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

HRID 1491510
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HRID 1491510 반응식
[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]
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참가 물질

8

반응물 4

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

생성물 1

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

시약·촉매·용매 3

HCID 3007855Zincchloride
촉매
HCID 962Water용매
HCID 8028Tetrahydrofuran용매2회

반응 조건

온도
50 °C

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-8db1f19507f44e9eb90f0ce4444c48c3
출처 데이터셋
uspto-grants-1994_12
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
USRE034805

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