Lithium diisopropylamide → (S)-5,11-Dihydro-5-(1-[4-methylphenylsulphonyl]-2-pyrrolidinylmethyl)dibenzo[b,e][1,4]thiazepine

HRID 1460489ノート

反応式

HRID 1460489 の反応式
C([N-]C(C)C)(C)C.[Li+].COC1C=CC(CCN2CCC[C@H]2C[N:23]2[C:29]3[CH:30]=[CH:31][CH:32]=[CH:33][C:28]=3[CH2:27][S:26][C:25]3[CH:34]=[CH:35][CH:36]=[CH:37][C:24]2=3)=CC=1.[CH3:40][C:41]1[CH:46]=[CH:45][C:44]([S:47]([N:50]2[CH2:54][CH2:53][CH2:52][C@H:51]2[CH2:55]OS(C2C=CC(C)=CC=2)(=O)=O)(=[O:49])=[O:48])=[CH:43][CH:42]=1>CCCCCC.COCCOC>[CH3:40][C:41]1[CH:42]=[CH:43][C:44]([S:47]([N:50]2[CH2:54][CH2:53][CH2:52][C@H:51]2[CH2:55][N:23]2[C:29]3[CH:30]=[CH:31][CH:32]=[CH:33][C:28]=3[CH2:27][S:26][C:25]3[CH:34]=[CH:35][CH:36]=[CH:37][C:24]2=3)(=[O:48])=[O:49])=[CH:45][CH:46]=1

参加物

6

反応物 3

HCID 2724682Lithium diisopropylamideHCID 9824029(S)-5,11-Dihydro-5-[1-(4-methoxyphenethyl)-2-pyrrolidinylmethyl]dibenzo[b,e][1,4]thiazepineHCID 10905672{(2S)-1-[(4-methylphenyl)sulfonyl]pyrrolidin-2-yl}methyl 4-methylbenzenesulfonate

生成物 1

HCID 22841645(S)-5,11-Dihydro-5-(1-[4-methylphenylsulphonyl]-2-pyrrolidinylmethyl)dibenzo[b,e][1,4]thiazepine収率 88.9%

試薬・触媒・溶媒 2

HCID 8058Hexane溶媒HCID 80711,2-Dimethoxyethane溶媒

実験手順

Lithium diisopropylamide (4.3 ml of a 1.5M solution in hexane) was added to a solution of 5,11-dihydrodibenzo[b,e][1,4]thiazepine (see Example 1 for source) (1.0 g) in DME (25 ml) and the mixture stirred at room temperature for 15 minutes, treated with (S)-1-(4-methylphenylsulphonyl)-2-(4-methylphenylsulphonyloxymethyl)pyrrolidine (3.9 g) (prepared by the method of P. Karrer and K. Ehrhardt, Helv. Chim. Acta, 34, 2202 (1951)), heated under reflux for 2.5 hours, allowed to cool to room temperature, quenched with 2M hydrochloric acid and extracted with ethyl acetate. The organic extract was washed with water, dried over sodium sulphate and evaporated under reduced pressure. The residue was purified by chromatography on silica gel, performing a gradient elution initially using hexane as eluant and changing to hexane/ethyl acetate (90:10). Appropriate fractions were combined and evaporated under reduced pressure to give the title compound as a colourless solid, (0.93 g, 44%), m.p. 88°-90° C., [α]589 25 -115° (c=0.62 in ethanol).

後処理

  1. customprepared by the method of P
  2. temperatureActa, 34, 2202 (1951)), heated
  3. temperatureunder reflux for 2.5 hours
  4. temperatureto cool to room temperature
  5. customquenched with 2M hydrochloric acid
  6. extractionextracted with ethyl acetate
  7. extractionThe organic extract
  8. washwas washed with water
  9. dry with materialdried over sodium sulphate
  10. customevaporated under reduced pressure
  11. customThe residue was purified by chromatography on silica gel
  12. washa gradient elution initially using hexane as eluant
  13. customevaporated under reduced pressure

出典と根拠

ORDレコード
ord-a5135c786e1445139372059a6deba598
出典データセット
uspto-grants-1991_12
特許番号
US05071844

反応ノート

読み込み中…