Crystallographic and NMR investigation of ergometrine and methylergometrine, two alkaloids from claviceps purpurea
Ergometrine and methylergometrine are two alkaloids that are used as maleate salts for the prevention and control of postpartum hemorrhage. Although the two molecules have been known for a long time, few and discordant crystallographic and NMR spectroscopic data are available in the literature. With the aim of providing more conclusive data, we performed a careful NMR study for the complete assignment of the 1H, 13C, and 15N NMR signals of ergometrine, methylergometrine, and their maleate salts. This information allowed for a better definition of their conformational equilibria. In addition, the stereochemistry and the intermolecular interactions in the solid state of the two maleate salts were deeply investigated by means of single-crystal X-ray diffraction, showing the capability of these derivatives to act as both hydrogen-bond donors and acceptors, and evidencing a correlation between the number of intermolecular interactions and their different solubility.
The invention provides an ergometrine preparation method. Under an alkaline condition, sphacelic acid and L-amino propanol react to prepare ergometrine by using T3P as a condensing agent. By means of the method disclosed by the invention, the ergometrine yield is greatly improved, the problem of relatively lower yield in the prior art is solved, and economical benefit of the industry is improved.
The invention particularly provides a method for preparing racemized ergotic acid by using fermented wastes. The method comprises the following operation steps: firstly, taking wastes obtained by fermenting claviceps purpurea, and generating a hydrolysis reaction in alcohol solvents in the presence of strong base; secondly, removing the alcohol solvents from a hydrolysis reaction product, then acidifying until a pH value is 3.5 to 4.0, and extracting a separated solid matter 1 by using a mixed solution of methanol and ammonia water; thirdly, removing a solvent from an extracting solution, and beating an obtained solid matter 2 by using water and alcohol solvents of C1 to C5 in sequence, thus obtaining the racemized ergotic acid. The invention also provides the method for preparing ergonovine by using the fermented wastes. The method disclosed by the invention is simple and low in cost; no complex splitting process is needed, the reaction is easy to operate, large-scale production is easy, and recycling of the wastes is realized; after the prepared ergonovine is only beaten and purified, the optical purity is 98 percent or above; the ergonovine is suitable for industrial production.