Heptane → HCID 11024585, compound

HRID 2069992Notes

Reaction equation

HRID 2069992 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].[H][H].CCCCCCC>C(O)(=O)C.[Ni]>[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)[CH:23]1[CH:14]([CH2:15][C:16]2[C:21]([NH:22]1)=[CH:20][CH:19]=[CH:18][CH:17]=2)[CH2:13]3)=[O:11]

Participants

6

Reactant 3

HCID 8900HeptaneHCID 24360CamptothecinHCID 178418361HCID 178418361, compound

Product 1

HCID 11024585HCID 11024585, compoundYield 96.8%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 176Acetic AcidSolvent

Conditions

Temperature
110 °C

Procedure

In a 350 mL high pressure autoclave, 6 g (17.2 mmol) of camptothecin was suspended in 60 mL of acetic acid, and into which 2.4 g of stabilized nickel catalyst (N113) was added. After substituting the atmosphere in the autoclave with hydrogen, the suspension was heated at 110° C. under 2.0 MPa for 3 hours with stirring, whereat the starting material disappeared. The reaction liquid was cooled off to room temperature, filtered on 3 g of Celite and washed with 30 mL of acetic acid. The filtrate was washed with heptane (once with 80 mL and twice with 60 mL each), extracted with 60 mL of chloroform, and the organic layer was washed successively with 30 mL of water and 30 mL of saturated saline. The organic layer was dried over 2 g of magnesium sulfate, filtered and concentrated. To the resulting orange colored oil, 10 mL of chloroform was added and heated at 35° C. to form a homogeneous solution. Upon adding thereto 10 mL of heptane, a precipitate was formed. Distilling the solvent off under reduced pressure and drying the residue, 5.8 g of 1,2,6,7-tetrahydrocamptothecin was obtained as an orange colored powder (yield: 96.8%, in which the diastereoisomeric ratio* was 21:76).

Workup

  1. customThe reaction liquid
  2. temperaturewas cooled off to room temperature
  3. filtrationfiltered on 3 g of Celite
  4. washwashed with 30 mL of acetic acid
  5. washThe filtrate was washed with heptane (once with 80 mL
  6. extractiontwice with 60 mL each), extracted with 60 mL of chloroform
  7. washthe organic layer was washed successively with 30 mL of water and 30 mL of saturated saline
  8. dry with materialThe organic layer was dried over 2 g of magnesium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated
  11. additionTo the resulting orange colored oil, 10 mL of chloroform was added
  12. temperatureheated at 35° C.
  13. customto form a homogeneous solution
  14. additionUpon adding
  15. distillationDistilling the solvent off under reduced pressure
  16. customdrying the residue

Sources & evidence

ORD record
ord-8e0a800e1fdf40819b25a03abe90fac2
Source dataset
uspto-grants-2012_10
Patent number
US08299251B2

Reaction notes

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