Preparation method of optically pure dextro cloprostenol sodium
A kind of dextro-cloprostol, optical technology, applied in the preparation field of d-cloprostol sodium, can solve the problem of no preparation method of d-cloprostol sodium and the like
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Embodiment 1
[0074] Step (1). Preparation of nortricyclic dimethyl ester:
[0075]
[0076] Put 31g of paraformaldehyde (dried at 60°C for 1h and finely ground) into a 1000ml three-necked bottle, add 500ml (98%) of formic acid and 4ml (98%) of sulfuric acid. Add 92g of 2,5-norbornadiene dropwise at 25°C, the internal temperature must not exceed 30°C, the solution turns brownish black after 17 hours of reaction, remove formic acid by distillation under reduced pressure at 70°C, and wash the residue with sodium bicarbonate aqueous solution until neutral , TLC detection. The product nortricyclic dimethyl ester in reaction formula (1) is made, and the product is liquid, and the yield is 65%.
[0077] Step (2). Preparation of keto acid:
[0078]
[0079] Add 3000ml of acetone and nortricyclodimethyl ester (all the nortricyclodimethyl ester prepared in step (1)) into a 5000ml three-necked flask, cool to 9°C, add 9ml of Jones oxidant dropwise, and control the reaction temperature at about...
Embodiment 2-4
[0141] The detailed method of Embodiment 2-4 is the same as that of Embodiment 1, except that some parameters are changed, and the above chemical reaction can be completed, and the detailed parameter changes are shown in the table below.
[0142] Specific implementation parameter table
[0143]
[0144]
[0145] The following abbreviations are used in this document:
[0146] R-: right-handed
[0147] TLC: thin layer chromatography
[0148] THF: Tetrahydrofuran
[0149] DIBAL-H: Diisobutylaluminum hydride
[0150] HPLC: High Performance Liquid Chromatography
[0151] Mp: melting point
[0152] bp: boiling point
[0153] Jones oxidizing agent: solution of chromium trioxide in concentrated sulfuric acid
[0154] PTS: p-toluenesulfonic acid.
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