Triethylamine → 6-(1-Dodecynyl)-2-pyridinecarboxaldehyde

HRID 235160

反応式

HRID 235160 の反応式
Br[C:2]1[N:7]=[C:6]([CH:8]=[O:9])[CH:5]=[CH:4][CH:3]=1.[CH:10]#[C:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH3:21].C(N(CC)CC)C>O1CCCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[C:10]([C:2]1[N:7]=[C:6]([CH:8]=[O:9])[CH:5]=[CH:4][CH:3]=1)#[C:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH3:21]

参加物

8

反応物 3

HCID 8471Triethylamine2 回HCID 698211-Dodecyne3 回HCID 27570096-Bromopyridine-2-carbaldehyde

生成物 1

HCID 183731096-(1-Dodecynyl)-2-pyridinecarboxaldehyde収率 29%

試薬・触媒・溶媒 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒2 回HCID 6102075Dichlorobis(triphenylphosphine)palladium触媒HCID 178418476HCID 178418476、化合物触媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
40 °C

実験手順

To a solution of 6-bromo-2-pyridinecarboxaldehyde (3.0 g) in tetrahydrofuran (10 ml), was added sequentially bis(triphenylphosphine)palladium(II) chloride (0.178 g), copper(I)iodide (0.024 g), 1-dodecyne (3.25 ml), and triethylamine (2.12 ml). The solution was stirred at 40° C. overnight. The reaction mixture was cooled to room temperature, charged again with bis(triphenylphosphine)palladium (II) chloride (0.024 g), copper (I) iodide (0.024 g), and triethylamine (2.12 ml), and 1-dodecyne (3.25 ml), and tetrahydrofuran (5.0 ml), and heated at 40° C. for 5 hrs. The reaction mixture was again cooled and recharged as above, and heated at 40° C. for 24 hrs. The cooled mixture was concentrated, taken up in ethyl acetate (100 ml), washed with water and saturated sodium chloride solution, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was taken up in ethyl acetate (100 ml) and filtered. The filtrate was combined with material from a similar reaction run 1.43 g of the carboxaldehyde and proportionate amounts of the catalysts, 1-dodecyne, and solvent. The filtrate was concentrated. The residue was purified by flash chromatography using 1.5% ethyl acetate/hexane followed by 1% ethyl acetate/hexane as eluents. The appropriate fractions were collected and concentrated to yield 2.24 g (29%) of product, as an oil.

後処理

  1. temperatureThe reaction mixture was cooled to room temperature
  2. temperatureheated at 40° C. for 5 hrs
  3. temperatureThe reaction mixture was again cooled
  4. temperatureheated at 40° C. for 24 hrs
  5. concentrationThe cooled mixture was concentrated
  6. washwashed with water and saturated sodium chloride solution
  7. dry with materialdried over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. concentrationthe filtrate was concentrated
  10. filtrationfiltered
  11. customThe filtrate was combined with material from a similar reaction
  12. concentrationThe filtrate was concentrated
  13. customThe residue was purified by flash chromatography
  14. customThe appropriate fractions were collected
  15. concentrationconcentrated

出典と根拠

ORDレコード
ord-8531f43721384aa69de8006ccfdf860e
出典データセット
uspto-grants-1997_01
特許番号
US05597838

関連ノート

読み込み中…