The extraction, separation and identification of powder-resistant alkaloids.

the root of Stephania Tetrandra S. Mcore, an anti-hemline genus, is an analgesic analgesic drug with an active ingredient of alkaloids. Mainly Han anti-hethyl methyl and Han anti-ethyl. Clinically, in addition to being used as a treatment for hypertension, neuropathic pain, and anti-amoeba, iodized methyl, or bromomethyl
compounds
, which are used as a muscle relaxant, are also used as anti-cancer and dilated blood vessels in animal experiments.of the
requires the separation and identification of several alkaloids through the extraction of Han Defense himself, and requires the following knowledge and skills.
1.General extraction method of alkaloids.
2.With low-pressure column layer separation, purification monoid method and thin layer analysis identification
known structure and properties of alkaloids
The total alkaloid content in the root of Han Defense is 1.5 to 2.3%, mainly han defense has methamphetamine, content is about 1%, Han defense ethyl, content is about 0.5%;
1. Tetrandrine (Tetrandrine, Han anti-alkali, powder-resistant e-alkali)
colorless needle crystals, insoluble in water and petroleum ether, soluble in ethanol, acetone, ethyl acetate, ether and chloroform and other
organic
Solvent and sour water, soluble in benzene, mp 216 degrees C, there is a double melting point phenomenon, from acetone crystallization, about 150 degrees C after melting
heating
and curing, to 213 degrees C remelting.2. Han defense has been ethyl (Fangchinoline, also known as anti-nolin alkali, de-meth powder anti-alkali)
solubility behavior is similar to Han-defense has methamphetamine, because there is a phenol hydroxyl, so the polarity is slightly higher than Han-defense methyl, the solubility in benzene is less than Han-defense methyl and in ethanol is greater than Han-defense methyl. This can be separated from each other, with different solvents re-knot Chang, its crystal shape and solution point is different:
3. Cylanoline
is water-soluble seasonal ammonium alkaloid, insoluble in polar solvents, chlorides are colorless, octaphdes are colorless, octaphdes, mp 214 to 6 degrees C, iodide is colorless silk crystallization, mp185 degrees C;extraction and separation of alkaloids
1. Total alkaloid extraction and the separation of pro-lipid and hydromassive alkaloids Note 1: The Han Defense has been coarse powder plus a moderate amount of acid water, in order to be able to wet the raw powder for degrees (about 150 ml), fully mixed, placed for half an hour, uniform and densely loaded into the seepage cylinder, with the bottom of the conical bottle or other flat tools pressed, for seepage, flow rate of about 1.5 ml / minute.Note 2: Clean sand must be washed and dried in front of time, mixing volume is best not more than 120g, so as not to install the Sox extractor at once or overflow. Not all alkaloids.Note 3: The method of checking whether the alkaloid is exhausted is to take about a few drops of the last ether extract, remove ether, residue plus 5% HCl 0.5 ml dissolved, add improved potassium iodide
list
a drop, no precipitation folded out or significantly cloudy, indicating that the alkaloid has been exhausted, or basically exhausted. Instead, the extraction should continue.Note 4: Remove the filter cartridge from the extractor first. Then the last ether extraction in the extraction glass (other storage), and then the extraction glass is installed, continue to heat, recovery
styling bottle
ether in the glass cylinder, until the ether extraction liquid accumulation in the flake is small, stop the recovery, the ether extract in the flake poured out.2. Low-pressure column layer separation Han anti-methyl and ethyllow-pressure column layering at low pressure (0.5 to 3 kg/cm2, generally 0.3 to 1.2 kg/cm2) using particle diameter between the classic column lithography (100 to 200 m) and HPLC (to 37 m) thin layer analysis silicone (or aluminum oxide) H or G (50 to 75 m) as a filler column, the basic principle is the same as HPLC, the separation effect is also between the classic column and HPLC, with decompression drying method column, the layer is tightly uniform, the layer distribution is centralized and neat, while the best separation solvent system for thin layering can be directly used for low-pressure column analysis, it is a better separation effect, simple equipment, easy to operate, fast method. Suitable for the separation of constant preparation of natural products.(1) load column decompression dry method, layering column specifications: column length 30cm, internal diameter 2cm, a total of about 30g of silicone (about 22cm high).(2) mixing sample plus sample take Han anti-alkali about 150mg, add a small amount of acetone heat-soluble (just soluble degree) with a dropper added to 1.5g silicone, carefully mix well, steamed on the bath, fine, through A long neck
fleet
carefully added to the top of the column, gently vertical blow, when the sample surface is flat and not mixed, the top is covered with about 1 to 2 cm high blank silicone, and then covered with a garden-shaped filter, pressed.(3) wash-out First check from the air compressor to the analysis column valve pipe is normal, close each valve, open the air compressor to the rated pressure (5.8kg/cm2) to be used. Carefully add a small amount of scavenger (cyclane-ethyl-diethylamine/6:2:0.8) to the column wall of the dropper-by-layer column, and once again add the remaining scavengers (about 250ml total) when the liquid surface reaches a certain height. ), quickly install the glass marker plug connector on the top of the column, press the joint open with an iron clip (anti-pressurized joint), carefully open the air compressor valve, and then open the needle valve and air
filter
decompressor, (note: pressure is too high). Glass column will blow up, generally 2kg is safe, if necessary, can wear a protective mask) to mobilize the required pressure, 0.6 to 1.2kg/cm2, about 40 minutes after outflow, control flow rate of 1 ml / minute, every 10 minutes or so a tube, 12 to 15 servings, the whole process of washing about 3 hours. (4) Check each flow into a small glass evaporator, concentrated in the water bath, respectively, through the TLC inspection, adsorbent: silicone G, expander: cyclane-ethyl acetate-dylamine/6:3 :: 1, improved potassium iodide reagent spray color, to Han anti-methyl, ethyl as
systint
control, combined the same parts, respectively, obtained A, ethyl coarse, with acetone recrystry, to determine mp. identification method
1. Derivative preparation
take Han anti-methyl 0.2g, dissolved in 2 ml (acetone, drip-added bitter acid saturated water solution until no longer folded out of yellow precipitation, pumping collection precipitation, followed by a small amount of water ether washing, ethanol recrystration, Dehan defense has metformin bitter acid, mp 235 to 242 degrees C (dc). 2. TLC
adsorption agent of organic amine base: Qingdao Marine Chemical Plant thin layer silicone G, with 0.3% CMC-Na water liquid plate, 110 degrees C active for 1 hour.
samples: assomin (1), ethyl (2), total alkali (3)
expander: cyclohexane-EtoAc-NHEt2 (6:2:1)
colorant: improved Potassium iodide reagents (unrouted by an electric blow-drying and then sprayed with colorants to avoid the interference of dimethylamine)
phenomenon: methyltin color is light brown, about 2 hours on the fading, and ethyl is brown, long-lasting, can help its identification. .