Hydrochloric Acid → HCID 19382524, compound

HRID 2400133Notes

Reaction equation

HRID 2400133 reaction equation
[C:1]([O:7][C:8]([CH3:11])([CH3:10])[CH3:9])(=[O:6])[CH2:2][C:3]([CH3:5])=[O:4].[C:12]([O-:18])(=[O:17])[CH2:13][C:14]([CH3:16])=[O:15].[C:19](Cl)(=[O:29])[C:20]1[CH:28]=[CH:27][C:23]([C:24](Cl)=[O:25])=[CH:22][CH:21]=1.[OH-].[Na+].Cl>C1(C)C=CC=CC=1>[CH3:9][C:8]([O:7][C:1](=[O:6])[CH:2]([C:3](=[O:4])[CH3:5])[C:19](=[O:29])[C:20]1[CH:28]=[CH:27][C:23]([C:24](=[O:25])[CH:13]([C:14](=[O:15])[CH3:16])[C:12]([O:18][C:8]([CH3:11])([CH3:10])[CH3:9])=[O:17])=[CH:22][CH:21]=1)([CH3:11])[CH3:10]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 7488Terephthaloyl chloride2×HCID 14798Sodium HydroxideHCID 15538Tert-butyl acetoacetateHCID 6971017Acetoacetate

Product 1

HCID 19382524HCID 19382524, compoundYield 50.7%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent3×

Conditions

Temperature
10 °C

Procedure

In a 51, 3-necked, RB flask equipped with a mechanical stirrer, nitrogen sparge, 2 addition funnels, and temperature probe was placed aqueous NaOH (67.7 g in 200 mL distilled water). The mixture was cooled to 10° C. and t-butyl acetoacetate (t-BAA) (259.1 g, 1.64 mol) in 500 ml toluene was added dropwise. Additional toluene (ca. 300 mL) was added to help disperse the solid acetoacetate anion and the reaction cooled to 5° C. Terephthaloyl chloride (159.1 g, 0.78 mol) dispersed in 500 ml toluene was added dropwise at such a rate as to keep the reaction temperature below 10° C. After addition of approximately half of the terephthaloyl chloride solution, co-addition of NaOH (64.4 g in 100 ml distilled water) was started--again at such a rate as to keep the temperature below 10° C. The resulting reaction was stirred for 6 additional hours, acidified with HCl to a pH of 5 and allowed to stand overnight. The resulting organic layer was separated from the aqueous phase, extracted with brine, dried over anhydrous MgSO4, concentrated in vacuo and the resulting crystals collected and washed with heptane to yield 176.7 g (50.7% yield) white crystals, mp 94°-96° C. The mother liquor from this crystallization was seeded to produce 84.8 g additional product collected. Over-all yield 261.5 g (75.1%).

Workup

  1. customIn a 51, 3-necked, RB flask equipped with a mechanical stirrer
  2. customnitrogen sparge
  3. addition2 addition funnels, and temperature probe
  4. temperaturethe reaction cooled to 5° C
  5. additionwas added dropwise at such a rate as
  6. customthe reaction temperature below 10° C
  7. customthe temperature below 10° C
  8. customThe resulting reaction
  9. customThe resulting organic layer was separated from the aqueous phase
  10. extractionextracted with brine
  11. dry with materialdried over anhydrous MgSO4
  12. concentrationconcentrated in vacuo
  13. customthe resulting crystals collected
  14. washwashed with heptane

Sources & evidence

ORD record
ord-f44fa7be95214028bc33666b914945d1
Source dataset
uspto-grants-1995_09
Patent number
US05453464

Reaction notes

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