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

HRID 1076176

반응식

HRID 1076176 반응식
[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]

참가 물질

8

반응물 4

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

생성물 1

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

시약·촉매·용매 3

HCID 176Acetic Acid용매HCID 8028Tetrahydrofuran용매HCID 8058Hexane용매

실험 절차

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 concentratead (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).

후처리

  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), and concentratead (water aspirator) to a crude residue
  6. distillationdistilled

출처 및 근거

ORD 기록
ord-a04ebf65a15c4b0d95ed96799ea115ff
출처 데이터셋
uspto-grants-1976_05
특허 번호
US03956284

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