Author Topic: LSD vs peptide coupling  (Read 14276 times)

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hest

  • Guest
tert amines
« Reply #20 on: August 29, 2004, 04:06:00 PM »
The Tert amines is added due to two reasons
one: after the coupling the reamains of the couplingreagent (ecept dcc) is an acid part therby the base ore your resulting amide would be an salt
Two: some of the reagents tends to produce the anhydride of the base iff the tert.base is not present (and deprot. the acid)

hest

  • Guest
Couplings
« Reply #21 on: August 29, 2004, 04:27:00 PM »
Amide bond formation: [R.Knorr, A.Trzeciak, W.Bannwarth, D.Gillessen, Tetrahedron Lett., 1989, 30(15), 1927-1930]

Acid (3 eq.) dissolved in DMF and Nem (MW 115, 4 eq., r=0.91) and TBTU (MW 321, 3eq.) is added. Wait 5 min, then add amine to the mixture. Reaction time 10min-2h

Coupling with PyBOP
. Martinez et al. J. Med. Chem. 28 pp1874 (1986).

J. Coste et al, Tetrahedron Lett. 31 pp.205 (1990)

3eq.acid, 4 eql PyBOP (520.3 g/mol), and 6 eq DIEA (129ul/mmol) in DMF then add amine reac time 10min-1h


coupling with HATU
L.A. Carpino, J. Am. Chem. Soc. 115 pp. 4397-4398 (1993)

acid (3 eq), HATU (2.8 eq), HOAt (1 eq) and NEM (3 eq) are mixed in DMF and preactivated 1-2 min at R.T. then add amine. reaction time 10-20 min.



Solvents. Usual couplings are done in DMF but that is becourse we are talking solid phase chemistry. When wee use wet chemistry DCM or something els will do the trick, as long as all the componets stay in solution

armageddon

  • Guest
-
« Reply #22 on: August 29, 2004, 05:14:00 PM »
nOOdle:
Do not use a soxhlet extractor for this preperation, surely you know lysergic acid diethylamide is severely destroyed by heat, the same should apply to lysergic acid amide. There is nothing wrong with pulverising the seeds, washing in nonpolar toluene or xylene to defat, then washing out with ethanol

Temperature? Weeeell...  LSA isn't that fragile - in plants it survives the summer without problems at least!  ;)  Maybe use soxhlet under vacuum (lower bp)? Soxhlet is superior because it is much quicker and uses way less solvent than the bucket method.. :)


hest: Thanks a lot!!!  :)

..but WTF is

Nem (MW 115, 4 eq., r=0.91)?
and HOAt (1 eq)?

DIEA is diisopropylethylamine, I would guess?


Greetz, A


hest

  • Guest
bases
« Reply #23 on: August 29, 2004, 05:40:00 PM »
Nem N-Ethylmorpholine

http://www.polycarboninds.com/html_pages/activ_for_pep_synth.html



HOAt adition might be more important when working with acive esters (the Pfp esters usual used in solid phase chemistry)

HA

armageddon

  • Guest
thanks again
« Reply #24 on: August 29, 2004, 10:48:00 PM »
"HOAt is a coupling additive that can be used in conjuction with active ester (OPfp, ODhbt) and carbodiimide (DCC, DIPCDI, EDC) chemistry. Recent research has shown that HOAt is a superior coupling additive in both solution and solid-phase synthesis when compared to HOBt1. HOAt enhances coupling yields in solution by 6-32 fold and reduces the loss of chiral integrity by up to 50%.2,3 The HOAt molecule incorporates both key elements of the 1:1 mixture of HOBt and a tertiary amine; in couplings involving active esters, this results in greater catalytic activity than HOBt alone."

...seems like ANY tertiary amine in 3x excess over carboxylic acid should do just fine to soak up any acidic by-products!  ;D  (but HOAt seems useful with CDI, too)

 - now THAT'S good news dare I say!

