HCID 22633822, compound → HCID 22633815, compound

HRID 2417142Notes

Reaction equation

HRID 2417142 reaction equation
[C:1]([C:5]1[CH:6]=[C:7]([O:15][C:16]2[CH:17]=[C:18]([CH:29]=[C:30]([O:32][C:33]3[CH:38]=[C:37]([C:39]([CH3:42])([CH3:41])[CH3:40])[CH:36]=[C:35]([C:43]([CH3:46])([CH3:45])[CH3:44])[CH:34]=3)[CH:31]=2)[C:19]([C:21]2[CH:26]=[CH:25][C:24]([O:27]C)=[CH:23][CH:22]=2)=[O:20])[CH:8]=[C:9]([C:11]([CH3:14])([CH3:13])[CH3:12])[CH:10]=1)([CH3:4])([CH3:3])[CH3:2]>Br.[Br-].C([P+](CCCC)(CCCC)CCCC)CCCCCCCCCCCCCCC>[C:11]([C:9]1[CH:8]=[C:7]([O:15][C:16]2[CH:17]=[C:18]([CH:29]=[C:30]([O:32][C:33]3[CH:38]=[C:37]([C:39]([CH3:42])([CH3:41])[CH3:40])[CH:36]=[C:35]([C:43]([CH3:46])([CH3:45])[CH3:44])[CH:34]=3)[CH:31]=2)[C:19]([C:21]2[CH:22]=[CH:23][C:24]([OH:27])=[CH:25][CH:26]=2)=[O:20])[CH:6]=[C:5]([C:1]([CH3:4])([CH3:3])[CH3:2])[CH:10]=1)([CH3:12])([CH3:13])[CH3:14]

Participants

4

Reactant 1

HCID 22633822HCID 22633822, compound

Product 1

HCID 22633815HCID 22633815, compound

Reagents, catalysts & solvents 2

HCID 84716Hexadecyltributylphosphonium bromideCatalystHCID 260Hydrogen BromideSolvent3×

Conditions

Temperature
50 °C

Procedure

2.80 g (4.5 mmoles) of 3,5-bis-(3,5-di-tert.-butylphenyloxy)4′-methoxybenzo-phenone are dissolved under argon in 100 ml of hydrobromic acid solution (33% in acetic acid). 0.23 g (0.5 mmole) of: hexadecyltributylphosphonium bromide is added thereto. The solution is stirred for 3 hours at 50° C. The course of the reaction is followed by thin layer chromatography. An additional 100 ml of hydrobromic acid (33% in glacial acetic acid) and 20 ml of aqueous hydrobromic acid (48%) are added to the reaction solution. The solution is stirred for a further 18 hours under reflux. After cooling the solution, the reaction mixture is poured onto ice and extracted several times with diethyl ether. The combined organic phases are washed with saturated NaCl solution. The product is dried over magnesium sulfate and the solvent is removed in vacuo. The crude product is chromatographed on silica gel (silica gel 60, 0.040-0.063 mm, Merck) using a mixture of n-hexane/ethyl acetate (9:1). After removing the solvent and drying the residue in a high vacuum, 2.47 g (90%) of a white solid are obtained.

Workup

  1. stirringThe solution is stirred for a further 18 hours
  2. temperatureunder reflux
  3. temperatureAfter cooling the solution
  4. additionthe reaction mixture is poured onto ice
  5. extractionextracted several times with diethyl ether
  6. washThe combined organic phases are washed with saturated NaCl solution
  7. dry with materialThe product is dried over magnesium sulfate
  8. customthe solvent is removed in vacuo
  9. customThe crude product is chromatographed on silica gel (silica gel 60, 0.040-0.063 mm, Merck)
  10. additiona mixture of n-hexane/ethyl acetate (9:1)
  11. customAfter removing the solvent
  12. dry with materialdrying the residue in a high vacuum, 2.47 g (90%) of a white solid
  13. customare obtained

Sources & evidence

ORD record
ord-fe6549cccc83421e9dd8f6ca0525eafd
Source dataset
uspto-grants-2004_11
Patent number
US06825312B2

Reaction notes

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