Ethyl bromoacetate → Ethyl 3-(6-Chloro-8-Methyl-2H-Chromen-3-yl)-2-Butenoate

HRID 1110425ノート

反応式

HRID 1110425 の反応式
Br[CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4].[C:8]([C:11]1CO[C:14]2[C:19]([CH:20]=1)=[CH:18][CH:17]=[CH:16][CH:15]=2)(=O)[CH3:9].[Cl-:21].[NH4+].[CH3:23][O:24][CH2:25]OC>BrCC(OCC)=O.C1COCC1.C1C=CC=CC=1.[Zn]>[Cl:21][C:17]1[CH:18]=[C:19]2[C:23](=[C:15]([CH3:14])[CH:16]=1)[O:24][CH2:25][C:11]([C:8]([CH3:9])=[CH:2][C:3]([O:5][CH2:6][CH3:7])=[O:4])=[CH:20]2

参加物

9

反応物 4

HCID 7748Ethyl bromoacetateHCID 8020Dimethoxymethane2 回HCID 25517Ammonium ChlorideHCID 400671-(2H-1-Benzopyran-3-yl)ethanone

生成物 1

HCID 54555991Ethyl 3-(6-Chloro-8-Methyl-2H-Chromen-3-yl)-2-Butenoate

試薬・触媒・溶媒 4

HCID 7748Ethyl bromoacetate触媒HCID 23994Zinc触媒HCID 241Benzene溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

A volume of dimethoxymethane sufficient to cover 0.108 g-at. of zinc is added into a round-bottomed flask equipped with a stirrer, a dropping funnel, a condenser and a thermometer. A few drops of pure ethyl bromoacetate are then added. The reaction is primed by gentle heating (with the flame of a lighter). The reaction is then maintained by the dropwise addition of 0.1 mmol of ethyl bromoacetate dissolved in anhydrous dimethoxymethane. The rate of addition is adjusted so that the temperature does not exceed 40° C. After the addition, the reaction medium is stirred for a further 30 minutes at room temperature, and 0.083 mmol of 3-acetylchromene, dissolved in anhydrous THF, is then added in a single portion. The reaction medium is stirred for a further 15 minutes and then hydrolyzed with saturated ammonium chloride solution. After 3 successive extractions with ethyl acetate, the organic extracts are dried over magnesium sulfate and the solvents removed. 50 mmol of the expected product are dissolved in 50 ml of benzene and 1 ml of phosphorus oxychloride is added. The mixture is brought to reflux for 1 h 30 min. After being cooled, the reaction medium is poured into 100 ml of water. The benzene phase is decanted and the aqueous phase extracted with 2×50 ml of diethyl ether. After the organic extracts have been washed with saturated sodium hydrogen carbonate solution to neutrality and dried and the solvents have been removed, the ester is purified on a column of silica gel (SiO2 : 70-230 mesh; eluent CH2Cl2).

後処理

  1. customequipped with a stirrer, a dropping funnel, a condenser
  2. temperatureby gentle heating (with the
  3. temperatureflame of a lighter)
  4. additionThe rate of addition
  5. customdoes not exceed 40° C
  6. additionAfter the addition
  7. additionis then added in a single portion
  8. stirringThe reaction medium is stirred for a further 15 minutes
  9. extractionAfter 3 successive extractions with ethyl acetate
  10. dry with materialthe organic extracts are dried over magnesium sulfate
  11. customthe solvents removed

出典と根拠

ORDレコード
ord-b7f6be5aa7854b9aa767ef2f5d53caf3
出典データセット
uspto-grants-1990_12
特許番号
US04975454

反応ノート

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