Propargyl alcohol → 3-Quinolin-3-ylprop-2-yn-1-ol

HRID 1370010

反応式

HRID 1370010 の反応式
Br[C:2]1[CH:3]=[N:4][C:5]2[C:10]([CH:11]=1)=[CH:9][CH:8]=[CH:7][CH:6]=2.[CH2:12]([OH:15])[C:13]#[CH:14].C(N(CC)CC)C>C([O-])(O)=O.[Na+].[Cu]I>[N:4]1[C:5]2[C:10](=[CH:9][CH:8]=[CH:7][CH:6]=2)[CH:11]=[C:2]([C:14]#[C:13][CH2:12][OH:15])[CH:3]=1

参加物

6

反応物 3

HCID 7859Propargyl alcoholHCID 8471Triethylamine2 回HCID 214133-Bromoquinoline

生成物 1

HCID 6501423-Quinolin-3-ylprop-2-yn-1-ol収率 88.3%

試薬・触媒・溶媒 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 516892Sodium Bicarbonate溶媒

実験手順

To a dry 2-L three-necked flask previously purged with nitrogen was charged 3-bromoquinoline (118.77 g, 570 mmol), propargyl alcohol (71.9 g, 1.28 mol, 2.25 equiv), triethylamine (1500 mL), copper(I) iodide (3.62, 19 mmol, 0.033 equiv) and dichlorobis(triphenyl-phosphine) palladium(II) (6.67 g, 9.5 mmol). The mixture which resulted was mechanically stirred and heated to reflux for 3 hours. Upon cooling the triethylamine solution was mechanically stirred and heated to reflux for 3 hours. Upon cooling, the triethylamine solution was filtered and washed with triethylamine (300 mL). The filtrate was then concentrated under reduced pressure to provide solids which were suspended in 5% aq. NaHCO3 (600 mL) and extracted with ethyl acetate (1×600 mL). The solids which were left after filtration were treated in the same manner. The combined ethyl acetate extracts were stirred with silica gel (15 g) and decolorizing carbon (3 g) before being filtered through a bed of celite. The filtrate was concentrated under reduced pressure to provide a tan colored solid which was vacuum oven dried at 45° C. overnight. The 3-(3-quinolyl)-2-propyn-1-ol was isolated in 92.14 g (88.3% yield). MS(CI): (M+H)+ at 184; 1H NMR (300 MHz CDCl3) δ4.56 (s, 2H), 4.70 (s, broad, 1H), 7.57 (m, 1H), 7.70 (m, 1H), 7.77 (d, 1H), 8.10 (d, 1H), 8.10 (s, 1H), 9.05 (s, 1H).

後処理

  1. customTo a dry 2-L three-necked flask previously purged with nitrogen
  2. customThe mixture which resulted
  3. temperatureheated
  4. temperatureto reflux for 3 hours
  5. stirringwas mechanically stirred
  6. temperatureheated
  7. temperatureto reflux for 3 hours
  8. temperatureUpon cooling
  9. filtrationthe triethylamine solution was filtered
  10. washwashed with triethylamine (300 mL)
  11. concentrationThe filtrate was then concentrated under reduced pressure
  12. customto provide solids which
  13. extractionextracted with ethyl acetate (1×600 mL)
  14. waitThe solids which were left
  15. filtrationafter filtration
  16. additionwere treated in the same manner
  17. stirringThe combined ethyl acetate extracts were stirred with silica gel (15 g)
  18. filtrationbefore being filtered through a bed of celite
  19. concentrationThe filtrate was concentrated under reduced pressure
  20. customto provide a tan colored solid which
  21. customdried at 45° C. overnight

出典と根拠

ORDレコード
ord-a463d10a1a0543899f2879ce00cf2124
出典データセット
uspto-grants-2003_06
特許番号
US06579986B2

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