Thioglycolic Acid → 3-Ethoxycarbonyl-4-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]phenyl-fluorene

HRID 539386Notes

Reaction equation

HRID 539386 reaction equation
Br[C:2]1[CH:14]=[CH:13][C:12]2C3C(=CC(Br)=CC=3)[C:5](=[O:16])[C:4]=2[CH:3]=1.[C:17](OCC)(=O)[C:18]1[C:19](=[CH:21][CH:22]=[CH:23][CH:24]=1)O.S[CH2:30][C:31](O)=[O:32].CS(O)(=O)=O.COCCOCCOCCO[C:50]1[CH:55]=[C:54](S([O-])(=O)=O)[CH:53]=[CH:52][C:51]=1C.C(=O)([O-])[O-].[K+].[K+].[CH2:67]1[O:84][CH2:83][CH2:82][O:81]CCOCCOC[CH2:73][O:72][CH2:71][CH2:70][O:69][CH2:68]1>C(Cl)(Cl)Cl.CN(C)C=O>[CH2:31]([O:32][C:5]([C:4]1[CH:3]=[C:2]([C:24]2[C:18]3[CH2:17][C:51]4[C:50](=[CH:55][CH:54]=[CH:53][CH:52]=4)[C:19]=3[CH:21]=[CH:22][CH:23]=2)[CH:14]=[CH:13][C:12]=1[O:81][CH2:82][CH2:83][O:84][CH2:67][CH2:68][O:69][CH2:70][CH2:71][O:72][CH3:73])=[O:16])[CH3:30]

Participants

10

Reactant 7

HCID 1133Thioglycolic AcidHCID 6395Methanesulfonic AcidHCID 8365Ethyl SalicylateHCID 11430Potassium CarbonateHCID 2855718-Crown-6HCID 2599222,7-Dibromo-9-fluorenoneHCID 1317319672-[2-(2-Methoxyethoxy)ethoxy]ethoxy-p-toluenesulfonate

Product 1

HCID 866815343-Ethoxycarbonyl-4-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]phenyl-fluoreneYield 39,791.301%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
75 °C

Procedure

52.5 g (0.16 mol) of 2,7-dibromo-9-fluorenone, 154.8 g (0.93 mol) of ethyl salicylate, and 1.4 g (0.016 mol) of mercaptoacetic acid were placed into a flask having a volume of 3,000 mL, and the atmosphere in the flask was replaced by nitrogen gas. Methanesulfonic acid (630 mL) was further added into the flask and the mixture was stirred overnight at 75° C. The mixture was allowed to cool. When the mixture was added to ice water and the resultant mixture was stirred for 1 hour, a solid was generated. The generated solid was separated by filtration and the solid was washed with heated acetonitrile. The washed solid was dissolved into acetone. A solid was obtained by recrystallization from the obtained acetone solution and separated by filtration. The obtained solid (62.7 g), 2-[2-(2-methoxyethoxy)ethoxy]ethoxy-p-toluenesulfonate (86.3 g, 0.27 mmol), potassium carbonate (62.6 g, 0.45 mmol), and 18-crown-6 (7.2 g, 0.027 mol) were dissolved into N,N-dimethylformamide (DMF) (670 mL). The obtained solution was transferred to a flask and stirred overnight at 105° C. The obtained solution was allowed to cool to the room temperature. The mixture is added to ice water, and the resultant mixture was stirred for 1 hour. Chloroform was added the solution to perform liquid separation and extraction. 2,7-dibromo-9,9-bis[3-ethoxycarbonyl-4-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]phenyl-fluorene (compound B) (51.2 g) was obtained by concentrating the obtained solution. The yield was 31%.

Workup

  1. temperatureto cool
  2. customThe generated solid was separated by filtration
  3. washthe solid was washed with heated acetonitrile
  4. dissolutionThe washed solid was dissolved into acetone
  5. customA solid was obtained by recrystallization from the obtained acetone solution
  6. customseparated by filtration
  7. customThe obtained solution was transferred to a flask
  8. stirringstirred overnight at 105° C
  9. temperatureto cool to the room temperature
  10. customliquid separation and extraction

Sources & evidence

ORD record
ord-d930f6c6b60246d5b6bbf2537b6f39fb
Source dataset
uspto-grants-2014_10
Patent number
US08866134B2

Reaction notes

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