Sciencemadness Discussion Board

TMA-2: Several questions on a particular synthesis

pharmacological - 22-5-2006 at 23:00

Hey everyone,

This is my first post here, though i've been browing for a while. I'd hate to post something that is against the rules here at the boards, but i looked around and didn't really find any rules, so here goes nothing:

The following questions pertain to the following synthesis:

2,4,5-Trimethoxyphenyl-2-nitropropene
100g asarone in 1 l ether was placed in a 3 l rb flask with a saturated solution of 500g sodium nitrite in water and setup on a mag stirrer. A pressure equalized addition funnel which was filled with 800ml of 25% sulfuric acid was then affixed to the flask and dripped into the solution over a period of 5 hours with magnetic stirring. After the 5 hours it was allowed to sit over night (about 14 hours...). In the morning the solution was filtered then the filter cake was washed with water then ethanol then ether. The resulting cake of crystals was dissolved in 500 ml ethanol with 50 g sodium carbonate in it with mag stirring and gentle heat (below 30 c). Once it was completely dissolved it was allowed to cool 1 hour then 1.5kg of ice was added then adding 1l dilute hydrochloric acid acidified it. It was allowed to sit about 1 hour at 0°C then filtered and washed with water and then let dry. This yielded 1/2 cm yellow needle crystals of the 2,4,5 substituted nitropropene with a mp of 100°C.

Yield = about 78 g

2,4,5-Trimethoxyphenyl-2-propanone
75 g of this nitropropene were placed in a rb flask rigged for reflux and addition funnel via claisen adapter with 60g iron filings and 1.2g ferric chloride in 100ml toluene. This solution was brought to reflux then 110g concentrated hydrochloric acid were dripped in over the course of 4 hours. Continue reflux for an additional hour after addition is complete then let cool to room temperature. Solution was then flushed with 2l water and subsequently extracted four times with 200ml ether. The ether extract was dried overnight over drierite filtered then the majority of the ether was distilled off before vacuum drying the ketone.

Yield = about 40g

2,4,5-Trimethoxyphenyl-2-aminopropane Hydrochloride (TMA-2 HCl)
40g ketone was placed in a rb flask setup for simple distillation with 35 ml formamide 4ml 90% formic acid (adjust as necessary to achieve 4.5 ph) and slowly brought up to about 140 c over 4 hours. (This is interactive at this point. what you are looking for is a few small streams of bubbles, kind of like a coke fizzing when about half flat...). Keep the temperature as low as the reaction will allow and raise the temperature only when necessary to keep reaction going. Check the ph about every 4 hours and add formic as necessary to keep ph about 4.5 after 28 hours the reaction temperature had reached the ceiling temperature of 180 c (about 25 ml water had distilled over by this point...). The solution was allowed to cool for 2 hours then extracted four times with 100ml benzene or toluene, then the benzene/toluene was distilled off and the solution is put in a rb rigged for reflux 35 ml concentrated hydrochloric acid is added and it is refluxed for 8 hours. The solution is then cooled for 1 hour and then chilled to 15c basified with 10% sodium hydroxide and extracted four times with 100ml ether. This extract was dried overnight over drierite and filtered in the morning before vacuum evaporating the amine oil. The oil was gassed in the normal manner to yield fine white crystals with an mp of 189°C.

Yield = 36.5g of high energy FUN! [ TMA-2 Hydrochloride ]


Additional notes:

Ritter:

Take it from someone who knows: Randolph Carter has been around here since day 1 but it appears his writing skills (when you can actually read what he wrote) are far advanced compared to his proficiency in organic synthesis. There is no way he produced the ultra-high yields of TMA-2 via Leukart reaction as claimed in the writeup at Rh’s. Phenylacetones simply do not work as well as other ketones with this rxn. If the rxn. is run as Randolph described, you will be lucky to isolate anything greater than a 30% yield of primary amine.


Questions:

1)Is it the beta or the alpha isomer of asarone that is used? I've searched around for hours, but i have not come up with any conclusive results. I am leaning towards the beta isomer, but im not sure.

2)At what pressure and temperature should acorus calamus oil be distilled to give asarone?

3)What does that comment at the end of the synthesis mean?

4)Can the ether be replaced with toluene, or possible dichloromethane?

5)By iron fillings, do they mean pure Fe fillings, or an oxide of some sort? If so, which oxide (II or III?)

