Toluene → HCID 15143267, compound

HRID 481150Notes

Reaction equation

HRID 481150 reaction equation
[CH:1]1[C:2]([CH2:9][OH:10])([CH2:7][OH:8])[CH2:3][CH2:4][CH2:5][CH:6]=1.[C:11]1([CH3:17])[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.[CH2:18]([O:20][C:21](OCC)(OCC)[O:22]CC)C>C(O)C.O>[CH2:3]1[C:2]2([CH2:9][O:10][C:21]3([O:20][CH2:18][C:11]4([CH2:16][CH2:15][CH:14]=[CH:13][CH2:12]4)[CH2:17][O:22]3)[O:8][CH2:7]2)[CH2:1][CH2:6][CH:5]=[CH:4]1

Participants

6

Reactant 3

HCID 1140TolueneHCID 66213Tetraethyl orthocarbonateHCID 20387250(Cyclohex-2-ene-1,1-diyl)dimethanol

Product 1

HCID 15143267HCID 15143267, compound

Reagents, catalysts & solvents 2

HCID 702EthanolSolvent2×HCID 962WaterSolvent

Procedure

To a three-necked round-bottomed flask, equipped with a Dean-Stark trap (20 mL), a reflux condenser, a thermometer and a magnetic stir bar, was placed 2,2-cyclohexene-dimethanol 1 (15.78 g, 111 mmol) and 400 mL of toluene under an atmosphere of N2. The mixture was brought to reflux and maintained at reflux temperature for 2 hours to azeotropically remove any moisture. About 100 mL (5×20 mL) of azeotropic mixture was collected in the Dean-Stark trap. The mixture was then allowed to slowly cool to room temperature and 0.3 g of anhydrous para-toluenesulfonic acid (PTSA) was added, followed by dropwise addition of tetraethylorthocarbonate (TEOC, 11.7 mL, 56 mmol). The resulting mixture was brought to reflux to azeotropically remove ethanol generated during the reaction. The azeotropic mixture was shaken with salt water to determine the amount (volume) of ethanol collected. The reaction was monitored by GC (5 min at 105° C., a 20° C./min rise to 225° C.) and/or by TLC (silica gel, 15% ether/hexanes). After a total of 160 m L of azeotropic mixture (12.3 mL of ethanol) was collected, the reaction mixture was allowed to reflux for an additional 2 hours and then allowed to stir at 102° C. overnight. The reaction mixture was allowed to slowly cool to room temperature and then neutralized by the addition of 1 mL of triethylamine. The resulting mixture was allowed to stir at room temperature for an additional 30 min, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure to give a light yellowish solid. The crude material was then purified by flash chromatography (silica gel, 15-25% ether/hexanes) or by recrystallization from refluxing ethyl ether/hexanes (v/v 1:1). The desired product 8,10,19,20-tetraoxatrispiro[5.2.2.5.2.2]henicosa-2,14-diene 2 (DCH) was obtained as white crystals in 80% yield. Mp (DSC) 118° C.; 1H-NMR (CDCl3, 300 MHz) a 126.20, 124.29, 114.82, 70.21, 30.62, 26.56, 21.42; IR (KBr pellet) (cm−1) 3020, 2920, 2850, 1630, 1440, 1365, 1250, 1225, 1190, 1100, 1025, 1000, 935, 920, 650; Anal. Calcd for C16H26O5: C, 69.84; H, 8.27; Found: C, 69.68; H, 8.42.

Workup

  1. customTo a three-necked round-bottomed flask, equipped with a Dean-Stark trap (20 mL), a reflux condenser
  2. temperatureto reflux
  3. temperaturemaintained
  4. temperatureat reflux temperature for 2 hours
  5. customto azeotropically remove any moisture
  6. customAbout 100 mL (5×20 mL) of azeotropic mixture was collected in the Dean-Stark trap
  7. addition0.3 g of anhydrous para-toluenesulfonic acid (PTSA) was added
  8. customgenerated during the reaction
  9. customcollected
  10. custom5 min
  11. customat 105° C.
  12. customto 225° C.
  13. customAfter a total of 160 m L of azeotropic mixture (12.3 mL of ethanol) was collected
  14. temperatureto reflux for an additional 2 hours
  15. temperatureto slowly cool to room temperature
  16. additionneutralized by the addition of 1 mL of triethylamine
  17. stirringto stir at room temperature for an additional 30 min
  18. dry with materialdried over anhydrous magnesium sulfate
  19. filtrationfiltered
  20. concentrationconcentrated under reduced pressure
  21. customto give a light yellowish solid
  22. customThe crude material was then purified by flash chromatography (silica gel, 15-25% ether/hexanes) or by recrystallization
  23. temperaturefrom refluxing ethyl ether/hexanes (v/v 1:1)

Sources & evidence

ORD record
ord-44a933cee8234d0cb50c2bf39e9f4cd4
Source dataset
uspto-grants-2003_11
Patent number
US06653486B2

Reaction notes

Loading…