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Acetic Acid → Dimethyl 2-Oxo-3-methylheptylphosphonate

HRID 442449
ノート
印刷プレビュー

反応式

HRID 442449 の反応式
[CH3:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4].C([Li])CCC.[CH3:13][CH:14]([CH2:20][CH2:21][CH2:22][CH3:23])[C:15](OCC)=[O:16].C(O)(=O)C>O1CCCC1.CCCCC>[CH3:13][CH:14]([CH2:20][CH2:21][CH2:22][CH3:23])[C:15](=[O:16])[CH2:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

7

反応物 4

HCID 176Acetic AcidHCID 12958Dimethyl methylphosphonateHCID 12714009Ethyl 2-methylhexanoateHCID 178418339Butyllithium

生成物 1

HCID 12906670Dimethyl 2-Oxo-3-methylheptylphosphonate収率 32.6%

試薬・触媒・溶媒 2

HCID 8003Pentane溶媒
HCID 8028
Tetrahydrofuran
溶媒
2 回

反応条件

温度
-60 °C

実験手順

A stirred solution of dimethyl methylphosphonate (54 g.) in dry tetrahydrofuran (390 ml.) at -45° to -50° C. was treated, dropwise during 20 minutes, with a solution of butyl lithium (32 g.) in pentane (250 ml.). Stirring was continued at that temperature for a further 10 minutes, and then the mixture was cooled to -60° C. and treated, dropwise during 15 minutes, with a solution of ethyl 2-methyl-hexanoate (34.5 g.) in tetrahydrofuran (120 ml.). The mixture was stirred at -60° C. for a further 90 minutes and then at room temperature for 3 hours, and then it was treated with acetic acid (42 ml.), evaporated to dryness in vacuo, and the residue treated with water (170 ml.). The mixture was extracted twice with diethyl ether and the combined ethereal extracts washed with water, dried over sodium sulphate and evaporated to dryness in vacuo. The residue was distilled to give dimethyl 3-methyl-2-oxoheptylphosphonate (16.8 g.), b.p. 93°-94° C./0.2mm.Hg.

後処理

  1. stirringThe mixture was stirred at -60° C. for a further 90 minutes
  2. waitat room temperature for 3 hours
  3. customevaporated to dryness in vacuo
  4. additionthe residue treated with water (170 ml.)
  5. extractionThe mixture was extracted twice with diethyl ether
  6. washthe combined ethereal extracts washed with water
  7. dry with materialdried over sodium sulphate
  8. customevaporated to dryness in vacuo
  9. distillationThe residue was distilled

出典と根拠

ORDレコード
ord-11a604c956a24e28a5ce5ae7408cb575
出典データセット
uspto-grants-1977_08
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US04045467

反応ノート

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