6)Does the first step (add of 100g asarone in 1liter ether) require a reflux condenser?

7)In the second step, is the nitropene mixed with the iron fillings, ferric chloride and toluene?



I DO NOT want to infuriate anyone with this post, so if it is breaking any rules, please let me know and I will edit/delete as neccessary =]

Thanks in advance for any help

[Edited on 23-5-2006 by pharmacological]

stoichiometric_steve - 23-5-2006 at 10:30

i can assure you that instead of making the ketone and reducing that to the amine, you should go for my famous Steve Reduction(TM) using Sodium Borohydride, Zinc and Formic Acid. gives nice yields, easy to do, easy to get.

daeron - 24-5-2006 at 00:07

^with all respect to the steve reduction, Pd/C with formate salts works as well(in pH<4), >80% yield if done properly....esp since Na borohydride is raising eyebrows these days in europe

[Edited on 24-5-2006 by daeron]

[Edited on 24-5-2006 by daeron]

pharmacological - 24-5-2006 at 00:11

Thank you, i'm sure that is a viable option, but in the states, Pd/C raises quite a few eyebrows itself

stoichiometric_steve - 24-5-2006 at 01:22

Quote:
Originally posted by daeron
^with all respect to the steve reduction, Pd/C with formate salts works as well(in pH<4), >80% yield if done properly....esp since Na borohydride is raising eyebrows these days in europe


you don't live in europe, i guess? NaBH4 is as readily available and doesn't really raise anything.
but still, making weak presumptions raises quite a few eyebrows in europe ;)

about CTH: do you have any proper sources/writeups that describe a successful CTH procedure other than the what was available from the hive?

Organikum - 24-5-2006 at 19:40

Randolph Carter knew very well what what he did.

But nevertheless the Leukard is prone to make red tar.



[Edited on 25-5-2006 by Organikum]

[Edited on 25-5-2006 by Organikum]

daeron - 23-6-2006 at 05:43

Quote:
Originally posted by stoichiometric_steve
you don't live in europe, i guess? NaBH4 is as readily available and doesn't really raise anything.
but still, making weak presumptions raises quite a few eyebrows in europe ;)

about CTH: do you have any proper sources/writeups that describe a successful CTH procedure other than the what was available from the hive?


actually i do live there, and one of the things i had to do in the past for my work was the Pt,Ru&Pd catalysed hydrogenisations and oxydations, and i assure you altho the order of NaBH4 was covered by a rather famous company i still had to give a shitload of data to the authorities regarding my purchase. so yes it will raise eyebrows, and i dont really approve of one giving advice that may send somewun to a shitlocker. if it worked for you it doesnt mean it will be the same in diff countries, esp that i can vouche that in NL and DE you will raise eyebrows.

as for the refs, there are two one by a indian guy cheslav or sumthing, which i cant get a hold of anymore and the other was regarding the nitroalcohols from tet. let.
the procedure was tested w great excess of NH4,K&Na formates and Pt&Pd on C on rashigs rings, solid foams(TfuckinM) and conventional slurry, yielding from 45 to approx 90% of corresponding amine. that writeup from the ol hive (98 if i remember well) works.

btw the Zn and Fe reductions were used for 2c-x and failed, Pt/C gave ~50ish, Pt,H2+P worked well

Attachment: transfer hydrogenation.pdf (104kB)
This file has been downloaded 2029 times

flyingbanana - 23-6-2006 at 13:46

1) i don't think it should matter since the reaction probably proceeds through cation intermediate. beta-asarone is the major isomer in calamus oil

2) it all depends

3) reported high yield is probably false, given the usual low yields of the leuckart

4) no. you want the nitrous acid to bubble up through the organic layer, so you want it to be on top. additionally, there have been many experiments done with other solvents (pet. ether, hexane, etc.) and the conclusion was only freshly distilled pure ether gave decent yields. diisopropyl ether worked, but not as well.

5) metallic iron

6) ??? the mixing is not exothermic, in fact it is better if you cool the flask in an ice bath during the addition. under an inert atmosphere is even better

7) ????

