Acetic Acid → Dimethyl 2-oxo-3-phenoxypropylphosphonate

HRID 462095ノート

反応式

HRID 462095 の反応式
[CH3:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4].P(=O)([O-])[O-].[CH2:12]([Li])[CH2:13][CH2:14][CH3:15].[C:17]([OH:20])(=O)[CH3:18].[O:21]1CC[CH2:23][CH2:22]1>CCCCCC>[O:21]=[C:22]([CH2:23][O:20][C:17]1[CH:18]=[CH:15][CH:14]=[CH:13][CH:12]=1)[CH2:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4]

参加物

7

反応物 5

HCID 176Acetic AcidHCID 406CID 406HCID 8028TetrahydrofuranHCID 12958Dimethyl methylphosphonateHCID 178418339Butyllithium

生成物 1

HCID 580104Dimethyl 2-oxo-3-phenoxypropylphosphonate

試薬・触媒・溶媒 1

HCID 8058Hexane溶媒

実験手順

A solution of 33.2 g (268 mmoles) dimethyl methylphosphonate (Aldrich) in 360 ml dry tetrahydrofuran was cooled to -78° in a dry nitrogen atmosphere. To the stirred phosphonate solution was added 118 ml of 2.34 M n-butyllithium in hexane solution (Alfa Inorganics, Inc.) dropwise over a period of 18 minutes at such a rate that the reaction temperature never rose above -65°. After an additional 5 minutes stirring at -78°, 22.2 g (134 mmole) methyl 2-phenoxy acetate was added dropwise at a rate that kept the reaction temperature less than -70° (20 minutes). After 3.5 hours at -78° the reaction mixture was allowed to warm to ambient temperature, neutralized with 14 ml acetic acid and rotary evaporated to a white gel. The gelatinous material was taken up in 175 ml water, the aqueous phase extracted with 100 ml portions of chloroform (3x), the combined organic extracts were backwashed (50 cc H2O), dried (MgSO4), and concentrated (water aspirator) to a crude residue and distilled, b.p. 172°-175° (0.5 mm) to give 24.6 g dimethyl 2-oxo-3-phenoxypropylphosphonate.

後処理

  1. customthe reaction temperature less than -70° (20 minutes)
  2. waitAfter 3.5 hours at -78° the reaction mixture was allowed
  3. customrotary evaporated to a white gel
  4. extractionthe aqueous phase extracted with 100 ml portions of chloroform (3x)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated (water aspirator) to a crude residue
  7. distillationdistilled

出典と根拠

ORDレコード
ord-081b553045c0491580ca0e90d0620945
出典データセット
uspto-grants-1977_12
特許番号
US04065472

反応ノート

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