Hexanoyl chloride, 2-[2,4-bis(1,1-dimethylpropyl)phenoxy]- → HCID 13007989, compound

HRID 1016718Notes

Reaction equation

HRID 1016718 reaction equation
C(OC1C=CC(OC2C=CC(C(CC)(C)C)=CC=2)=C([N+]([O-])=O)C=1)C1C=CC=CC=1.C([O-])=O.[K+].[NH2:34][C:35]1[C:36]([O:42][C:43]2[CH:48]=[CH:47][C:46]([C:49]([CH2:52][CH3:53])([CH3:51])[CH3:50])=[CH:45][CH:44]=2)=[CH:37][CH:38]=[C:39]([OH:41])[CH:40]=1.[C:54]([C:59]1[CH:73]=[C:72]([C:74]([CH2:77][CH3:78])([CH3:76])[CH3:75])[CH:71]=[CH:70][C:60]=1[O:61][CH:62]([CH2:66][CH2:67][CH2:68][CH3:69])[C:63](Cl)=[O:64])([CH2:57][CH3:58])([CH3:56])[CH3:55]>O.C1(C)C=CC=CC=1.[Pd].C(O)(C)C>[C:54]([C:59]1[CH:73]=[C:72]([C:74]([CH2:77][CH3:78])([CH3:75])[CH3:76])[CH:71]=[CH:70][C:60]=1[O:61][CH:62]([CH2:66][CH2:67][CH2:68][CH3:69])[C:63]([NH:34][C:35]1[C:36]([O:42][C:43]2[CH:48]=[CH:47][C:46]([C:49]([CH2:52][CH3:53])([CH3:50])[CH3:51])=[CH:45][CH:44]=2)=[CH:37][CH:38]=[C:39]([OH:41])[CH:40]=1)=[O:64])([CH2:57][CH3:58])([CH3:55])[CH3:56]

Participants

9

Reactant 4

HCID 112547Hexanoyl chloride, 2-[2,4-bis(1,1-dimethylpropyl)phenoxy]-HCID 2735122Potassium FormateHCID 13007987HCID 13007987, compoundHCID 13007988HCID 13007988, compound

Product 1

HCID 13007989HCID 13007989, compoundYield 91%

Reagents, catalysts & solvents 4

HCID 23938PalladiumCatalystHCID 962WaterSolvent2×HCID 1140TolueneSolvent2×HCID 3776IsopropanolSolvent

Conditions

Temperature
60 °C

Procedure

In a 500-ml flask, place 19.6 g (0.05 m) of 5-benzyloxy-2-(4-t-pentyl-phenoxy)-nitrobenzene (3b), 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 40 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-pentylphenoxy)-phenol (4b; Y=4-t-pentylphenoxy) 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′32 1-(2,4-di-t-pentylphenoxy)pentyl and Z=Cl) in 80 ml of toluene slowly in drop wise over 1 hr period. Stir the mixture at 15° C. for another 30 min. Filter off catalyst and wash with a small volume of toluene and water. Separate toluene solution, wash with 100 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 27.4 g (91%) of 5-{2-(2,4-di-t-pentylphenoxy)hexanoyl}amino-4-(4-t-pentylphenoxy)-phenol (5b; Y=4-t-pentylphenoxy and R′=1-(2,4-di-t-pentylphenoxy)pentyl).

Workup

  1. temperatureCool the reaction mixture
  2. stirringStir the mixture at 15° C. for another 30 min
  3. filtrationFilter off catalyst
  4. washwash with a small volume of toluene and water
  5. washSeparate toluene solution, wash with 100 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-38da38f2c4bb4dfb868eee0d4e6d3dab
Source dataset
uspto-grants-2002_11
Patent number
US06476202B1

Reaction notes

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