Isomeric_Fred - 25-6-2006 at 02:35

Fred is some1 else, who had to reregister since he formatted his pc and lost the passes.
anyway, Fred just wanted to say that Steve's Reduction(TM) worked well for 2,5-dimethoxynitrostyrene (with roughly 60% yield), and 4-iodo-2,5-dimethoxy-nitrostyrene was also tried with about the same yield.
Steve's procedure was followed closely, only thing differing is that due to DMNS properties and likelihood of polymerization, temperatures had to be kept low with a water bath, and the styrene addition to the NaBH4/alcohol solution had to be done in very small additions. It is a bit of pain in the ass to reduce a large batch with this tek of this particular compound, but it works well... Dont dismiss anything before you try it.

daeron - 25-6-2006 at 04:16

fair enough, since the failed substituted nitrostirene reductions were done personally via Fe while an....associate tryed the Zn one repeatedly w/out success(there is no reason to not trust her since she used the developed catalyst w success).

however i dont think that any experiments will be done anytime soon, since Pd and Pt are abundant in the lab

Isomeric_Fred - 26-6-2006 at 07:09

is there a possibility that you could write down ur working method for the Pd or Pt hydrogenation system? it would be highly appreciated...

daeron - 29-6-2006 at 00:36

no problem, but if you all dont mind this will be after my, really deserved vacation:)

gylone - 6-7-2006 at 06:16

Hi

can somebody give me more informations about the
Steve Reduction(TM) using Sodium Borohydride, Zinc and Formic Acid .

Lady TMA-2

Sandmeyer - 5-11-2006 at 11:01

Quote:
Yield = 36.5g of high energy FUN! [ TMA-2 Hydrochloride ]


If he actually sucseeded I doubt he would have made the statement about "FUN"...



I couldn't help it... :)

Ullmann - 5-11-2006 at 17:23

Yes, i agree with your point Sandmeyer, fun is not very appropriate for this particular compound...

This picture is a great description of the effects... ;-)

Nicodem - 6-11-2006 at 01:14

The definition of fun is highly dependent on personal and ideological views. A consumer, a masochist, a scientist, a teenager and so on, can all have completely different opinions on what is fun for them. I don't know what Randolph Carter meant when using the word "FUN" but I would not consider the TMA-2 experience as fun, much less FUN. It is certainly very profound and terrible at the same time, but it does not fit my view of what fun is, just as it does not fit my view of what suffering is. It is a completely different dimension of experience that to me is beyond fun or suffering (as demonstrated by the above illustration).

However, I can easily imagine that some perverted gothic weirdo would see it as fun. :D

Maybe Randolph was indeed one such weirdo and Ritter's doubts about the success of the Leuckart reaction are somewhat unfounded. Indeed the (2,4,5-trimethoxyphenyl)acetone should by theory be less prone to self condensing than plain phenylacetone itself. This, and a more careful conduct of the reaction, might have led to high yields. However, I personally still believe that Randolph's 78% reported yield for the Leuckart and hydrolysis combined is very suspect to say the least. But unless he is here to defend his method there is no point in developing such suspicions any further.

randolph_carter - 7-11-2006 at 13:38

howdeeee.........
after lurking around here for QUITE some time and perusing the available textual info on some of my compounds of interest, i had almost given up and decided to try my hand again at running a "board" for ALL the disjointed beez.......
i have long since shut down the previous hot wired reality board i put up out of paranoia after seeing the implosion at the hivage......
but as to this discussion.......

where to start??????

1- yes beta is predominant
2- 185 - 200 degress celsius
3- i would assume the comment at the end was about doubts as to the "actual" yield.....my experience with this particular compound is always "close" to this yield....
4-i always used ether but "pick your favorite poison er solvent" as they say on europa
5- iron filings were purchased and were electrolytically prepared
6- yes a reflux is "reccomended" or your results may vary with your mileage.....
7- yes mix away swabbies.....

FUN......
it all depends on your state of mind and environment....
read: gotta have a good set and setting for ANY serious psychedia.......
also our group of swingerz found that it facilitated the breakdown of interpersonal/couple barriers to OPEN group sexuality with the proper set and setting....

ifn ya brung the whole media brainwash load inta the experience i am SURE you had a darkly tinged experience with this compound.....

have you ever did 500mg of 3-4-5 methoxy-phenethylamine????

ifn ya bung yer deathkult of amerika baggage into that you would have a HELL of an experience as well.....
but go into it with a WIDEASSED OPEN heart and soul and be open to what it's about and boingo....

it doesn't give that "gothic" feel....

i know what ya be ravin about on that angle.....

as to yields once again.....

