Hexanoyl chloride, 2-[2,4-bis(1,1-dimethylpropyl)phenoxy]- → HCID 18763750, compound

HRID 1058215Notes

Reaction equation

HRID 1058215 reaction equation
C([N:8]1[C:12]2[CH:13]=[C:14]([O:20][C:21]3[CH:26]=[CH:25][C:24]([C:27]([CH3:30])([CH3:29])[CH3:28])=[CH:23][CH:22]=3)[C:15]([N+:17]([O-])=O)=[CH:16][C:11]=2[O:10][C:9]1=[O:31])C1C=CC=CC=1.C([O-])=O.[K+].NC1C(OC2C=CC(C(C)(C)C)=CC=2)=CC2NC(=O)OC=2C=1.[C:58]([C:63]1[CH:77]=[C:76]([C:78]([CH2:81][CH3:82])([CH3:80])[CH3:79])[CH:75]=[CH:74][C:64]=1[O:65][CH:66]([CH2:70][CH2:71][CH2:72][CH3:73])[C:67](Cl)=[O:68])([CH2:61][CH3:62])([CH3:60])[CH3:59]>O.C1(C)C=CC=CC=1.[Pd].C(O)(C)C>[C:58]([C:63]1[CH:77]=[C:76]([C:78]([CH2:81][CH3:82])([CH3:79])[CH3:80])[CH:75]=[CH:74][C:64]=1[O:65][CH:66]([CH2:70][CH2:71][CH2:72][CH3:73])[C:67]([NH:17][C:15]1[C:14]([O:20][C:21]2[CH:26]=[CH:25][C:24]([C:27]([CH3:28])([CH3:30])[CH3:29])=[CH:23][CH:22]=2)=[CH:13][C:12]2[NH:8][C:9](=[O:31])[O:10][C:11]=2[CH:16]=1)=[O:68])([CH2:61][CH3:62])([CH3:59])[CH3:60]

Participants

9

Reactant 4

HCID 112547Hexanoyl chloride, 2-[2,4-bis(1,1-dimethylpropyl)phenoxy]-HCID 2735122Potassium FormateHCID 18673277HCID 18673277, compoundHCID 18673279HCID 18673279, compound

Product 1

HCID 18763750HCID 18763750, compoundYield 72%

Reagents, catalysts & solvents 4

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

Conditions

Temperature
60 °C

Procedure

In a 500-ml flask, place 17.4 g (0.04 m) of 3-N-benzyl-5-(-t-butylphenoxy)-6-nitro-benzoxazol-2-one (5b), 70 ml of isopropyl alcohol and 35 ml of toluene. Heat the mixture to 60° C. Add 0.8 g of 5% Pd/C wet with 1 ml of water and 16.8 g (0.2 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 6-amino-5-(4-t-butylphenoxy)-benzoxazol-2-one (6b; Y=4-t-butylphenoxy) to 15° C. and add 16.2 g (0.04 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 60 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 180 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 18.1 g (72%) of 6-{2-(2,4-di-t-pentylphenoxy)hexanoyl}amino-5-(4-t-butylphenoxy)-benzoxazol-2-one (Formula I, Y=4-t-butylphenoxy 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 180 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-d88ce131afa045bda4b0d7d5f60aa856
Source dataset
uspto-grants-2003_02
Patent number
US06515176B1

Reaction notes

Loading…