Hexanoyl chloride, 2-[2,4-bis(1,1-dimethylpropyl)phenoxy]- → HCID 13007985, compound

HRID 1016717Notes

Reaction equation

HRID 1016717 reaction equation
C(OC1C=CC(OC2C=CC(C(C)(C)C)=CC=2)=C([N+]([O-])=O)C=1)C1C=CC=CC=1.C([O-])=O.[K+].[NH2:33][C:34]1[C:35]([O:41][C:42]2[CH:47]=[CH:46][C:45]([C:48]([CH3:51])([CH3:50])[CH3:49])=[CH:44][CH:43]=2)=[CH:36][CH:37]=[C:38]([OH:40])[CH:39]=1.[C:52]([C:57]1[CH:71]=[C:70]([C:72]([CH2:75][CH3:76])([CH3:74])[CH3:73])[CH:69]=[CH:68][C:58]=1[O:59][CH:60]([CH2:64][CH2:65][CH2:66][CH3:67])[C:61](Cl)=[O:62])([CH2:55][CH3:56])([CH3:54])[CH3:53]>O.C1(C)C=CC=CC=1.[Pd].C(O)(C)C>[C:48]([C:45]1[CH:46]=[CH:47][C:42]([O:41][C:35]2[C:34]([NH:33][C:61](=[O:62])[CH:60]([O:59][C:58]3[CH:68]=[CH:69][C:70]([C:72]([CH2:75][CH3:76])([CH3:73])[CH3:74])=[CH:71][C:57]=3[C:52]([CH2:55][CH3:56])([CH3:54])[CH3:53])[CH2:64][CH2:65][CH2:66][CH3:67])=[CH:39][C:38]([OH:40])=[CH:37][CH:36]=2)=[CH:43][CH:44]=1)([CH3:51])([CH3:50])[CH3:49]

Participants

9

Reactant 4

HCID 112547Hexanoyl chloride, 2-[2,4-bis(1,1-dimethylpropyl)phenoxy]-HCID 2735122Potassium FormateHCID 13007983HCID 13007983, compoundHCID 13007984HCID 13007984, compound

Product 1

HCID 13007985HCID 13007985, compoundYield 92%

Reagents, catalysts & solvents 4

HCID 23938PalladiumCatalystHCID 962WaterSolvent3×HCID 1140TolueneSolvent2×HCID 3776IsopropanolSolvent

Conditions

Temperature
60 °C

Procedure

In a 500-ml flask, place 18.9 g (0.05 m) of 5-benzyloxy-2-(4-t-butyl-phenoxy)-nitrobenzene (3a), 80 ml of isopropyl alcohol and 40 ml of toluene. Heat the mixture to 60° C. Add 1.0 g of 5% Pd/C wet with 1 ml of water and 21.0 g (0.25 m) of potassium formate in 30 ml of water. Stir the reaction mixture vigorously at 60°-70° C. for 3 hrs under nitrogen. Cool the reaction mixture containing 5-amino-4-(4-t-butylphenoxy)phenol (4a, Y=4-t-butylphenoxy) to 15° C. and add 20.3 g (0.05 m×1.05 @95%) of 2-(2,4-di-t-pentylphenoxy)hexanoyl chloride (R′COZ; R′=1-(2,4-di-t-pentylphenoxy)pentyl and Z=Cl) in 80 ml of toluene slowly over 10 min. Stir the mixture at room temperature for another 30 min and add 100 ml of water. Filter off catalyst and wash with a small volume of toluene and water. Separate toluene solution, wash with 200 ml of 1N HCl twice, and concentrate under a reduced pressure to a thick oil. Add 200 ml of heptane to the oil with gentle stirring. Cool in an ice-water bath for 1 hr. Collect solid, wash with heptane, and dry in a vacuum oven to give 27.0 g (92%) of 4-(4-t-butylphenoxy)-5-{2-(2,4-di-t-pentylphenoxy)hexanoyl}amino-phenol (5a; Y=4-t-butylphenoxy and R′=1-(2,4-di-t-pentylphenoxy)pentyl).

Workup

  1. temperatureCool the reaction mixture
  2. stirringStir the mixture at room temperature for another 30 min
  3. filtrationFilter off catalyst
  4. washwash with a small volume of toluene and water
  5. washSeparate toluene solution, wash with 200 ml of 1N HCl twice
  6. concentrationconcentrate under a reduced pressure to a thick oil
  7. additionAdd 200 ml of heptane to the oil with gentle stirring
  8. temperatureCool in an ice-water bath for 1 hr
  9. customCollect solid
  10. washwash with heptane
  11. customdry in a vacuum oven

Sources & evidence

ORD record
ord-21e2352b42744bfdb5d32dbddfc42b45
Source dataset
uspto-grants-2002_11
Patent number
US06476202B1

Reaction notes

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