Ethanol → Disnogamycin

HRID 2052226Notes

Reaction equation

HRID 2052226 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:43])=[C:16]4[C:41](=[O:42])[C:22]5[C:23]([OH:40])=[CH:24][C:25]6[C@@:32]7([CH3:34])[O:33][C@H:28]([C@@H:29]([OH:39])[C@H:30]([N:36]([CH3:38])[CH3:37])[C@H:31]7[OH:35])[O:27][C:26]=6[C:21]=5[C:19](=[O:20])[C:17]4=[CH:18][C:13]=3[C@@H:12](C(O)=O)[C@:11]([OH:48])([CH3:47])[CH2:10]2)[C@H:5]([O:49][CH3:50])[C@@:4]([O:52][CH3:53])([CH3:51])[C@H:3]1[O:54][CH3:55].C(Cl)(Cl)Cl.CCO>CN(C=O)C.CO>[CH3:1][C@@H:2]1[O:7][C@@H:6]([O:8][C@@H:9]2[C:14]3[C:15]([OH:43])=[C:16]4[C:41](=[O:42])[C:22]5[C:21](=[C:26]6[O:27][C@@H:28]7[O:33][C@@:32]([CH3:34])([C@H:31]([OH:35])[C@@H:30]([N:36]([CH3:38])[CH3:37])[C@@H:29]7[OH:39])[C:25]6=[CH:24][C:23]=5[OH:40])[C:19](=[O:20])[C:17]4=[CH:18][C:13]=3[CH2:12][C@:11]([OH:48])([CH3:47])[CH2:10]2)[C@H:5]([O:49][CH3:50])[C@@:4]([O:52][CH3:53])([CH3:51])[C@H:3]1[O:54][CH3:55]

Participants

6

Reactant 3

HCID 702EthanolHCID 6212ChloroformHCID 152473(2R,4R,5R,6R,11S,13S,14R)-11-[(6-Deoxy-3-C-methyl-2,3,4-tri-O-methyl-alpha-L-mannopyranosyl)oxy]-4-(dimethylamino)-3,5,8,10,13-pentahydroxy-6,13-dimethyl-9,16-dioxo-3,4,5,6,9,11,12,13,14,16-decahydro-2H-2,6-epoxytetraceno[1,2-b]oxocine-14-carboxylic acid (incorrect configuration definition!)

Product 1

HCID 152474Disnogamycin

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6228DimethylformamideSolvent

Procedure

A solution of 12.3 g of nogalamycinic acid in a mixture of 20 ml of DMF and 50 ml of CH3OH was prepared by heating. After the solution had stood at room temperature overnight, it was put on 500 g of silica and eluted with CHCl3 --MeOH starting with 99:1 and gradually increasing the concentration of CH3OH until a ratio of 4:1 was reached. The elution was followed by thin layer chromatography (tlc) (CHCl3 --MeOH--H2O; 78:20:2) and collecting those fractions containing only nogamycin (Rf 0.5). A total of 3.9 g was obtained. One and one-half grams was recrystallized from acetone-CH3OH (85:15). Obtained: 259 mg, mp 210°-215° C.; αD +273° (C 0.923, CHCl3); uv (EtOH) λmax nm 236 (ε51,700), 259 (ε25,850), 290 (ε10,050) and 478 (ε16,100); ir (Nujol) 3500, 1670, 1630, 1575, 1295, 1230, 1110, 1055, 1005, 920, 890, 838, 778, 762 and 724 cm-1 ; mass spectrum m/e 729; 'H NMR (d7 -DMF) 1.14, 1.23, 1.37, 1.69 (12 H, 4 CH3C), δ2.07-2.38, 2.83-3.0 (m, 4 H, 2 CH2), 2.42 [s, 6 H, (CH3)2N], δ3.13, 3.42, 3.52 (3 S, 9 H, 3 CH3O), 3.3-4.2 (m, CHO, CHN), 4.95 (m, 1 H, benzylic CHO), δ5.32 (d, 1 H, anomeric), δ5.68 (1 H, anomeric) δ7.16, 7.32 (2s, 2 H, aromatic); 13C NMR (CDCl3) δ15.2, 18.3, 24.2, 30.4 (4 CH3C), 30.8 (CH2), δ41.5 [(CH3)2N], δ44.1 (CH2) δ48.7, 59.0, 61.4 (3 CH3O), δ66.4-88.6 (CO and CN), δ96.79 and 99.81 (anomeric), δ113.1-161.4 (aromatic), δ179.7 and 190.8 (carbonyl). Anal. calcd. for C37H47NO14 : C, 60.96; H, 6.55; N, 1.92. Found: C, 58.55; H, 6.42; N, 1.94.

Workup

  1. customwas prepared
  2. temperatureby heating
  3. washeluted with CHCl3
  4. temperatureMeOH starting with 99:1 and gradually increasing the concentration of CH3OH until a ratio of 4:1
  5. washThe elution
  6. customcollecting those fractions
  7. additioncontaining only nogamycin (Rf 0.5)
  8. customA total of 3.9 g was obtained
  9. customOne and one-half grams was recrystallized from acetone-CH3OH (85:15)
  10. customObtained

Sources & evidence

ORD record
ord-85b3bc2183c84f83a8e428e65b13a67f
Source dataset
uspto-grants-1980_01
Patent number
US04183860

Reaction notes

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