Triphenylphosphine → methyl (RS)-3-(1-cyclopropyl-prop-2-ynyloxy)-4,5-dimethoxy-benzoate

HRID 964968

反応式

HRID 964968 の反応式
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:10]=[C:11](O)[C:12]=1[O:13][CH3:14])[C:6]([O:8][CH3:9])=[O:7].[CH:16]1([CH:19]([OH:22])[C:20]#[CH:21])[CH2:18][CH2:17]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>C1(C)C=CC=CC=1>[CH:16]1([CH:19]([O:22][C:11]2[CH:10]=[C:5]([CH:4]=[C:3]([O:2][CH3:1])[C:12]=2[O:13][CH3:14])[C:6]([O:8][CH3:9])=[O:7])[C:20]#[CH:21])[CH2:18][CH2:17]1

参加物

6

反応物 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 3431191-Cyclopropylprop-2-yn-1-olHCID 2733956Methyl 3-hydroxy-4,5-dimethoxybenzoate

生成物 1

HCID 54377500methyl (RS)-3-(1-cyclopropyl-prop-2-ynyloxy)-4,5-dimethoxy-benzoate

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒2 回

反応条件

温度
5 °C

実験手順

63.6 g of methyl 3,4-dimethoxy-5-hydroxy-benzoate [E. Spath and H. Roder, Monatsh. fur Chemie, 43, 93 (1923)], 38.5 g of (RS)-1-cyclopropyl-prop-2-yn-1-ol and 118 g of triphenylphosphine were dissolved in 600 ml of toluene under argon and cooled to 5° C. A solution of 70 ml of diethyl azodicarboxylate in 150 ml of toluene was slowly added dropwise thereto at 5° C. over 90 min. The mixture was stirred at 5° C. for a further 1 hr. and at 20° C. for 3 hrs. Then, 300 ml of toluene were distilled off on a rotary evaporator and the suspension obtained was stirred in an ice bath for 30 min. The separated triphenylphosphine oxide was filtered off and the filtrate was evaporated. The resulting oil was chromatographed on silica gel with hexane/ethyl acetate 4:1, then 3:1. Crystallization was effected from diethyl ether and hexane. There was obtained methyl (RS)-3-(1-cyclopropyl-prop-2-ynyloxy)-4,5-dimethoxy-benzoate as white crystals.

後処理

  1. waitand at 20° C. for 3 hrs
  2. distillationThen, 300 ml of toluene were distilled off on a rotary evaporator
  3. customthe suspension obtained
  4. stirringwas stirred in an ice bath for 30 min
  5. filtrationThe separated triphenylphosphine oxide was filtered off
  6. customthe filtrate was evaporated
  7. customThe resulting oil was chromatographed on silica gel with hexane/ethyl acetate 4:1
  8. customCrystallization

出典と根拠

ORDレコード
ord-26a6e4fe57844be886e38b37d5444c66
出典データセット
uspto-grants-1998_06
特許番号
US05773446

関連ノート

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