what i can't find is it's degrative pathways.
it is the kykeon of old with a new twist.
only the ergines were soluble in cold water and hence did'nt cause gangrenous effects like ergotamine.
Hoffman's secret of allegedly using wood ash to hydrolyse the ergotamine to ergine is also postulated.
the new twist would be the use of longer chain aldehydes.
when the kykeon was mixed with wine high in acetaldehyde it would form the n-hydroxyethylamide.
now the question i pose is what keeps this in equilibrium?
is it the formation of the aminal or the ketal?
say for example if this were isolated would keeping the molecule immobile and protected from uv light by using antioxidant acids like maleic acids be sufficient.
this is a project of urgency because there will be a costumed man passing out doses of candy this halloween

all levity aside i think the stabilty goes out the window when it dries something tells me it exists as a ketal or a hemiacetal.
so it would be wise to form a stable ketal so it does'nt spontaneously dehydrate.
anecdoctally peppermint schnapps was used it contains tepines and acetaldehyde along with isovalerone which is 3,4,-dimethoxy-1-benzaldehyde.
this aldehyde is to hinderred to react with ergine but not so to form the ketal adduct with the lysergic-n-ethyl hydroxyamide not only this a very stable adduct or ketal which could withstand hardy conditions as it is an actived ring afterall.
hmmm?

kykeon rediscovered, and redefined by the vespiary.
who wishes to undertake this project???
then the profits shall be used for a vacation to elusis/

well the byzantine knew something we don't because apparently kykeon is just being rediscoved in popuar culture and in the scientific community.
kind of like the ancient batteries.

****There is an extremely good thread on 'LAH' over at the black site. which sheds some light on this matter (uhh heemm!!!)

TLC indicates that under pretty anhydrous conditions there is a change to the alkaloidal composition of ipomoea seed extract when treated with pure acetaldehyde in methanol.

The same work indicates, there is no change to the alkaloidal composition when the seed extract is treated with acetaldehyde in methanol in the presence of water.

The change appears to be conversion of the iI]iso[/i]ergine into ergine and also isoLAH into LAH, ie C8 epimerisation there does not appear to be formation of LAH in any significant amounts other than perhaps as an intermediate. c8 epimerisation is a well known phenomenon with ergolines, and is solvent and temperature dependent.

So I think that the minuscule amount of acetaldehyde in peppermint along with the large amounts of water in the standard teks means LAH theory is pretty much bull, but there might actually be some basis to the myth, peppermint might encourage c8 alpha to beta epimerisation as a solvent effect. iso compounds are pretty inactive psychoactives but have peripheral activity, and conversion of some of the iso compounds to the psychoactive 8 beta compounds would possibly reduce the peripheral side effects and increase the psychedelic potency.

Also Lysergic acid hydroxyethylamide is pretty stable only slowly hydrolysing to the amide**


mmkkayyy we are talking about wines high in acetaldehyde and all the fermentation enzymes nice theory but i think it's more complex than that.
i think kykeon is the "vin alberto hoffamani"

alas

causing the fermentation of paspalli of this strain there is prodution to day 12 then the party is over and the lysergichydroxyamide gets anerobically converted to clavines and 8-hydroxy derivativives also.
funny how the czechs are doing all this work too.\

in simplicity

the liver combines lysergic acid amide and acetaldehyde in vivo to form the hydroxyamide.

further evidence


Just an experiment (done with pure Acetaldehyde) I grabbed over at a non-named site about advanced drug chemistry:

Method

5.0120g of seeds were mixed with 20ml deionised water and sonicated for 10 minutes. The resulting cloudy water was then filtered off, and the seeds dried. The seeds were then finely ground with 20ml hexane and 500 mg washed silver sand, then the mixture sonicated for 20 minutes, the hexane was removed by filtration and the solids washed with hexane. The filtrate on complete evaporation contained 16.5 mg of off white solids. These were discarded.
The filter cake was then ground with 20ml 80%MeOH : water, for 10 minutes until thoroughly reduced then sonicated for 20 minutes, then filtered, to give a clear yellow filtrate. The filter cake was supsended in 80% MeOH and sonicated for 30 minutes. Then filterered and the cake washed with 20ml 80% MeOH. The combined filtrates and washings were stripped of volatiles at high vacuum 35 degrees C bath temperature, to give 345 mg of a gummy yellow material. This material was then dissolved as much as possible in 100% MeOH and filtered to give a yellow clear solution.
The solution gave a purple color with Dimethylaminobenzaldehyde Hcl and was fluorescent light blue under LW UV.
The filtered MeOH extract was divided into 4 equal portions and placed in vials.
Vial 1- diluted to 50% with MeOH nothing added
Vial 2- diluted to 50% with MeOH nothing added
Vial 3- diluted to 50% with water, 10% V/V neat acetaldehyde added.
Vial 4-diluted to 50% with MeOH 10% V/V neat acetaldehyde added


