Ethyl Acetoacetate → N-(1-Carboethoxy-propen-1-yl-2)-daunorubicin

HRID 621718Notes

Reaction equation

HRID 621718 reaction equation
[CH3:1][C@@H:2]1[O:7][C@@H:6]([O:8][C@@H:9]2[C:14]3=[C:15]([OH:32])[C:16]4[C:28](=[O:29])[C:27]5[C:22](=[CH:23][CH:24]=[CH:25][C:26]=5[O:30][CH3:31])[C:20](=[O:21])[C:17]=4[C:18]([OH:19])=[C:13]3[CH2:12][C@@:11]([OH:36])([C:33]([CH3:35])=[O:34])[CH2:10]2)[CH2:5][C@H:4]([NH2:37])[C@@H:3]1[OH:38].[C:39]([CH2:42][C:43]([O:45][CH2:46][CH3:47])=[O:44])(=O)[CH3:40].C1(C)C=CC=CC=1.CC(C)=O>C(Cl)Cl>[CH3:47][CH2:46][O:45][C:43](/[CH:42]=[C:39](/[NH:37][C@@H:4]1[C@H:3]([OH:38])[C@H:2]([CH3:1])[O:7][C@@H:6]([O:8][C@@H:9]2[C:14]3[C:13](=[C:18]([OH:19])[C:17]4[C:20](=[O:21])[C:22]5[CH:23]=[CH:24][CH:25]=[C:26]([O:30][CH3:31])[C:27]=5[C:28](=[O:29])[C:16]=4[C:15]=3[OH:32])[CH2:12][C@@:11]([OH:36])([C:33]([CH3:35])=[O:34])[CH2:10]2)[CH2:5]1)\[CH3:40])=[O:44]

Participants

5

Reactant 3

HCID 8868Ethyl AcetoacetateHCID 30323DaunorubicinHCID 20247278Toluene acetone

Product 1

HCID 6447915N-(1-Carboethoxy-propen-1-yl-2)-daunorubicin

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

0.53 gram of daunorubicin in a free base is dissolved in 100 ml of methylene chloride. 1 ml of ethyl acetylacetate is added to the solution by constant stirring. The entire mixture is agitated for 12 hours at room temperature in a nitrogenic atmosphere. The reaction is checked by means of thin-layer chromatography on a silica gel in a toluene-acetone system in a ratio of 8:1. The solution is then evaporated until a small volume of composition remains and, the final product is pecipitated by the addition of a mixture of ethyl ether and hexane in a ratio of 1:1. The precipitated results from the mixture of acetone and ethyl ether. 0.4 g of N-(1-carboethoxy-propen-1-yl-2)-daunorubicin is obtained which corresponds to 60 percent of the theoretical yield. The composition decomposes at 151°-154° C., M.S.F.D. m/z 639 (M+, 80 percent of relative intensity); 640 (M+ +1, 100 percent of relative intensity); IR (KBr)ν=1590, 1610, 1650, 1670, 1715, 1720, cm-1 (chelate and free carbonyl groups).

Workup

  1. customThe solution is then evaporated until a small volume of composition
  2. additionthe final product is pecipitated by the addition of a mixture of ethyl ether and hexane in a ratio of 1:1
  3. customThe precipitated results from the mixture of acetone and ethyl ether

Sources & evidence

ORD record
ord-5593bb73fe7f41b4913e8ef522b891d3
Source dataset
uspto-grants-1989_04
Patent number
US04824944

Reaction notes

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