Acetic Acid → Dimethyl 2-oxo-2-phenylethylphosphonate

HRID 1389029ノート

反応式

HRID 1389029 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]C.C(O)(=O)C.[O:21]1[CH2:25][CH2:24][CH2:23][CH2:22]1>CCCCCC>[O:21]=[C:25]([C:24]1[CH:14]=[CH:13][CH:12]=[CH:22][CH:23]=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 569473Dimethyl 2-oxo-2-phenylethylphosphonate収率 29%

試薬・触媒・溶媒 1

HCID 8058Hexane溶媒

実験手順

A solution of 74.5 g (600 mmoles) dimethyl methylphosphonate (Aldrich) in 750 ml dry tetrahydrofuran was cooled to -78° in a dry nitrogen atmosphere. To the stirred phosphonate solution was added 265 ml of 2.34 M n-butyllithium in hexane solution (Alfa Inorganics, Inc.) dropwise over a period of 30 minutes at such a rate that the reaction temperature never rose above -65°. After an additional 5 minutes stirring at -78°, 41 g (300 mmole) of methyl azoate was added dropwise at a rate that kept the reaction temperature less than -70° (10 minutes). After 1 hour at -78° the reaction mixture was allowed to warm to ambient temperature, neutralized with 35 ml acetic acid and rotary evaporated to a white gel. The gelatinous material was taken up in 75 ml water, the aqueous phase extracted with 300 ml portions of ether (3x), the combined organic extracts were backwashed (50 cc H2O), dried (MgSO4), and concentrated (water aspirator) to a crude residue and distilled, b.p. 130°-5° (0.04 mm) to give 35 g (29%) dimethyl 2-oxo-2-phenylethylphosphonate (2a).

後処理

  1. addition41 g (300 mmole) of methyl azoate was added dropwise at a rate that
  2. customthe reaction temperature less than -70° (10 minutes)
  3. waitAfter 1 hour at -78° the reaction mixture was allowed
  4. customrotary evaporated to a white gel
  5. extractionthe aqueous phase extracted with 300 ml portions of ether (3x)
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated (water aspirator) to a crude residue
  8. distillationdistilled

出典と根拠

ORDレコード
ord-4b59926ac9f946be84dceb54d7de561d
出典データセット
uspto-grants-1981_01
特許番号
US04243595

反応ノート

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