Sodium Carbonate → 4-[3-[6-(3-Benzo[1,3]dioxol-5-yl-5-methanesulfonyl-phenoxy)-hexyl]-2-(2-ethoxycarbonyl-ethyl)-phenoxy]-butyric acid ethyl ester

HRID 418080ノート

反応式

HRID 418080 の反応式
[CH2:1]([O:3][C:4](=[O:40])[CH2:5][CH2:6][CH2:7][O:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][O:21][C:22]2[CH:27]=[C:26]([S:28]([CH3:31])(=[O:30])=[O:29])[CH:25]=[C:24](I)[CH:23]=2)[C:10]=1[CH2:33][CH2:34][C:35]([O:37][CH2:38][CH3:39])=[O:36])[CH3:2].[C:41](=[O:44])([O-])[O-:42].[Na+].[Na+]>C(COC)OC.C(O)C.O.C(OCC)(=O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:1]([O:3][C:4](=[O:40])[CH2:5][CH2:6][CH2:7][O:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][O:21][C:22]2[CH:27]=[C:26]([S:28]([CH3:31])(=[O:30])=[O:29])[CH:25]=[C:24]([C:9]3[CH:14]=[CH:13][C:12]4[O:42][CH2:41][O:44][C:11]=4[CH:10]=3)[CH:23]=2)[C:10]=1[CH2:33][CH2:34][C:35]([O:37][CH2:38][CH3:39])=[O:36])[CH3:2]

参加物

8

反応物 2

HCID 10340Sodium CarbonateHCID 578630374-{2-(2-Ethoxycarbonyl-ethyl)-3-[6-(3-iodo-5-methanesulfonyl-phenoxy)-hexyl]-phenoxy}-butyric Acid Ethyl Ester

生成物 1

HCID 578630894-[3-[6-(3-Benzo[1,3]dioxol-5-yl-5-methanesulfonyl-phenoxy)-hexyl]-2-(2-ethoxycarbonyl-ethyl)-phenoxy]-butyric acid ethyl ester収率 172.5%

試薬・触媒・溶媒 5

HCID 178418397HCID 178418397、化合物触媒HCID 702Ethanol溶媒HCID 962Water溶媒2 回HCID 80711,2-Dimethoxyethane溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
80 °C

実験手順

A solution of 4-{2-(2-ethoxycarbonyl-ethyl)-3-[6-(3-iodo-5-methanesulfonyl-phenoxy)-hexyl]-phenoxy}-butyric acid ethyl ester (1.14 g, 1.65 mmol) in dimethoxyethane (15 mL) was stirred for 5 minutes at room temperature under nitrogen atmosphere. Then, tetrakis(triphenylphosphine)palladium(0) (386 mg, 0.33 mmol) was added at room temperature and the resulting light yellow solution was heated to 80° C. and stirred for 5 minutes. At this period, a solution of 3,4-(methylenedioxyphenyl)boronic acid (566 g, 3.3 mmol) in ethanol (16 mL) was added followed by a solution of sodium carbonate (351 mg, 3.3 mmol) in water (1.0 mL). The resulting light yellow suspension was stirred for 15 h at reflux. Then, the reaction mixture was cooled to room temperature and diluted with water (50 mL) and ethyl acetate (50 mL). The two layers were separated and the aqueous layer was extracted with ethyl acetate (2×50 mL). The combined organic extracts were washed with water (100 mL) and brine solution (100 mL). The organic layer was dried over anhydrous magnesium sulfate and filtration of the drying agent and removal of the solvent under reduced pressure gave the colored residue which was purified by using an ISCO 80 g column, eluting with 0-20% ethyl acetate in hexanes to afford 4-[3-[6-(3-benzo[1,3]dioxol-5-yl-5-methanesulfonyl-phenoxy)-hexyl]-2-(2-ethoxycarbonyl-ethyl)-phenoxy]-butyric acid ethyl ester (972 mg, 86%) as a light brown viscous oil: ES(+)-HRMS m/e calcd for C37H46O10S (M+Na)+ 705.2704, found 705.2703.

後処理

  1. waitAt this period
  2. stirringThe resulting light yellow suspension was stirred for 15 h
  3. temperatureat reflux
  4. temperatureThen, the reaction mixture was cooled to room temperature
  5. customThe two layers were separated
  6. extractionthe aqueous layer was extracted with ethyl acetate (2×50 mL)
  7. washThe combined organic extracts were washed with water (100 mL) and brine solution (100 mL)
  8. dry with materialThe organic layer was dried over anhydrous magnesium sulfate and filtration of the drying agent and removal of the solvent under reduced pressure
  9. customgave the colored residue which
  10. customwas purified
  11. washeluting with 0-20% ethyl acetate in hexanes

出典と根拠

ORDレコード
ord-cbbfcb093c604c709e1317d1a1131cf2
出典データセット
uspto-grants-2012_01
特許番号
US08093253B2

反応ノート

読み込み中…