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Hydrochloric Acid → 2,7-Dimethyl-3,6-ditert-butyl-fluorene

HRID 1050652
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HRID 1050652 반응식
[CH3:1]OC(C)(C)C.BrC1[C:20]([C:21]([CH3:24])([CH3:23])[CH3:22])=[CH:19][C:18]2[C:17]3[C:12](=[CH:13][C:14](Br)=[C:15]([C:25]([CH3:28])([CH3:27])[CH3:26])[CH:16]=3)[CH2:11][C:10]=2[CH:9]=1.C[Mg]Br.Cl.C(O[CH2:37][CH3:38])C>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(Cl)Cl>[CH3:1][C:14]1[C:15]([C:25]([CH3:27])([CH3:26])[CH3:28])=[CH:16][C:17]2[C:18]3[C:10](=[CH:9][C:37]([CH3:38])=[C:20]([C:21]([CH3:22])([CH3:24])[CH3:23])[CH:19]=3)[CH2:11][C:12]=2[CH:13]=1
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참가 물질

8

반응물 5

HCID 313Hydrochloric AcidHCID 3283Diethyl Ether2회HCID 15413tert-Butyl methyl etherHCID 135475422,7-Dibromo-3,6-DI-tert-butyl-9H-fluoreneHCID 178418573HCID 178418573, 화합물

생성물 1

HCID 219826932,7-Dimethyl-3,6-ditert-butyl-fluorene수율 63%

시약·촉매·용매

2
HCID 44119782Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)촉매HCID 6344Dichloromethane용매

실험 절차

Under a nitrogen atmosphere, 100 mL of dehydrated tertbutyl methyl ether was added to 5.03 g (11.5 mmol) of 2,7-dibromo-3,6-ditert-butyl-fluorene synthesized in Synthesis Example 1-1 (i) and 0.196 g (0.24 mmol) of PdCl2(dppf).CH2Cl2, and the mixture was stirred. This solution was cooled in an ice bath, and 19.2 mL (57.6 mmol) of a 3 mol/L diethyl ether solution of methyl magnesium bromide was added dropwise over 15 minutes. The mixture was heated to reflux for 5 days. The mixture was left to be naturally cooled, and 1 N hydrochloric acid was then added dropwise in an ice bath to terminate the reaction. Diethyl ether was added to perform liquid-liquid phase separation, and the organic layer was washed two times with a saturated aqueous solution of sodium hydrogen carbonate, two times with water, and once with saturated brine, and dried over magnesium sulfate. The solvent was distilled off, and the residue was subjected to separation by silica gel chromatography to obtain a target product as a white powder (yield 2.07 g (63%)). The target product was identified by 1H-NMR.

후처리

  1. temperatureThis solution was cooled in an ice bath
  2. temperatureThe mixture was heated
  3. temperatureto reflux for 5 days
  4. waitThe mixture was left
  5. temperatureto be naturally cooled
  6. customto terminate
  7. customthe reaction
  8. customliquid-liquid phase separation
  9. washthe organic layer was washed two times with a saturated aqueous solution of sodium hydrogen carbonate, two times with water
  10. dry with materialonce with saturated brine, and dried over magnesium sulfate
  11. distillationThe solvent was distilled off
  12. customthe residue was subjected to separation by silica gel chromatography

출처 및 근거

ORD 기록
ord-93acf26f32b54cf4b0a1716136658707
출처 데이터셋
uspto-grants-2016_07
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US09382356B2

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