Acetaldehyde → HCID 9886691, compound

HRID 564695Notes

Reaction equation

HRID 564695 reaction equation
[CH3:1][CH2:2][C@@:3]1([OH:26])[C:8](=[O:9])[O:7][CH2:6][C:5]2[C:10]([N:12]3[C:24](=[CH:25][C:4]1=2)[C:23]1[N:22]=[C:21]2[C:16]([CH:17]=[CH:18][CH:19]=[CH:20]2)=[CH:15][C:14]=1[CH2:13]3)=[O:11].[CH:27](=[O:29])[CH3:28].S(=O)(=O)(O)O.C(OO)(C)(C)C>O.O.O.O.O.O.O.O.S([O-])([O-])(=O)=O.[Fe+2]>[CH3:1][CH2:2][C@@:3]1([OH:26])[C:8](=[O:9])[O:7][CH2:6][C:5]2[C:10]([N:12]3[C:24](=[CH:25][C:4]1=2)[C:23]1[C:14](=[C:15]([C:27]([CH3:28])=[O:29])[C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][C:21]=2[N:22]=1)[CH2:13]3)=[O:11]

Participants

7

Reactant 4

HCID 177AcetaldehydeHCID 1118Sulfuric AcidHCID 6410tert-Butyl hydroperoxideHCID 24360Camptothecin

Product 1

HCID 9886691HCID 9886691, compoundYield 75%

Reagents, catalysts & solvents 2

HCID 62662Ferrous sulfate heptahydrateCatalystHCID 962WaterSolvent3×

Procedure

Camptothecin (5 g, 14.36 mmol) was dissolved in trifluoroacetic acid/acetic acetic acid (60 mL; ratio, 1:1) and deionized water added (15 mL) along with freshly distilled acetaldehyde (20 mL; excess) followed by dropwise addition of concentrated sulfuric acid (5 mL) at 0° C. using an ice bath over a period of 15 minutes. To the above stirred reaction medium is then introduced a 70% aqueous solution of t-butylhydroperoxide (3 ml) followed by iron sulfate heptahydrate (7.8 g, 28 mmol) in 1 mL water. The reaction mixture was then stirred at 0° C. to 25° C. for an additional 24 hours. The reaction mixture was then diluted with water and extracted with diethyl ether (500 mL×1), chloroform (250 mL×1) and then n-butanol (250 mL ×4). The organic portions were extracted out using diethyl ether and chloroform and discarded as fractions lacking desired product, while the n-butanol portion was concentrated to dryness at 40° C. and the crude product was recrystallized from a 90% chloroform/methanol mixture to furnish 4.2 g of the title compound (75% yield).

Workup

  1. customof 15 minutes
  2. customreaction medium
  3. stirringThe reaction mixture was then stirred at 0° C. to 25° C. for an additional 24 hours
  4. extractionextracted with diethyl ether (500 mL×1), chloroform (250 mL×1)
  5. extractionThe organic portions were extracted
  6. concentrationwhile the n-butanol portion was concentrated to dryness at 40° C.
  7. customthe crude product was recrystallized from a 90% chloroform/methanol mixture

Sources & evidence

ORD record
ord-2b620f8610b4459796c8a25f0fb8fb92
Source dataset
uspto-grants-2001_01
Patent number
US06169080A

Reaction notes

Loading…