Bong-seeking bisphosphonate rhein ester derivates and preparation method thereof
A technology of rhein ether and bisphosphonic acid, which can be used in the fields of medicinal chemistry and bone and joint disease treatment, and can solve problems such as reducing the quality of life of patients
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Embodiment 1
[0060] Example 1: 2-(1-Acetoxy-3-methoxycarbonyl-9,10-dihydro-9,10-diox-8-anthraquinone) oxyethyl-thio-ethyl bisphosphonic acid Synthesis of tetramethyl ester (compound 1):
[0061] Dissolve 1-acetoxyrhein methyl ester in tetrahydrofuran, add 2-hydroxyethyl-thio-ethyl bisphosphonate tetramethyl ester and triphenylphosphine, stir and add dropwise azo at -2°C Diethyl dicarboxylate, react with Mitrarobium at room temperature for 16 hours, evaporate the tetrahydrofuran in a water bath at 40°C under reduced pressure, add ethyl acetate to dissolve the residue, wash with water and saturated brine successively, and dry the organic layer with anhydrous sodium sulfate. Using petroleum ether: ethyl acetate=3:1 (V / V) as the eluent, column chromatography separates the light yellow product, which is the target compound.
[0062] Mass ratio of 1-acetoxyrhein methyl ester to tetrahydrofuran, 2-hydroxyethyl-thio-ethyl bisphosphonate tetramethyl, triphenylphosphine, diethyl azodicarboxylate and eth...
Embodiment 2
[0063] Example 2: 2-(1-Acetoxy-3-methoxycarbonyl-9,10-dihydro-9,10-diox-8-anthraquinone)oxyethyl-thio-ethyl bisphosphonic acid Synthesis of tetraethyl ester (compound 2):
[0064] Dissolve 1-acetoxyrhein methyl ester in tetrahydrofuran, add 2-hydroxyethyl-thio-ethyl bisphosphonate tetraethyl and triphenylphosphine, stir and drop at -5°C under ice salt bath Add diethyl azodicarboxylate, carry out Mitrarobium reaction at room temperature for 16 hours, evaporate tetrahydrofuran under reduced pressure in a water bath at 30°C, add ethyl acetate to dissolve the residue, wash with water and saturated brine successively, and use anhydrous sulfuric acid for the organic layer After drying with sodium, using petroleum ether:ethyl acetate=3:1 (V / V) as the eluent, column chromatography separates the light yellow product, which is the target compound.
[0065] Mass ratio of 1-acetoxyrhein methyl ester to tetrahydrofuran, 2-hydroxyethyl-thio-ethyl bisphosphonate tetraethyl, triphenylphosphine, d...
Embodiment 3
[0066] Example 3: 2-(1-Acetoxy-3-methoxycarbonyl-9,10-dihydro-9,10-diox-8-anthraquinone) oxyethyl-thio-ethyl bisphosphonic acid Synthesis of tetrabenzyl ester (compound 3):
[0067] Dissolve 1-acetoxyrhein methyl ester in tetrahydrofuran, add 2-hydroxyethyl-thio-ethyl bisphosphonate tetrabenzyl and triphenylphosphine, stir and add dropwise under ice salt bath at 0℃ Diethyl azodicarboxylate, react with Mitreirob at room temperature for 16 hours, evaporate tetrahydrofuran under reduced pressure at 45°C in a water bath, add ethyl acetate to dissolve the residue, wash with water and saturated brine successively, and use anhydrous sodium sulfate for the organic layer After drying, using petroleum ether:ethyl acetate=3:1 (V / V) as the eluent, column chromatography separates the light yellow product, which is the target compound.
[0068] Mass ratio of 1-acetoxyrhein methyl ester to tetrahydrofuran, 2-hydroxyethyl-thio-ethyl bisphosphonate tetrabenzyl, triphenylphosphine, diethyl azodicar...
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