(beginning to wonder about which coupling reagent should be favoured - think it is pyBOP...  :) )




Benzotriazole-1-yl-oxy-tris-pyrrolidino-phosphonium hexafluorophosphate

CAS NO.: 128625-52-5; C18H28N6OP2F6; M.W. 520.3
Solubility: 1 mmole in 2 ml DMF clearly soluble
HPLC: purity: ? 97.00%.

The standard in situ coupling reagent for solid phase peptide synthesis [1-5]. This product can replace BOP in all applications without loss of performance. Unlike uronium-based reagents, PyBOP® does not give rise to guanidinated by-products during cyclization and fragment condensation reactions.


[1] J. Martinez, et al. (1985) J. Med. Chem., 28, 1874.
[2] J. Coste, et al. (1990) Tetrahedron Lett., 31, 205.
[3] G. B. Fields, et al. in "Innovation & Perspectives in Solid Phase Synthesis, 1st International Symposium", R. Epton (Eds), SPCC UK Ltd., Birmingham, 1990, pp. 241.
[4] T. Høeg-Jensen, et al. (1991) Tetrahedron Lett., 32, 7617.
[5] R. von Eggelkraut-Gottanka, et al. (2003) Tetrahedron Lett., 44, 3551.


taken from: NovaBiochem Cat.-Nr. 01-62-0016 (

http://www.merckbiosciences.co.uk/product/01-62-0016

)




So the suggested procedure so far would look like this:

Aquire seeds, crush, dry in dessicator (or similar). Defat by extracting thoroughly with nonpolar (preferably low-boiling, like DCM), remove solvent traces with vacuum, extract *very* thoroughly with lots of dry methanol (maybe using vacuum soxhlet), concentrate in vacuo, then column chromatograph and maybe a/b to isolate LSA, hydrolyze LSA to lysergic acid (KOH).

Separate iso- from lsyergic (HNO3) and isomerize with KOH. Combine the two  portions of "normal" (non-iso) lysergic acid, and separate optically pure d-lysergic acid via tartrate. Store cold/dark and under inert gas.

Make diethylamine from DEET bug repellant. (make sure you have very good purity here, too)

Make trimethylamine with one of the known methods (I would go for paraform/NH4Cl/160°C, but that's just me) or aquire any other tertiary amine - Purify *very* thorougly...

Turn off the light - illuminate your lab with candles... :)

Dissolve 1 molar eq. d-lysergic acid tartrate in ice-cold analytical grade DCM (dried over mol. sieves) in brown glass flask under inert gas atmosphere,  add 1.1 eq. pyBOP followed by 4 eq. tertiary amine as the free base, stir for five minutes. Then add 2 eq. diethylamine hydrochloride and stir for 3 hours under cooling. When reaction is completed (check with kaiser test), quench with conc. ammonium hydroxide, separate the organic layer, extract 4x with more DCM, combine organics. Wash 2x with ice-cold d.H2O, then 2x with brine (use analytical grade NaCl here, NO TABLE SALT please!) and dry thoroughly with molecular sieves. Place in small evaporation flask (brown glass), rinse sieves 3x with small amount of DCM, and evaporate solvent with a rotovap. Column chromatograph residue to (hopefully) get pure d-lysergic acid diethyl amide.


 - any comments, improvements, critique? What could be done different? And any input about the solvent/rf. values to use for chromatographing the starting material amine, as well as the product amide?


Greetz, A


armageddon

  • Guest
more on chromatography
« Reply #25 on: August 30, 2004, 07:36:00 AM »
And more useful stuff:

http://www.erowid.org/plants/morning_glory/morning_glory_extraction2.shtml



Post 505109

(doktor_alternate: "practicality of large scale column chromatography", Chemicals & Equipment)


Post 488767

(Freemings: "LSD chromatographia", Tryptamine Chemistry)


Post 482624

(Sleen: "LSD  - CDI Method?", Tryptamine Chemistry)
(this one answers the chromatography question quite well)


Post 436693

(chemotype: "hmmm...  250 mg of ergotamine tartrate", Tryptamine Chemistry)
(this is even better  :) )


--

and a very sad thread, too: 

Post 350684 (missing)

(Rhodium: "Half-a-Pint - RIP", General Discourse)

(May you have a happy lab time there, Halfapint! The HIVE collective will never forget you.)

