Triphenylphosphine → 2,6-Difluoro-3-(2-(2-methoxyethoxy)ethoxy)benzoic acid

HRID 2069122ノート

反応式

HRID 2069122 の反応式
[F:1][C:2]1[C:11]([OH:12])=[CH:10][CH:9]=[C:8]([F:13])[C:3]=1[C:4]([O:6]C)=[O:5].[CH2:14]([OH:20])[CH2:15][O:16][CH2:17][CH2:18]O.[CH3:21]OC.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C.[OH-].[Na+]>C1COCC1.O>[F:1][C:2]1[C:11]([O:12][CH2:18][CH2:17][O:16][CH2:15][CH2:14][O:20][CH3:21])=[CH:10][CH:9]=[C:8]([F:13])[C:3]=1[C:4]([OH:6])=[O:5]

参加物

8

反応物 5

HCID 11776TriphenylphosphineHCID 14798Sodium HydroxideHCID 5363146Diisopropyl azodicarboxylateHCID 212256572-(2-Hydroxyethoxy)ethanol;methoxymethaneHCID 46311127Methyl 2,6-difluoro-3-hydroxybenzoate

生成物 1

HCID 585647682,6-Difluoro-3-(2-(2-methoxyethoxy)ethoxy)benzoic acid収率 69.4%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-78 °C

実験手順

A mixture of methyl 2,6-difluoro-3-hydroxybenzoate (500 mg, 2.66 mmol), diethyleneglycol-monomethyl ether (479 mg, 3.99 mmol) and PPh3 (1046 mg, 3.99 mmol) in THF (12.0 mL) was purged with nitrogen, cooled to −78° C. and then DIAD (753 μl, 3.99 mmol) added over 5 min. The reaction mixture was warmed to RT and after 1 hr an aq solution of NaOH (2M, 10 mL) and water (10 mL) were added and the mixture was stirred rapidly at RT for 1 hr. The resulting mixture was extracted with ether (50 mL) and the organic layer was back-extracted with aq NaOH (1M, 20 mL). The combined (basic) aqueous phases were extracted twice with ether and then acidified to pH 1 by the addition of conc. hydrochloric acid and the mixture extracted three times with ether. The combined ether extracts were dried (MgSO4) and evaporated in vacuo to afford the title compound as a white solid (0.51 g, 65%); Rt 1.81 min, (Method 1, basic); m/z 275 (M−H)− (ES−).

後処理

  1. customwas purged with nitrogen
  2. additionwere added
  3. extractionThe resulting mixture was extracted with ether (50 mL)
  4. extractionthe organic layer was back-extracted with aq NaOH (1M, 20 mL)
  5. extractionwere extracted twice with ether
  6. additionacidified to pH 1 by the addition of conc. hydrochloric acid
  7. extractionthe mixture extracted three times with ether
  8. dry with materialThe combined ether extracts were dried (MgSO4)
  9. customevaporated in vacuo

出典と根拠

ORDレコード
ord-de959f7e6f60459d80673e9eca298e49
出典データセット
uspto-grants-2012_10
特許番号
US08299074B2

反応ノート

読み込み中…