After standing in the dark at room temp for 2 hrs samples were taken and subjected to HPLC and TLC.
TLC Merck Kieselgel 60 F254 silica. Not dried. Solvent 4:1 Chloroform Methanol Saturated atmosphere
Detection UV absorbtion 254 nm, LW UV fluorescence, Erlichs reagent

attached tlc of vial 2 and vial 4 showing a reaction in pure methanol, it seems that acetaldehyde may invert C8 chmistry of the inine alkaloids???

no reaction occured with acetaldehyde in 50% methanol. or on dilution with water. TLC to come.



this gives me pause would'nt the same reactions be going on in common yeast if one were to add the desired aldehyde to the yeast could one expect n-hydroxformation???

****The acetaldehyde and LSA combination to make this new LSD derivative sounds fascinating.. It seems like it should work in theory in a slightly acidic condition so as to activate the carbonyl in acetaldehyde and allow the amide portion to act as a nucleophile. I dont know too much about the chemistry of LSD but I hear its a very fragile molecule and it doesnt last very long in many sorts of conditions. A highly acidic condition is probably going to be detrimental to the molecule.

Also if you acidify it too much the nitrogen may actually protonate and render the amide completely useless for nucleophillic attack and the molecule will remain as LSA.

Seems like to make this work you're going to have to find the perfect balance between [H+] (im guessing a pH lower than 4-5 will start hurting the molecule? and distilled water. Keep all halogens away, they destroy the molecule!***


ding ding ding!!!

people have been having repeated sucess with this, extractiong into solultions of water chilled at ph 4 by means of citric acid and adding sherry wine for a few hours.

Sorry for just skimming and getting a general idea - been real busy, but I believe* these links will show to me at least interesting and maybe reveal some little jewels...

hxxp://www.shroomery.org/forums/showflat.php/Number/8446365#8446365
hxxp://www.shroomery.org/forums/showflat.php/Number/9100250#9100250

i may have been off base because that graph discusses the aldol product at n-1 of indole
but this prooves amido caronylation occours and is acid catalyzed
http://onlinelibrary.wiley.com/doi/10.1002/chem.200305048/abstract
of course we're talking about an amine aldehyde dienophile reaction.
from what i read a weakly acidic solution will split it clean in two.
easier just to make the real lsd nice pipe dream.
kykeon is actually this: the bad ergot alkaloids are'nt soluble in cold water while the good ones are that's all it is.

this thread calls it out like this:
there are so many aldehydes in mint oils that something's gotta give and form a stable adduct.
http://www.bluelight.ru/vb/showthread.php?t=373027&highlight=Big+Dandy&page=5

isobutylaldehyde has to be more stablile because the hydoxy is beta

what my pea brain does'nt see happenening is this;
isbutaraldehyde forming an enol that attacks the amide, with out some kind of super base.

Shouldn't peptide coupling of lysergic acid with ethanolamine accomplish the synthesis of LS-OHEt ? Might have to bear this one in mind should the ergot project ever bear fruit.

Case closed? how so? given that morning glory seeds and the like are active anyway, did the aztec drink peppermint schnapps with their ololiuqi? I doubt it

well the liver defies all chemical logic it seems to be doing the actual job.

Immunoassay for 2-oxo-3-hydroxy LSD
United States Patent 6548645

LSD is absorbed fairly rapidly by the gastrointestinal tract, and its plasma half-life has been calculated to be about 3 hours in man. Animal studies indicate that LSD is inactivated via hepatic oxidation. It is extensively metabolized with only negligible amounts of unchanged drug appearing in the urine and feces, with most of the metabolites being excreted in the urine. Possible metabolic transformations may be hydrolysis to lysergic acid, N-demethylation to nor-LSD and oxidation to 2-oxo-LSD. Studies with urine samples from human volunteers receiving LSD demonstrate that the drug or its closely related metabolites can be detected in the urine by radioimmunoassay (RIA) for several days following administration.