A


hest

  • Guest
More Acid
« Reply #26 on: August 30, 2004, 09:40:00 AM »
From J.Med.Chem 1992,35, 203-211


N-( (R )-l-Methylpropyl)-9,lO-didehydro-6-methylergoline-
B&carboxamide (2)
. (+)-Lysergic acid monohydrate
(150 mg, 0.52 mmol) and 25 mL of dry, ethanol-free CHCl, were
placed in a flamedried 50 d, three-necked, round-bottom flask
equipped with a condenser, N2 line, and septa inlets. The stirred
slurry was brought to reflux in a preheated 90 "C oil bath after
which 384 mg (5.2 mmol) of (R)-(-)-2-butylamine (Aldrich) in 1.0
simultaneously, via syringe, over 3 min. The mixture was allowed
to stir at reflux for an additional 5 min and was then cooled to
room temperature. The clear amber CHC13 solution was then
washed with 1 M NHdOH (3 x 30 mL) and brine (1 X 10 mL)
and dried (Na,SO,). The drying agent was removed by fitration,
and the solution was concentrated in the dark by rotary evaporation
at 30 "C.
The residue was purXed and fractionated by radial centrifugal
chromatography (Chromatotron, Harrison Research) using a silica
gel rotor and eluting with ethyl acetate in an N2-ammonia atmosphere.
TLC (silica gel, EtOAeNH3) showed a large blue
fluorescent product spot at R, 0.21 corresponding to the (R)-2-
butyllprgamide and a much smaller spot at Rf 0.15 corresponding
to the S isomer. The faster moving component was collected and
concentrated by rotary evaporation. The residue was taken up
into CH2ClZ, washed with HzO, and dried (MgSOJ, and the
CHzClz was removed by rotary evaporation followed by pumping
under high vacuum. The free base (158 mg, 94% yield) was taken
up into 2 mL of methanol, and 57 mg of maleic acid in 0.75 mL
of methanol was added. The maleate salt (1:l stoichiometry)
spontaneously crystallized as a white crystalline solid mp 210
"C dec; lH NMR (free base, CDClJ S 0.91 (t, J = 7.5 Hz, 3 H),
1.13 (d, J = 6.7 Hz, 3 H), 1.36-1.56 (m, 2 H), 2.60 (s,3 H), 2.68-2.82
(m, 2 H), 3.05-3.13 (m, 1 H), 3.31-3.56 (m, 3 H), 3.89-3.98 (m,
(m, 3 H), 8.15 (br 8, 1 H); [(Y]D = +48" (c = 0.1, HZO); IR (free
base, neat) 1650 cm-l (C=O). Anal. (CzrH&I3O5) C, H, N.
N - (( S ) - 1 -Met hylpropyl)-g, 1 0-didehydro-6-met hylergolina88-
carboxamide (3)
. An exact replication of the above
procedure using 150 mg of (+)-lysergic acid monohydrate and 384
mg of (S)-(+)-2-butylamine (Aldrich) gave 154 mg (91.7% yield)
of the free base. The free base in methanol was combined with
55 mg of maleic acid in methanol to again yield a white aytalline
solid with 1:l stoichiometry: mp 213 "C dec; 'H NMR (free base,
CDC13) 6 0.93 (t, J = 7.5 Hz, 3 H), 1.13 (d, J = 6.7 Hz, 3 H),
1.37-1.58 (m, 2 H), 2.60 (a, 3 H), 2.66-2.82 (m, 2 H), 3.05-3.13
(m, 1 H), 3.31-3.56 (m, 3 H), 3.89-3.98 (m, 1 H), 6.45 (e, 1 H),
6.60 (d, J = 8.0 Hz, 1 H), 6.92 (8, 1 H), 7.12-7.23 (m, 3 H), 8.02
(br 8, 1 H); [(Y]D = +59" (c = 0.1, HzO); IR (free base, neat) 1650
cm-l ( C 4 ) . Anal. (CurH~N305) C, H, N.




