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Formaldehyde → (Z)-3-(2-Bromo-6,11-dihydrodibenz[b,e]oxepin-11-ylidene)-N,N-dimethylpropylamine

HRID 2351116
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 2351116
Br.[Br-].[CH3:3][N:4]([CH3:27])[CH2:5][CH2:6][CH2:7][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C([Li])CCC.[Br:33][C:34]1[CH:49]=[CH:48][C:37]2[O:38][CH2:39][C:40]3[CH:47]=[CH:46][CH:45]=[CH:44][C:41]=3[C:42](=O)[C:36]=2[CH:35]=1.C=O>O1CCCC1.CCCCCC.CS(C)=O>[Br:33][C:34]1[CH:49]=[CH:48][C:37]2[O:38][CH2:39][C:40]3[CH:47]=[CH:46][CH:45]=[CH:44][C:41]=3/[C:42](=[CH:7]/[CH2:6][CH2:5][N:4]([CH3:27])[CH3:3])/[C:36]=2[CH:35]=1
KomponentenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

8

Edukt 4

HCID 712Formaldehyde2×HCID 129291312-Bromo-6H-dibenz[b,e]oxepin-11-oneHCID 23651404(3-(Dimethylamino)propyl)triphenylphosphonium bromide hydrobromideHCID 178418339Butyllithium

Produkt 1

HCID 67782130(Z)-3-(2-Bromo-6,11-dihydrodibenz[b,e]oxepin-11-ylidene)-N,N-dimethylpropylamine

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 679Dimethyl SulfoxideLösungsmittel3×HCID 8028TetrahydrofuranLösungsmittel2×HCID 8058HexaneLösungsmittel

Versuchsvorschrift

Anhydrous 3-(dimethylamino)propyltriphenylphosphonium bromide hydrobromide (39.4 g., 0.08 mole) was suspended in 450 mL of dry tetrahydrofuran and 100 mL of a solution of n-butyl lithium in hexane (1.6M) was added dropwise at 0° C. under a nitrogen atmosphere during a 30 minute period. After an additional 10 minutes, 2-bromo-6,11-dihydrodibenz[b,e]oxepin-11-one (16.8 g., 0.06 mole) in 150 mL dry tetrahydrofuran was added slowly to the deep red solution and the reaction mixture was then refluxed for 18 hours. The reaction mixture was poured onto ice-water, and the mixture was extracted with diethyl ether. The ether layer was concentrated under reduced pressure and the residue was suspended in water and then acidified with 6N hydrochloric acid. The acidic aqueous layer was washed with hexanes and then was concentrated to give a gummy residue. The residue was crystallized from ethyl acetate/methanol to provide 5.3 g. of pure Z-isomer as its hydrochloride salt, m.p. 201°-204° C. The mother liquor was chromatographed on a silica gel column (Waters Associates-Prep. 500) with ethyl acetate/methanol (8:2) to give an additional 2.55 g. of pure Z-isomer as the hydrochloride salt and 2.79 g. of E-isomer as its hydrochloride salt, m.p. 230°-233° C. pmr (Z-isomer) (DMSO/d6) δ: 7.25-7.44 (m, 6H, aromatic), 6.81 (degenerate d, J=9.1 Hz, 1H, H4), 5.72 (t, J=7.1 Hz, 1H, CH=), 5.22 (s, 2H, CH2O), 3.18 (m, 2H, NCH2), 2.70 (m, 2H, CH2), 2.66 (s, 6H, NMe2). pmr (E-isomer) (DMSO/d6) δ: 7.23-7.50 (m, 6H, aromatic), 6.70 (d, J=8.6 Hz, 1H, H4), 6.10 (t, J=7.2 Hz, 1H, CH=) 5.15 (br s, 2H, CH2O), 3.07 (m, 2H, NCH2), 2.65 (s, 6H, NMe2), 2.50 (m overlap with DMSO, 2H, CH2).

Aufarbeitung

  1. temperaturethe reaction mixture was then refluxed for 18 hours
  2. additionThe reaction mixture was poured onto ice-water
  3. extractionthe mixture was extracted with diethyl ether
  4. concentrationThe ether layer was concentrated under reduced pressure
  5. washThe acidic aqueous layer was washed with hexanes
  6. concentrationwas concentrated
  7. customto give a gummy residue
  8. customThe residue was crystallized from ethyl acetate/methanol
  9. customto provide 5.3 g
  10. customThe mother liquor was chromatographed on a silica gel column (Waters Associates-Prep. 500) with ethyl acetate/methanol (8:2)
  11. customto give an additional 2.55 g

Quellen und Nachweise

ORD-Eintrag
ord-61089abff6df485792ee666b4adc3ea5
Quelldatensatz
uspto-grants-1989_10
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US04871865

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