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Dimethyl methylphosphonate → Dimethyl 2-oxo-4-(3,4-dimethoxyphenyl)butylphosphonate

HRID 569640
ノート
印刷プレビュー

反応式

HRID 569640 の反応式
C([Li])CCC.[CH3:6][P:7](=[O:12])([O:10][CH3:11])[O:8][CH3:9].[CH3:13][O:14][C:15]1[CH:16]=[C:17]([CH2:23][CH2:24][C:25](OC)=[O:26])[CH:18]=[CH:19][C:20]=1[O:21][CH3:22]>CCCCCC.O1CCCC1.[Cl-].[Na+]>[O:26]=[C:25]([CH2:24][CH2:23][C:17]1[CH:18]=[CH:19][C:20]([O:21][CH3:22])=[C:15]([O:14][CH3:13])[CH:16]=1)[CH2:6][P:7](=[O:12])([O:10][CH3:11])[O:8][CH3:9]
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 3

HCID 12958Dimethyl methylphosphonateHCID 520347Methyl 3-(3,4-dimethoxyphenyl)propanoateHCID 178418339Butyllithium

生成物 1

HCID 20147936Dimethyl 2-oxo-4-(3,4-dimethoxyphenyl)butylphosphonate収率 28.5%

試薬・触媒・溶媒 3

HCID 5234Sodium Chloride溶媒HCID 8028
Tetrahydrofuran
溶媒
2 回
HCID 8058Hexane溶媒

反応条件

温度
-78 °C

実験手順

To a mixture cooled at -78° C. of 50 ml of 2.1M n-butyl lithium solution in hexane and 100 ml of tetrahydrofuran, was added dropwise 12.4 g of dimethyl methylphosphonate. The mixture was stirred at -78° C. for 30 minutes, and thereafter 22.4 g of methyl 3-(3,4-dimethoxyphenyl)propionate [synthesized from 3,4-dimethoxycinnamic acid in 2 steps: (a) esterification (HCl--CH3OH) and (b) reduction (Pd/C--H2)] and 100 ml of tetrahydrofuran were added dropwise to the mixture. Then, the reaction was continued at -78° C. for 22 hours. The reaction mixture was poured in 500 ml of saturated aqueous sodium chloride solution. After neutralization and extraction with dichloromethane, the extract was dried and concentrated to give crude product. By purification of the crude product by means of column chromatography (silica gel/hexane:ethyl acetate=1:4), 9.0 g of the above caption compound was obtained.

後処理

  1. waitThen, the reaction was continued at -78° C. for 22 hours
  2. extractionAfter neutralization and extraction with dichloromethane
  3. customthe extract was dried
  4. concentrationconcentrated
  5. customto give crude product
  6. customBy purification of the crude product by means of column chromatography (silica gel/hexane:ethyl acetate=1:4)

出典と根拠

ORDレコード
ord-8709608733304e8d8035a1795b7ee7de
出典データセット
uspto-grants-1988_03
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US04733002

反応ノート

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