Ammonia → 1,3,7,9-tetratert-butyl-11-fluoro-5-methyl-5H-benzo(d)(1,3,2)benzodioxaphosphocine

HRID 846462

Reaction equation

HRID 846462 reaction equation
[CH:1]([C:18]1[CH:23]=[C:22]([C:24]([CH3:27])([CH3:26])[CH3:25])[CH:21]=[C:20]([C:28]([CH3:31])([CH3:30])[CH3:29])[C:19]=1[OH:32])([C:3]1[CH:8]=[C:7]([C:9]([CH3:12])([CH3:11])[CH3:10])[CH:6]=[C:5]([C:13]([CH3:16])([CH3:15])[CH3:14])[C:4]=1[OH:17])[CH3:2].P(Cl)(Cl)Cl.Cl.C(C1C=CC=CC=1O)(C1C=CC=CC=1O)C.P1(Cl)OC2C(C(C)(C)C)=CC(C(C)(C)C)=CC=2C(C)C2C=C(C(C)(C)C)C=C(C(C)(C)C)C=2O1.P(Cl)([O-])[O-].[P:92]([F:95])([O-])[O-].N>C(Cl)Cl.N1C=CC=CC=1>[P:92]1([F:95])[O:17][C:4]2[C:5]([C:13]([CH3:16])([CH3:14])[CH3:15])=[CH:6][C:7]([C:9]([CH3:12])([CH3:10])[CH3:11])=[CH:8][C:3]=2[CH:1]([CH3:2])[C:18]2[CH:23]=[C:22]([C:24]([CH3:27])([CH3:26])[CH3:25])[CH:21]=[C:20]([C:28]([CH3:31])([CH3:30])[CH3:29])[C:19]=2[O:32]1

Participants

11

Reactant 8

HCID 222AmmoniaHCID 313Hydrochloric Acid2×HCID 24387Phosphorus trichlorideHCID 1188992,2'-Ethylidenebis(4,6-di-tert-butylphenol)HCID 110602032,4,8,10-Tetra-tert-butyl-6-chloro-12-methyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocineHCID 13530914EthylidenebisphenolHCID 18378001FluorophosphiteHCID 22015288Chlorophosphite

Product 1

HCID 863481,3,7,9-tetratert-butyl-11-fluoro-5-methyl-5H-benzo(d)(1,3,2)benzodioxaphosphocineYield 80.5%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
45 °C

Procedure

To a reaction vessel equipped with a turbine agitator and a reflux condenser was charged 375 g of methylene chloride, 250 g 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 5 g pyridine and 83 g PCl3. The stirred solution was heated to reflux (45° C.) and held at reflux for 22 hours. Byproduct HCl was vented to a scrubber. About 350 g of additional methylene chloride was added during the reaction to replace that lost through the vent and further dilute the reaction. GC analysis showed conversion of the above ethylidenebisphenol to 2,2'-ethylidenebis(4,6-di-tert-butylphenyl) chlorophosphite. While still at reflux, 13.1 g of anhydrous gaseous HF was fed to the reaction mixture through a dip leg. HF feed required 101/2 hours. Byproduct HCl was vented to a scrubber. GC analysis showed conversion of the above chlorophosphite to the corresponding fluorophosphite to be complete. Gaseous ammonia was immediately fed to the reaction to neutralize the mixture. The reaction mass was filtered to remove ammonium chloride. The filtrate was heated to distill out methylene chloride which was replaced by adding isopropanol. The temperature reached 81° C. at the end of the methylene chloride removal. The mixture was cooled to 30° C. giving a 50 weight percent solids slurry in isopropanol. The solids were removed and the wet cake was washed with isopropanol and dried under vacuum yield 223 g (80.5 percent yield) of 2,2'-ethylidenebis(4,6-di-tert-butylphenyl) fluorophosphite.

Workup

  1. customTo a reaction vessel equipped with a turbine agitator and a reflux condenser
  2. temperatureThe stirred solution was heated
  3. temperatureat reflux for 22 hours
  4. additionfurther dilute
  5. customthe reaction
  6. temperatureWhile still at reflux
  7. custom2 hours
  8. filtrationThe reaction mass was filtered
  9. customto remove ammonium chloride
  10. temperatureThe filtrate was heated
  11. distillationto distill out methylene chloride which
  12. additionby adding isopropanol
  13. customThe temperature reached 81° C. at the end of the methylene chloride removal
  14. temperatureThe mixture was cooled to 30° C.
  15. customgiving a 50 weight percent solids slurry in isopropanol
  16. customThe solids were removed
  17. washthe wet cake was washed with isopropanol

Sources & evidence

ORD record
ord-7139c3e4ab1c4911b505b38eee0bf603
Source dataset
uspto-grants-1992_08
Patent number
US05136075

Linked notes

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