Hydrochloric Acid → HCID 22414788, compound

HRID 1721360Notes

Reaction equation

HRID 1721360 reaction equation
[CH3:1][C:2]([CH3:7])=[CH:3][C:4](Cl)=[O:5].[C:8]([C:12]1[CH:17]=[CH:16][CH:15]=[C:14]([C:18]([CH3:21])([CH3:20])[CH3:19])[C:13]=1[OH:22])([CH3:11])([CH3:10])[CH3:9].O.[ClH:24]>C(Cl)Cl.Cl[Ti](Cl)(Cl)Cl>[Cl:24][C:2]([CH3:7])([CH3:1])[CH2:3][C:4]([C:16]1[CH:17]=[C:12]([C:8]([CH3:11])([CH3:10])[CH3:9])[C:13]([OH:22])=[C:14]([C:18]([CH3:21])([CH3:20])[CH3:19])[CH:15]=1)=[O:5]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 962WaterHCID 314052,6-Di-tert-butylphenolHCID 1023943-Methyl-2-butenoyl chloride

Product 1

HCID 22414788HCID 22414788, compound

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-10 °C

Procedure

In a 12 L round bottom flask, equipped with internal thermometer, mechanical stirrer, addition funnel and septum inlet, is placed a solution of 3,3-dimethylacryloylchloride (146 g, 1.23 mol) in CH2Cl2 (1000 mL). The stirred solution is cooled in a CH2Cl2 -dry ice bath to -10° C., and then TiCl4 (1M in CH2Cl2, 1476 mL, 1.47 mol, 1.2 eq) is added via canula at a rate such that the reaction mixture does not warm above -5° C. The solution is stirred for 10 min after addition is complete, and then a solution of 2,6-di-tert-butylphenol (253.4 g, 1.23 mol, 1.0 eq) in CH2Cl2 (500 mL) is added dropwise via addition funnel. The rate of addition is adjusted to maintain the reaction temperature below 0° C. After addition is complete, the cold bath is removed, and the mixture is allowed to stir at ambient temperature for 4 h. TLC analysis (EtOAc:hexane, 1:9) indicates the reaction to be complete. H2O (2 L) is added carefully, and the mixture is transferred to a 6 L extraction funnel. The organic phase is separated, washed with additional H2O (2×1000 mL), dried over Na2SO4, filtered, and returned to the 12 L reaction vessel. Ethereal HCl (1M, Aldrich, 2000 mL) is added. After stirring 2 h, the solution is transferred to the 6 L separatory funnel, and washed with H2O (3×1 L). The organic phase is dried over Na2SO4, filtered into a 10-L round bottom flask, and rotary evaported. The residue is taken up in 1 L pentane, and kept at -4° C. overnight. The resulting crystalline solid is filtered off and dried to give 3-chloro-1-(3, 5-di-tert-butyl-4-hydroxyphenyl )-3-methylbutan-1-one.

Workup

  1. customIn a 12 L round bottom flask, equipped with internal thermometer, mechanical stirrer, addition funnel and septum inlet
  2. temperaturedoes not warm above -5° C
  3. additionafter addition
  4. additionThe rate of addition
  5. temperatureto maintain the reaction temperature below 0° C
  6. additionAfter addition
  7. customthe cold bath is removed
  8. stirringto stir at ambient temperature for 4 h
  9. customthe reaction
  10. extractionthe mixture is transferred to a 6 L extraction funnel
  11. customThe organic phase is separated
  12. washwashed with additional H2O (2×1000 mL)
  13. dry with materialdried over Na2SO4
  14. filtrationfiltered
  15. customreturned to the 12 L reaction vessel
  16. stirringAfter stirring 2 h
  17. washwashed with H2O (3×1 L)
  18. dry with materialThe organic phase is dried over Na2SO4
  19. filtrationfiltered into a 10-L round bottom flask
  20. waitkept at -4° C. overnight
  21. filtrationThe resulting crystalline solid is filtered off
  22. customdried

Sources & evidence

ORD record
ord-288fa25d46dc44dcbfaa6ce6f8245af0
Source dataset
uspto-grants-1996_04
Patent number
US05510361

Reaction notes

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