YES RED TAR CAN BE A PROBLEM!!!!!!

this was not my first drive around this block.......
the first time was NOWHERE NEAR that yield......

as to the efficiency for the leukart-wallach.......
look to p2p - nmethylformamide reduction which routinely yields 90%+ yields when ran properly (i can consistently better 90%....)

ifn ya are skilled it is rewarding experimentation.....

if ya got more questions complaints etc....
i will gladly discuss them with ya.....

enjoy life dudes/dudettes....

"....and remember little ones, love is real not fade away, so pass some on today......"

friends don't let friends and lovers make love in groups of less than three.....
try it you'll like it!!!!!!

oh and by the by here is the whole article for reference.....


TMA-2 from Sweet Flag Root (Acorus Calamus)
By Randolph Carter - The Perennial Dream Questor

--------------------------------------------------------------------------------

Introduction
Sweet flag grows throughout most of north amerika east of the rockies in the wild state in wet areas where wild rice and reeds would feel at home. I found immense stands in Tennessee and northern Mississippi.Therefore my granola-head sensibilities were not offended by the copious gathering, for extraction and transplanting of this aquatic plant to the wilds of extreme north Georgia. It's most prevalent constituents are asarone, eugenol and esters of acetic and heptic acids. Even though this treatise includes my full dreams from the plant roots, I would be remiss if I did not point out that calamus oil is readily available from most of the usual suspects who deal in essential oils. I have found that this is a MUCH more attractive from scratch type of synthesis than sassafras / safrole ever dreamt of being. That is my impetus for doing this research, to wit what can I use that is VERY prevalent in my area to produce a most dreamy not-drug. My experiences with the results of this procedure have been VERY favorable received in most tests (which have been VERY extensive). Field testing indicates that dosages in the 25 to 50 mg range result in some VERY fine psychedelic dreams that are quite facilitative to sexually enjoyment with single or multiple sexual partners unlike many heavy psychedelics.

Anyways here is the rest of the story as paul harvey sez...

Steam Extraction Technique
The extractor is about 2' in height and about 16" in diameter made of stainless steel and has tight fitting "connections".Imagine a large pot with a drain spigot on the bottom, on top of the pot is an approx 1 1/2 gal "steamer" with sealing lid and a bottom of preforated holes. (i lined the bottom of this with fine gauge stainless steel screen finer than pipe screens..from industrial sources to minimize grit and small pieces of root fibers...) To operate i dreamed that i charged the "basket" with all the ground roots (ground by a small hammer mill used on the farm for other herbs we sell...chopped root would work equally well we feel...)the top was sealed on with silicone stopcock/joint grease and it was heated to boiling and maintained there for about 6 hours per load (7 loads required for 10 kg...). After cooling down the top is removed and the water with an oil layer was drained into a nalgene carboy with spigot which allowed for a "crude" seperation of the oil and a small amount of water. Then it was shook in the carboy with the applicable washes mentioned below before being put in a "real" 2l sep funnel for final seperation.

Calamus Essential Oil
Approximately 10 kg of dried calamus root were steam distilled with the help of the above mentioned stainless steel juicer/extractor obtained through cumberland general store. (This item is commonly found in seed catalogs from several companies as well). This yielded 330 g of viscid light yellow oil with a bitter taste, which was only slightly soluble in water. After separating the oil, the oil was washed with first a water solution of sodium carbonate then water then it was seperated from the water layer then dried over drierite overnight before further usage.

Yield = about 320 g clean calamus oil.

Asarone
Next this oil was fractionally distilled to yield a fraction at 185 to 200°C which was chiefly asarone.

Yield = about 210g

2,4,5-Trimethoxyphenyl-2-nitropropene
100g asarone in 1 l ether was placed in a 3 l rb flask with a saturated solution of 500g sodium nitrite in water and setup on a mag stirrer. A pressure equalized addition funnel which was filled with 800ml of 25% sulfuric acid was then affixed to the flask and dripped into the solution over a period of 5 hours with magnetic stirring. After the 5 hours it was allowed to sit over night (about 14 hours...). In the morning the solution was filtered then the filter cake was washed with water then ethanol then ether. The resulting cake of crystals was dissolved in 500 ml ethanol with 50 g sodium carbonate in it with mag stirring and gentle heat (below 30 c). Once it was completely dissolved it was allowed to cool 1 hour then 1.5kg of ice was added then adding 1l dilute hydrochloric acid acidified it. It was allowed to sit about 1 hour at 0°C then filtered and washed with water and then let dry. This yielded 1/2 cm yellow needle crystals of the 2,4,5 substituted nitropropene with a mp of 100°C.

