Hydrochloric Acid → Methyl 5-benzyl-3-(chloromethylene)-2,3,4,5-tetrahydro-1-benzoxepin-7-carboxylate

HRID 1791029ノート

反応式

HRID 1791029 の反応式
C([Li])CCC.[Cl-].[Cl:7][CH2:8][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[CH2:28]([CH:35]1[C:41]2[CH:42]=[C:43]([C:46]([O:48][CH3:49])=[O:47])[CH:44]=[CH:45][C:40]=2[O:39][CH2:38][C:37](=O)[CH2:36]1)[C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1.Cl>O1CCCC1.ClCCl.O>[CH2:28]([CH:35]1[C:41]2[CH:42]=[C:43]([C:46]([O:48][CH3:49])=[O:47])[CH:44]=[CH:45][C:40]=2[O:39][CH2:38][C:37](=[CH:8][Cl:7])[CH2:36]1)[C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1

参加物

8

反応物 4

HCID 313Hydrochloric AcidHCID 197823(Chloromethyl)triphenylphosphonium chlorideHCID 11415645HCID 11415645、化合物HCID 178418339Butyllithium

生成物 1

HCID 69666958Methyl 5-benzyl-3-(chloromethylene)-2,3,4,5-tetrahydro-1-benzoxepin-7-carboxylate収率 53%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
0 °C

実験手順

1.1 equivalents of n-butyllithium are added to a suspension of 40 mg (0.12 mmol) of chloromethyltriphenylphosphonium chloride in 3 ml of tetrahydrofuran cooled to 0° C. After stirring for one hour, the ylide is added at 0° C. via a hollow tube to 30 mg (0.1 mmol) of methyl 5-benzyl-3-oxo-2,3,4,5-tetrahydro-1-benzoxepin-7-carboxylate, prepared according to example 9. After stirring at ambient temperature for 30 minutes, water, 1N hydrochloric acid and dichloromethane are added. The phases are separated by settling and then the aqueous phase is extracted three times with dichloromethane. The combined organic phases are washed with brine, are then dried and are finally concentrated under vacuum. The crude reaction product is then purified by chromatography on silica gel (ethyl acetate/heptane 5/95) to provide 18 mg (53%) of methyl 5-benzyl-3-(chloromethylene)-2,3,4,5-tetrahydro-1-benzoxepin-7-carboxylate in the form of a mixture of two isomers in a Z/E ratio (60/40); exact mass (CI): calculated 343.11009; found 343.11027.

後処理

  1. customprepared
  2. stirringAfter stirring at ambient temperature for 30 minutes
  3. customThe phases are separated
  4. extractionthe aqueous phase is extracted three times with dichloromethane
  5. washThe combined organic phases are washed with brine
  6. customare then dried
  7. concentrationare finally concentrated under vacuum
  8. customThe crude reaction product
  9. customis then purified by chromatography on silica gel (ethyl acetate/heptane 5/95)

出典と根拠

ORDレコード
ord-ab5491429d1d407e8b0a4e35322d8bac
出典データセット
uspto-grants-2006_07
特許番号
US07071340B2

反応ノート

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