4-(2-Propyn-1-yl)morpholine → 5-(Morpholin-4-yl)pent-3-yn-2-one

HRID 62386

反応式

HRID 62386 の反応式
CC#N.C(=O)=O.[CH2:7]([N:10]1[CH2:15][CH2:14][O:13][CH2:12][CH2:11]1)[C:8]#[CH:9].C([Mg]Cl)(C)C.CON(C)[C:24](=[O:26])[CH3:25]>C1COCC1>[N:10]1([CH2:7][C:8]#[C:9][C:24](=[O:26])[CH3:25])[CH2:15][CH2:14][O:13][CH2:12][CH2:11]1

参加物

6

反応物 4

HCID 4129414-(2-Propyn-1-yl)morpholineHCID 537505N-Methoxy-N-methylacetamideHCID 86587134Acetonitrile dry iceHCID 178418918HCID 178418918、化合物

生成物 1

HCID 674677495-(Morpholin-4-yl)pent-3-yn-2-one収率 71.1%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒3 回

実験手順

To a cooled (−40° C., CH3CN/CO2) solution of 4-(2-propyn-1-yl)morpholine (2.2 g, 17.58 mmol) in THF (5 mL) was added dropwise via. syringe under N2 a solution of 2 M isopropylmagnesium chloride in THF (10 mL, 20.00 mmol). The reaction was stirred for 1 hr then a solution of N-methoxy-N-methylacetamide (2.2 mL, 20.69 mmol) in THF (5 mL) was added in one portion. The reaction was stirred for 2 hr (allowed to slowly warm to RT), quenched with aq. NH4Cl, extracted with EtOAc, washed with brine, dried (Na2SO4), filtered and evaporated to dryness under vacuum. The remaining was purified by silica gel chromatography (Analogix, SF25-60 g, 0 to 80% EtOAc in hexanes). The pure fractions were combined and evaporated to dryness to give the product 5-(4-morpholinyl)-3-pentyn-2-one (2.09 g, 12.50 mmol, 71.1% yield) as a yellow oil. 1H NMR (400 MHz, DMSO-d6) δ 3.62-3.57 (m, 4H), 3.56 (s, 2H), 2.49-2.43 (m, 4H), 2.34 (s, 3H). MS(ES)+ m/e 168.0 [M+H]+.

後処理

  1. additionwas added dropwise via
  2. stirringThe reaction was stirred for 2 hr (
  3. customquenched with aq. NH4Cl
  4. extractionextracted with EtOAc
  5. washwashed with brine
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. customevaporated to dryness under vacuum
  9. customThe remaining was purified by silica gel chromatography (Analogix
  10. customevaporated to dryness

出典と根拠

ORDレコード
ord-b27e0939465846849ade5c6635761deb
出典データセット
uspto-grants-2016_09
特許番号
US09446041B2

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