Peganum Harmala No Manske Extraction Experiment

[uma]

Preface: After a bit a refinement I found that this experiment produced notable results, so I decided to share the experiment. However this is not intended to replace the Manske method or any type of declaration that the results are completely pure and do not require further refinement.

I conducted some experiments with peganum harmala involving extracting the alkaloids without using the Manske extraction method. During the experiments it I found a lot of the filtering problems after alkaloids where precipitated out by making the peganum harmala+water solution more alkaline, were due to non-polar compounds being released. I am unsure what these compounds are exactly.

I found by using d-limonene after making the solution alkaline it allowed for removal of these non-polar compounds. And afterwards simple water washing could be used to remove the unwanted compounds that are water soluble. Something else I found interesting was there seems some compound while in the solution containing the d-limonene that look like alkaloid solids but are not. When removed and tested on some absorbent paper they seem to melt into what I can only describe as a small oil blobs which slowly get absorbed by the paper. These kind of float in the d-limonene layer and in between the water layer. And should be removed. Below is the outline of the experiment attached is an image of the filter and alkaloids after drying.

Note: Excessive filtering isn’t needed in the second step it just has to be well enough not to allow any dirt like contaminates to pass into the solution. Also because this can be done easily with various containers and tools I didn’t create a material list.

1. Heat 100g whole peganum harmala seeds in 500ml water at 230c for 2.5hrs

2. Filter using a coarse disk (170-200 micron pore) filter funnel.

3. While the solution is still hot, slowly add sodium hydroxide while stirring until the solution turns a brown milky color.

4. Refrigerate container long enough for all of the alkaloids to settle at the bottom.

5. Siphon off (do not pour) as much water as possible without disturbing the alkaloids resting at the bottom of the container.

6. Slowly add 300ml fresh water followed by 50ml d-limonene. Stir well or if using a jar shake well then heat to 160c for 30mins. Refrigerate the container for long enough for all the alkaloids to settle at the bottom.

7. Siphon off (do not pour) all of the d-limonene including anything floating in the d-limonene layer or in-between the d-limonene and water layers. Followed by siphoning off as much of the remaining water without disturbing the alkaloids.

8. Slowly add 400ml fresh water. Refrigerate the container for long enough for all of the alkaloids to settle at the bottom. Siphon off (do not pour) as much water as possible without disturbing the alkaloids. Repeat this step least one more time.

9. Filter the remaining solution through 3 stacked coffee filters in a funnel. Wash the alkaloids by slowly adding a minimal amount of water into the filter and allow it to completely drain. Wash the alkaloids with a least 500ml water. Remove the filter combination from the funnel and lay it out to allow the alkaloids to dry.

 

[uma]

After attempting a number of clean up experiments I came across something interesting. It seems when the material from the previous experiment was heated to 250c inside of a beaker white crystals begin to form in the tan colored powder. And around 260c vapor begins to be released, the vapor condenses into white crystals when it came in contact with the walls of the beaker. When the crystals were placed in water they did not dissolve even when the water was heated. I began to come to the assumption that the crystals are most likely from the harmalas. Also it seemed that there was no visible liquid transition phase when going from the solid crystals to vapor.

So I came up with an idea to try dry heating the material to point where the unwanted materials would char while leaving the harmalas crystallized. Because the charred materials would be reduced to mostly carbon an acid/base extraction could be used to isolate the alkaloids. The extraction method was then further modified. The end result netted off white powder that was physically soft and is assumed to be mostly pure harmala alkaloids.

For the images attached:
0. An image of the crystals from the initial dry heating experiment. (Sorry about the quality)
A. The appearance of the alkaloids collected in step 5.
B. The appearance of the alkaloids after the charring in step 6.
C. The final result after step 9.

Extraction Steps:
1. 100g of whole peganum harmala seeds were heated at 240c for 2hours in 600ml of vinegar in a 1000ml beaker.

2. Using a coarse fritted buchner filter the vinegar solution was collected then placed in another 1000ml beaker.

3. While stirring on a hotplate set at 200c, sodium carbonate was added to the vinegar solution until it stop reacting. Additional sodium carbonated was added until the color shifted and the alkaloids begain precipitating out. Followed by adding 100ml d-limonene and stirring for 5mins. The beaker was removed from the hotplate.

4. 400ml fresh water was then added to the beaker and then beaker containing the basified solution was refrigerated over a number of hours to allow alkaloid content to settle to the bottom of the beaker.

5. A majority of the solution was siphoned off and the remaining alkaloid content and water solution passed through a paper filter. The filter paper was allowed to dry and the alkaloids where collected.

6. A portion of the powder was then placed into a 70mmx50mm recrystallization dish. The recrystallization dish was placed on a hot plate and heated at 300c until all the material was thoroughly charred. Turning of the material was done with the aid of a stir rod.

7. The recrystallization dish was allowed to cool, and powder was added to 600ml beaker containing 300ml of vinegar and stirred for one minute and allowed to sit for 10mins.

8. The solution was then filtered into another 600ml beaker to remove the insoluble materials. While stirring at 200c; sodium carbonate was added to the solution until it stop reacting. Additional sodium carbonate was added until the color shifted and the alkaloids stated precipitating out. Followed by adding 300ml fresh water to the basified solution. Then beaker was refrigerated for three hours which at that point all of the alkaloids rested at the bottom of the beaker.

9. The solution was then filtered through filter paper. The filter paper was then laid out to dry. Once the alkaloids were completely dry they were collected.

 

[Chan]

Thanks, will try this next time, sounds good!

 

[ganesh]

I conducted some experiments with peganum harmala involving extracting the alkaloids without using the Manske extraction method. During the experiments it I found a lot of the filtering problems after alkaloids where precipitated out by making the peganum harmala+water solution more alkaline, were due to non-polar compounds being released. I am unsure what these compounds are exactly.

This sounds interesting, but surely the point of Manske is to create a salt, that is also free of the quinazoline alkaloids?

This extraction of yours appears to be a 'possible' cleaning stage of a freebase. Then again, was there possible miniscule D Limonene contamination?, which explains the charring effects? and would the charring evap off a certain remaining freebase?

One wonders, but the last photo does look very clean, compared to the dark tan freebase earlier pics.

 

[downwardsfromzero]

Instead of charring, how about carrying out the sublimation at reduced pressure? This would be a fairly straightforward procedure. (Old thread, btw!)

Somewhere in the original harmala alkaloid papers by Fritzsche this charring-with-crystals effect is mentioned.