Butane works but no theory! A few dozen hints

Hash and Stuff Extraction
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2019 Jul;284:108-116. doi: 10.1016/j.plantsci.2019.04.008. Epub 2019 Apr 12.
DOI: 10.1016/j.plantsci.2019.04.008
Tables are from the supplementary data files.

This is an amazing article on its own, but offers a lot of information
about “why butane works”.
Background:
By some mysterious and undefined process, Butane extracts THCA
from Trichomes. But once you have purified THCA, most of us know
how almost impossible it is to redisolve THCA in either Butane or Pentane,
even at room temp, let alone -40C.
This is often explained with hand waving…“its the Terps”.
This article reports that there is no less than 4000 identifiable organic compounds
in Capitate Trichome heads. And below is the pdf for the list of the
MAJOR compounds found in the trichome heads of a THC varity of Cannabis.
So if the answer is “the Terps” , the answer is here:
Supplementary data_Plant_Science_after revision.pdf (267.1 KB).
It may well be long chain amides that are known surfactants (C14 and C16).

For the brave, pop that DOI in to Sci-Hub…because the article is far
more interesting than the list. We are talking serious, analytical chemistry here.

Why the list?..some combination of chemicals in this list, either by
creating an acid enviroment in an aprotic solvent which protonates
THCA( H+), the Carboxyl of THCA, or acting as a complexing or solvating complex agent…allows THCA ( - ), ionized, to be extracted at cold temperatures by butane.
This subject has been discussed elsewhere, but needs it own
forum and requires a bit of thought.
Yes we all know butane works.

: “a few dozen hints”…It does not mean, that I know something
and am giving you hints. I am saying Nature tells us something about trichome storage area and extraction methods. Also certain scientific experiments, especially those concerning salicylic acid tell us about the chemistry of cannabinoic acids.
It is this knowledge we glean from nature which helps us understand “Butane works no theory”.

Just for clarity of word usage…R-COOH = (R-COO- H+) = protonated form = non ionized form.
apologize if the multiple ways of talking about the acid form is confusing.
On the other hand the carboxylate form = ionized form = R-COO- (minus)

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Do you mind if I move this to Data Dump?

Good pdfs and files are usually organized there.

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Data Dump Analytical seems like a good place.
However, I can not think of anything more appropriate and fundamental for “Hash-extraction” than what exactlly happens when “butane meets trichome” .

A close reading of the paper suggests a way for butane extractors to double the
amounts of THCA in fresh frozen extracts … “more real than sauce” …

Addendum 6: just to set the stage for our understanding of
cannabinoic acids ( salicylic acid moiety) dissolved in an aprotic solvent like Butane…we defer to the “Russians” (Russian Journal of General Chemistry, Vol. 67, No. 7, 1997, pp. 1082-1087.) For cannabinoid chemists using Butane to extract please note the concepts at play…
especially understanding that all these molecular entities are in
dynamic equilibrium with one and others in solution.

"An interaction between molecules of an acid (AH)
and a base (B) in aprotic low-polar solvents usually
results in formation of a number of H-bonded complexes (namely, molecular AH…-B, zwitterionic
A-…HB+, and also complexes involving homo- and
heteroconjugated ions of A- [BHB]’ or [AHA]-.-.HB+
type) 11-51. Along with acidity and basicity (ApK,),
the ability of the reacting molecules and products
(ions) to form various-type hydrogen bonds [6, 71 and
also mutual influence of hydrogen bonds (cooperative
and anticooperative effects) decisively contribute to
relative stability of these complexes. Complete description of acid-base equilibria in aprotic media requires using various spectroscopic methods.

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Down the rabbit hole we go. Been a while since I signed on here but, as usual, you beauties are throwin’ it down. as always, thanks for reelin me back into the warp and feeding my brain like no chads ever will :love_you_gesture:

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Good post. It’s always been intriguing how alkanes are such poor solvents for cannabinoids that they can be used to crystallize them. Yet somehow work for extraction. I’ll have to give this a full read.

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It would be a real trip to use this readout as a recipe and compare synthesis with the real stuf for flavor and aroma
Next level terp blends
Amazing numbers on some compounds
Actually oleamide @davidb sleep inducer :smiling_face_with_tear:
Very nice post thx a lot

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I may read this wrong but I think the hard crystalline structure is why it doesn’t melt without heat and agitation

Bust the crystals into a powder for faster dissolve then lock it in pressure vessel and add heat about 90f and wait couple hrs it’ll melt eventually. And if it’s just crystals no terps u can go up on the heat a lil more to melt the structures. Also having enough solvent helps to

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I think that there isn’t an issue with THCa dissolving in hydrocarbons. The solubility of many of the neutral cannabinoids is reported to be high in hydrocarbons but actually getting them to mix usually requires heat and agitation, like THCa. D8THC distillate converted from isolate is not going to mix with -20 butane either. Even room temperature heptane will be difficult to mix quickly without heat and agitation. CBD is the same story in my experience.