This is amides of lysergacid made by the old synthesis by Nichols. look at the yeald's >90% on a sub g. scale.
Read also J.Med.Chem 1995,38,958-966 here Nicholas et.al produse amides from racemic amines and then purify them on their rotochrome (just a fancy prep. TLC plate). Yeald in the 90's (high 40's of each isomer)


n00dle

  • Guest
So the suggested procedure so far would look...
« Reply #27 on: August 30, 2004, 10:56:00 AM »
So the suggested procedure so far would look like this:

Aquire seeds, crush, dry in dessicator (or similar). Defat by extracting thoroughly with nonpolar (preferably low-boiling, like DCM), remove solvent traces with vacuum, extract *very* thoroughly with lots of dry methanol (maybe using vacuum soxhlet), concentrate in vacuo, then column chromatograph and maybe a/b to isolate LSA, hydrolyze LSA to lysergic acid (KOH).

if you chromatograph it it will be pure, no need to a/b extract it. a/b extraction should be done before chromatograph, only if the quantity of extract is quite large.

Separate iso- from lsyergic (HNO3) and isomerize with KOH.
Use tetrabutylammonium hydroxide with or without NaOH to get 3-2.8-0% iso-lysergic acid plus this hydroxide yeilds 30% yeilds. Precipitate the trace isomers and throw them out (not enough to bother hydrolysing). This will save lots of time doing multiple hydrolysis.

Combine the two  portions of "normal" (non-iso) lysergic acid
(wont be necesarry if one uses tetrabutylammonium hydroxide)
and separate optically pure d-lysergic acid via tartrate.
Seperate/store as the maleic salt as it has been shown that lysergic acid stored as the maleate salt is even more stable than tartarate.
Store cold/dark and under inert gas.

Make diethylamine from DEET bug repellant. (make sure you have very good purity here, too)

Make trimethylamine with one of the known methods (I would go for paraform/NH4Cl/160°C, but that's just me) or aquire any other tertiary amine - Purify *very* thorougly... ( Electrolysis looks good here. Keep the monomethylamine for other things ;) )

Turn off the light - illuminate your lab with candles...smile (yes i was thinking that, since candles dont put off UV or put off very little?

Your prep was good but there were lots of little things, like the order that would be better, so i re-wrote it.

Get your lysergic acid from the step before, still as base, and chuck it straight into this already-prepared reaction system, there is no point storing it as lysergic acid tartarate. Plus, it needs to be freebased for coupling, so you'd have to spend -more- time freebasing it gently. Anyways, since the PyBOP is the main reaction mechanism, this is to be added last, of the rxn: 4eq triethylamine, 2eq diethylamine hcl, 1eq lysergic acid in minimal NP solvent, and 1.05PyBOP.

SWIM is considering a syringe rxn. Suck up the triethylamine first, then lysergic acid tartarate in d.h2o, then diethylamine hcl in d.h2o, then pybop in water (hoping it's soluble in water). Take the syringe, dump it in your fridge and don't open it for a few hours. This might save people the hassle of creating an inert atmosphere. Boiled water shouldn't contain much dissolved gasses. Just fill any leftover space in the syringe with d.h2o and you should have an environment that is inert enough for the 1-2 hour reaction.

Chromatograph with hexane/ethyl acetate in 5% fractions. Still not sure which of these fractions to collect. I guess evaporate them all and find the one that has the most solid product, this is probably the 'peak' of the spectrum containing the most of the lsd product.