Yield = about 78 g

2,4,5-Trimethoxyphenyl-2-propanone
75 g of this nitropropene were placed in a rb flask rigged for reflux and addition funnel via claisen adapter with 60g iron filings and 1.2g ferric chloride in 100ml toluene. This solution was brought to reflux then 110g concentrated hydrochloric acid were dripped in over the course of 4 hours. Continue reflux for an additional hour after addition is complete then let cool to room temperature. Solution was then flushed with 2l water and subsequently extracted four times with 200ml ether. The ether extract was dried overnight over drierite filtered then the majority of the ether was distilled off before vacuum drying the ketone.

Yield = about 40g

2,4,5-Trimethoxyphenyl-2-aminopropane Hydrochloride (TMA-2 HCl)
40g ketone was placed in a rb flask setup for simple distillation with 35 ml formamide 4ml 90% formic acid (adjust as necessary to achieve 4.5 ph) and slowly brought up to about 140 c over 4 hours. (This is interactive at this point. what you are looking for is a few small streams of bubbles, kind of like a coke fizzing when about half flat...). Keep the temperature as low as the reaction will allow and raise the temperature only when necessary to keep reaction going. Check the ph about every 4 hours and add formic as necessary to keep ph about 4.5 after 28 hours the reaction temperature had reached the ceiling temperature of 180 c (about 25 ml water had distilled over by this point...). The solution was allowed to cool for 2 hours then extracted four times with 100ml benzene or toluene, then the benzene/toluene was distilled off and the solution is put in a rb rigged for reflux 35 ml concentrated hydrochloric acid is added and it is refluxed for 8 hours. The solution is then cooled for 1 hour and then chilled to 15c basified with 10% sodium hydroxide and extracted four times with 100ml ether. This extract was dried overnight over drierite and filtered in the morning before vacuum evaporating the amine oil. The oil was gassed in the normal manner to yield fine white crystals with an mp of 189°C.

Yield = 36.5g of high energy FUN! [ TMA-2 Hydrochloride ]


--------------------------------------------------------------------------------

pantone159 - 20-11-2006 at 18:37

I have no experience with this compound, but it sounds like Shulgin liked the effects.

http://www.erowid.org/library/books_online/pihkal/pihkal158....
Quote:

(with 40 mg) Beautiful plus 3. Some visuals, but not intrusive. Moderate, good-mannered kaleidoscopic imagery against dark. Music superb. Clear thinking. Calmly cosmic. This is a seminal, or archetypal psychoactive material. A very good experience and good for repeats. About 10-12 hrs. Sleep difficult but OK.

jon - 24-1-2009 at 20:55

i have a question about this why not simply halogenate that double propenyl bond then react it with aqueous KOH under reflux to give the halohydrin intermdiate via sn2 with hydroxide and then the elimination product epoxide and finally the ketone all in the same pot.
I'm aware that an activated ring such as this would not stand up to peracid oxidations because the carbcation generated at the benzylic carbon during the pinacol rearrangement is to reactive and give a bis-tetrahydrofuran product. since this ring is so highly activated.
as stated somewhere on rhodium's page.
the exact nomenclature eludes me.
so the questions are as follows:
the carbocation formed during the in-situ rearrangement in this case is done under basic conditions.
in contrast to the pinacol rearrangement, so is this a viable and simple route to the ketone?
question # 2:
KOH is known to split alkyl-aryl ethers in protic solvents but only under extreme conditions but since this ring is so highly substituted would that be a plausable outcome?

[Edited on 25-1-2009 by jon]

Sauron - 24-1-2009 at 23:42

I have a question too. Why are you revivying a 3 year old dead drug thread?

Ebao-lu - 25-1-2009 at 02:33

Quote:
the carbocation formed during the in-situ rearrangement in this case is done under basic conditions.
in contrast to the pinacol rearrangement, so is this a viable and simple route to the ketone?

