Benzaldehyde → (2S,3R,4R,5S,6S)-2-(aminomethyl)-6-[(1R,2R,3S,4R,6S)-4,6-diamino-3-[(2S,3R,4S,5S,6R)-4-amino-3,5-dihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-2-hydroxycyclohexyl]oxyoxane-3,4,5-triol

HRID 971459

Reaktionsgleichung

Reaktionsgleichung von HRID 971459
[CH2:1]1[C@H:6]([NH2:7])[C@@H:5]([O:8][C@H:9]2[O:14][C@H:13]([CH2:15][NH2:16])[C@@H:12]([OH:17])[C@H:11]([OH:18])[C@H:10]2[OH:19])[C@H:4]([OH:20])[C@@H:3]([O:21][C@H:22]2[O:27][C@H:26]([CH2:28][OH:29])[C@@H:25]([OH:30])[C@H:24]([NH2:31])[C@H:23]2[OH:32])[C@@H:2]1[NH2:33].OS(O)(=O)=O.Cl.C([BH3-])#N.[Na+].C(=O)C1C=CC=CC=1>O.CO.CO.C(Cl)(Cl)Cl>[CH2:1]1[C@H:6]([NH2:7])[C@@H:5]([O:8][C@@H:9]2[O:14][C@@H:13]([CH2:15][NH2:16])[C@H:12]([OH:17])[C@@H:11]([OH:18])[C@@H:10]2[OH:19])[C@H:4]([OH:20])[C@@H:3]([O:21][C@H:22]2[O:27][C@H:26]([CH2:28][OH:29])[C@@H:25]([OH:30])[C@H:24]([NH2:31])[C@H:23]2[OH:32])[C@@H:2]1[NH2:33]

Komponenten

8

Edukt 4

HCID 240BenzaldehydeHCID 313Hydrochloric Acid2×HCID 441374Kanamycin A SulfateHCID 5003444Sodium cyanoborohydride

Produkt 1

HCID 11274101(2S,3R,4R,5S,6S)-2-(aminomethyl)-6-[(1R,2R,3S,4R,6S)-4,6-diamino-3-[(2S,3R,4S,5S,6R)-4-amino-3,5-dihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-2-hydroxycyclohexyl]oxyoxane-3,4,5-triol

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 887MethanolLösungsmittelHCID 962WaterLösungsmittelHCID 21584188Chloroform methanolLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

Kanamycin A sulphate (24.3 g., 0.03 mole) was dissolved in water (150 ml.) and the pH adjusted to 6 by the dropwise addition of 5N hydrochloric acid. Sodium cyanoborohydride (1.95 g., 0.03 mole) was added and the mixture was cooled to 0° C. and stirred while a solution of benzaldehyde (3.61 g., 0.033 mole) dissolved in methanol (15 ml.) was added slowly over the course of 2 1/2 hours. The mixture was allowed to warm to room temperature. After 16 hours the pH of the solution was adjusted to 5.5 by the addition of 1N hydrochloric acid and the solution was filtered and added to a column of Amberlite CG-50 ion-exchange resin in the ammonium-ion form. Elution first with water and then with a gradient of ammonium hydroxide of increasing concentration from 0-0.7N gave as major product 3-N-benzylkanamycin A contaminated with some 1-N-benzyl derivative (5.0 g., 28%) Rf 0.44 in methanol-chloroform-17% ammonium hydroxide 4:1:2. (Kanamycin A gave an Rf value of 0.15).

Aufarbeitung

  1. additionwas added slowly over the course of 2 1/2 hours
  2. temperatureto warm to room temperature
  3. filtrationthe solution was filtered
  4. additionadded to a column of Amberlite CG-50 ion-exchange resin in the ammonium-ion form
  5. washElution first with water
  6. temperaturewith a gradient of ammonium hydroxide of increasing
  7. concentrationconcentration from 0-0.7N
  8. customgave as major product

Quellen und Nachweise

ORD-Eintrag
ord-2653f3c8e3a6495dbeca559964c45727
Quelldatensatz
uspto-grants-1979_07
Patentnummer
US04160082

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