8-Bromodibenzo[B,E]oxepin-11(6H)-one → (Z)-3-(8-Bromo-6,11-dihydrodibenz[b,e]oxepin-11-ylidene)-N,N-dimethylpropylamine

HRID 1650229Notes

Reaction equation

HRID 1650229 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:49]=[CH:48][C:37]2[C:38](=O)[C:39]3[CH:46]=[CH:45][CH:44]=[CH:43][C:40]=3[O:41][CH2:42][C:36]=2[CH:35]=1>CCCCCC.O1CCCC1>[Br:33][C:34]1[CH:49]=[CH:48][C:37]2/[C:38](=[CH:7]/[CH2:6][CH2:5][N:4]([CH3:27])[CH3:3])/[C:39]3[CH:46]=[CH:45][CH:44]=[CH:43][C:40]=3[O:41][CH2:42][C:36]=2[CH:35]=1

Participants

6

Reactant 3

HCID 200859148-Bromodibenzo[B,E]oxepin-11(6H)-oneHCID 23651404(3-(Dimethylamino)propyl)triphenylphosphonium bromide hydrobromideHCID 178418339Butyllithium

Product 1

HCID 86743423(Z)-3-(8-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 (24.5 g, 48 mmole), 96 mmole of n-butyl lithium in hexane, and 8-bromo-6,11-dihydrodibenz[b,e]oxepin-11-one (10 g, 34.6 mmole) were reacted in 580 mL dry tetrahydrofuran by the procedure of Example I, step b. This provided an E/Z (1:3.5) isomeric mixture of bromoamines. Recrystallization of the mixture from diethyl ether gave 0.17 g of Z-isomer and 1.8 g of an E/Z (1:4) (assayed by HPLC on C18) isomeric mixture which was used in the next step without further purification. pmr (Z-isomer) (CDCl3) δ: 7.38-7.44 (m, 2H, H7 and H9); 7.13-7.18 (m, 3H, aromatic H); 6.84-6.93 (m, 2H, H2 and H4); 5.70 (t, 1H, CH=); 5.15 (br s, 2H, ArCH2O); 2.55 (q, 2H, CH2); 2.43 (t, 2H, NCH2 ); 2.22 (s, 6H, NMe2).

Workup

  1. customThis provided
  2. customRecrystallization of the mixture from diethyl ether
  3. customgave 0.17 g of Z-isomer and 1.8 g of an E/Z (1:4) (assayed by HPLC on C18) isomeric mixture which
  4. customwas used in the next step without further purification

Sources & evidence

ORD record
ord-e21c9457b41e4f74bfc3aaa5d65396dc
Source dataset
uspto-grants-1990_05
Patent number
US04923892

Reaction notes

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