Formic Acid → 4-Boc-3-(2-carboxy-ethyl)-morpholine

HRID 524579ノート

反応式

HRID 524579 の反応式
C(O)=O.C(N(CC)CC)C.[CH:11]([CH:13]1[CH2:18][O:17][CH2:16][CH2:15][N:14]1[C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])=O.[CH3:26][C:27]1(C)[O:34]C(=O)CC(=O)[O:28]1>[OH-].[Na+]>[C:22]([O:21][C:19]([N:14]1[CH2:15][CH2:16][O:17][CH2:18][CH:13]1[CH2:11][CH2:26][C:27]([OH:34])=[O:28])=[O:20])([CH3:25])([CH3:24])[CH3:23]

参加物

6

反応物 4

HCID 284Formic AcidHCID 8471TriethylamineHCID 162492,2-Dimethyl-1,3-dioxane-4,6-dioneHCID 22342783Tert-butyl 3-formylmorpholine-4-carboxylate

生成物 1

HCID 534250424-Boc-3-(2-carboxy-ethyl)-morpholine収率 40.3%

試薬・触媒・溶媒 1

HCID 14798Sodium Hydroxide溶媒

反応条件

温度
100 °C

実験手順

A mixture of formic acid (2.26 mL, 58.9 mmol) and triethylamine (3.36 mL, 24.11 mmol) was stirred for 5 minutes in an ice bath. To the mixture were added tert-butyl 3-formylmorpholine-4-carboxylate (0.47 g, 2.2 mmol) and Meldrum's acid (0.32 g, 2.2 mmol) in turn at 0° C. The reaction mixture was heated at 100° C. for 5 hours, and cooled down in an ice bath. To the resulting mixture was added aqueous NaOH solution (2 mol/L, 40 mL). The aqueous layer was extracted with EtOAc (50 mL×3) and the organic layer was discarded. To the aqueous layer was added EtOAc (80 mL), and the mixture was adjusted to pH 4-5 with HCl (1 mol/L) under stirring. The aqueous layer was extracted with EtOAc (80 mL). The organic layer was dried over anhydrous Na2SO4, then filtered and the filtrate was concentrated in vacuo to give the title compound as a white solid (0.23 g, 40%). The compound was characterized by the following spectroscopic data:

後処理

  1. temperaturecooled down in an ice bath
  2. extractionThe aqueous layer was extracted with EtOAc (50 mL×3)
  3. additionTo the aqueous layer was added EtOAc (80 mL)
  4. stirringunder stirring
  5. extractionThe aqueous layer was extracted with EtOAc (80 mL)
  6. dry with materialThe organic layer was dried over anhydrous Na2SO4
  7. filtrationfiltered
  8. concentrationthe filtrate was concentrated in vacuo

出典と根拠

ORDレコード
ord-5a06b252f6b54bf4ada29a6f44e92503
出典データセット
uspto-grants-2016_05
特許番号
US09340538B2

反応ノート

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