Trifluoroacetic acid → 5-Chloro-1'-[trans-3-(4-chlorophenyl)allyl]spiro[perhydro-azepine-3,3'-piperidine]

HRID 83980

Reaction equation

HRID 83980 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5](/[CH:8]=[CH:9]/[CH2:10][N:11]2[CH2:17][CH2:16][CH2:15]/[C:14](=[CH:18]/OC)/[CH2:13][CH2:12]2)=[CH:4][CH:3]=1.[ClH:21].ClC1C=C[C:26]([NH:29]N)=CC=1.F[C:32](F)(F)[C:33](O)=O.C([SiH](CC)CC)C.[OH-].[NH4+]>C(Cl)(Cl)Cl.ClCCl>[Cl:21][CH:33]1[CH2:32][CH2:26][NH:29][CH2:13][C:14]2([CH2:15][CH2:16][CH2:17][N:11]([CH2:10]/[CH:9]=[CH:8]/[C:5]3[CH:4]=[CH:3][C:2]([Cl:1])=[CH:7][CH:6]=3)[CH2:12]2)[CH2:18]1

Participants

8

Reactant 5

HCID 6422Trifluoroacetic acidHCID 12052TriethylsilaneHCID 14923Ammonium HydroxideHCID 71600Hydrazine, (4-chlorophenyl)-, hydrochloride (1:1)HCID 68924237[(e)-3-(4-Chloro-phenyl)-allyl]-4-[1-methoxy-meth-(z)-ylidene]-perhydro-azepine

Product 1

HCID 689278545-Chloro-1'-[trans-3-(4-chlorophenyl)allyl]spiro[perhydro-azepine-3,3'-piperidine]

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 6344DichloromethaneSolvent

Procedure

A mixture of -[(E)-3-(4-Chloro-phenyl)-allyl]-4-[1-methoxy-meth-(Z)-ylidene]-perhydro-azepine (0.6 g) and 4-chlorophenylhydrazine hydrochloride (0.41 g) in chloroform (20 ml) was treated with trifluoroacetic acid (2.1 ml) and heated at reflux under argon for 18 hours. The reaction mixture was cooled to room temperature, triethylsilane (3.1 ml) was added and the solution refluxed for 2 hours. The reaction mixture was cooled to room temperature, diluted with dichloromethane, neutralised with 30% aqueous ammonium hydroxide, washed with brine, dried (sodium sulphate) and concentrated. The dark residue was purified by silica gel chromatography (cyclohexane:ethyl acetate 1:9) to afford 5-chloro-1′-[trans-3-(4-chlorophenyl)allyl]spiro[perhydro-azepine-3,3′-piperidine] (529 mg). MS (ES+) 387/389 (M+H′).

Workup

  1. temperatureheated
  2. temperatureat reflux under argon for 18 hours
  3. temperaturethe solution refluxed for 2 hours
  4. temperatureThe reaction mixture was cooled to room temperature
  5. washwashed with brine
  6. dry with materialdried (sodium sulphate)
  7. concentrationconcentrated
  8. customThe dark residue was purified by silica gel chromatography (cyclohexane:ethyl acetate 1:9)

Sources & evidence

ORD record
ord-5ea29847c5bb4082a666dc9a4d12ab29
Source dataset
uspto-grants-2014_09
Patent number
US08846907B2

Linked notes

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