Methanol → Calix[4]arene

HRID 732164Notes

Reaction equation

HRID 732164 reaction equation
[C:1]1([C:7]#[C:8][C:9]2[CH:14]=[CH:13][C:12]([CH2:15][C:16](=[O:32])[CH2:17][C:18]3[CH:23]=[CH:22]C(C#CC4C=CC=CC=4)=CC=3)=CC=2)[CH:6]=[CH:5][CH:4]=[CH:3]C=1.C[CH:34]([OH:36])C.[C:37]1(C)C=[CH:41][CH:40]=[CH:39][CH:38]=1.[OH-:44].C([N+]([CH2:58][CH2:59][CH2:60][CH3:61])(CCCC)CCCC)CCC.[CH3:62][OH:63]>>[CH2:58]1[C:59]2=[C:62]([OH:63])[C:40](=[CH:41][CH:61]=[CH:60]2)[CH2:39][C:38]2=[C:37]([OH:44])[C:6](=[CH:5][CH:4]=[CH:3]2)[CH2:1][C:7]2=[CH:8][CH:9]=[CH:14][C:13](=[C:34]2[OH:36])[CH2:12][C:15]2=[CH:22][CH:23]=[CH:18][C:17]1=[C:16]2[OH:32]

Participants

6

Reactant 5

HCID 887MethanolHCID 1140TolueneHCID 3776Isopropanol2×HCID 2723671Tetrabutylammonium HydroxideHCID 579767661,3-Bis[4-(phenylethynyl)phenyl]propan-2-one

Product 1

HCID 562409Calix[4]arene

Conditions

Temperature
2 °C

Procedure

A portion of the tetraketone containing pendant discotic moieties (0.01 mole) prepared in the manner of I) above, 1,3-bis(4-phenylethynylphenyl)-2-propanone (0.021 mole), 2-propanol (200 milliliters) and toluene (133 milliliters), are added to a 1 liter four neck Morton flask. The reactor is additionally outfitted with a chilled (2° C.) condenser, a thermometer with thermostatically controlled heating mantle, a Claisen adaptor with addition funnel and nitrogen sparge tube, and a glass stirring shaft with a turbine-type polytetrafluoroethylene stirrer which is coupled to a variable speed motor to provide mechanical stirring. The addition funnel is charged under a dry nitrogen atmosphere with 1M tetrabutylammonium hydroxide in methanol (0.53 milliliter) diluted into 2-propanol (10.5 milliliters). Stirring, sparging with nitrogen (0.3 liter per minute) and heating commences, and once the stirred slurry reaches 80° C., the sparge tube is removed and replaced with an overhead inlet for the nitrogen. Dropwise addition of the solution in the addition funnel to the refluxing stirred slurry commences and is completed over the next 20 minutes, during which time, the yellow slurry is transformed to a deep red solution. HPLC analysis is employed to determine conversion of the reactants, concurrent with optimum formation of the desired double Aldol condensation product and minimum coproduct formation. At the completion of the reaction, heating ceases, the heating mantle is removed from the reactor, additional 2-propanol (180 milliliters) is added to the reactor and the reaction mixture is cooled using a cooling fan on the reactor exterior. Once the stirred slurry cools to 30° C., the product is recovered via filtration through a coarse fritted glass funnel. The crystalline product on the funnel is washed with 2-propanol until a visually clear filtrate is obtained. Drying in a vacuum oven at 60° C. provides a 90 percent isolated yield of the A4B2M2 monomer as a purple colored crystalline powder. HPLC analysis demonstrates the presence of greater than 95 area percent of the desired monomer product:

Workup

  1. additionA portion of the tetraketone containing pendant discotic moieties (0.01 mole)
  2. temperaturea thermometer with thermostatically controlled heating mantle
  3. additiona Claisen adaptor with addition funnel
  4. customnitrogen sparge tube
  5. customto provide mechanical stirring
  6. stirringStirring
  7. customsparging with nitrogen (0.3 liter per minute)
  8. temperatureheating commences
  9. customreaches 80° C.
  10. customthe sparge tube is removed
  11. customreplaced with an overhead inlet for the nitrogen
  12. additionDropwise addition of the solution in the addition funnel to the refluxing
  13. stirringstirred slurry commences
  14. customis completed over the next 20 minutes, during which time
  15. customconcurrent with optimum formation of the desired double Aldol condensation product and minimum coproduct formation
  16. customAt the completion of the reaction
  17. temperatureheating ceases
  18. customthe heating mantle is removed from the reactor, additional 2-propanol (180 milliliters)
  19. additionis added to the reactor
  20. temperaturethe reaction mixture is cooled
  21. customcools to 30° C.
  22. filtrationthe product is recovered via filtration through a coarse fritted glass funnel
  23. washThe crystalline product on the funnel is washed with 2-propanol until a visually clear filtrate
  24. customis obtained
  25. customDrying in a vacuum oven at 60° C.
  26. customprovides a 90 percent
  27. customisolated yield of the A4B2M2 monomer as a purple colored crystalline powder

Sources & evidence

ORD record
ord-e02bb67e95e94ee781393fca4d47a7c4
Source dataset
uspto-grants-2009_09
Patent number
US07585928B2

Reaction notes

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