressure and the residue is purified by flash chromatography using a gradient of 14-100% EtOAc/hexane as eluent to give the title compound as a yellow solid. 1H NMR (CDCl3): 7.85-7.83 (d, J=8.59 Hz, 1H), 7.45-7.20 (m, 8H), 7.09-7.07 (d, J=7.58 Hz, 1H), 6.88-6.86 (dd, J=1.52 Hz, 8.34 Hz, 2 H), 5.80-5.79 (d, J=4.80 Hz, 1H), 5.22-5.14 (q, J=12.12, 2H), 4.74-4.69 (m, 1H), 3.37-3.32 (q, J=5.56 Hz, 1H), 3.19-3.08 (m, 2H), 3.04-2.97 (m, 1H), 2.81-2.65 (m, 2H). (M−1)−=401.

Workup

  1. temperatureto maintain the temperature below −30° C
  2. stirringstirred for 2 hours
  3. extractionthe solution is extracted with CH2Cl2
  4. washThe organic layer is washed with water, 5% NaOH and brine
  5. dry with materialthen is dried over MgSO4
  6. customThe solvent is removed under reduced pressure
  7. customthe residue is purified by flash chromatography

Sources & evidence

ORD record
ord-d992f94cf1134d3da173027173f7fd40
Source dataset
uspto-grants-2011_12
Patent number
US08084448B2

Reaction notes

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