Monobenzone → HCID 68869865, compound

HRID 2112013Notes

Reaction equation

HRID 2112013 reaction equation
[OH:1][CH2:2][CH2:3][C:4]1[CH:5]=[C:6]([CH:19]=[CH:20][CH:21]=1)[O:7][CH2:8][C:9]1[CH:18]=[CH:17][CH:16]=[CH:15][C:10]=1[C:11]([O:13][CH3:14])=[O:12].[CH2:22]([O:29][C:30]1[CH:35]=[CH:34][C:33](O)=[CH:32][CH:31]=1)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(/C(OC(C)C)=O)=N\C(OC(C)C)=O>C1(C)C=CC=CC=1>[CH2:22]([O:29][C:30]1[CH:35]=[CH:34][C:33]([O:1][CH2:2][CH2:3][C:4]2[CH:5]=[C:6]([CH:19]=[CH:20][CH:21]=2)[O:7][CH2:8][C:9]2[CH:18]=[CH:17][CH:16]=[CH:15][C:10]=2[C:11]([O:13][CH3:14])=[O:12])=[CH:32][CH:31]=1)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1

Participants

6

Reactant 4

HCID 7638MonobenzoneHCID 11776TriphenylphosphineHCID 5363146Diisopropyl azodicarboxylateHCID 68870382HCID 68870382, compound

Product 1

HCID 68869865HCID 68869865, compoundYield 39%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

Methyl 2-{[3-(2-hydroxyethyl)phenoxy]methyl}benzoate (0.5 g, 1.75 mmol), 4-(benzyloxy)phenol (0.35 g, 1.75 mmol) and triphenylphosphine (0.5 g, 1.92 mmol) was added to a dry round bottomed flask and fitted with septum. Dry toluene (10 ml) was added and N2 was flushed through the mixture for 5 minutes. Diisopropyl (E)-diazene-1,2-dicarboxylate (0.39 g, 1.92 mmol) was added dropwise and the solution was stirred at room temperature. After three hours another equivalent of reagents was added and stirred for one hour. After removing the solvent by evaporation the crude was purified by preparative HPLC (started with acetonitrile/buffer 60/40 and then the acetonitrile concentration was increased to 100%, the buffer was a mixture of acetonitrile/water 10/90 and ammonium acetate (0.1 M, column KR-100-7-C8, 50 mm×250 mm, flow 40 ml/min)). The product containing fractions were pooled and the acetonitrile was removed by evaporation. EtOAc (10 ml) was added and the organic phase was washed with two portions of brine and dried (MgSO4). Removing the solvent by evaporation gave 0.319 g methyl 2-[(3-{2-[4-(benzyloxy)phenoxy]ethyl}phenoxy)methyl]benzoate (yield 39%).

Workup

  1. customfitted with septum
  2. customN2 was flushed through the mixture for 5 minutes
  3. additionAfter three hours another equivalent of reagents was added
  4. stirringstirred for one hour
  5. customAfter removing the solvent
  6. customby evaporation the crude
  7. customwas purified by preparative HPLC (
  8. concentrationthe acetonitrile concentration
  9. temperaturewas increased to 100%
  10. additiona mixture of acetonitrile/water 10/90 and ammonium acetate (0.1 M, column KR-100-7-C8, 50 mm×250 mm, flow 40 ml/min))
  11. additionThe product containing fractions
  12. customthe acetonitrile was removed by evaporation
  13. additionEtOAc (10 ml) was added
  14. washthe organic phase was washed with two portions of brine
  15. dry with materialdried (MgSO4)
  16. customRemoving the solvent
  17. customby evaporation

Sources & evidence

ORD record
ord-6d40d2b348e84ad189c220190fc67d7b
Source dataset
uspto-grants-2009_04
Patent number
US07521461B2

Reaction notes

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