If there is a benzylic carbocathion during epoxide isomerization, then what's the difference form the pinacol rearrangement then? Besides, i've never heared that pinacol rearrangement on such ring-activated compounds is problematic(perhaps could you give some refference)?
Concerning your question, KOH + epoxide will no way give a carbocathion, it can either open the epoxide ring, or abstract hydrogen causing E2-elimination, but not carbocathion. If it is realy the case(basic rearrangement of epoxide to ketone is possible, and acidic is not), then better to make the epoxide directly from asarone, with peracetic acid, and then basicly rearrange it. Still, i think that KOH is not a good choice for epoxide isomerization to ketone.
Quote:
KOH is known to split alkyl-aryl ethers in protic solvents but only under extreme conditions but since this ring is so highly substituted would that be a plausable outcome?

Also never heared of this. Ether bond is known to be very resistant to base treatment. What do you mean by extreme conditions, and why you suppose "highly substituted" product should react easier? Could you give some refference? Very interesting (as a method for eugenol demethylation and isomerization in one pot).

Concerning the thread discussion - isn't it better to make TMA-2 by reduction of nitropropene directly? (with NaBH4, Al/Hg, LiAlH4 etc)?
(ps Sauron and mods, i hope you dont mind if i post to this druggie thread, though it is absolutely useless, it is not strictly prohibited too)

[Edited on 25-1-2009 by Ebao-lu]

jon - 25-1-2009 at 10:46

you're right i can't locate the reference but i know you don't use acids on highly activated rings to reararrange the epoxide, Lithium Iodide is probably the best choice.
the condidtions for ether cleavage with koh is something like KOH ethylene glycol and ridiculously high temps like 300 C (but this is for ortho ether cleavage which are the most difficult to cleave) so it's no issue there are discussions about base demethylations on ally benzenes but they give predominantly the demethylated carboxylic acids salts.
this is in molten NaOH.

[Edited on 25-1-2009 by jon]

starman - 28-1-2009 at 08:40

Quote:
Originally posted by jon
i have a question about this why not simply halogenate that double propenyl bond then react it with aqueous KOH under reflux to give the halohydrin intermdiate via sn2 with hydroxide and then the elimination product epoxide and finally the ketone all in the same pot.



[Edited on 25-1-2009 by jon]


I don't know if it applies identically with asarone but Varenne and Godfrey(Compt.rend. 140 (1905),591.) certainly proceeded similarly with anethole dibromides in alcoholic potassium "in the cold". The glycol (epoxide?) is then familiarly treated with H2SO4 to yeild the ketone.

HollowMan - 2-2-2015 at 17:27

Hi,
does someone of you read this posts?
http://www.lycaeum.org/hive/messages/2347.html
its about problems which can occur during preparation of the pseudonitrosite for example:

"Jesus, that's liquid N2O3 condensing in your flask. I suggest using an erlenmeyer flask, which will produce a thicker layer of ether above the NaNO2 soln., helping with the absorption. This indicates there is a big excess of free N2O3 in solution, which easily destroys everything. Take your time, add that HCl really slow!

: Muki's Pseudochemist has realized that BUBBLES ARE BAD. If bubbling in noted, N2O3 is being wasted and addition of HCl should be slowed. N2O3 should dissolve in the ether til saturated?

NOOOO, don't saturate your ether with N2O3. Always keep the amount of free, unreacted N2O3 low. Bubbling is not that bad. I didn't calculate it myself, but you have a big excess of NaNO2 soln. there.
:
: : When ether layer turns red, it's probably too late. Stop addition much earlier.

: Yes, but stop with the monomer or the dimer? Monomer could be separated out MUCH more simply because, unlike the dimer, it lacks the consistency of well-chewed gum. Sep. funnel in a jiff.

I see, a misunderstanding. Monomer and dimer here mean the following: in solution there is always the monomer (blue or green). Insolid form, it's always the dimer. And the monomers combine spontaneously to form the dimer, even in ether solution. So stop when you think you have produced enough precipitate, and BEFORE the color of the ether layer changes into dirty brown/red or whatever (my experiments are long ago).

: Simulated experiment: avoiding the bubbles. Add HCl as slowly as possible with the goal of no bubbles. When HCl can no longer be added without bubbles, then it's done.

Probably impossible. I used addition funnel, magnetic stirring and added over several hours. But there was always visible bubbling."

