Sulfur-containing shikonin oxime derivative and uses thereof
A technology of shikonin oxime and derivatives, applied in the field of medicine
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Embodiment 1
[0052] This embodiment relates to a preparation method of a thioether racemate shikonin oxime derivative with structural formula (III), such as figure 1 shown, including the following steps:
[0053] Step 1: Suspend the activated zinc powder (30.0g, 0.46mol) in anhydrous tetrahydrofuran (120mL), and slowly add bromoisoamylene (24.0mL, 0.21mol) dropwise under the protection of nitrogen. Stir at room temperature. After 2 hours, quickly divide the reaction solution into 50mL centrifuge tubes, centrifuge at 4000rpm for 10min, and take the supernatant (completely remove zinc powder) for later use. Take 1,4,5,8-tetramethoxy-2-naphthylcarbaldehyde (8.0g, 29.0mmol) and dissolve it in anhydrous tetrahydrofuran (60mL). Under nitrogen protection, the prepared metal bromide (supernatant solution) was slowly added into the reaction flask, the reaction solution changed from yellow to white foam, and the stirring reaction was continued at room temperature for 2 hours. After tetrahydrofuran...
Embodiment 2
[0098] This embodiment relates to a preparation method of a thioester racemate shikonin oxime derivative with structural formula (IV), such as figure 1 shown, including the following steps:
[0099] Steps 1 and 2 in this embodiment are the same as steps 1 and 2 in Embodiment 1.
[0100] Step 3 synthetic general method, the product obtained in step 2 (0.5mmol), 4-dimethylaminopyridine (0.25mmol) and carboxylic acid R 2 COOH (0.6mmol) was suspended in anhydrous dichloromethane, and N,N-dicyclohexylcarbodiimide (0.6mmol) was added in batches under ice-bath conditions. After the addition was completed, it was stirred overnight at room temperature. A white solid was precipitated, and the white solid increased after adding petroleum ether. After standing at 4°C for 1 h, it was filtered, the solvent was evaporated, and 2-(1-acylthio-4-methyl-3-pentenyl)- 1,4,5,8-tetramethoxynaphthalene derivative, colorless oil.
[0101] Using the above method, when the carboxylic acid R 2 COOH, ...
Embodiment 3
[0192] This embodiment relates to a preparation method of thioether optically pure shikonin oxime derivatives with structural formula (VI), such as figure 2 shown, including the following steps:
[0193] Step 1, optically pure (R)-2-(1-hydroxyl-4-methyl-3-pentenyl)-1,4,5,8-tetramethoxynaphthalene (preparation method such as Figure 4 ) was dissolved in toluene, 0.52 equivalent of Lawson’s reagent was added, under the protection of nitrogen, reacted at 90°C for 8 minutes, TLC detected that the raw material point disappeared, added an appropriate amount of water to the reaction solution, cooled, separated the organic layer, evaporated to remove the solvent, and the silica gel column Chromatographic separation to obtain optically pure (R)-2-(1-mercapto-4-methyl-3-pentenyl)-1,4,5,8-tetramethoxynaphthalene, brown oil, yield 75%. 1 H NMR (400MHz, CDCl 3 ):δ6.89(s,1H,Ar-H),6.75(s,2H,ArH),5.02(t,J=7.2Hz,1H,CH=C),4.73(dd,J 1 =12.4,J 2 =7.2Hz,1H,ArC H OH),3.88(s,3H,OCH 3 ),3.85(...
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