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Iodine → 6-[3-(1,1-Dimethyldecyl)-4-methoxyphenyl]-2-naphthoic acid

HRID 2165525
ノート
印刷プレビュー

反応式

HRID 2165525 の反応式
[CH3:1][C:2]([C:13]1[CH:18]=[C:17](Br)[CH:16]=[CH:15][C:14]=1[O:20][CH3:21])([CH3:12])[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH3:11].[Mg].II.Br[C:26]1[CH:27]=[C:28]2[C:33](=[CH:34][CH:35]=1)[CH:32]=[C:31]([C:36]([O:38]C)=[O:37])[CH:30]=[CH:29]2>C1COCC1.[Cl-].[Zn+2].[Cl-].O>[CH3:1][C:2]([C:13]1[CH:18]=[C:17]([C:26]2[CH:27]=[C:28]3[C:33](=[CH:34][CH:35]=2)[CH:32]=[C:31]([C:36]([OH:38])=[O:37])[CH:30]=[CH:29]3)[CH:16]=[CH:15][C:14]=1[O:20][CH3:21])([CH3:12])[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH3:11]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

8

反応物 4

HCID 807IodineHCID 8541342-Bromo-6-methoxycarbonylnaphthaleneHCID 5462224MagnesiumHCID 136335572-(1,1-Dimethyldecyl)-4-bromo anisole

生成物 1

HCID 189527686-[3-(1,1-Dimethyldecyl)-4-methoxyphenyl]-2-naphthoic acid

試薬・触媒・溶媒 3

HCID 3007855Zincchloride
触媒
HCID 962Water溶媒
HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
50 °C

実験手順

A solution of 16 g (45 mmol) of 2-(1,1-dimethyldecyl)-4-bromo anisole in 60 ml of THF is slowly added to 1.3 g (54 mmol) of magnesium and a crystal of iodine. The mixture is slightly heated at the beginning of the addition until the reaction of formation of the Grignard is initiated. Then the remainder of the solution containing the brominated derivative is added in a manner to maintain a regular reflux. Once the addition is complete, the mixture is stirred for 30 minutes at 50° C. and then cooled to ambient temperature. 7.4 g (54 mmol) of zinc chloride in solution in 50 ml of THF are added. The mixture is stirred for 30 minutes at ambient temperature, 6.6 g (25 mmol) of methyl 6-bromo-2-naphthoate are added and then 175 mg of NiCl2 /DPPE complex. The mixture is stirred for 3 hours at ambient temperature at which point 250 ml of water are added. The THF is evaporated under reduced pressure and the residue is extracted with dichloromethane, dried and the solvent evaporated. The residue is purified by passage through a silica column (eluant: mixture of 60% dichloromethane and 40% hexane). On evaporation, a solid is obtained which is recrystallized twice in hexane to give the methyl ester of 6-[3-(1,1-dimethyldecyl)-4-methoxyphenyl]-2-naphthoic acid: 7.05 g (61%). Melting point: 92° C.

後処理

  1. temperatureThe mixture is slightly heated at the beginning of the addition until the reaction of formation of the Grignard
  2. additionThen the remainder of the solution containing the brominated derivative
  3. additionis added in a manner
  4. temperatureto maintain a regular reflux
  5. additionOnce the addition
  6. temperaturecooled to ambient temperature
  7. stirringThe mixture is stirred for 30 minutes at ambient temperature
  8. stirringThe mixture is stirred for 3 hours at ambient temperature at which
  9. additionare added
  10. customThe THF is evaporated under reduced pressure
  11. extractionthe residue is extracted with dichloromethane
  12. customdried
  13. customthe solvent evaporated
  14. customThe residue is purified by passage through a silica column (eluant: mixture of 60% dichloromethane and 40% hexane)
  15. customOn evaporation
  16. customa solid is obtained which
  17. customis recrystallized twice in hexane

出典と根拠

ORDレコード
ord-5bb72c3f5289453ea6db235c478c2f56
出典データセット
uspto-grants-1990_07
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US04940696

反応ノート

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