Benzoyl chloride → HCID 11069003, compound

HRID 1582430Notes

Reaction equation

HRID 1582430 reaction equation
C([O:8][C@H:9]1[C@H:13]2[O:14][CH2:15][C@@:10]1([CH2:26][O:27]C(=O)C1C=CC=CC=1)[O:11][C@H:12]2[N:16]1[CH:24]=[N:23][C:22]2[C:17]1=[N:18][CH:19]=[N:20][C:21]=2[NH2:25])C1C=CC=CC=1.[C:36](Cl)(=[O:43])[C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1>CO.C1CCCCC=1.CO.ClCCl.[OH-].[OH-].[Pd+2]>[OH:8][C@H:9]1[C@H:13]2[O:14][CH2:15][C@:10]1([CH2:26][OH:27])[O:11][C@H:12]2[N:16]1[CH:24]=[N:23][C:22]2[C:17]1=[N:18][CH:19]=[N:20][C:21]=2[NH:25][C:36](=[O:43])[C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1

Participants

6

Reactant 2

HCID 7412Benzoyl chlorideHCID 20598836HCID 20598836, compound

Product 1

HCID 11069003HCID 11069003, compoundYield 70.1%

Reagents, catalysts & solvents 3

HCID 9942167Palladium hydroxideCatalystHCID 19796094HCID 19796094, compoundSolventHCID 21226129Dichloromethane methanolSolvent

Procedure

A mixture of compound 19 (0.95 g, 2.01 mmol) and Pd(OH)2/C (20%, 1 g) was suspended in methanol/cyclohexene (1:1, 20 mL) and refluxed overnight. The reaction mixture was cooled to rt, filtered through Celite™ column, and concentrated under reduced pressure. The residue was co-evaporated with anhydrous pyridine (2×20 mL), dissolved in anhydrous pyridine, and cooled in ice-bath. Benzoyl chloride (1.15 mL, 10 mmol) was added dropwise and the mixture was stirred at RT for 20 h. Reaction was then quenched by addition of ice-cold water (40 mL), and washed with dichloromethane (2×50 mL). The organic layers were combined, concentrated under reduced pressure, re-dissolved in pyridine/methanol (1:2, 30 mL), and 2 M aqueous NaOH (5 mL) was added. After 15 min, the mixture was neutralised with acetic acid (5 mL) and solvents were removed to give an oily residue. The latter was suspended in 5% methanol/dichloromethane, applied to a silica gel column and eluted by 5 to 15% of methanol/dichloromethane as a solvent. The fractions containing compound 20 were concentrated to yield 0.54 g (70%) of glass-like solid material with the same chromatographic mobility as authentic compound.

Workup

  1. temperaturerefluxed overnight
  2. filtrationfiltered through Celite™ column
  3. concentrationconcentrated under reduced pressure
  4. dissolutiondissolved in anhydrous pyridine
  5. temperaturecooled in ice-bath
  6. customReaction
  7. customwas then quenched by addition of ice-cold water (40 mL)
  8. washwashed with dichloromethane (2×50 mL)
  9. concentrationconcentrated under reduced pressure
  10. dissolutionre-dissolved in pyridine/methanol (1:2, 30 mL)
  11. addition2 M aqueous NaOH (5 mL) was added
  12. waitAfter 15 min
  13. customwere removed
  14. customto give an oily residue
  15. washeluted by 5 to 15% of methanol/dichloromethane as a solvent
  16. additionThe fractions containing compound 20
  17. concentrationwere concentrated

Sources & evidence

ORD record
ord-21a989ad6a6145919fe62f59a5a7921e
Source dataset
uspto-grants-2004_05
Patent number
US06734291B2

Reaction notes

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