9-Bromo-6,11-dihydro-11-oxodibenz[b,e]oxepin → (Z)-3-(9-Bromo-6,11-dihydrodibenz[b,e]oxepin-11-ylidene)-N,N-dimethylpropylamine

HRID 2351121Notes

Reaction equation

HRID 2351121 reaction equation
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:35]=[CH:36][C:37]2[CH2:43][O:42][C:41]3[CH:44]=[CH:45][CH:46]=[CH:47][C:40]=3[C:39](=O)[C:38]=2[CH:49]=1>CCCCCC.O1CCCC1>[Br:33][C:34]1[CH:35]=[CH:36][C:37]2[CH2:43][O:42][C:41]3[CH:44]=[CH:45][CH:46]=[CH:47][C:40]=3/[C:39](=[CH:7]\[CH2:6][CH2:5][N:4]([CH3:27])[CH3:3])/[C:38]=2[CH:49]=1

Participants

6

Reactant 3

HCID 129291399-Bromo-6,11-dihydro-11-oxodibenz[b,e]oxepinHCID 23651404(3-(Dimethylamino)propyl)triphenylphosphonium bromide hydrobromideHCID 178418339Butyllithium

Product 1

HCID 23053922(Z)-3-(9-Bromo-6,11-dihydrodibenz[b,e]oxepin-11-ylidene)-N,N-dimethylpropylamine

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

Anhydrous 3-(dimethylamino)propyltriphenylphosphonium bromide hydrobromide (31 g., 60.9 mmole), 122 mmole of n-butyl lithium in hexane, and 9-bromo-6,11-dihydrodibenz[b,e]oxepin-11-one (12.7 g., 43.8 mmole) were reacted in 750 mL dry tetrahydrofuran by the procedure of Example I, Step b. This provided an E/Z (1:6) isomeric mixture of bromoamines. Recrystallization of the mixture from ethyl acetate/methanol gave 1.2 g. of pure Z-isomer as its hydrochloride salt, melting range 91°-100° C. and 2.16 g. of an E/Z (1:4) isomeric mixture which was used in the next step without further purification. pmr (Z-isomer) (CDCl3) δ: 6.94-7.46 (m, 7H, aromatic), 5.64 (t, J=8.0 Hz, 1H, CH=), 5.15 (br s, 2H, CH2O), 3.07 (m, 4H, NCH2CH2), 2.75 (s, 6H, NMe2).

Workup

  1. customThis provided
  2. customRecrystallization of the mixture from ethyl acetate/methanol
  3. customgave 1.2 g
  4. customof an E/Z (1:4) isomeric mixture which was used in the next step without further purification

Sources & evidence

ORD record
ord-d91178887b6746da932540a4613f6145
Source dataset
uspto-grants-1989_10
Patent number
US04871865

Reaction notes

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