Sodium Hydroxide → HCID 11361281、化合物

HRID 29687ノート

反応式

HRID 29687 の反応式
C[O:2][C:3](=[O:25])[C:4]1[CH:9]=[CH:8][C:7]([CH2:10][O:11]/[N:12]=[CH:13]/[C:14]2[CH:19]=[CH:18][C:17]([C:20]([CH3:23])([CH3:22])[CH3:21])=[CH:16][CH:15]=2)=[CH:6][C:5]=1[Br:24].[OH-].[Na+]>>[Br:24][C:5]1[CH:6]=[C:7]([CH2:10][O:11]/[N:12]=[CH:13]/[C:14]2[CH:15]=[CH:16][C:17]([C:20]([CH3:23])([CH3:22])[CH3:21])=[CH:18][CH:19]=2)[CH:8]=[CH:9][C:4]=1[C:3]([OH:25])=[O:2]

参加物

3

反応物 2

HCID 14798Sodium HydroxideHCID 57449661methyl 2-bromo-4-[[(E)-(4-tert-butylphenyl)methylideneamino]oxymethyl]benzoate

生成物 1

HCID 11361281HCID 11361281、化合物収率 94%

実験手順

To a solution of 2-bromo-4-[({[(1E)-(4-tert-butylphenyl)methylidene]amino}oxy)methyl]benzoic acid methyl ester (0.43 g, 1.07 mmol), in 10/5/3 tetrahydrofuran/ethanol/water (24 mL) was added 2.5 M sodium hydroxide solution (4 mL). This mixture was heated to reflux for 3 hours and then allowed to cool back to room temperature. The mixture was concentrated to approximately ¼ volume and partitioned between ethyl acetate and brine. The aqueous layer was acidified to approximately pH 1 using 1 N hydrochloric acid. The layers were then separated. The aqueous layer was extracted with one additional portion of ethyl acetate. The organics were combined, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The crude material was dissolved in hot methylene chloride and crystallized out by the addition of room temperature hexanes (60 mL), and allowing the mixture to sit for 2 hours to give 2-bromo-4-[({[(1E)-(4-tert-butylphenyl)methylidene]amino}oxy)methyl]benzoic acid (0.39 g, 94%) as a white solid. mp=162-163° C. 1H NMR (500 MHz, DMSO-d6); δ 13.35 (bs, 1H), 8.31 (s, 1H), 7.74 (d, 1H), 7.71 (s, 1H), 7.52 (d, 2H), 7.46 (d, 1H), 7.42 (d, 2H), 5.19 (s, 2H), 1.26 (s, 9H). Mass spec (MW 390.28); (ES+) m/z 390.0, (ES−) m/z 388.3. Elemental analysis; Calculated for C19H20BrNO3: C, 58.47; H, 5.17; N, 3.59. Found: C, 57.99; H, 5.03; N, 3.41.

後処理

  1. temperatureThis mixture was heated
  2. temperatureto reflux for 3 hours
  3. concentrationThe mixture was concentrated to approximately ¼ volume
  4. custompartitioned between ethyl acetate and brine
  5. customThe layers were then separated
  6. extractionThe aqueous layer was extracted with one additional portion of ethyl acetate
  7. dry with materialdried over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. dissolutionThe crude material was dissolved in hot methylene chloride
  11. customcrystallized out by the addition of room temperature hexanes (60 mL)

出典と根拠

ORDレコード
ord-debfa4f737a3476aac883c551043cebf
出典データセット
uspto-grants-2008_09
特許番号
US07420083B2

反応ノート

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