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

HRID 1875549Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1875549
[Cl:1][C:2]1[CH:20]=[CH:19][C:5]([CH:6]=[CH:7][CH2:8][N:9]2[CH2:14][CH2:13][C:12](=[CH:15]OC)[CH:11]([CH3:18])[CH2:10]2)=[CH:4][CH:3]=1.Cl.[Cl:22][C:23]1[CH:28]=[CH:27][C:26]([NH:29]N)=[CH:25][CH:24]=1.FC(F)(F)C(O)=O.C([SiH](CC)CC)C.[OH-].[NH4+]>C(Cl)(Cl)Cl.ClCCl>[Cl:22][C:23]1[CH:24]=[C:25]2[C:12]3([CH2:13][CH2:14][N:9]([CH2:8]/[CH:7]=[CH:6]/[C:5]4[CH:19]=[CH:20][C:2]([Cl:1])=[CH:3][CH:4]=4)[CH2:10][CH:11]3[CH3:18])[CH2:15][NH:29][C:26]2=[CH:27][CH:28]=1

Komponenten

8

Edukt 5

HCID 6422Trifluoroacetic acidHCID 12052TriethylsilaneHCID 14923Ammonium HydroxideHCID 71600Hydrazine, (4-chlorophenyl)-, hydrochloride (1:1)HCID 688000601-(4-Chlorocinnamyl)-4-[1-methoxy-methylidene]-3-methyl-piperidine

Produkt 1

HCID 687996445-Chloro-1'-[trans-3-(4-chlorophenyl)allyl]-3'-methyl-spiro[indoline-3,4'-piperidine]Ausbeute 98,2 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6212ChloroformLösungsmittelHCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

A mixture of 1-(4-chlorocinnamyl)-4-[1-methoxy-methylidene]-3-methyl-piperidine (1.25 g) and 4-chlorophenylhydrazine hydrochloride (0.85 g) in chloroform (43 ml) was treated with trifluoroacetic acid (4.3 ml) and heated at reflux under argon for 12 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 aqueous ammonium hydroxide, washed with brine, dried (sodium sulphate) and concentrated. The dark residue was purified by silica gel chromatography (cyclohexane:ethyl acetate 1:1+0.5% triethylamine) to afford 5-chloro-1′-[trans-3-(4-chlorophenyl)allyl]-3′-methyl-spiro[indoline-3,4′-piperidine] (1.63 g). 1H NMR (600 MHz, CDCl3) 0.69 (d, J=9 Hz, 3H), 1.89 (m, 2H), 2.0 (m, 3H), 2.86 (dd, 1H), 2.95 (m, 1H), 3.17 (d, J=7.2 Hz, 2H), 3.31 (d, J=12 Hz, 1H), 3.58 (d, J=12 Hz, 1H), 3.65 (m, 1H), 6.30 (dt, J=7.2, 18.0 Hz, 1H), 6.49 (d, J=8.0 Hz, 1H), 6.50 (d, J=7.0 Hz, 1H), 2H), 6.94 (d, J=0.9 Hz, 1H), 6.97 (dd, J=7.0, 0.9 Hz, 1H), 7.25-7.33 (m, 4H); MS (ES+) 387/389 (M+H+).

Aufarbeitung

  1. temperatureheated
  2. temperatureat reflux under argon for 12 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 1:1+0.5% triethylamine)

Quellen und Nachweise

ORD-Eintrag
ord-6f50f24f712044b782409f0875ea2e45
Quelldatensatz
uspto-grants-2012_11
Patentnummer
US08309567B2

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