Whereas the antibodies react strongly to LSD, the antibodies have low cross-reactivity (in the range of only 30-45%, molar ratio) to several LSD metabolites, including 2PATENT -oxo-3-hydroxy-LSD. While Salamone, S. J. et al. failed to recognize that 2-oxo-3-hydroxy-LSD is indeed an endogenous LSD metabolite as oppose to be a “tentative” metabolite, it is now becoming evident that 2-oxo-3-hydroxy-LSD may be the most prevalent metabolite of LSD. Thus, there remains a considerable need for compositions and methods applicable for generating antibodies specific for the LSD metabolite, 2-oxo-3-hydroxy-LSD. The production of these antibodies would greatly facilitate detecting the presence of LSD or LSD metabolites in a clinical sample, and confirming LSD abuse in a clinical setting.

http://www.freepatentsonline.com/6548645.html

Short-Term Stability of Lysergic Acid Diethylamide (LSD), N-Desmethyl-LSD, and 2-Oxo-3-hydroxy-LSD in Urine, Assessed by Liquid Chromatography–Tandem Mass Spectrometry
Gisela Skopp1a, Lucia Pötsch2, Rainer Mattern1 and Rolf Aderjan1
Clinical Chemistry 48: 1615-1618, 2002;
http://www.clinchem.org/cgi/content/full/48/9/1615

So in summary it is inactivated fairly rapidly by oxidation in the liver and more specifically the major metabolite comes about via hepatic oxidation to form 2-oxo-LSD and to a lesser extent hepatic N-demethylation to form nor-LSD. Not hepatic aldol addition! I know the next thing will be nor-LSD is active (but that was not the point!). Orally, LSH is too labile to survive the trip through the gastrointestinal tract you would need sublingual administration. Orally, it would just produce acetaldehyde in vivo, which would produce hangover type nausea!

Case closed? how so? given that morning glory seeds and the like are active anyway, did the aztec drink peppermint schnapps with their ololiuqi? I doubt it

I agree the people tripping are feeling the effects of ergine, is there any data that even suggests LSH is active in man? I have only seen literature suggesting it is more toxic than LSD, and subjective accounts from people that claimed they where taking LSH because they extracted ergine with peppermint schnapps and they where producing it in there liver (I have no trouble believing they where tripping balls, but it was not on LSH produced while extracting, also if they were not very careful they would have lost any endogenous LSH the seeds did contain).

no but the kykeon was mixed with fermenting bread and mint both contain isobutaraldehyde in good concentration

the butatalmide is actually stronger than lsd that is singly substituted with H on the other side of the amide it has 4 carbons just like diethyl amine if we can add an iso butyl group to lsa we would have legal lsd.
and stronger too.

The compound from the paper you talked about;

Lysergic acid-2-aminobutane that was postulated to have a higher potency than d-lysergic acid-diethylamide, so now you are talking about schiffs base formation with ergine and isobutaraldehyde followed by reduction? Probably more efficient to proceed with lysergic acid and the amine, via coupling. If it turned out to be active I think is a good idea.

probably the same thing happens with fresh morning glory seeds too.

Yeah no doubt, there is actually an extraction technique for LSH in the Arcamone et al paper being passed around.

Production of a new lysergic acid derivative in submerged culture by a strain of Claviceps paspali Stevens & Hall
BY F . ARCAMONE, E . B. CHAIN, F . R . S . , A. FERRETTI, A. MINGHETTI, P. PENNELLA, A. TONOLO AND LIDIA VERO
International Centre for Chemical Microbiology
Istituto Superiore di Sanita, Rome

It was evident LSH was the only alkaloid produced by the strain of Claviceps Paspali used in these studies, but was transformed into D-lysergic acid amide and D-isolysergic acid amide during the working-up operations of the culture filtrates when these were carried out over a prolonged time period at room temperature, the isolation of LSH was attempted at a lower temperature and with the minimum of delay. The procedure was as follows...

http://127.0.0.1/talk/index.php?PHPSESSID=p29gkp5h53ii4pgu32tsjvp1p4&action=dlattach;topic=1188.0;attach=2388

now an intersting line of research conducted some years ago had to do with phenylacetylcarbinol by fermentation conducted by means of various yeasts done under aerobic
conditions using candidida yeasts and the like.
before i get to longwinded it was found that the "acetonoylation" reaction where basically an aldol addition of acetaldehyde to benzaldehyde involved and activated form of acetaldehyde.
activated by an enzyme, organikum wore the crown in his understanding of this  biochemistry.
so this is basically what's happening with lysegic acid amide; alainine is adding to it to give two products.
one of them being 1-hydroxylysergic cid hydroxy ethylamide. and the other the beta propanolamide.