Novel idea: When you have chromatographed your LSD, mix it with some free ascorbic acid to form Lysergic Acid Diethylamide Ascorbate. It has been shown in psylocibin that as the ascorbate salt, was stable at room temperature and light exposure and did not readily oxidise to psilocin. Since ascorbic acid is an antioxidant, and LSD is not stored in light normally, the main amount of oxidation will be from oxygen in the air. It is SWIMs oppinion that since psilocybin ascorbate did not oxidise at RT/light, that LSD ascorbate will probably be even more resistant to oxidation than lsd tartarate or lsd maleate. (Comments plz?)

hest

  • Guest
Acid
« Reply #28 on: August 30, 2004, 12:20:00 PM »
Quote from Tikhal

EXTENSIONS AND COMMENTARY : LSD is an unusually fragile molecule and some comments are in order as to its stability and storage. As a salt, in water, cold, and free from air and light exposure, it is stable indefinitely. There are two sensitive aspects of its structure. The position of the carboxamide attachment, the 8-position, is affected by basic, or high pH, conditions. Through a process called epimerization, this position can scramble, producing isolysergic acid diethylamide, or iso-LSD. This product is biologically inactive, and represents a loss of a proportionate amount of active product. A second and separate point of instability is the double bond that lies between this 8-position and the aromatic ring. Water or alcohol can add to this site, especially in the presence of light (sunlight with its ultraviolet energy is notoriously bad) to form a product that has been called lumi-LSD, which is totally inactive in man. Oh yes, and often overlooked, there may be only an infinitesimal amount of chlorine in treated tap water, but then there is only an infinitesimal amount of LSD in a typical LSD solution. And since chlorine will destroy LSD on contact, the dissolving of LSD in tap water is not appropriate.



I Think that Shulgin has a good point here. The big LSD-killer is not light but chlorine ions.

And for the reaction 1: use DCM or DMF as solvent. 2: Don't use the Hydrochloride of DEA use the freebase.
3 seperate on an prep.TLC plate, up to 1g can bee splited at once, an you don't have to learn collumchrom first.


And n00dle could you give me the ref for the tetrabutylammonium hydroxide hydrolysation, I would love to read it


n00dle

  • Guest
reference
« Reply #29 on: August 30, 2004, 02:56:00 PM »

armageddon

  • Guest
order of reactands
« Reply #30 on: August 30, 2004, 04:07:00 PM »
nOOdle: "Plus, it needs to be freebased for coupling, so you'd have to spend -more- time freebasing it gently. Anyways, since the PyBOP is the main reaction mechanism, this is to be added last, of the rxn: 4eq triethylamine, 2eq diethylamine hcl, 1eq lysergic acid in minimal NP solvent, and 1.05PyBOP."

You don't need tor freebase it when you use the tetiary amine as a free base - it will do this in situ if enough excess tert. amine is present - same thing like with diethylamine*HCl. But as the neutralization produces heat: maybe it would really be better to work only with free bases and forget about in-situ basification..

About the order of reactands: "pyBOP reacts with the acid to give an acyloxyphosphonium salt and the amine reacts with this intermediate to give the end product." - as I stated before.

So maybe it would be better to first mix lysergic acid with pyBOP and tetiary amine buffer, let stir for x minutes to form the acyloxy salt, and then add diethylamine to be coupled with and stir for 2-3h.


About the candles emitting almost no UV light: yes, that was my thought behind it, too - and the total amount of light is also very small, although they still allow for enough lighting to be able to work with... not to forget the mystic atmosphere... :)

Chromatograph with hexane/ethyl acetate in 5% fractions. Still not sure which of these fractions to collect. I guess evaporate them all and find the one that has the most solid product, this is probably the 'peak' of the spectrum containing the most of the lsd product.

Maybe one could check with a small UV light and collect the fluorescent band/spot/fraction when chromatographing 'cid..

