Acetic Acid → Dimethyl 3-(3-chlorophenoxy)-2-oxopropylphosphonate

HRID 1389179ノート

反応式

HRID 1389179 の反応式
C([Li])CCC.[CH3:6][P:7](=[O:12])([O:10][CH3:11])[O:8][CH3:9].[Cl:13][C:14]1[CH:15]=[C:16]([CH:24]=[CH:25][CH:26]=1)[O:17][CH2:18][C:19](OCC)=[O:20].C(O)(=O)C>CCCCCC.O1CCCC1>[Cl:13][C:14]1[CH:15]=[C:16]([CH:24]=[CH:25][CH:26]=1)[O:17][CH2:18][C:19](=[O:20])[CH2:6][P:7](=[O:12])([O:10][CH3:11])[O:8][CH3:9]

参加物

7

反応物 4

HCID 176Acetic AcidHCID 12958Dimethyl methylphosphonateHCID 735422Ethyl 2-(3-chlorophenoxy)acetateHCID 178418339Butyllithium

生成物 1

HCID 3566446Dimethyl 3-(3-chlorophenoxy)-2-oxopropylphosphonate収率 58.3%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 8058Hexane溶媒

反応条件

温度
-60 °C

実験手順

A solution of n-butyl lithium (16.0 g) in hexane (160 ml) was added to a stirred solution of dimethyl methylphosphonate (26.9 g) in anhydrous tetrahydrofuran (150 ml) at -60° C. in an atmosphere of nitrogen during 20 minutes. The solution was maintained at -60° C. for a further period of 10 minutes and was then treated with a solution of ethyl 3-chlorophenoxyacetate (23.4 g) in anhydrous tetrahydrofuran (50 ml) at -60° C. during a further period of 10 minutes. This solution was stirred at -60° C. for 90 minutes and then stirred at ambient temperature for 2 hours. The solution was treated with acetic acid (21 ml) and the solvents were evaporated under reduced pressure. Water (60 ml) was added to the residue and the mixture was extracted with diethyl ether. The ethereal solution was washed with water, with aqueous sodium bicarbonate solution (10% w/v) and with water, dried over magnesium sulphate, and evaporated. The resulting residue was left to stand at ambient temperature overnight. The resulting colourless crystals were filtered off, washed with a small volume of diethyl ether, and recrystallised from a mixture of petroleum ether (b.p. 40°-60° C.) and toluene, to give dimethyl 3-(3-chlorophenoxy)-2-oxopropylphosphonate (18.6 g) in the form of colourless needles, m.p. 78°-79° C. [elemental analysis: C, 44.9; H, 5.1; P, 10.7%. C11H14ClO5P requires C, 45.1; H, 4.8; P, 10.6%. νmax 825, 865, 1030, 1160, 1270, 1335, 1600 and 1735 cm-1 ].

後処理

  1. stirringstirred at ambient temperature for 2 hours
  2. customthe solvents were evaporated under reduced pressure
  3. additionWater (60 ml) was added to the residue
  4. extractionthe mixture was extracted with diethyl ether
  5. washThe ethereal solution was washed with water, with aqueous sodium bicarbonate solution (10% w/v) and with water
  6. dry with materialdried over magnesium sulphate
  7. customevaporated
  8. waitThe resulting residue was left
  9. waitto stand at ambient temperature overnight
  10. filtrationThe resulting colourless crystals were filtered off
  11. washwashed with a small volume of diethyl ether
  12. customrecrystallised from a mixture of petroleum ether (b.p. 40°-60° C.) and toluene

出典と根拠

ORDレコード
ord-168edd778b5e4f2495c158b3d6075deb
出典データセット
uspto-grants-1981_01
特許番号
US04243683

反応ノート

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