I also tried making the pseudonitrosite of asarone, but I got really bad yield (about 25%)
So i have a some questions about :
1)Do I just need asarone(deskilled from indian calamus oil) for this experiment or does it just work (or even better) with alpha, beta asarone?
2)During the addition of the H2SO4 should i cool to about 1°C to get more N2O3 instead of NO<->NO2?
3)What happens, if the ether layer get discolored (red/brownish) does it mean there is an excess if N2O3? (Thats what happened last time)
4) Does an excess of N203 really damage the pseudonitrosite?
5)After addition of H2SO4 should i stir over night or just 2 hours further on?

There are 2 slightly different preparations of pseudonitrosites available on erowid:

https://www.erowid.org/archive/rhodium/chemistry/pseudonitro...
https://www.erowid.org/archive/rhodium/chemistry/tma2.html

They use different reaction times and quantities of NaNO2.
Which one is preferable?

Best regards in advance :D

morganbw - 7-2-2015 at 04:38

Quote: Originally posted by HollowMan  
Hi,
does someone of you read this posts?
http://www.lycaeum.org/hive/messages/2347.html
its about problems which can occur during preparation of the pseudonitrosite for example:

"Jesus, that's liquid N2O3 condensing in your flask. I suggest using an erlenmeyer flask, which will produce a thicker layer of ether above the NaNO2 soln., helping with the absorption. This indicates there is a big excess of free N2O3 in solution, which easily destroys everything. Take your time, add that HCl really slow!

: Muki's Pseudochemist has realized that BUBBLES ARE BAD. If bubbling in noted, N2O3 is being wasted and addition of HCl should be slowed. N2O3 should dissolve in the ether til saturated?

NOOOO, don't saturate your ether with N2O3. Always keep the amount of free, unreacted N2O3 low. Bubbling is not that bad. I didn't calculate it myself, but you have a big excess of NaNO2 soln. there.
:
: : When ether layer turns red, it's probably too late. Stop addition much earlier.

: Yes, but stop with the monomer or the dimer? Monomer could be separated out MUCH more simply because, unlike the dimer, it lacks the consistency of well-chewed gum. Sep. funnel in a jiff.

I see, a misunderstanding. Monomer and dimer here mean the following: in solution there is always the monomer (blue or green). Insolid form, it's always the dimer. And the monomers combine spontaneously to form the dimer, even in ether solution. So stop when you think you have produced enough precipitate, and BEFORE the color of the ether layer changes into dirty brown/red or whatever (my experiments are long ago).

: Simulated experiment: avoiding the bubbles. Add HCl as slowly as possible with the goal of no bubbles. When HCl can no longer be added without bubbles, then it's done.

Probably impossible. I used addition funnel, magnetic stirring and added over several hours. But there was always visible bubbling."

I also tried making the pseudonitrosite of asarone, but I got really bad yield (about 25%)
So i have a some questions about :
1)Do I just need asarone(deskilled from indian calamus oil) for this experiment or does it just work (or even better) with alpha, beta asarone?
2)During the addition of the H2SO4 should i cool to about 1°C to get more N2O3 instead of NO<->NO2?
3)What happens, if the ether layer get discolored (red/brownish) does it mean there is an excess if N2O3? (Thats what happened last time)
4) Does an excess of N203 really damage the pseudonitrosite?
5)After addition of H2SO4 should i stir over night or just 2 hours further on?

There are 2 slightly different preparations of pseudonitrosites available on erowid:

https://www.erowid.org/archive/rhodium/chemistry/pseudonitro...
https://www.erowid.org/archive/rhodium/chemistry/tma2.html

They use different reaction times and quantities of NaNO2.
Which one is preferable?

Best regards in advance :D


I have no interest in this chemical but if I did I would do several small scale reactions using the different parameters you mentioned and attempt to characterize the reaction.

Once you have a favorable reaction then look into Design Of Experiments (DOE) to optimize it.

HollowMan - 9-2-2015 at 15:55

its pretty interesting did u ever try?
Anyway the key is just to drop h2so4 until ether layer doesn't go green anymore und there is no yellow precipitate going down. After this the top layer will start to chance the color to a kind of orange. Thats the point to stop or better a bit further. Cooling was applied during beginning of addition. Yield of pseudonitrosite was 60-62% with this method.
just half of volume (h2so4) was needed. Good washing of pseudonitrosite is essential because naso4 is pretty but solvable in water.