Nitrostyrene reduction, what happened?

[KidCurry]

SWIM once a long time ago when it still was legal tried a Zn/HCl reduction of 3,4,5-TMNS but something seems to have gone very wrong.

Nitrostyrene mixed with zinc were added to methanol and HCl over 2-3 hours, temperature slowly, slowly raising to 25-30 degrees. 50cl HCl was added, and after another hour more zinc was introduced to the heterogenous mix. This was let to stand with occassional stirring for 14 hours.

The zinc was filtered, and the filtrate was washed once with 100ml toluene. The methanol/HCl-solution was basified with NaOH and something preticipated (probably zinc oxide?), which made the solution very milky and a bit thick. The white preticipate did not dissolve and it was extracted three times with 100ml toluene.

Zinc oxide (or something) after addition of first ml base:


Milky liquid after addition of all base:


Toluene (after extraction) washed with 100ml water in separatory funnel:


Toluene was washed twice with 100ml water. Dried with anhydrous MgSO4, filtered and then gassed with HCl. A lot of crystals came out of solution, and were filtered. This was supposed to be mescaline, but after drying it was going to be recrystallised from 2-propanol. Crystals did not dissolve, 250ml of boiling IPA (and on waterbath) was added, and instead of dissolving it just made a fluffy mess (reminded me of the preticipate first seen when basifying the mixture).

Crystals coming out of toluene while gassing:


Crystals collected in Büchner-funnel:


Is all SWIM have done zinc oxide? And if so,  how come it came over with the toluene extractions, and if so why the heck did it crystallise when gassed? If not, and it really is mescaline, how come it did not dissolve in 250ml boiling IPA?

Strange cloud in IPA:


EDIT: Apparently it's NOT zinc oxide, since swim just remembered that it dissolved in water. So, then what is it? So strange.

[Rhodium]

Do you know for a fact that mescaline hydrochloride should be soluble in hot IPA (just checking the obvious)?

[KidCurry]

Well, of course  SWIM is not 100% sure but according to fellow members of this board that should be the case (SWIM was adviced to recrystallise from either ethanol or IPA).

EDIT: If it's not mescaline, what could it be? What kind of side products could the reduction have made? Obviously it's the salt of something and it's not zinc oxide. It really sucks that SWIM didn't have access to a melting point apparatus or something else to confirm purity/what it really is.

Somebody here must have expereince with mesacline, should about 8g M-HCl be soluble in almost 250ml boiling IPA? And how does it look?

[Rhodium]

Can you make an acid/base extraction, dry the freebase and then make the sulfate salt instead? Mescaline sulfate crystals are easy to prepare and forms very distinctive crystals, see

Post 426832

(terbium: "Not acid sulfate.", Chemistry Discourse)

[KidCurry]

Unfortunately SWIM doesn't have that possibility since sulphuric acid is very hard to get hands on where SWIM lives.

Actually, SWIM guesses that's it's probably just two alternatives left:
1) Discard crystals, and wait for mescaline to become legal and try the reduction again.
2) Bioassay, which doesn't seem like a very good or promising project (ingesting 2-300mg of unkown chemicals seems like a BAD idea).

SWIM is not in any way a very experienced chemist, and he really fails to understand what the crystals are if they're not mescaline (everything seemed good until recrystallisation was supposed to take place), and if they in fact are how come they don't dissolve in the IPA.

According to imp:
"For the hydrochloride salt, IPA/acetone works wonderfully as a recrystallization solvent."

So, maybe SWIM should filter the crystals, and then try another recrystallisation using IPA/acetone (the question is if he means either one of them, or a dual solvent system and if so what ratio?).

SWIM forgot one picture, which is supposed to show some yellow oily substance (mescaline freebase?) on top of milky mixture after basifying:

[Vitus_Verdegast]

- Can zinc oxide be gassed out of a toluene solution with hydrochloric acid on planet Earth?  

- Why haven't I measured the melting point of the impure product yet? Surely even if the temperature is lower due to the crudeness of the product, it could assure me that it is certainly not zinc oxide and may well be my desired product.

[ChemMang]

If your freebase which looks right to me smells horribly of this raw fishy-type smell (that is characteristic of phenethylamine freebases) then you are good to go man!  Go for Mesc Hcl if you can't obtain HgSO4.  Adios
Best of Luck.

[KidCurry]

Thanks for all the help, and advice.
SWIM now has confirmed the "mystery" compound to be mescaline. 

Altough the yields were HORRIBLE. This is probably due to a major fuckup, when SWIM first filtered the crystals he got the genious idea to wash them with water not thinking of that it actually is the salt. Rebasify and then only one extraction was made with toluene. Then also, toluene was only gassed once. SWIM will next time watch out for stupid ideas, and also gas the toluene again after filtering off the first batch. SWIM bets he lost atleast some grams due to this miserable re-workup.

Still, very easy and comfortable route. The only hassle is the addition of zinc/nitrostyrene which takes a lot of time and is really really boring. Workup was no problems. Next time, SWIM's not going to stress it, and give it the time it really takes.

Two questions:
1) Is it a good idea to completely dry the crystals before recrystallisation takes place? Will a bit wet crystals result in lower yields?

2) When extraction the amine with toluene, is it better to do 3x100ml extractions or divide it into maybe 5x60ml? Also, how long should I let the toluene/water stand before separating, will it give more product if it stands for let's say 30 minutes, or is it ok to just wait till the two phases separate?

[Rhodium]

1. Wet with what solvent? Is the solvent miscible with the solvent you are recrystallizing from? Is the substance insoluble or partly soluble in the solvent it's wetted with?

2. Allowing the phases to separate is enough (including any slowly rising/sinking droplets). Regarding extraction sizes, see

Post 453799 (missing)

(Rhodium: "Theory of Extraction", Newbee Forum)

[KidCurry]

1). Miscible and not soluble (or very little).
For example, nitrostyrene formation from aldehyde, wet with methanol and some water, and then recrystallisation from for example ethanol or ipa. Should not be any problems, right?

2). Thanks!

[Rhodium]

In that case there is no difference.