Acetaldehyde → HCID 9886691, compound

HRID 377622Notes

Reaction equation

HRID 377622 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>FC(F)(F)C(O)=O.O.O.O.O.O.O.O.O.S([O-])([O-])(=O)=O.[Fe+2].C(O)(=O)C>[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

9

Reactant 4

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

Product 1

HCID 9886691HCID 9886691, compoundYield 75%

Reagents, catalysts & solvents 4

HCID 62662Ferrous sulfate heptahydrateCatalystHCID 176Acetic AcidSolventHCID 962WaterSolvent3×HCID 6422Trifluoroacetic acidSolvent

Procedure

Camptothecin (5 g, 14.36 mmols) was dissolved in trifluoroacetic acid: acetic acid (60 mL; ratio, 1:1) and added deionized water (15 mL) and 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 min. To the above stirred reaction medium is then introduced 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 using 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 gm of the title compound (75% yield).

Workup

  1. customof 15 min
  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-e0f3eb5b0a7f48559814e693c16ef1d3
Source dataset
uspto-grants-2000_02
Patent number
US06028078

Reaction notes

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