Oxygen → 1,4-Bis(trifluoroethenyl)benzene

HRID 1493732

반응식

HRID 1493732 반응식
I[C:2]([F:6])=[C:3]([F:5])[F:4].I[C:8]1[CH:13]=[CH:12][C:11](I)=[CH:10][CH:9]=1.O=O>[Zn].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd].C(COC)OC>[F:6][C:2]([C:8]1[CH:13]=[CH:12][C:11]([C:2]([F:6])=[C:3]([F:5])[F:4])=[CH:10][CH:9]=1)=[C:3]([F:5])[F:4]

참가 물질

7

반응물 3

HCID 977OxygenHCID 12208p-DiiodobenzeneHCID 67755Trifluoroiodoethylene

생성물 1

HCID 138606631,4-Bis(trifluoroethenyl)benzene수율 65%

시약·촉매·용매 3

HCID 23994Zinc촉매HCID 11979704Tetrakis(triphenylphosphine)palladium촉매HCID 80711,2-Dimethoxyethane용매

실험 절차

A 5 liter 3-necked round bottom flask is fitted with a mechanical stirrer, a nitrogen padded reflux condenser and a rubber septum. Glyme (100 ml) and activated zinc granules (11.50 g, 0.18 mole) are added to the flask along with a magnetic stirring bar. The flask is then purged with nitrogen for 15 minutes, after which time iodotrifluoroethylene (20.3 g, 0.098 mole) is added slowly via syringe through the septum. After 20 minutes of stirring the mixture begins to turn brown and get warm. After 2 hours a white precipitate begins to form. After stirring is continued without heat for 4 hours, the flask is opened under a slow nitrogen purge and 1,4-diiodobenzene (16.0 g, 0.0485 mole) is added along with palladium tetrakis(triphenylphosphine) (0.57 g, 0.00049 mole). The mixture is stirred overnight, resulting in the formation of a large amount of suspended solid. The reaction is allowed to stir an additional 24 hours, after which it is filtered, and the precipitate is washed with hexane (3 times with 50 ml each wash). The filtrates are combined and evaporated at 30° C. on a rotary evaporator to provide a residue which is purified by column chromatography (neutral alumnia, hexane eluent) to give 7.50 g of CF2 =CF--Ph--CF=CF2 as product (0.0315 mole, 65% yield). This product is analysed by GC/MS and gives the following spectrum: m/e: 238 (100%): 188 (12.0%); 187 (46.4%): 169 (92.0%): 138 (18.8%): 99 (16.3%); 81 (12.3%): 69 (30.1%). The material is found to be air sensitive, fuming acid gasses if left exposed to oxygen.

후처리

  1. customA 5 liter 3-necked round bottom flask is fitted with a mechanical stirrer
  2. temperaturea nitrogen padded reflux condenser
  3. customThe flask is then purged with nitrogen for 15 minutes
  4. customget
  5. temperaturewarm
  6. waitAfter 2 hours a white precipitate begins
  7. customto form
  8. stirringAfter stirring
  9. temperaturewithout heat for 4 hours
  10. custompurge
  11. stirringThe mixture is stirred overnight
  12. customresulting in the formation of a large amount of suspended solid
  13. stirringto stir an additional 24 hours
  14. filtrationafter which it is filtered
  15. washthe precipitate is washed with hexane (3 times with 50 ml each wash)
  16. customevaporated at 30° C. on a rotary evaporator
  17. customto provide a residue which
  18. customis purified by column chromatography (neutral alumnia, hexane eluent)
  19. customto give 7.50 g of CF2 =CF--Ph--CF=CF2 as product (0.0315 mole, 65% yield)
  20. customgives the following spectrum
  21. waitif left

출처 및 근거

ORD 기록
ord-5a58f656161d4ae6acd83e68cfdf3a99
출처 데이터셋
uspto-grants-1991_06
특허 번호
US05023380

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