Reacción #54193

Ecuación de reacción

aluminum chloride

daunomycinone

daunomycinone

→

(+)-carminomycinone

Disolventes

oxalic acid

benzene

Condiciones de reacción

Tratamiento posterior

1. 1
   OtroThe reaction gradually turned purple
2. 2
   workup.STIRRINGstirring
3. 3
   workup.ADDITIONthe layers mixed thoroughly until the color
4. 4
   ExtracciónThe aqueous phase was extracted once with chloroform (10 ml)
5. 5
   workup.ADDITIONthe chloroform added to the benzene
6. 6
   LavadoThe combined organic phases were washed once with water
7. 7
   Secadodried over anhydrous sodium sulfate
8. 8
   Concentraciónconcentrated

Procedimiento

Natural daunomycinone (14.7 mg) was taken up in anhydrous benzene (100 ml). Sea sand (1 g) was added and the mixture was stirred until all the daunomycinone went into solution. The reaction was stirred under nitrogen and anhydrous aluminum chloride (0.22 g) was added. The reaction gradually turned purple; stirring was continued at room temperature overnight. The reaction was worked up by pouring in aqueous oxalic acid (25 ml., 25%) and the layers mixed thoroughly until the color was discharged. The aqueous phase was extracted once with chloroform (10 ml) and the chloroform added to the benzene. The combined organic phases were washed once with water, dried over anhydrous sodium sulfate and concentrated to give (+)-carminomycinone, Rf = 0.16 (on silica gel, 3% methanol in methylene chloride, v/v). The mass spectrum showed 384 (M+, 45%), 366 (7%), 348 (100%), 341 (3%), 333 (21%), 323 (67%), 305 (19%), 295 (39%, 277 (16%), 249 (8%). The NMR (CDCl3) taken using Fourier-transform spectroscopy gave δ 13.47, 12.96, 12.17 (s, 1H ea); 7.14-7.25 (m, 3H), 2.43 (s, 3H), 2.27 (m, 2H); the vv spectrum showed maxma at 527, 512, 492, 480 and 466 nm.

Fuente