O-Xylene → HCID 13007991, compound

HRID 431303Notes

Reaction equation

HRID 431303 reaction equation
[C:1]([C:6]1[CH:41]=[C:40]([C:42]([CH2:45][CH3:46])([CH3:44])[CH3:43])[CH:39]=[CH:38][C:7]=1[O:8][CH:9]([CH2:34][CH2:35][CH2:36][CH3:37])[C:10]([NH:12][C:13]1[C:22]([O:23][C:24]2[CH:29]=[CH:28][C:27]([C:30]([CH3:33])([CH3:32])[CH3:31])=[CH:26][CH:25]=2)=[CH:21][C:16]2[NH:17]C(=O)[O:19][C:15]=2[CH:14]=1)=[O:11])([CH2:4][CH3:5])([CH3:3])[CH3:2].C1(C)C(C)=CC=CC=1.[OH-].[Ca+2].[OH-]>C(O)CO>[NH2:17][C:16]1[CH:21]=[C:22]([O:23][C:24]2[CH:25]=[CH:26][C:27]([C:30]([CH3:33])([CH3:32])[CH3:31])=[CH:28][CH:29]=2)[C:13]([NH:12][C:10](=[O:11])[CH:9]([O:8][C:7]2[CH:38]=[CH:39][C:40]([C:42]([CH2:45][CH3:46])([CH3:44])[CH3:43])=[CH:41][C:6]=2[C:1]([CH2:4][CH3:5])([CH3:3])[CH3:2])[CH2:34][CH2:35][CH2:36][CH3:37])=[CH:14][C:15]=1[OH:19]

Participants

5

Reactant 3

HCID 7237O-XyleneHCID 6093208Calcium HydroxideHCID 18763750HCID 18763750, compound

Product 1

HCID 13007991HCID 13007991, compoundYield 85%

Reagents, catalysts & solvents 1

HCID 174Ethylene GlycolSolvent

Conditions

Temperature
80 °C

Procedure

In a 250-ml flask inert with nitrogen, place 11.3 g (0.018 m) of 6-{2-(2,4-di-t-pentylphenoxy)hexanoyl}amino-5-(4-t-butylphenoxy)-benzoxazol-2-one (2, Y=4-t-butylphenoxy and R′=1-(2,4-di-t-pentylphenoxy)pentyl), 120 ml of xylene, 12 ml of ethylene glycol, and 8.0 g of calcium hydroxide. Heat under reflux collecting approximately 7 ml of water-ethylene glycol and 20 ml of xylene in a Dean-Stark trap. Detach the trap and heat under reflux for 5 hrs. Cool to 80° C. and add 100 ml of toluene, 100 ml of hot water, 25 ml of acetic acid, and 2 g sodium hydrosulfite. Stir the mixture at 60°-65° C. for 15 min and filter through a Celite pad to remove interlayer insolubles. Separate toluene-xylene solution, wash with 100 ml of hot water +12 ml of acetic acid +2 g sodium hydrosulfite and 100 ml of hot water twice, and concentrate under a reduced pressure to a thick oil. Dissolve the oil in 200 ml of heptane, add seed crystals, and stand at room temperature over night. Cool in an ice-water bath for 1 hr, collect solid, wash with heptane, and dry in a vacuum oven to give 9.2 g (85%) of 2-amino-5-{2-(2,4-di-t-pentylphenoxy)hexanoyl}amino-4-(4-t-butylphenoxy)-phenol (Formula I; Y=4-t-butylphenoxy and R′=1-(2,4-di-t-pentylphenoxy)pentyl).

Workup

  1. temperatureHeat
  2. temperatureunder reflux
  3. customcollecting approximately 7 ml of water-ethylene glycol and 20 ml of xylene in a Dean-Stark trap
  4. temperatureDetach the trap and heat
  5. temperatureunder reflux for 5 hrs
  6. additionadd 100 ml of toluene, 100 ml of hot water, 25 ml of acetic acid, and 2 g sodium hydrosulfite
  7. filtrationfilter through a Celite pad
  8. customto remove interlayer insolubles
  9. washSeparate toluene-xylene solution, wash with 100 ml of hot water +12 ml of acetic acid +2 g sodium hydrosulfite and 100 ml of hot water twice
  10. concentrationconcentrate under a reduced pressure to a thick oil
  11. dissolutionDissolve the oil in 200 ml of heptane
  12. additionadd seed crystals
  13. waitstand at room temperature over night
  14. temperatureCool in an ice-water bath for 1 hr
  15. customcollect solid
  16. washwash with heptane
  17. customdry in a vacuum oven

Sources & evidence

ORD record
ord-d5f54d3362cf4b0c9ecdf55c4cbc7eb3
Source dataset
uspto-grants-2003_12
Patent number
US06657083B2

Reaction notes

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