I dont know especially because like the paper says the beam test makes quinones so it possible youre making quinones when you do this process and converting them back to a colorless hydroquinone when you add acid… remember quinones aren’t tested for on hplc you use ms so they very likely co elude on hplc, if they didn’t people wouldnt need ms to test for them
The proof you’re making quinones is in the fact it changes color
This is quinone… its probably a carboxyl salt also but its still a quinone
This is something we should do more research on because quinones are toxic from my understanding and if youre making cbd a hydroquinone without know it it could be bad
@moronnabis — question for you since this is your wheelhouse. If you dissolve CBDA in ethanol, shift pH basic to form the purple carboxylate salt, then acidify with HCl and recover CBDA — does that reversibility rule out quinone formation? My understanding is that quinone formation is an oxidative transformation that wouldn’t reverse with simple acidification. You’d need a reducing agent, not just HCl. Is that correct?
And for comparison — this is essentially the same reaction as base water extraction of CBDA, just in ethanol instead of water. Base deprotonates the carboxylic acid to form the water-soluble carboxylate salt, acid reprotonates it and you recover CBDA. Nobody argues that base water extraction is forming quinones. Why would the same acid-base chemistry in ethanol suddenly become an oxidation reaction?
An easy way to test this is to do your process in an inert environment, sparge the water also and if it doesn’t turn purple you know quinones aren’t forming
For the CBDa salt it is for edibles only, very good there, not to be smoked…
The salt reacts in your stomach to form KCl + H2O and CBDa…
Most people are deficient in potassium to begin with so it helps in two ways.
Edit: The salt form I make is done in anhydrous ethanol… You gotta get the water out later that is formed from the reaction and takes a little bit but 150f at full vac its done in a few hr.
What’s the pH of the base you use in water? Is it a strong or weak base? Magsil makes quinone and is ph in water is 9-10 so if what you use is higher it’s likely it’s forming quinone
This doesn’t matter since the ethanol has an oh group that can be protonated or deprotonated
It is pure KOH… But mixed into ethanol, then added to CBDa in ethanol… no water is used other than what is made from the reaction.
I match the KOH to the CBDA mole for mole — one molecule of base for every carboxylic acid group. The reaction converts completely and reverses completely, which is just stoichiometric acid-base chemistry.
Yeah the ending apparent pH is pretty high, 9-10 for dry powder, 8-9 if you keep it liquid (which is actually a little bit red…). Once you take it to dryness it transitions to the full purple.
Yeah thats the carboxylate salt form… I have some down in my tool chest still from 6 years ago, I could put in hot water and it will dissolve right in and turns back to the white-clear first until you overload the water. Eventually it turns purple also and the pH climbs.
Id take you up on that but tbh i haven’t had my lab put back together since coming back from OKC 3 years ago, its still sitting in storage out there i hoping to have it back soon
I am going to be setting up a small bench top reflux setup to attempt to make 2 new molecules that are in the literature that no one is making atm (one being cbnd) im hoping i can succeed at these and then mess with the feds if the hemp ban goes through since both are supposed to be psychoactive and are a cbd skeleton
The one thing I will say about the debate over the carboxyl salt being purple and/or it being quinone thats purple is the literature reports the beam test works on the non acid versions of cbd and cbg meaning the color happens regardless if the salt is formed
As much as I might seem like i dont like these debates i actually really do, making gummies which i do full time now doesnt require much thinking and it gets boring. I love science especially cannabinoid science so i want to say i appreciate the back and forth even if it seems like i dont. I will go back and edit out the negative comments i made about your equipment and such.
I appreciate you cleaning up the past comments so we can move forward professionally — that means a lot and says a lot about your character.
And man, CBNd is a rabbit hole I’ve already been down. I’ve done a bunch of playing around with it. I was able to get some mild peaks going CBN → CBNd in ethanol with submerged UV in a light-tight environment under stirring with various conditions. I have the CBNd CRM but it’s pretty old now — I do know where it lands on my SRI GC though - see below.
I also tried short-cutting it going CBD → CBNd directly, but ended up making what literature calls CBF and CBX instead — which I also marked on my GC. They land way late after CBN, just like the papers describe. So that route is probably a dead end for CBNd specifically, but interesting chemistry nonetheless.
I will dig into my other computer that has all my old reference papers on it that covers all of this and will link it.