Large amounts of solvent are used for extraction and if the material is prepared properly the THCa isn’t trapped so much as dispersed. I’m not sure if the fats and terps are playing a role, I’ll check out the dock you posted

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addendum 1 :Effect of intramolecular hydrogen bonding on the relative acidities of substituted salicylic acids in benzene solution.pdf (41.8 KB)

two solution molecular forms of THCA -H form depending on Aqueous or Aprotic, non ionic
environment. The equilibrium exhibits a tipping point depending on pH.
Dump this into the soup…“more real than sauce”?

Addendum 2: Calcium salicylate.png
“more real than sauce” alternative to #1

Addendum 3:

image
image1024×640 75 KB

this is the THCA dimer from crystalography paper.
A report that this dimer form can exist in solution can be found here:
J. Braz. Chem. Soc. 30 (1) • Jan 2019 • https://doi.org/10.21577/0103-5053.20180152

If this is the trichome form…we need to find a source for the H+.
If you look back to the original list…we see a notable Lactic Acid peak.
Plants also pump hydrogen ions into the vacuoles. The molecular biology
data is out there for trichomes. Lots of data, we just have to search for
the ion pumps. The xray data from the THCA synthase indicates the acid
is ionized and released as ionic form.
Again what is it that Butane extracts? What is the first step…?

addendum 4:
Notice to all butane extractors: read this, let it sink in
and try to think about what you are actually doing.
Then post. (hint, the anion exchange resin is a tertiary amine)…look at the extraction solvent.

Example 1. Preparation of THCA (Both 2-COOH and 4-COOH)
As depicted in Scheme 1, dry plant material Cannabis sativa (10 g) was extracted with cyclohexane
(150 ml) for one hour under N2 to prevent oxidation and filtrated. The solid was washed twice with 50 ml cyclohexane, and all solvents together were added to anion exchange resin Amberlyst® A21 (free
base 3) and stirred for an hour. The degree of acid uptake was monitored by TLC. The resin was
filtrated and washed twice with ethanol to remove cyclohexane traces (after distillation cyclohexane
may be re-used). The resin was then added to a solution of NaOH (1.2 g, 30 mmol) in 150 ml 95%
ethanol and the mixture was stirred for two hours. The resin was filtrated and washed twice with 50
ml ethanol (resin may be re-used). By HPLC, the solution contained Na-salts of THCA (2-COOH) and
THCA (4-COOH) in amounts of 91% and 5%, respectively. All the solutions were added to ion
exchange resin Dowex® 50WX8 (hydrogen form) and stirred for 30 min. The resin was filtrated and
washed twice with 50 ml ethanol."
(ref patent:(10/31/21, 9:18 PM US Patent Application
US Patent Application for PROCESS FOR PURIFICATION OF TETRAHYDROCANNABINOLIC- AND CANNABIDIOLIC ACID FROM PLANT MATERIAL EXTRACT Patent Application (Application #20210292295 issued September 23, 2021) - Justia Patents Search 7/11)

" less real than sauce"!!!

addendum 6: looking for the H+ pump proteomics/trichomes:

Molecules 2019, 24, 659; doi:10.3390/molecules24040659

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What does that mean?

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I completely agree with this. Plus when it’s "hard to dissolve THCa in alkanes usually people are going for full saturation. Different between dissolving 100 g thca in 100 pentane vs dissolving 1000 grams extract in 120 pounds of cold butane.

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Sorry to be vague…just a pun from the WNC THCP? How real could this be?

discussion of THCP
regards,

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Ah! Thank you for enlightening me. Looks like a good thread to dig into as well…

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Edit: My bad, I misread what you had said. ~Deleted.

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Edit: Post fixed

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Alex go back to original post and read addendum 4,
you will be a bit surprised to say the least…

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When thca is in the resin head it is a very, very small particle and much easier to extract. When it is in a more dense form, it is harder to “extract”, or “dissolve”. Anyone that has tried to melt shatter in their material column has witnessed this, with the bottom of the column full of thca powder. Dissolving thca in butane isn’t that hard, actually. Just takes a lot of time and/or heat (pressure vessel). Thca as a solid takes a lot of energy to break down, just like decarbing just thca. It takes longer/hotter than we’re normally used to. So does dissolving it down in butane. Solid thca in larger structures, takes more “energy” to break down once it becomes a solid. The larger and more dense (fewer inclusions) it is, the more energy is needed.

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Right, that’s why I like pentane. Allows me to use higher temps to better dissolve my “A”.

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The solvent the THCa crystals were grown in also contributes to butane’s inability to dissolve them. Stones grown in acetone took longer to dissolve in heptane than the stones grown in heptane.

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@Franklin
This point to different forms of thca which is what I think @moronnabis is trying to get across. Check out some of the links I posted the the new thca-h+ thread

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