Iodine → 2-Chloro-4,6-bis[4-(2-ethylhexyloxy)phenyl]-s-triazine

HRID 232901Notes

Reaction equation

HRID 232901 reaction equation
[Mg].II.[CH2:4]([CH:6]([CH2:16][CH2:17][CH2:18][CH3:19])[CH2:7][O:8][C:9]1[CH:14]=[CH:13][C:12](Br)=[CH:11][CH:10]=1)[CH3:5].[N:20]1[C:27](Cl)=[N:26][C:24](Cl)=[N:23][C:21]=1[Cl:22]>O1CCCC1>[Cl:22][C:21]1[N:23]=[C:24]([C:12]2[CH:13]=[CH:14][C:9]([O:8][CH2:7][CH:6]([CH2:4][CH3:5])[CH2:16][CH2:17][CH2:18][CH3:19])=[CH:10][CH:11]=2)[N:26]=[C:27]([C:12]2[CH:13]=[CH:14][C:9]([O:8][CH2:7][CH:6]([CH2:4][CH3:5])[CH2:16][CH2:17][CH2:18][CH3:19])=[CH:10][CH:11]=2)[N:20]=1

Participants

6

Reactant 4

HCID 807IodineHCID 7954Cyanuric chlorideHCID 5462224Magnesium2×HCID 225907671-Bromo-4-[(2-ethylhexyl)oxy]benzene

Product 1

HCID 190861852-Chloro-4,6-bis[4-(2-ethylhexyloxy)phenyl]-s-triazineYield 69.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
40 °C

Procedure

A 100 ml sulfonating flask equipped with stirrer, condenser, drying tube, dropping funnel and internal thermometer is charged under inert gas (dry nitrogen) with 3.65 g (0.15 mol) of magnesium turnings, and a few crystals of iodine are added as catalyst. 150 ml of anhydrous tetrahydrofuran are added, and a solution of 42.8 g (0.15 mol) of 4-(2-ethylhexyloxy)bromobenzene in 30 ml of tetrahydrofuran is added dropwise over a period of 45 minutes (room temperature). After slight heating on a water bath (40° C.), the Grignard reaction starts (cloudiness, exothermic reaction). The reaction mixture is stirred at 40° C. for one hour and then under reflux (66° C.) until the magnesium is almost completely dissolved (about 30 minutes). After cooling to room temperature, the Grignard solution is added dropwise at 0°-20° C. to a solution of 9.2 g (0.05 mol) of cyanuric chloride in 40 ml of tetrahydrofuran over a period of 60 minutes (350 ml sulfonating flask, stirrer, condenser, drying tube, dropping funnel, internal thermometer, inert gas). The mixture is stirred overnight under reflux (66° C.) and then evaporated to dryness. The residue is stirred in 100 ml of ice 2N hydrochloric acid and then extracted with 200 ml of toluene. The organic phase is shaken twice with 10% brine, dried over sodium sulfate and evaporated. The crude product (40.3 g, red oil) is still very impure (thin-layer chromatogram). For purification it is dissolved in 80 ml of 1:1 toluene/hexane and chromatographed over silica gel (5 cm×45 cm). 18.2 g (69.5%) of 2-chloro-4,6-bis[4-(2-ethylhexyloxy)phenyl]-s-triazine are isolated as a yellow resin.

Workup

  1. customequipped with stirrer, condenser
  2. customdrying tube
  3. customthe Grignard reaction
  4. custom(cloudiness, exothermic reaction)
  5. dissolutionis almost completely dissolved (about 30 minutes)
  6. temperatureAfter cooling to room temperature
  7. custom(350 ml sulfonating flask, stirrer, condenser, drying tube, dropping funnel, internal thermometer, inert gas)
  8. stirringThe mixture is stirred overnight
  9. temperatureunder reflux (66° C.)
  10. customevaporated to dryness
  11. stirringThe residue is stirred in 100 ml of ice 2N hydrochloric acid
  12. extractionextracted with 200 ml of toluene
  13. stirringThe organic phase is shaken twice with 10% brine
  14. dry with materialdried over sodium sulfate
  15. customevaporated
  16. customFor purification it
  17. dissolutionis dissolved in 80 ml of 1:1 toluene/hexane
  18. customchromatographed over silica gel (5 cm×45 cm)

Sources & evidence

ORD record
ord-42d9de88b1cf4848b5bbaea05b514812
Source dataset
uspto-grants-1997_01
Patent number
US05591850

Reaction notes

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