CID 406 → Dimethyl [4-(furan-2-yl)-2-oxobutyl]phosphonate

HRID 1679317

反応式

HRID 1679317 の反応式
[CH3:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4].P(=O)([O-])[O-].C([Li])CCC.[O:17]1[CH:21]=[CH:20][CH:19]=[C:18]1[CH2:22][CH2:23][C:24](OC)=[O:25]>O1CCCC1.CCCCCC.C(O)(=O)C>[O:25]=[C:24]([CH2:23][CH2:22][C:18]1[O:17][CH:21]=[CH:20][CH:19]=1)[CH2:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4]

参加物

8

反応物 4

HCID 406CID 406HCID 12958Dimethyl methylphosphonateHCID 263167Methyl 3-(2-furyl)propanoateHCID 178418339Butyllithium

生成物 1

HCID 13941306Dimethyl [4-(furan-2-yl)-2-oxobutyl]phosphonate収率 32.8%

試薬・触媒・溶媒 3

HCID 176Acetic Acid溶媒HCID 8028Tetrahydrofuran溶媒HCID 8058Hexane溶媒

実験手順

A solution of 25 g (0.21 mole) dimethyl methylphosphonate (Aldrich) in 300 ml dry tetrahydrofuran was cooled to -78° in a dry nitrogen atmosphere. To the stirred phosphonate solution was added 80 ml of 2.67 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°, 16.0 g (.104 mole) methyl 3-(2-furyl)propionate 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 6 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 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. 148°-50° (0.5 mm) to give 8.4 g dimethyl 2-oxo-4-(2-furyl)butylphosphonate (2C).

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-b1403f90f13d4195954916c5cb1f97c1
出典データセット
uspto-grants-1978_03
特許番号
US04080368

関連ノート

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