And:

Post 415643

(Lilienthal: "LSD is not that light sensitive as you might think", Tryptamine Chemistry)

"Table II illustrates that fluorescent light can cause decommposition of LSD in transparent containers when they are placed in close proximity [15 cm] to the light source. Under these conditions, the half-life of LSD was approximately 4 weeks. As the distance between the source of fluorescent light and the samples increased, the percent of LSD decomposition decreased. The results demonstrate that LSD can withstand normal room light conditions at a constant temperature of 25°C for 1 week without noticeable structural change."


:)


Greetz, A


hest

  • Guest
Coupling with PyBOP
« Reply #31 on: August 30, 2004, 05:18:00 PM »

So maybe it would be better to first mix lysergic acid with pyBOP and tetiary amine buffer, let stir for x minutes to form the acyloxy salt, and then add diethylamine to be coupled with and stir for 2-3h.




Yes that is eksatly how you perform an usual peptide couling.


n00dle

  • Guest
Helping ratios
« Reply #32 on: August 30, 2004, 06:09:00 PM »
PyBop MW 520.39672
Lysergic acid MW 268.315
Diethylamine MW = 73.14
Triethylamine MW 101.2
Lysergic Acid Amide MW = 269.315
Tetrabutylammonium Hydroxide MW = 259.4744
NaOH MW = 39.99707

Based on these MW's that SWIM found, and based on using 1gram of peptide coupler (was most expensive chemical in rxn) the following numbers were formed, could someone plz check them.

Hydrolysis
1.5eq TBAOH x 1eq NaOH x 1eq purified woodrose alkaloids
0.003405mol Tetrabutylammonium hydroxide : 0.00227mol NaOH : 0.00227mol purified woodrose alkaloids
0.8835gm Tetrabutylammonium hydroxide : 0.09079gm NaOH : 0.6125gm purified woodrose alkaloids
Rxn = 80% efficiency, Yeilds 0.49gm Lysergic Acid.

Coupling
1.05eq peptide coupler : 1eq lysergic acid : 2eq diethylamine : 4eq triethylamine
0.00192mol pybop to 0.001828mol lysergic acid to 0.003656mol diethylamine to 0.007312mol triethylamine
1 gram pyBOP : 0.49gm lysergic acid : 0.2674gm diethylamine : 0.7399gm triethylamine

rxn efficiency unknown, but assumed high 90's.
Yeilds lysergic acid diethylamide.

armageddon

  • Guest
partial agreement ;^)
« Reply #33 on: August 30, 2004, 07:02:00 PM »
I don't know if you can calculate with the alkaloid mw being that of LSA - there are some other alkaloids as well, with different mw's of course - so better use more here to get enough lysergic. Also I'm very unfamiliar with this tetrabutylammonium hydroxide hydrolysis: does it produce almost no iso and mainly the d-isomer, too? Or would one still have to isolate optically active isomers via tartrate? (notice to myself: maybe I should read the link nOOdle provided us with  :) ).

And about the price of pyBOP: I've seen 5 grams for 110 bucks - think the woodrose thingie would be the more expensive part, at least if your house isn't incidentally covered with them... ;)

Everything else seems right so far.

Greetz A


n00dle

  • Guest
Yeah, one should weigh the woodrose extract...
« Reply #34 on: August 30, 2004, 09:01:00 PM »
Yeah, one should weigh the woodrose extract and hydrolyse based upon this, since the ergot alkaloids will weigh slightly differently. Then chromatograph to pure lysergic acid, etc.

The tetrabutylammonium hydroxide gave hydrolysis yeilds of 80% with 3% iso-lysergic acid or less.

