Pyridine → Trifluoroacetyladriamycin-14-valerate

HRID 259022Notes

Reaction equation

HRID 259022 reaction equation
[CH3:1][C@@H:2]1[O:7][C@@H:6]([O:8][C@@H:9]2[C:18]3[C:13](=[C:14]([OH:32])[C:15]4[C:24](=[O:25])[C:23]5[CH:26]=[CH:27][CH:28]=[C:29]([O:30][CH3:31])[C:22]=5[C:20](=[O:21])[C:16]=4[C:17]=3[OH:19])[CH2:12][C@@:11]([OH:37])([C:33]([CH2:35][OH:36])=[O:34])[CH2:10]2)[CH2:5][C@H:4]([NH:38][C:39]([C:41]([F:44])([F:43])[F:42])=[O:40])[C@@H:3]1[OH:45].N1C=CC=CC=1.[C:52](Cl)(=[O:57])[CH2:53][CH2:54][CH2:55][CH3:56]>C(Cl)(Cl)Cl>[CH3:56][CH2:55][CH2:54][CH2:53][C:52]([O:36][CH2:35][C:33]([C@:11]1([OH:37])[CH2:12][C:13]2[C:18](=[C:17]([OH:19])[C:16]3[C:20](=[O:21])[C:22]4[C:29]([O:30][CH3:31])=[CH:28][CH:27]=[CH:26][C:23]=4[C:24](=[O:25])[C:15]=3[C:14]=2[OH:32])[C@@H:9]([O:8][CH:6]2[O:7][CH:2]([CH3:1])[CH:3]([OH:45])[CH:4]([NH:38][C:39]([C:41]([F:44])([F:42])[F:43])=[O:40])[CH2:5]2)[CH2:10]1)=[O:34])=[O:57]

Participants

5

Reactant 3

HCID 1049PyridineHCID 61186Valeryl chlorideHCID 73551N-Trifluoroacetyladriamycin2×

Product 1

HCID 41744Trifluoroacetyladriamycin-14-valerate

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

A solution containing 5.0 mg. of N-trifluoroacetyladriamycin dissolved in 0.5 ml. of anhydrous pyridine was treated with 18 microliters of valeroyl chloride, which was added in small portions over a two-day period. The reaction was monitored by thin layer chromatography and when the presence of N-trifluoroacetyladriamycin could no longer be observed, the reaction mixture was diluted with 10 ml. of chloroform. The chloroform solution was extracted three times with pH 4 gaseous buffer and once with pH 7 buffer. The dried chloroform solution was then evaporated under reduced pressure, and the residue was purified by preparative thin layer chromatography on silica gel G with chloroform:methanol:water (120:20:1 by volume) as the solvent system. The major orange-colored band was removed and washed free of silica gel with a mixture of methanol and ethyl acetate. Upon evaporation of the methanol and ethyl acetate, 2.19 mg. of N-trifluoroacetyladriamycin-14-valerate was obtained. This material was idential by spectral and chromatographic comparison with samples of N-trifluoroacetyladriamycin-14-valerate prepared by the earlier described methods.

Workup

  1. additionA solution containing 5.0 mg
  2. additionwas added in small portions over a two-day period
  3. additionthe reaction mixture was diluted with 10 ml
  4. extractionThe chloroform solution was extracted three times with pH 4 gaseous buffer
  5. customThe dried chloroform solution was then evaporated under reduced pressure
  6. customthe residue was purified by preparative thin layer chromatography on silica gel G with chloroform:methanol:water (120:20:1 by volume) as the solvent system
  7. customThe major orange-colored band was removed
  8. washwashed free of silica gel with a mixture of methanol and ethyl acetate
  9. customUpon evaporation of the methanol and ethyl acetate, 2.19 mg

Sources & evidence

ORD record
ord-74b2f1a772f8492c9896b1dec6b4fb32
Source dataset
uspto-grants-1977_07
Patent number
US04035566

Reaction notes

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