Methanol → tert-butyl 5'-((hydroxyimino)methyl)-3'H-spiro[azetidine-3,1-isobenzofuran]-1-carboxylate

HRID 1508318ノート

反応式

HRID 1508318 の反応式
[CH:1]([C:3]1[CH:4]=[C:5]2[C:9](=[CH:10][CH:11]=1)[C:8]1([CH2:14][N:13]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:12]1)[O:7][CH2:6]2)=O.CO.Cl.[OH:25][NH2:26].C([O-])(=O)C.[Na+]>O>[OH:25][N:26]=[CH:1][C:3]1[CH:4]=[C:5]2[C:9](=[CH:10][CH:11]=1)[C:8]1([CH2:14][N:13]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:12]1)[O:7][CH2:6]2

参加物

6

反応物 4

HCID 887MethanolHCID 443297Hydroxyamine hydrochlorideHCID 517045Sodium AcetateHCID 89994580tert-butyl 5'-formyl-3'H-spiro[azetidine-3,1'-isobenzofuran]-1-carboxylate

生成物 1

HCID 131734382tert-butyl 5'-((hydroxyimino)methyl)-3'H-spiro[azetidine-3,1-isobenzofuran]-1-carboxylate

試薬・触媒・溶媒 1

HCID 962Water溶媒2 回

実験手順

To a stirred solution of tert-butyl 5′-formyl-3′H-spiro[azetidine-3,1-isobenzofuran]-1-carboxylate (Preparation 42, 1.5 g, 5.184 mmol, 1 eq) in mixture of methanol (20 mL) and water (10 mL) was added hydroxyl amine hydrochloride (0.537 g, 7.777 mmol, 1.5 eq) followed by addition of sodium acetate (0.765 g, 9.332 mmol, 1.8 eq) at room temperature. Resulting reaction mixture was stirred at room temperature for 24 hours. After complete consumption of starting material, reaction mixture was concentrated in vacuo to afforded yellow colored residue, which was diluted by water (70 mL) and extracted with ethyl acetate (3×30 mL). Combined organic phase was washed with brine solution (50 mL), dried over anhydrous Na2SO4 and concentrated under reduced pressure to get yellow semi solid (1.9 g, crude). Crude was purified by Combiflash using 40 g Redisep column. Desired compound was eluted in 24% ethyl acetate in hexane to afford title compound as yellow semi solid (1.1 g, 69.62%). 1H NMR (400 MHz, CDCl3) δ: 1.47 (s, 9H), 4.13 (d, J=9.6 Hz, 2H), 4.31 (d, J=9.84 Hz, 2H), 5.10 (s, 2H), 7.43 (s, 1H), 7.47 (d, J=7.88 Hz, 1H), 7.56 (d, J=7.92 Hz, 1H), 8.14 (s, 1H). (m/z): 303.3 (M−H).

後処理

  1. customResulting
  2. customreaction mixture
  3. customAfter complete consumption of starting material, reaction mixture
  4. concentrationwas concentrated in vacuo
  5. customto afforded yellow colored residue, which
  6. extractionextracted with ethyl acetate (3×30 mL)
  7. washCombined organic phase was washed with brine solution (50 mL)
  8. dry with materialdried over anhydrous Na2SO4
  9. concentrationconcentrated under reduced pressure
  10. customto get yellow semi solid (1.9 g, crude)
  11. customCrude was purified by Combiflash
  12. washDesired compound was eluted in 24% ethyl acetate in hexane

出典と根拠

ORDレコード
ord-03c827e4b1684b71bf923717bb7f5125
出典データセット
uspto-grants-2015_12
特許番号
US09221835B2

反応ノート

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