If you’re setting up a benchtop reflux for this, happy to share what I’ve learned so you’re not repeating the same dead ends I already hit.
If you dont mind me asking what oxidation reaction were you running on it? I found the same thing to be true, i tried cbd>cbnd with Sulphur and pd/c but it would either convert to something else or go to thc then cbn
I have a way to make it which should prevent that bottom bond from closing but its a 2 step reaction. The clean up is more intense also because of this, this is all theoretical chemistry as i havent been able to talk to an actual chemist about it but i think itll work
I wish DrTphd was still around he was my go to for things like this havent found another true organic chemist that i can bounce idea off of
Yeah the same - sulfur and pd/c… guess you could say great minds think alike
I also played with p-chloranil as you can see with my GC peak data. It starts yellow and forms a clear square crystal… The other product is what I think would possibly be exo-THC but I am not sure as I never did get around to buying a CRM for it just yet.
I technically have a MS but it still needs work before I can connect the two together. Vac leaks and what not. Both are used equipment that I fixed and got back into calibration so I could have cheap testing equipment haha… $6k for the GC all in, $1200 so far on the MS all in.
this is a very good question actually. And it shows you have explored the chemistry as bit yourself.
And it is complicated for sure. early on I thought about just extracting with either basified ethanol..and at pH that would deprotonate the etoh =. EtO- a bit. And as you might imagine …got a rash intro to the quinones. Purples….and yes, no amount of acid seems to save you from purple death…My rule of thumb became if you got “there” , you have made permanent mistake ,..move on.
so yes you can use a bit of ethanol soak and followed by the base water Addition, but one has to be careful about homogenizing and introduction of oxygen to prevent some oxidation to purple quinones…Or just extracting with base water works very well and is a rather rapid process. But you have to be careful about your choice of counter ion, and remain cognizant of its hydration sphere size and the ph that is achieved, and. Your choice of parameters . To be sure , choose your pH value and check it in the presence of biomass, ie. The biomass to base water ratio. An important concept to realize is the biomass, itself, acts as a solid state buffer, and you have to be sure what ratio you need to over come it, or for that matter choose a ratio you might be comfortable with and then titrate to pH you desire. The pH you desire (11-14) might be dependent on what you choose to be your next step? If you are just going to acidify, well it doesn’t matter much, other than a pH you are not experiencing purple oxidation, if so lower it. Look closely at the different Patents available to read for more detailed advice. I am being vague in some regards here , due to proprietary detail, but the guidance is firm, and I am glad to see you and others are beginning to utilize the MANY uses of switching back and forth between non-polar aprotic and polar protic with pH adjustment. Pararameters. It opens an entire book of new steps of separation chemistries just thinking about the “ANIONS”..involved. Neither the neurtal state or the anion state in polar Protic solvent is anything like the molecular species one might imagine by looking at a model diagram. Both states have an intermolecular hydrogen bonded ring, six membered. The neutral and anionic state differ in their conformations. The anion conformation for THCA , this intramolecular form is so strong , like salicylate , the bond approached energies similar to covalent -like categories. The polar protic salts ..in solution as ion pairs , are with this form. Your choice of counter ion, in polar protic , can control whether the polar pair is soluble in polar -aprotic. One additional point..is that as you change the polar protic solvent, e.g. water to ethanol…the pKa of the acids changes , usually they get higher, considerably higher.
Sorry , I had two versions one corrected and the other raw..side of pool in bright sunlight …I pushed the reply to the wrong one…this makes a bit more sense.
This might be a little off topic but i thought maybe you could shine some light on this as its one of the things me and @Zack_illuminated were discussing
If you introduce an acid to hu 331, you can get a hydro quinone to form from my understanding. In your opinion do you think cbd hydroquinone would be purple still???
See my post linked below for a little backround, the paper i cited didnt say anything about cbd HQs color and im personally wondering if maybe it could be colorless as some people can clean the color up with acidification but obviously that would only convert the quinone to a hydroquinone
Zach was also on IG a couple years ago posting videos of him shooting glass bottles in nature, And leaving the glass for wildlfe to step on. When I asked him about picking up the glass I got a response similar to this thread about why its ok to leave shattered glass out for deer to step on. Extraction differences aside- As a second amendment supporter, and someone who respects hunting, this guy sucks.
havent found another true organic chemist that i can bounce idea off of