Methanol → Diphenyl(pyrrolidin-3-yl)acetonitrile

HRID 2371879ノート

反応式

HRID 2371879 の反応式
[C:1]([C:3]([CH:16]1[CH2:20][CH2:19][N:18](S(C2C=CC(C)=CC=2)(=O)=O)[CH2:17]1)([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)#[N:2].C1(O)C=CC=CC=1.[OH-].[Na+].CO>Br.O.CCCCCC.C1(C)C=CC=CC=1>[C:1]([C:3]([CH:16]1[CH2:20][CH2:19][NH:18][CH2:17]1)([C:10]1[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=1)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)#[N:2]

参加物

8

反応物 4

HCID 887MethanolHCID 996PhenolHCID 14798Sodium HydroxideHCID 22340524{1-[(4-Methylphenyl)sulfonyl]-3-pyrrolidinyl}(diphenyl)acetonitrile

生成物 1

HCID 13633741Diphenyl(pyrrolidin-3-yl)acetonitrile

試薬・触媒・溶媒 3

HCID 260Hydrogen Bromide溶媒HCID 962Water溶媒HCID 21889329Toluene hexane溶媒

反応条件

温度
0 °C

実験手順

A solution of 3-(R,S)-(1-cyano-1,1-diphenylmethyl)-1-tosylpyrrolidine (21 g--see Preparation 6(A)) and phenol (21 g) in 48% aqueous hydrobromic acid (240 ml) was heated under reflux for 2 hours. The mixture was cooled to 0° C. in an ice bath and basified (pH 12) by the slow addition of 50% aqueous sodium hydroxide (280 ml). Methanol (10 ml) was added and the mixture was stirred for 15 minutes then diluted with water (300 ml). The mixture was extracted with dichloromethane (3×200 ml), the combined extracts were dried (MgSO4) and concentrated in vacuo to give an oil. The oil was dissolved in 1:1 hexane/toluene (500 ml) and washed with 0.5M hydrochloric acid (3×500 ml). The aqueous extracts, together with some oil which separated during the extraction, were basified (pH 12) by the addition of aqueous sodium hydroxide (12 g in 20 ml water) and the mixture was extracted with dichloromethane (3×150 ml). The combined dichloromethane extracts were dried (MgSO4) and concentrated in vacuo to give an oil which was purified by column chromatography on silica eluting with dichloromethane containing methanol (0% up to 10%). The product-containing fractions were combined and concentrated in vacuo to give the title compound as a oil, yield 10 g.

後処理

  1. temperatureunder reflux for 2 hours
  2. extractionThe mixture was extracted with dichloromethane (3×200 ml)
  3. dry with materialthe combined extracts were dried (MgSO4)
  4. concentrationconcentrated in vacuo
  5. customto give an oil
  6. washwashed with 0.5M hydrochloric acid (3×500 ml)
  7. customThe aqueous extracts, together with some oil which separated during the extraction
  8. additionby the addition of aqueous sodium hydroxide (12 g in 20 ml water)
  9. extractionthe mixture was extracted with dichloromethane (3×150 ml)
  10. dry with materialThe combined dichloromethane extracts were dried (MgSO4)
  11. concentrationconcentrated in vacuo
  12. customto give an oil which
  13. customwas purified by column chromatography on silica eluting with dichloromethane
  14. additioncontaining methanol (0% up to 10%)
  15. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-14a5ab1a40554df485e5b5c6ff140b27
出典データセット
uspto-grants-1992_03
特許番号
US05096890

反応ノート

読み込み中…