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Ammonium Chloride → cis-3-Benzyl-6-bromo-8-methyl-1,2,3,4,4a,9a-hexahydro-3-aza-fluoren-9-one

HRID 1714141
Notes
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Reaction equation

HRID 1714141 reaction equation
[CH2:1]([N:8]1[CH2:13][CH2:12][CH:11]([C:14]([O:16]C)=O)[CH:10]([C:18]2[CH:23]=[C:22]([CH3:24])[CH:21]=[C:20]([Br:25])[CH:19]=2)[CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[NH4+].[Cl-]>O>[CH2:1]([N:8]1[CH2:9][C@H:10]2[C@H:11]([C:14](=[O:16])[C:23]3[C:18]2=[CH:19][C:20]([Br:25])=[CH:21][C:22]=3[CH3:24])[CH2:12][CH2:13]1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

4

Reactant 2

HCID 25517Ammonium ChlorideHCID 68501586Methyl 1-benzyl-3-(3-bromo5-methyl-phenyl)piperidine-4-carboxylate

Product 1

HCID 16117545cis-3-Benzyl-6-bromo-8-methyl-1,2,3,4,4a,9a-hexahydro-3-aza-fluoren-9-oneYield 6.9%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
180 °C

Procedure

A mixture of methyl 1-benzyl-3-(3-bromo-5-methyl-phenyl)piperidine-4-carboxylate (12.2 g, 30.3 mmol) from step B and polyphosphoric acid (124 g) was heated at 180° C. for 3 h then cooled to 0.20° C. To the reaction mixture H2O and saturated NH4Cl aqueous solution were added, successively then extracted with EtOAc. The combined organic solution was dried over MgSO4, filtered and concentrated in vacuo. The residue was chromatographed in silica gel column (Hex/EtOAc 9/1) to obtain the title compound (760 mg, 2.1 mmol): MS (ES) 370.1 (M+H).

Workup

  1. temperaturethen cooled to 0.20° C
  2. extractionsuccessively then extracted with EtOAc
  3. dry with materialThe combined organic solution was dried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe residue was chromatographed in silica gel column (Hex/EtOAc 9/1)

Sources & evidence

ORD record
ord-a2274898c54944458dc73cea78f94952
Source dataset
uspto-grants-2010_09
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US07795436B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes