Water → (3E)-3-Dibenz(b,e)oxepin-11(6H)-ylidene-N-methyl-1-propanamine

HRID 1894777

反応式

HRID 1894777 の反応式
Br.[Br-].[CH3:3][NH:4][CH2:5][CH2:6][CH2:7][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C([Li])CCC.[CH:32]1[C:42]2[C:41](=O)[C:40]3[CH:44]=[CH:45][CH:46]=[CH:47][C:39]=3[CH2:38][O:37][C:36]=2[CH:35]=[CH:34][CH:33]=1.O>O1CCCC1.CCCCCCC>[CH3:3][NH:4][CH2:5][CH2:6]/[CH:7]=[C:41]1\[C:40]2[C:39]([CH2:38][O:37][C:36]3[C:42]\1=[CH:32][CH:33]=[CH:34][CH:35]=3)=[CH:47][CH:46]=[CH:45][CH:44]=2

参加物

7

反応物 4

HCID 962WaterHCID 78259Dibenz[b,e]oxepin-11(6H)-oneHCID 19897074[3-(Methylamino)propyl]triphenylphosphonium Bromide HydrobromideHCID 178418339Butyllithium

生成物 1

HCID 6433351(3E)-3-Dibenz(b,e)oxepin-11(6H)-ylidene-N-methyl-1-propanamine

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒HCID 8900Heptane溶媒

実験手順

Desmethyldoxepin is prepared according to the following method. Anhydrous 3-methylaminopropyltriphenylphosphonium bromide hydrobromide (1530 g) prepared as in U.S. Pat. No. 3,509,175, is suspended in 4.5 L dry tetrahydrofuran and 6.0 moles of butyl lithium in heptane is added during 1 hour. After an additional 30 minutes, 483 g of 6,11-dihydrodibenz[b,e]oxepin-11-one, is added to the deep red solution and the reaction is maintained at reflux for 10 hours. Water, 500 mL, is added at room temperature and the solvent is removed in vacuo. The crude residue is treated with 10% hydrochloric acid until acidic (pH 2) and then 1.5 L benzene is added. After stirring, the mixture separates into three phases (an insoluble hydrochloride salt product phase, an aqueous phase and an organic phase). The benzene layer is removed by decantation and the remaining mixture is rendered basic with 10% sodium hydroxide solution and is extracted with 3×1500 mL portions of benzene. The benzene extracts are washed, then dried with anhydrous sodium sulfate and concentrated in a vacuum leaving a solid residue of desmethyldoxepin.

後処理

  1. customDesmethyldoxepin is prepared
  2. temperaturethe reaction is maintained
  3. temperatureat reflux for 10 hours
  4. customthe solvent is removed in vacuo
  5. additionThe crude residue is treated with 10% hydrochloric acid until acidic (pH 2)
  6. addition1.5 L benzene is added
  7. customThe benzene layer is removed by decantation
  8. extractionis extracted with 3×1500 mL portions of benzene
  9. washThe benzene extracts are washed
  10. dry with materialdried with anhydrous sodium sulfate
  11. concentrationconcentrated in a vacuum

出典と根拠

ORDレコード
ord-2756eb3b3c4649669a91ac1e3f3d43f9
出典データセット
uspto-grants-2013_08
特許番号
US08513299B2

関連ノート

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