Using tetrabutylammonium hydroxide requires a little under 0.7gm of total alkaloids. 200gm of seeds yeilds roughly 1gm, so about 150gm-180gm of seeds would be required for a 450mg lsd freebase synthesis. Commercially this would be expensive, but most ethnobotanists will have a woodrose plant, and since LSA is not the most inviting chemical to partake with, would probably have lots of seeds to sell/get rid of to a person at very discounted prices. (They would otherwise be wasted.)

armageddon

  • Guest
iso/normal and d/l
« Reply #35 on: August 30, 2004, 10:40:00 PM »
The tetrabutylammonium hydroxide gave hydrolysis yeilds of 80% with 3% iso-lysergic acid or less

What about d/l rotation? lysergic acid cannot only isomerize (iso/normal) but also has a optical rotation (d/l). Only the d-lysergic acid gives LSD-25. That's why I mention the tartrate purification all the time: it allows for separating d- from l-lysergic acid. Isomerization and rotation are not the same thing. And if a synthesis would start with a mixture of d/l lysergic acid, the product would partially consist of inactive l-lysergic aicd diethylamide and therefore, dosaging the product would be a wild guess. But if the synth starts with optically pure d-lys, the end product will have same optical purity.

So go get some l-tartaric acid - it is not only used for storage!  ;)

Greetz A


n00dle

  • Guest
Hm. I have no idea how much of d or l optical...
« Reply #36 on: August 31, 2004, 01:08:00 AM »
Hm. I have no idea how much of d or l optical types of lysergic acid would be formed on hydrolysis. Though since there is very little isomer formed, one might assume that the efficiency of this product might be very inclined to produce one or the other of the optical lysergic acids, and since we favour the active kind, and there are no preperations listing to seperate the optical isomers, one would assume the amount is so little that it would be negligible to save, aka, just toss it with the 3% iso when you chromatograph the crude lysergic acid. Chromatography should get you one molecular isomer and optical isomer of your choice anyhow, right?

armageddon

  • Guest
I think the d/l rotation cannot be changed...
« Reply #37 on: August 31, 2004, 01:42:00 AM »
I think the d/l rotation cannot be changed, and therefore you have to separate the optically active isomers somewhere in the process - either before isomerization, after it or after the coupling reaction.

But I'm not very sure about that; maybe some more experienced bee could help us with that  ;) ?


Another instruction on how to chromatograph LSD-25:

"A solid residue of 3.45 gm. comprising the "normal" and "iso" forms of d-lysergic acid N,N-diethylamide is obtained. This material is dissolved in 160 ml. of a 3-to-1 mixture of benzene and chloroform, and is chromatographed over 240 g. of basic alumia. As the chromatogram is developed with the same solvent, two blue fluroescing zones appear on the alumina column. The more rapidly moving zone is d-lysergic acid N,N-diethylamide which is eluted with about 3000 ml. of the same solvent as above, the course of the elution being followed by watching the downward movement of the more rapidly moving blue fluorescing zone. The eluate is treated with tartaric acid to form the acid tartrate of d-lysergic acid N,N-diethyl amide which is isolated. The acid tartrate of d-lysergic acid N,N-diethyl amide melts with decomposition at about 190-196 degrees centigrade.

The di-iso-lysergic acid N,N-diethyl amide which remains absorbed on the alumia column as the second fluroescent zone is removed from the column by elution with chloroform. The "iso" form of the amide is recovered by evaporating the chloroform eluate to dryness in vacuo."


(

../rhodium/chemistry
/lsdpatent.html

)


Greetz A


n00dle

  • Guest
Yes, but sadly that post doesnt mention ...
« Reply #38 on: August 31, 2004, 02:21:00 AM »
Yes, but sadly that post doesnt mention anything about the optical isomers.. :(

armageddon

  • Guest
sadly yes
« Reply #39 on: August 31, 2004, 04:21:00 AM »
I'm sorry, but I just thought there is some reason why the literature synths use d-lysergic no matter if iso or not, and I doubt that woodrose plants know anything about fractional crystallization via l-tartaric acid or optically active isomers - they simply give racemic LSA. And although having googled for a while, I wasn't able to find a satisfying answer..

Maybe some bee in the know could help here?


About your first post in this thread: It's too easy.. - there you have your complications.  :P  Not as easy as it looked at first sight. But we'll figure it out, would I say!  :)

Greetz A