Tetrahydrofuran → Dimethyl (3,3-dimethyl-2-oxo-4-phenylbutyl)phosphonate

HRID 437106ノート

反応式

HRID 437106 の反応式
[CH3:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4].O1CCCC1.C([Li])CCC.[CH3:18][C:19]([CH3:30])([CH2:23][C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)[C:20](Cl)=[O:21]>CCCCCC.C(O)(=O)C>[CH3:18][C:19]([CH3:30])([CH2:23][C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)[C:20](=[O:21])[CH2:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4]

参加物

7

反応物 4

HCID 8028Tetrahydrofuran2 回HCID 12958Dimethyl methylphosphonateHCID 133072292,2-Dimethyl-3-phenylpropanoyl chlorideHCID 178418339Butyllithium

生成物 1

HCID 14302191Dimethyl (3,3-dimethyl-2-oxo-4-phenylbutyl)phosphonate

試薬・触媒・溶媒 2

HCID 176Acetic Acid溶媒HCID 8058Hexane溶媒

実験手順

To a solution of 63 g. of dimethyl methylphosphonate in 600 ml. of tetrahydrofuran under nitrogen atmosphere at -75° C. is added with stirring 312 ml. of 1.6 M n-butyllithium in hexane. The condition is regulated so as to maintain a reaction temperature below -55° C. Ten minutes after the addition, 48.2 g. of the reaction product of step B above (2,2-dimethyl-3-phenylpropionyl chloride) in 15 ml. of tetrahydrofuran is added dropswise. The dropwise addition is regulated so as to maintain a reaction temperature below -60° C. The mixture is stirred at -75° C. for 2 hr. and at ambient temperature overnight. Acetic acid (20 ml.) is added and the tetrahydrofuran is removed by distillation. The residue is shaken with diethyl ether-methylene chloride (3:1, by volume) and dilute sodium bicarbonate solution. The organic layer is washed with saturated saline and then dried and concentrated. The residue is recrystallized in diethyl ether to give 54 g. of the title compound of this preparation. Melting point 49°-51° C.

後処理

  1. temperatureto maintain a reaction temperature below -55° C
  2. additionTen minutes after the addition, 48.2 g
  3. additionThe dropwise addition
  4. temperatureto maintain a reaction temperature below -60° C
  5. stirringThe mixture is stirred at -75° C. for 2 hr
  6. customat ambient temperature
  7. customovernight
  8. customthe tetrahydrofuran is removed by distillation
  9. stirringThe residue is shaken with diethyl ether-methylene chloride (3:1, by volume) and dilute sodium bicarbonate solution
  10. washThe organic layer is washed with saturated saline
  11. customdried
  12. concentrationconcentrated
  13. customThe residue is recrystallized in diethyl ether
  14. customto give 54 g

出典と根拠

ORDレコード
ord-7298d8885ce0402f8c54de50c8a687e8
出典データセット
uspto-grants-1977_06
特許番号
US04029693

反応ノート

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